KR102465241B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel compound and organic light emitting device using the same

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

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

An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic 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, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, it may be made of an electron injection layer, etc. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons It lights up when it falls back to the ground state.

The 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):

A compound represented by the following formula (1):

[Formula 1]

In Formula 1,

L ₁ To L ₃ are each independently, a single bond, or a substituted or unsubstituted C _6-60 arylene,

Ar ₁ is a substituent represented by the following formula (2),

[Formula 2]

In Formula 2,

A1 is each independently a benzene ring or a naphthalene ring fused with an adjacent pentacyclic ring, provided that at least one of A1 is a naphthalene ring,

Ar ₂ is a substituent represented by the following formula (3),

[Formula 3]

In Formula 3,

A2 is a benzene ring fused with two adjacent rings,

Ar ₃ is substituted or unsubstituted C _6-60 aryl.

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

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

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

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

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

(Definition of Terms)

및

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

and

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium, a halogen group, a cyano group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, an amino group, a phosphine oxide group, an alkoxy group, an aryloxy group, an alkyl group Thioxy group, arylthioxy group, alkylsulfoxy group, arylsulfoxy group, silyl group, boron group, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, aralkenyl group, alkylaryl group, alkylamine group, aralkylamine substituted or unsubstituted with one or more substituents selected from the group consisting of a group, a heteroarylamine group, an arylamine group, an arylphosphine group, or a heteroaryl containing at least one of N, O and S atoms, or It means substituted or unsubstituted in which two or more substituents among the substituents are connected. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

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

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

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

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

In the present specification, the boron group specifically includes a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron 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 number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

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

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

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

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

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

In Formula 1, at least one hydrogen may be substituted with deuterium.

Preferably, Ar ₁ is any one selected from the group comprising the following formulas:

In each of the above formulas, the dotted line is connected to L ₁ in the above formula (1).

Preferably, Ar ₂ is any one selected from the group comprising the following formulas:

.

.

More preferably, Ar ₂ is any one selected from the group comprising the following formulas:

.

.

Preferably, Ar ₃ is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, or triphenylenyl; Ar ₃ is unsubstituted or substituted with one or more deuterium.

Preferably, L ₁ and L ₂ are both single bonds.

Also, preferably L ₃ is a single bond, phenylene or naphthylene; L ₃ is unsubstituted or substituted with one or more deuterium or phenyl.

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

.

.

Meanwhile, the compound represented by Chemical Formula 1 may be prepared by a preparation method as shown in Scheme 1 below.

[Scheme 1]

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

In addition, the present invention provides an organic light emitting device including the compound represented by the formula (1). In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Formula 1 above. 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 multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. 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 electron blocking layer, and the electron blocking layer includes a compound represented by Formula 1 above.

In addition, the organic material layer may include a light emitting layer, and the light emitting layer includes the compound represented by Formula 1 above. In particular, the compound according to the present invention can be used as a host material for the red light emitting layer.

In addition, the organic 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 that simultaneously transports and injects electrons includes the compound represented by Formula 1 above.

In addition, the organic 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 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. Also, 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 the organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS. 1 and 2 .

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

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

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

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. and, after forming 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, spraying, roll coating, and the like, but is not limited thereto.

In addition to the above 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.

In one 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 generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

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

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. A material capable of transporting holes from the anode or hole injection layer to the light emitting layer as a hole transport material. A material with high hole mobility. This is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The electron suppression layer serves to improve the efficiency of the organic light emitting device by suppressing electrons injected from the cathode from being transferred to the anode without recombination in the light emitting layer.

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

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

Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group. As the styrylamine compound, a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes 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 light emitting layer. do. Specific examples include Al complex of 8-hydroxyquinoline; complexes comprising Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals 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-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

The organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side 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 compound represented by Formula 1 and the preparation of an organic light emitting device including the same will be described in detail in Examples below. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Synthesis Example 1

In a nitrogen atmosphere, sub1 (10 g, 46 mmol), formula a (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.7 g of Compound 1. (Yield 58%, MS: [M+H]+=590)

Synthesis Example 2

In a nitrogen atmosphere, sub1 (10 g, 46 mmol), formula b (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.5 g of Compound 2. (Yield 61%, MS: [M+H]+=590)

Synthesis Example 3

In a nitrogen atmosphere, sub1 (10 g, 46 mmol), formula c (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.4 g of Compound 3. (Yield 57%, MS: [M+H]+=590)

Synthesis Example 4

In a nitrogen atmosphere, sub1 (10 g, 46 mmol), formula d (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.1 g of Compound 4. (Yield 63%, MS: [M+H]+=590)

Synthesis Example 5

In a nitrogen atmosphere, sub1 (10 g, 46 mmol), formula e (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.2 g of compound 5. (Yield 67%, MS: [M+H]+=590)

Synthesis Example 6

In a nitrogen atmosphere, sub2 (10 g, 46 mmol), formula a (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.8 g of compound 6. (Yield 62%, MS: [M+H]+=590)

Synthesis Example 7

In a nitrogen atmosphere, sub2 (10 g, 46 mmol), formula b (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.7 g of Compound 7. (Yield 58%, MS: [M+H]+=590)

Synthesis Example 8

In a nitrogen atmosphere, sub2 (10 g, 46 mmol), formula c (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.9 g of compound 8. (Yield 55%, MS: [M+H]+=590)

Synthesis Example 9

In a nitrogen atmosphere, sub2 (10 g, 46 mmol), formula d (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19 g of compound 9. (Yield 70%, MS: [M+H]+=590)

Synthesis Example 10

In a nitrogen atmosphere, sub2 (10 g, 46 mmol), formula e (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.3 g of compound 10. (Yield 60%, MS: [M+H]+=590)

Synthesis Example 11

In a nitrogen atmosphere, sub3 (10 g, 46 mmol), formula a (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.2 g of compound 11. (Yield 55%, MS: [M+H]+=640)

Synthesis Example 12

In a nitrogen atmosphere, sub3 (10 g, 46 mmol), formula b (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.2 g of compound 12. (Yield 55%, MS: [M+H]+=640)

Synthesis Example 13

In a nitrogen atmosphere, sub3 (10 g, 46 mmol), formula c (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.9 g of compound 13. (Yield 61%, MS: [M+H]+=640)

Synthesis Example 14

In a nitrogen atmosphere, sub3 (10 g, 46 mmol), formula d (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.3 g of compound 14. (yield 59%, MS: [M+H]+=640)

Synthesis Example 15

In a nitrogen atmosphere, sub3 (10 g, 46 mmol), formula e (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.8 g of compound 15. (Yield 57%, MS: [M+H] + = 640)

Synthesis Example 16

In a nitrogen atmosphere, sub4 (10 g, 46 mmol), formula a (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.3 g of compound 16. (Yield 52%, MS: [M+H] + = 640)

Synthesis Example 17

In a nitrogen atmosphere, sub4 (10 g, 46 mmol), formula b (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.1 g of compound 17. (Yield 65%, MS: [M+H]+=640)

Synthesis Example 18

In a nitrogen atmosphere, sub4 (10 g, 46 mmol), formula c (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.8 g of compound 18. (Yield 64%, MS: [M+H]+=640)

Synthesis Example 19

In a nitrogen atmosphere, sub4 (10 g, 46 mmol), formula d (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.7 g of compound 19. (Yield 50%, MS: [M+H]+= 640)

Synthesis Example 20

In a nitrogen atmosphere, sub4 (10 g, 46 mmol), formula e (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.2 g of compound 20. (Yield 62%, MS: [M+H]+=640)

Synthesis Example 21

In a nitrogen atmosphere, sub5 (10 g, 46 mmol), formula a (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20 g of compound 21. (Yield 68%, MS: [M+H] + = 640)

Synthesis Example 22

In a nitrogen atmosphere, sub5 (10 g, 46 mmol), formula b (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.7 g of compound 22. (Yield 67%, MS: [M+H]+=640)

Synthesis Example 23

In a nitrogen atmosphere, sub5 (10 g, 46 mmol), formula c (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.6 g of compound 23. (Yield 53%, MS: [M+H]+=640)

Synthesis Example 24

In a nitrogen atmosphere, sub5 (10 g, 46 mmol), formula d (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.5 g of Compound 24. (Yield 63%, MS: [M+H]+= 640)

Synthesis Example 25

In a nitrogen atmosphere, sub5 (10 g, 46 mmol), formula e (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.6 g of compound 25. (Yield 60%, MS: [M+H]+=640)

Synthesis Example 26

In a nitrogen atmosphere, sub1 (10 g, 46 mmol), formula e (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.3 g of compound 26. (Yield 60%, MS: [M+H]+=590)

Synthesis Example 27

In a nitrogen atmosphere, sub1 (10 g, 46 mmol), formula f (23.2 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.6 g of compound 27. (Yield 70%, MS: [M+H]+=640)

Synthesis Example 28

In a nitrogen atmosphere, sub1 (10 g, 46 mmol), chemical formula g (24.5 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.7 g of compound 28. (Yield 58%, MS: [M+H]+=666)

Synthesis Example 29

In a nitrogen atmosphere, sub1 (10 g, 46 mmol), formula h (25.7 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19 g of compound 29. (Yield 60%, MS: [M+H]+= 690)

Synthesis Example 30

In a nitrogen atmosphere, sub1 (10 g, 46 mmol), formula i (27 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.1 g of compound 30. (Yield 58%, MS: [M+H]+= 716)

Synthesis Example 31

In a nitrogen atmosphere, sub2 (10 g, 46 mmol), formula j (28.3 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.8 g of compound 31. (Yield 70%, MS: [M+H]+= 740)

Synthesis Example 32

In a nitrogen atmosphere, sub2 (10 g, 46 mmol), formula k (23.2 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.5 g of compound 32. (Yield 63%, MS: [M+H]+= 640)

Synthesis Example 33

In a nitrogen atmosphere, sub2 (10 g, 46 mmol), formula I (24.5 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.1 g of compound 33. (Yield 56%, MS: [M+H]+=666)

Synthesis Example 34

In a nitrogen atmosphere, sub2 (10 g, 46 mmol), chemical formula m (28.4 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.8 g of compound 34. (Yield 64%, MS: [M+H]+= 742)

Synthesis Example 35

In a nitrogen atmosphere, sub2 (10 g, 46 mmol), formula n (28.4 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.8 g of compound 35. (Yield 67%, MS: [M+H]+= 742)

Synthesis Example 36

In a nitrogen atmosphere, sub3 (10 g, 46 mmol), formula o (27 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.3 g of compound 36. (yield 69%, MS: [M+H]+= 766)

Synthesis Example 37

In a nitrogen atmosphere, sub6 (10 g, 46 mmol), formula p (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.7 g of compound 37. (Yield 67%, MS: [M+H]+=640)

Synthesis Example 38

In a nitrogen atmosphere, sub6 (10 g, 46 mmol), formula q (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.5 g of compound 38. (Yield 63%, MS: [M+H]+= 640)

Synthesis Example 39

In a nitrogen atmosphere, sub6 (10 g, 46 mmol), formula r (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.5 g of compound 39. (Yield 63%, MS: [M+H]+= 640)

Synthesis Example 40

In a nitrogen atmosphere, sub6 (10 g, 46 mmol), chemical formulas (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.5 g of compound 40. (Yield 63%, MS: [M+H]+= 640)

Synthesis Example 41

In a nitrogen atmosphere, sub6 (10 g, 46 mmol), formula t (20.6 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.1 g of compound 41. (Yield 65%, MS: [M+H]+=640)

<Comparative Example 1>

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was 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 thus prepared ITO transparent electrode to a thickness of 1150 Å, 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. Then, the following EB-1 compound was vacuum-deposited to a thickness of 150 Å on the hole transport layer to form an electron blocking layer. Then, the following RH-1 compound and the following Dp-39 compound were vacuum-deposited on the EB-1 deposited film in a weight ratio of 98:2 to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed by vacuum-depositing the following HB-1 compound to a thickness of 30 Å on the light emitting layer. Then, on the hole blocking layer, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 to form an electron injection and transport layer to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

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

<Comparative Examples 2 to 8>

Device performance was measured in the same manner as in Comparative Example 1, except that the following compounds RH-2 to RH-10 were respectively used instead of RH-1 as a host material for the red light emitting layer.

<Examples 1 to 40>

Except for using each of the compounds 1 to 40 prepared by Synthesis Example instead of Comparative Example 1 as the host material for the red light emitting layer, it was carried out in the same manner as in Comparative Example 1, and device performance was measured.

As in Comparative Examples 1 to 10 and Examples 1 to 26, driving voltage, current efficiency, and lifespan were measured for the organic light emitting devices prepared using each compound as a red host material, and the results are shown in Table 1 below. It was.

Experimental example host material drive voltage
(V) current efficiency
(cd/A) life span
(T95%@10mA) Comparative Example 1 RH-1 5.52 15.35 79 Comparative Example 2 RH-2 5.41 14.15 68 Comparative Example 3 RH-3 5.35 14.62 84 Comparative Example 4 RH-4 5.15 14.90 59 Comparative Example 5 RH-5 5.52 14.07 63 Comparative Example 6 RH-6 5.14 15.08 80 Comparative Example 7 RH-7 5.16 13.76 59 Comparative Example 8 RH-8 5.43 15.13 80 Comparative Example 9 RH-9 5.32 16.17 58 Comparative Example 10 RH-10 5.33 13.80 98 Example 1 compound 1 4.42 26.41 169 Example 2 compound 2 4.32 25.25 184 Example 3 compound 3 4.70 25.36 170 Example 4 compound 4 4.58 23.34 175 Example 5 compound 5 4.54 26.12 189 Example 6 compound 6 4.41 23.49 172 Example 7 compound 7 4.49 24.12 175 Example 8 compound 8 4.20 23.82 179 Example 9 compound 9 4.42 23.14 182 Example 10 compound 10 4.39 25.11 181 Example 11 compound 11 4.37 20.99 171 Example 12 compound 12 4.44 21.88 177 Example 13 compound 13 4.58 22.29 190 Example 14 compound 14 4.50 25.24 181 Example 15 compound 15 4.44 25.15 167 Example 16 compound 16 4.32 23.11 171 Example 17 compound 17 4.23 22.25 180 Example 18 compound 18 4.59 23.23 194 Example 19 compound 19 4.29 24.61 186 Example 20 compound 20 4.42 23.82 172 Example 21 compound 21 4.22 23.423 173 Example 22 compound 22 4.44 24.28 182 Example 23 compound 23 4.63 26.33 170 Example 24 compound 24 4.50 24.81 172 Example 25 compound 25 4.13 22.10 180 Example 26 compound 26 4.52 24.33 169 Example 27 compound 27 4.67 21.38 175 Example 28 compound 28 4.57 21.68 169 Example 29 compound 29 4.58 22.22 175 Example 30 compound 30 4.39 21.22 185 Example 31 compound 31 4.19 24.25 169 Example 32 compound 32 4.20 23.87 168 Example 33 compound 33 4.21 23.59 170 Example 34 compound 34 4.38 23.11 197 Example 35 compound 35 4.08 23.00 188 Example 36 compound 36 4.29 24.10 187 Example 37 compound 37 4.06 22.49 179 Example 38 compound 38 4.18 22.69 180 Example 39 compound 39 4.28 21.16 176 Example 40 compound 40 4.32 20.98 198 Example 41 compound 41 4.55 24.22 168

As shown in Table 1, the organic light emitting device of the Example using the compound represented by Formula 1 as a host material for the red light emitting layer exhibited excellent properties in terms of driving voltage, luminous efficiency, and lifespan.

Considering that the luminous efficiency and lifespan characteristics of the organic light emitting device have a trade-off relationship with each other in general, the organic light emitting device employing the compound of the present invention exhibits significantly improved device characteristics compared to the comparative example device. can be found

1: Substrate 2: Anode
3: hole transport layer 4: light emitting layer
5: Electron injection and transport layer 6: Cathode
7: hole injection layer 8: electron suppression layer
9: hole blocking layer

Claims (10)

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

In Formula 1,
L ₁ To L ₃ are each independently, a single bond, or a substituted or unsubstituted C _6-60 arylene,
Ar ₁ is a substituent represented by the following formula (2),
[Formula 2]

In Formula 2,
A1 is each independently a benzene ring or a naphthalene ring fused with an adjacent pentacyclic ring, provided that at least one of A1 is a naphthalene ring,
Ar ₂ is any one selected from the group comprising the following formulas,

Ar ₃ is substituted or unsubstituted C _6-60 aryl.
According to claim 1,
Ar ₁ is any one selected from the group comprising the following formulas,
compound:

In each of the above formulas, the dotted line is connected to L ₁ in the above formula (1).
delete According to claim 1,
Ar ₂ is any one selected from the group comprising the following formulas,
compound:

According to claim 1,
Ar ₃ is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, or triphenylenyl,
Wherein Ar ₃ is unsubstituted or substituted with one or more deuterium,
compound.
According to claim 1,
L ₁ and L ₂ are both single bonds;
compound.
According to claim 1,
L ₃ is a single bond, phenylene or naphthylene,
The L ₃ is unsubstituted or substituted with one or more deuterium or phenyl,
compound.
According to claim 1,
Any one selected from the group comprising the following formulas,
compound:

An organic light emitting device comprising a first electrode, a second electrode provided to face the first electrode, and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises: An organic light emitting device comprising the compound according to any one of claims 1, 2, and 4 to 8.
10. The method of claim 9,
The organic material layer containing the compound is a light emitting layer,
organic light emitting device.

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