KR102583651B1 - 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 comprising the same}

The present invention relates to novel compounds and organic light-emitting devices containing them.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices using the organic light-emitting phenomenon have a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, so much research is being conducted.

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

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 novel compounds and organic light-emitting devices containing them.

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

[Formula 1]

In Formula 1,

A is a benzene ring fused with two adjacent rings,

R ₁ and R ₂ are substituted or unsubstituted C _1-60 alkyl; or substituted or unsubstituted C _6-60 aryl, or R ₁ and R ₂ are combined together to form a substituted or unsubstituted C _6-60 aromatic ring,

R ₃ is substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

L ₁ and L ₂ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; or a C _2-60 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O, and S.

In addition, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; and an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Formula 1. do.

The compound represented by the above-mentioned formula 1 can be used as a material for the organic layer of an organic light-emitting device, and can improve efficiency, low driving voltage, and/or lifespan characteristics of the organic light-emitting device. In particular, the compound represented by the above-mentioned formula 1 can be used as a hole injection, hole transport, hole injection and transport, light emitting, electron transport, or electron injection material.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
Figure 2 shows an example of an organic light emitting device consisting 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). It was done.
3 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (9), a light emitting layer (7), a hole blocking layer (10), and an electron transport and injection layer. An example of an organic light emitting device consisting of (12) and a cathode (4) is shown.

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

means a bond connected to another substituent.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkyl sulphoxy group; Aryl sulfoxy 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 substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more of the above-exemplified substituents linked. . For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

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

In the present specification, the oxygen of the ester group may be substituted with a straight-chain, branched-chain, or ring-chain 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 this specification, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound with the following structure, but is not limited thereto.

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

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

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

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

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

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

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as a phenyl group, biphenyl group, or terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., 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 combined with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be etc. However, it is not limited to this.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heterocyclic groups 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, and 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, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia These include, but are not limited to, a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group.

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

In Formula 1, one or more hydrogens may be replaced with deuterium.

Preferably, depending on the fusion position of A in Formula 1, Formula 1 is represented by the following Formula 1-1 or 1-2:

[Formula 1-1]

[Formula 1-2]

을 형성한다. Preferably, R ₁ and R ₂ are methyl; or phenyl, or R ₁ and R ₂ are bonded together

forms.

Preferably, R ₃ is phenyl, biphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, dibenzofuranyl, or dibenzothiophenyl.

Preferably, L ₁ and L ₂ are each independently a single bond, phenylene, or naphthylene, and more preferably a single bond.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, dibenzofuranyl, or dibenzothiophenyl. More preferably, at least one of Ar ₁ and Ar ₂ is phenyl.

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

Meanwhile, the compound represented by Chemical Formula 1 can be prepared by the manufacturing method shown in Scheme 1 below.

[Scheme 1]

Step 1 of Scheme 1 is an amine substitution reaction, and is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed according to what is known in the art. Step 2 of Scheme 1 is a Suzuki coupling reaction, and is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed according to what is known in the art. The manufacturing method may be further detailed in the manufacturing examples described later.

Additionally, the present invention provides an organic light-emitting device containing the compound represented by Formula 1 above. In one example, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; and an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer 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, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure that includes 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 to this and may include fewer organic layers.

Additionally, the organic material layer may include an electron blocking layer, and the electron blocking layer includes the compound represented by Chemical Formula 1.

Additionally, the organic layer may include a light-emitting layer, and the light-emitting layer includes the compound represented by Chemical Formula 1. In particular, the compound according to the present invention can be used as a dopant in the light-emitting layer.

Additionally, the organic layer may include an electron transport layer or an electron injection layer, and the electron transport layer or electron injection layer includes the compound represented by Formula 1.

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously performs electron transport and electron injection includes the compound represented by Formula 1.

Additionally, the organic layer includes a light-emitting layer and an electron transport layer, and the electron transport layer may include the compound represented by Formula 1.

Additionally, 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. Additionally, 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 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.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In this structure, the compound represented by Formula 1 may be included in the light-emitting layer.

Figure 2 shows an example of an organic light emitting device consisting 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). It was done. In this structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, hole transport layer, light emitting layer, and electron transport layer.

3 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (9), a light emitting layer (7), a hole blocking layer (10), and an electron transport and injection layer. An example of an organic light emitting device consisting of (12) and a cathode (4) is shown. In this structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, hole transport layer, electron blocking layer, light emitting layer, hole blocking layer, and electron transport and injection layer.

The organic light emitting device according to the present invention can be manufactured using materials and methods known in the art, except that at least one of the organic layers includes the compound represented by Formula 1 above. Additionally, 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 can be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, an anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation. It can be manufactured by forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device can be made 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 layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device. Here, the solution application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

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

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

The anode material is generally preferably a material with a large work function to facilitate hole injection into the organic layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); 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 are included, but are not limited to these.

The cathode material is generally preferably a material with a small work function to facilitate electron injection into the organic 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-layer structure materials such as LiF/Al or LiO ₂ /Al, but they are not limited to these.

The hole injection layer is a layer that injects holes from an electrode. The hole injection material has the ability to transport holes, has an excellent hole injection effect at the anode, a light-emitting layer or a light-emitting material, and has an excellent hole injection effect on the light-emitting layer or light-emitting material. A compound that prevents movement of excitons to the electron injection layer or electron injection material and has excellent thin film forming ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrilehexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. These include organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited to these.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light-emitting layer. It is a hole transport material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer, and is a material with high mobility for holes. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions, but are not limited to these.

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 recombining in the light-emitting layer.

The light-emitting material is a material capable of emitting light in the visible range by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and is preferably a material with good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV) series polymer; Spiro compounds; Polyfluorene, rubrene, etc., but are not limited to these.

The light emitting layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic ring-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, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives.

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

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light-emitting layer. The electron transport material is a material that can easily inject electrons from the cathode and transfer them to the light-emitting layer, and a material with high electron mobility is suitable. do. Specific examples include Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; Hydroxyflavone-metal complexes, etc., but are not limited to these. 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 with a low work function followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in each case followed 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 excellent electron injection effect from the cathode, a light-emitting layer or a light-emitting material, and hole injection of excitons generated in the light-emitting layer. A compound that prevents movement to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. and their derivatives, metals. Complex compounds and nitrogen-containing five-membered ring derivatives are included, but are not limited thereto.

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

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

Additionally, the compound represented by Formula 1 may be included in organic solar cells or organic transistors in addition to organic light-emitting devices.

The preparation of the compound represented by Formula 1 and an organic light-emitting device containing 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.

[Example]

Example 1: Preparation of Compound 1

In a nitrogen atmosphere, compound A (10 g, 28 mmol), compound sub1 (9.9 g, 30.8 mmol), and sodium tert-butoxide (5.4 g, 55.9 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subA-1 (8.6 g, yield 56%).

MS: [M+H] ⁺ = 548

In a nitrogen atmosphere, compound subA-1 (15 g, 27.4 mmol) and compound G (6.4 g, 30.1 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (15.1 g, 109.5 mmol) was dissolved in water (45 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare Compound 1 (13.9 g, yield 64%).

MS: [M+H] ⁺ = 793

Example 2: Preparation of Compound 2

In a nitrogen atmosphere, compound A (10 g, 28 mmol), compound sub2 (11.1 g, 30.8 mmol), and sodium tert-butoxide (5.4 g, 55.9 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subA-2 (9.6 g, yield 54%).

MS: [M+H] ⁺ = 638

In a nitrogen atmosphere, compound subA-2 (15 g, 23.5 mmol) and compound H (3.2 g, 25.9 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (13 g, 94 mmol) was dissolved in water (39 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2 (12.1 g, yield 76%).

MS: [M+H] ⁺ = 680

Example 3: Preparation of Compound 3

In a nitrogen atmosphere, compound A (10 g, 28 mmol), compound sub3 (13.1 g, 30.8 mmol), and sodium tert-butoxide (5.4 g, 55.9 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subA-3 (10 g, yield 51%).

MS: [M+H] ⁺ = 704

In a nitrogen atmosphere, compound subA-3 (15 g, 21.3 mmol) and compound H (2.9 g, 23.4 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (11.8 g, 85.2 mmol) was dissolved in 35 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 3 (6.5 g, yield 41%).

MS: [M+H] ⁺ = 749

Example 4: Preparation of Compound 4

In a nitrogen atmosphere, compound B (10 g, 28 mmol), compound sub4 (9.9 g, 30.8 mmol), and sodium tert-butoxide (5.4 g, 55.9 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subB-1 (9.5 g, yield 57%).

MS: [M+H] ⁺ = 598

In a nitrogen atmosphere, compound subB-1 (15 g, 25.1 mmol) and compound H (3.4 g, 27.6 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (13.9 g, 100.3 mmol) was dissolved in water (42 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 4 (6 g, yield 32%).

MS: [M+H] ⁺ = 754

Example 5: Preparation of Compound 5

In a nitrogen atmosphere, compound B (10 g, 28 mmol), compound sub5 (7.5 g, 30.8 mmol), and sodium tert-butoxide (5.4 g, 55.9 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subB-2 (9.3 g, yield 64%).

MS: [M+H] ⁺ = 522

In a nitrogen atmosphere, compound subB-2 (15 g, 28.7 mmol) and compound I (5.4 g, 31.6 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (15.9 g, 114.9 mmol) was dissolved in water (48 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol) was added. After reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 5 (12.3 g, yield 70%).

MS: [M+H] ⁺ = 614

Example 6: Preparation of Compound 6

In a nitrogen atmosphere, compound C (10 g, 20.8 mmol), compound sub5 (5.6 g, 22.8 mmol), and sodium tert-butoxide (4 g, 41.5 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subC-1 (7.9 g, yield 59%).

MS: [M+H] ⁺ = 646

In a nitrogen atmosphere, compound subC-1 (15 g, 23.2 mmol) and compound J (5.8 g, 25.5 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (12.8 g, 92.8 mmol) was dissolved in water (38 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 6 (12.2 g, yield 66%).

MS: [M+H] ⁺ = 794

Example 7: Preparation of Compound 7

In a nitrogen atmosphere, compound C (10 g, 20.8 mmol), compound sub6 (6.3 g, 22.8 mmol), and sodium tert-butoxide (4 g, 41.5 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subC-2 (7.1 g, yield 51%).

MS: [M+H] ⁺ = 676

In a nitrogen atmosphere, compound subC-2 (15 g, 22.2 mmol) and compound K (4.8 g, 24.4 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (12.3 g, 88.7 mmol) was dissolved in water (37 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 7 (11.4 g, yield 65%).

MS: [M+H] ⁺ = 794

Example 8: Preparation of Compound 8

In a nitrogen atmosphere, compound C (10 g, 20.8 mmol), compound sub7 (5.9 g, 22.8 mmol), and sodium tert-butoxide (4 g, 41.5 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subC-3 (7 g, yield 51%).

MS: [M+H] ⁺ = 660

In a nitrogen atmosphere, compound subC-3 (15 g, 22.7 mmol) and compound H (3 g, 25 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (12.6 g, 90.9 mmol) was dissolved in water (38 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 8 (6.9 g, yield 43%).

MS: [M+H] ⁺ = 702

Example 9: Preparation of Compound 9

In a nitrogen atmosphere, compound C (10 g, 20.8 mmol), compound sub8 (5 g, 22.8 mmol), and sodium tert-butoxide (4 g, 41.5 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subC-4 (9 g, yield 70%).

MS: [M+H] ⁺ = 620

In a nitrogen atmosphere, compound subC-4 (15 g, 24.2 mmol) and compound H (3.2 g, 26.6 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (13.4 g, 96.7 mmol) was dissolved in water (40 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 9 (4.8 g, yield 30%).

MS: [M+H] ⁺ = 662

Example 10: Preparation of Compound 10

In a nitrogen atmosphere, compound C (10 g, 20.8 mmol), compound sub9 (5.6 g, 22.8 mmol), and sodium tert-butoxide (4 g, 41.5 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subC-5 (9.4 g, yield 70%).

MS: [M+H] ⁺ = 646

In a nitrogen atmosphere, compound subC-5 (15 g, 23.2 mmol) and compound L (5.4 g, 25.5 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (12.8 g, 92.8 mmol) was dissolved in water (38 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 10 (11.4 g, yield 63%).

MS: [M+H] ⁺ = 778

Example 11: Preparation of Compound 11

In a nitrogen atmosphere, compound C (10 g, 20.8 mmol), compound sub4 (7.3 g, 22.8 mmol), and sodium tert-butoxide (4 g, 41.5 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subC-6 (8.5 g, yield 57%).

MS: [M+H] ⁺ = 722

In a nitrogen atmosphere, compound subC-6 (15 g, 20.8 mmol) and compound H (2.8 g, 22.8 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (11.5 g, 83.1 mmol) was dissolved in water (34 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 11 (9.7 g, yield 61%).

MS: [M+H] ⁺ = 764

Example 12: Preparation of Compound 12

In a nitrogen atmosphere, compound D (10 g, 20.8 mmol), compound sub10 (8.1 g, 22.8 mmol), and sodium tert-butoxide (4 g, 41.5 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subD-1 (10.4 g, yield 68%).

MS: [M+H] ⁺ = 736

In a nitrogen atmosphere, compound subD-1 (15 g, 20.4 mmol) and compound H (2.7 g, 22.4 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (11.3 g, 81.5 mmol) was dissolved in water (34 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 12 (11.9 g, yield 75%).

MS: [M+H] ⁺ = 778

Example 13: Preparation of Compound 13

In a nitrogen atmosphere, compound D (10 g, 20.8 mmol), compound sub11 (6.7 g, 22.8 mmol), and sodium tert-butoxide (4 g, 41.5 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subD-2 (8.9 g, yield 62%).

MS: [M+H] ⁺ = 696

In a nitrogen atmosphere, compound subD-2 (15 g, 21.5 mmol) and compound G (5 g, 23.7 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (11.9 g, 86.2 mmol) was dissolved in water (36 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 13 (9.6 g, yield 54%).

MS: [M+H] ⁺ = 829

Example 14: Preparation of Compound 14

In a nitrogen atmosphere, compound D (10 g, 20.8 mmol), compound sub8 (5 g, 22.8 mmol), and sodium tert-butoxide (4 g, 41.5 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subD-3 (7.6 g, yield 59%).

MS: [M+H] ⁺ = 620

In a nitrogen atmosphere, compound subD-3 (15 g, 24.2 mmol) and compound M (5.3 g, 26.6 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (13.4 g, 96.7 mmol) was dissolved in water (40 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 14 (7.5 g, yield 42%).

MS: [M+H] ⁺ = 738

Example 15: Preparation of Compound 15

In a nitrogen atmosphere, compound D (10 g, 20.8 mmol), compound sub5 (5.6 g, 22.8 mmol), and sodium tert-butoxide (4 g, 41.5 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subD-4 (8.2 g, yield 61%).

MS: [M+H] ⁺ = 646

In a nitrogen atmosphere, compound subD-4 (15 g, 23.2 mmol) and compound G (5.4 g, 25.5 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (12.8 g, 92.8 mmol) was dissolved in water (38 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 15 (12.1 g, yield 67%).

MS: [M+H] ⁺ = 778

Example 16: Preparation of Compound 16

In a nitrogen atmosphere, compound E (10 g, 20.8 mmol), compound sub4 (7.4 g, 22.9 mmol), and sodium tert-butoxide (4 g, 41.7 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subE-1 (7.5 g, yield 50%).

MS: [M+H] ⁺ = 720

In a nitrogen atmosphere, compound subE-1 (15 g, 20.8 mmol) and compound H (2.8 g, 22.8 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (11.5 g, 83.1 mmol) was dissolved in water (34 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 16 (12.5 g, yield 79%).

MS: [M+H] ⁺ = 762

Example 17: Preparation of Compound 17

In a nitrogen atmosphere, compound E (10 g, 20.8 mmol), compound sub5 (5.6 g, 22.9 mmol), and sodium tert-butoxide (4 g, 41.7 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subE-2 (9.4 g, yield 70%).

MS: [M+H] ⁺ = 645

In a nitrogen atmosphere, compound subE-2 (15 g, 23.3 mmol) and compound I (4.4 g, 25.6 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (12.9 g, 93.1 mmol) was dissolved in water (39 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 17 (12.7 g, yield 74%).

MS: [M+H] ⁺ = 736

Example 18: Preparation of Compound 18

In a nitrogen atmosphere, compound subE-3 (15 g, 23.3 mmol) and compound J (5.8 g, 25.6 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (12.9 g, 93.1 mmol) was dissolved in water (39 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 18 (6.6 g, yield 36%).

MS: [M+H] ⁺ = 792

Example 19: Preparation of Compound 19

In a nitrogen atmosphere, compound E (10 g, 20.8 mmol), compound sub12 (6.8 g, 22.9 mmol), and sodium tert-butoxide (4 g, 41.7 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subE-4 (8.5 g, yield 59%).

MS: [M+H] ⁺ = 694

In a nitrogen atmosphere, compound subE-4 (15 g, 21.6 mmol) and compound J (5.4 g, 23.8 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (11.9 g, 86.4 mmol) was dissolved in water (36 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 19 (6.7 g, yield 37%).

MS: [M+H] ⁺ = 842

Example 20: Preparation of Compound 20

In a nitrogen atmosphere, compound E (10 g, 20.8 mmol), compound sub13 (7.7 g, 22.9 mmol), and sodium tert-butoxide (4 g, 41.7 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subE-5 (7.6 g, yield 50%).

MS: [M+H] ⁺ = 734

In a nitrogen atmosphere, compound subE-5 (15 g, 20.4 mmol) and compound H (2.7 g, 22.5 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (11.3 g, 81.7 mmol) was dissolved in water (34 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 20 (10 g, yield 63%).

MS: [M+H] ⁺ = 776

Example 21: Preparation of Compound 21

In a nitrogen atmosphere, compound F (10 g, 20.8 mmol), compound sub14 (8.8 g, 22.9 mmol), and sodium tert-butoxide (4 g, 41.7 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subE-1 (9.1 g, yield 56%).

MS: [M+H] ⁺ = 784

In a nitrogen atmosphere, compound subF-1 (15 g, 19.1 mmol) and compound N (4.2 g, 21 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (10.6 g, 76.5 mmol) was dissolved in 32 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 21 (11.7 g, yield 68%).

MS: [M+H] ⁺ = 902

Example 22: Preparation of Compound 22

In a nitrogen atmosphere, compound F (10 g, 20.8 mmol), compound sub8 (5 g, 22.9 mmol), and sodium tert-butoxide (4 g, 41.7 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subE-2 (8.7 g, yield 68%).

MS: [M+H] ⁺ = 618

In a nitrogen atmosphere, compound subF-2 (15 g, 24.3 mmol) and compound O (6.4 g, 26.7 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (13.4 g, 97.1 mmol) was dissolved in water (40 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 22 (11.9 g, yield 63%).

MS: [M+H] ⁺ = 776

Example 23: Preparation of Compound 23

In a nitrogen atmosphere, compound F (10 g, 20.8 mmol), compound sub15 (8.1 g, 22.9 mmol), and sodium tert-butoxide (4 g, 41.7 mmol) were added to toluene (200 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved 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 compound subE-3 (9.4 g, yield 60%).

MS: [M+H] ⁺ = 750

In a nitrogen atmosphere, compound subF-3 (15 g, 20 mmol) and compound H (3.8 g, 22 mmol) were added to dioxane (300 ml), stirred, and refluxed. Afterwards, potassium phosphate (11.1 g, 80 mmol) was dissolved in 33 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 9 hours of reaction, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 23 (5.2 g, yield 33%).

MS: [M+H] ⁺ = 792

[Experimental example]

Experimental Example 1

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

On the ITO transparent electrode prepared in this way, the following HI-1 compound was formed as a hole injection layer to a thickness of 1150 Å, and the following A-1 compound 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 with a film thickness of 800 Å. Compound 1 prepared previously was vacuum deposited on the hole transport layer to form an electron blocking layer with a thickness of 150 Å. On the electron suppression layer, the following RH-1 compound and the following Dp-7 compound were vacuum deposited at a weight ratio of 98:2 to form a red light-emitting layer with a film thickness of 400 Å. The following HB-1 compound was vacuum deposited on the light emitting layer to form a hole blocking layer with a thickness of 30 Å. On the hole blocking layer, the following ET-1 compound and the following LiQ compound were vacuum deposited at a weight ratio of 2:1 to form an electron injection and transport layer with a film 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 materials was maintained at 0.4~0.7 Å/sec, the deposition rate of lithium fluoride of the cathode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2×10. An organic light emitting device was manufactured by maintaining ^-7 to 5×10 ^-6 torr.

Experimental Examples 2 to 23

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compounds listed in Table 1 below were used instead of Compound 1.

Comparative Experiment Examples 1 to 13

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compounds listed in Table 2 below were used instead of Compound 1. The compounds listed in Table 2 below are respectively as follows.

When current was applied to the organic light-emitting device manufactured in the above experimental and comparative experimental examples, the voltage, efficiency, and lifespan (T95) were measured (10 mA/cm ² ), and the results are shown in Tables 1 and 2 below. Lifespan T95 refers to the time it takes for luminance to decrease from the initial luminance (6000 nit) to 95%.

compound
(electron suppression layer) driving voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Life T95
(hr@10mA/cm ² ) Luminous color Experimental Example 1 Compound 1 3.67 24.5 174 Red Experimental Example 2 compound 2 3.68 24.1 187 Red Experimental Example 3 Compound 3 3.69 24.4 179 Red Experimental Example 4 Compound 4 3.61 25.3 184 Red Experimental Example 5 Compound 5 3.63 24.7 173 Red Experimental Example 6 Compound 6 3.70 24.5 204 Red Experimental Example 7 Compound 7 3.69 25.8 185 Red Experimental Example 8 Compound 8 3.73 23.5 190 Red Experimental Example 9 Compound 9 3.64 25.4 177 Red Experimental Example 10 Compound 10 3.61 26.1 184 Red Experimental Example 11 Compound 11 3.71 23.8 171 Red Experimental Example 12 Compound 12 3.69 24.7 203 Red Experimental Example 13 Compound 13 3.50 23.1 184 Red Experimental Example 14 Compound 14 3.63 24.9 171 Red Experimental Example 15 Compound 15 3.69 25.3 198 Red Experimental Example 16 Compound 16 3.63 24.2 187 Red Experimental Example 17 Compound 17 3.52 23.8 208 Red Experimental Example 18 Compound 18 3.70 24.7 171 Red Experimental Example 19 Compound 19 3.68 25.2 194 Red Experimental Example 20 Compound 20 3.59 24.5 185 Red Experimental Example 21 Compound 21 3.55 25.4 203 Red Experimental Example 22 Compound 22 3.58 23.6 185 Red Experimental Example 23 Compound 23 3.63 23.7 194 Red

compound
(electron suppression layer) driving voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Life T95
(hr@10mA/cm ² ) Luminous color Comparative Experiment Example 1 EB-1 4.11 20.8 148 Red Comparative Experiment Example 2 C-1 3.88 19.7 99 Red Comparative Experiment Example 3 C-2 3.89 19.5 87 Red Comparative Experiment Example 4 C-3 3.83 18.9 93 Red Comparative Experiment Example 5 C-4 3.82 18.7 93 Red Comparative Experiment Example 6 C-5 4.05 20.0 121 Red Comparative Experiment Example 7 C-6 4.07 21.3 133 Red Comparative Experiment Example 8 C-7 3.92 20.7 130 Red Comparative Experiment Example 9 C-8 3.90 20.8 141 Red Comparative Experiment Example 10 C-9 3.88 21.1 122 Red Comparative Experiment Example 11 C-10 3.93 20.2 138 Red Comparative Experiment Example 12 C-11 3.90 21.5 127 Red Comparative Experiment Example 13 C-12 3.94 20.9 144 Red

As shown in Tables 1 and 2, when the compound of the present invention was used as an electron suppression layer, the driving voltage was significantly lowered compared to the comparative example compound, and efficiency was also significantly increased, indicating that energy transfer from the host to the red dopant I could see that this was working well. In addition, it was found that the lifespan characteristics can be greatly improved while maintaining high efficiency, and this is due to the high stability of the compound of the present invention to electrons and holes. Therefore, it can be confirmed that the driving voltage, luminous efficiency, and lifespan characteristics of an organic light-emitting device can be improved when the compound of the present invention is used as a host for a red light-emitting layer.

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
9: electron blocking layer 10: hole blocking layer
11: Electron transport and injection layer

Claims (9)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
A is a benzene ring fused with two adjacent rings,
R ₁ and R ₂ are substituted or unsubstituted C _1-60 alkyl; or substituted or unsubstituted C _6-60 aryl, or R ₁ and R ₂ are combined together to form a substituted or unsubstituted C _6-60 aromatic ring,
R ₃ is phenyl, biphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, dibenzofuranyl, or dibenzothiophenyl,
L ₁ and L ₂ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; or a C _2-60 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O, and S.
According to paragraph 1,
Formula 1 is represented by the following formula 1-1 or 1-2,
compound:
[Formula 1-1]

[Formula 1-2]

.
According to paragraph 1,
R ₁ and R ₂ are methyl; or phenyl, or R ₁ and R ₂ are bonded together

forming,
compound.
delete According to paragraph 1,
L ₁ and L ₂ are each independently a single bond, phenylene, or naphthylene,
compound.
According to paragraph 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, dibenzofuranyl, or dibenzothiophenyl,
compound.
According to paragraph 1,
The compound represented by Formula 1 is any one selected from the group consisting of:
compound:

first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer is any of claims 1 to 3 and 5 to 7. An organic light-emitting device comprising the compound according to one clause.
According to clause 8,
The organic material layer containing the compound is an electron suppression layer,
Organic light emitting device.