KR20230148771A - 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) or (2):

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

X is O, or S,

R is substituted or unsubstituted C _6-60 aryl; One of R ₁ to R ₈ is a substituent represented by the following formula (3), and the remainder is hydrogen or deuterium; or

R is a substituent represented by Formula 3; R ₁ to R ₈ are each independently hydrogen or deuterium,

[Formula 3]

In Formula 3 above,

L is 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,

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 substituted or unsubstituted C _2-60 heteroaryl containing at least one selected from the group consisting of N, O, and S. ego,

However, when R is a substituent represented by Formula 3, the following structures are excluded from the substituent represented by Formula 3:

.

.

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 or 2. provides.

The compound represented by Formula 1 or 2 described above 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 Formula 1 or 2 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.

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

In this specification, or 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 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.

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 or 2, one or more hydrogens may be replaced with deuterium.

Preferably, R is phenyl, biphenylyl, or naphthyl, one of R ₁ to R ₈ is a substituent represented by Formula 3, and the remainder are hydrogen or deuterium.

Preferably, when R is a substituent represented by Formula 3 above, L is a single bond, phenylene, biphenyldiyl, or naphthylene; L ₁ and L ₂ are each independently a single bond, phenylene, biphenyldiyl, or naphthylene; Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, phenanthrenyl, dimethylfluorenyl, diphenylfluorenyl, di benzofuranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-carbazolyl; However, Ar ₁ and Ar ₂ are not both phenyl and neither are biphenyl-4-yl.

Preferably, L is a single bond, phenylene, biphenyldiyl, or naphthylene.

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

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, phenanthrenyl, dimethylfluorenyl, diphenylfluor orenyl, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-carbazolyl.

Preferably, Ar ₁ and Ar ₂ are different from each other.

Representative examples of compounds represented by Formula 1 or 2 are as follows:

Meanwhile, the present invention provides a method for producing a compound represented by Chemical Formula 1, as shown in Schemes 1 and 2 below, respectively. Scheme 1 below refers to the case where R is a substituent represented by Formula 3, and Scheme 2 below refers to the case where one of R ₁ to R ₈ is a substituent represented by Formula 3, and is represented by Formula 2 Compounds can also be prepared by referring to:

[Scheme 1]

[Scheme 2]

In Schemes 1 and 2, the remaining definitions except for X ₁ are as defined above, and X ₁ is halogen, more preferably chloro or bromo. The reaction is a Suzuki coupling reaction or an amine substitution reaction, and is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for this substitution 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 or 2 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 or 2. provides.

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 layer may include a light-emitting layer, and the light-emitting layer includes a compound represented by Formula 1 or 2. In particular, the compound according to the present invention can be used as a host for a 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 a compound represented by Formula 1 or 2.

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously performs electron transport and electron injection includes a compound represented by Formula 1 or 2.

Additionally, the organic layer includes a light-emitting layer and an electron transport layer, and the electron transport layer may include a compound represented by Formula 1 or 2.

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 or 2 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 or 2 may be included in one or more of the hole injection layer, hole transport layer, light emitting layer, and electron transport 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 a compound represented by Formula 1 or 2. 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 or 2 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 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 or 2 may be included in an organic solar cell or an organic transistor in addition to an organic light-emitting device.

Below, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are provided only to make the present invention easier to understand, and the content of the present invention is not limited thereto.

[Example]

Example 1

In a nitrogen atmosphere, compound sub1 (15 g, 40.1 mmol), compound amine1 (13.5 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 13.3 g of Compound 1. (Yield 54%, MS: [M+H] ⁺ = 615)

Example 2

In a nitrogen atmosphere, compound sub1 (15 g, 40.1 mmol), compound amine2 (14.1 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 13.1 g of Compound 2. (Yield 52%, MS: [M+H] ⁺ = 629)

Example 3

In a nitrogen atmosphere, compound sub1 (15 g, 40.1 mmol), compound amine3 (14.1 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 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 13.8 g of Compound 3. (Yield 55%, MS: [M+H] ⁺ = 629)

Example 4

In a nitrogen atmosphere, compound sub1 (15 g, 40.1 mmol), compound amine4 (17.3 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 19.7 g of Compound 4. (Yield 70%, MS: [M+H] ⁺ = 704)

Example 5

Compound sub1 (15 g, 40.1 mmol) and compound amine5 (19.2 g, 42.1 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (16.6 g, 120.2 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 3 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3 g of Compound 5. (Yield 79%, MS: [M+H] ⁺ = 705)

Example 6

Compound sub1 (15 g, 40.1 mmol) and compound amine6 (18.6 g, 42.1 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (16.6 g, 120.2 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.6 g of Compound 6. (Yield 78%, MS: [M+H] ⁺ = 691)

Example 7

In a nitrogen atmosphere, compound sub2 (15 g, 40.1 mmol), compound amine7 (14.7 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 15.7 g of compound 7. (Yield 61%, MS: [M+H] ⁺ = 643)

Example 8

Compound sub3 (15 g, 33.3 mmol) and compound amine8 (18.1 g, 35 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (13.8 g, 99.9 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reaction for 3 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.4 g of Compound 8. (Yield 62%, MS: [M+H] ⁺ = 843)

Example 9

Compound sub4 (15 g, 40.1 mmol) and compound amine9 (19.8 g, 42.1 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (16.6 g, 120.2 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 2 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.8 g of compound 9. (Yield 79%, MS: [M+H] ⁺ = 721)

Example 10

In a nitrogen atmosphere, compound sub4 (15 g, 40.1 mmol), compound amine10 (14.5 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 15.1 g of compound 10. (Yield 59%, MS: [M+H] ⁺ = 639)

Example 11

In a nitrogen atmosphere, compound sub5 (15 g, 40.1 mmol), compound amine11 (15.2 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 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 16.5 g of compound 11. (Yield 63%, MS: [M+H] ⁺ = 655)

Example 12

In a nitrogen atmosphere, compound sub6 (15 g, 59.1 mmol), compound amine12 (21.7 g, 62.1 mmol), and sodium tert-butoxide (8.5 g, 88.7 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 21.4 g of compound 12. (Yield 64%, MS: [M+H] ⁺ = 567)

Example 13

Compound sub6 (15 g, 59.1 mmol) and compound amine13 (28.2 g, 62.1 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (24.5 g, 177.4 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.4 g of Compound 13. (Yield 63%, MS: [M+H] ⁺ = 628)

Example 14

Compound sub6 (15 g, 59.1 mmol) and compound amine14 (32.9 g, 62.1 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (24.5 g, 177.4 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reaction for 2 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30.8 g of compound 14. (Yield 74%, MS: [M+H] ⁺ = 704)

Example 15

In a nitrogen atmosphere, compound sub6 (15 g, 59.1 mmol), compound amine15 (25.5 g, 62.1 mmol), and sodium tert-butoxide (8.5 g, 88.7 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 21.5 g of compound 15. (Yield 58%, MS: [M+H] ⁺ = 628)

Example 16

In a nitrogen atmosphere, compound sub7 (15 g, 40.1 mmol), compound amine16 (17.7 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 17.7 g of compound 16. (Yield 62%, MS: [M+H] ⁺ = 715)

Example 17

In a nitrogen atmosphere, compound sub7 (15 g, 40.1 mmol), compound amine17 (14.1 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 17.1 g of compound 17. (Yield 63%, MS: [M+H] ⁺ = 679)

Example 18

In a nitrogen atmosphere, compound sub8 (15 g, 40.1 mmol), compound amine18 (17.3 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 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 16.6 g of compound 18. (Yield 55%, MS: [M+H] ⁺ = 754)

Example 19

Compound sub9 (15 g, 40.1 mmol) and compound amine19 (20.3 g, 42.1 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (16.6 g, 120.2 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 2 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4 g of compound 19. (Yield 63%, MS: [M+H] ⁺ = 731)

Example 20

In a nitrogen atmosphere, compound sub9 (15 g, 40.1 mmol), compound amine20 (17.3 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 16.3 g of compound 20. (Yield 58%, MS: [M+H] ⁺ = 704)

Example 21

In a nitrogen atmosphere, compound sub10 (15 g, 40.1 mmol), compound amine21 (14.1 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 16.6 g of compound 21. (Yield 66%, MS: [M+H] ⁺ = 629)

Example 22

In a nitrogen atmosphere, compound sub10 (15 g, 40.1 mmol), compound amine22 (15.2 g, 42.1 mmol), and sodium tert-butoxide (5.8 g, 60.1 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 15.2 g of compound 22. (Yield 52%, MS: [M+H] ⁺ = 731)

Example 23

Compound sub11 (15 g, 59.1 mmol) and compound amine23 (28.9 g, 62.1 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (24.5 g, 177.4 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reaction for 4 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.2 g of Compound 23. (Yield 72%, MS: [M+H] ⁺ = 639)

Example 24

Compound sub12 (15 g, 40.1 mmol) and compound amine24 (22.3 g, 42.1 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (16.6 g, 120.2 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 4 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.2 g of compound 24. (Yield 68%, MS: [M+H] ⁺ = 780)

Example 25

Compound sub13 (15 g, 40.1 mmol) and compound amine25 (20.3 g, 42.1 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (16.6 g, 120.2 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.6 g of Compound 25. (Yield 67%, MS: [M+H] ⁺ = 731)

Example 26

In a nitrogen atmosphere, compound sub14 (15 g, 38.4 mmol), compound amine26 (17.1 g, 40.4 mmol), and sodium tert-butoxide (5.5 g, 57.6 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 18.9 g of compound 26. (Yield 67%, MS: [M+H] ⁺ = 734)

Example 27

In a nitrogen atmosphere, compound sub14 (15 g, 38.4 mmol), compound amine27 (14.7 g, 40.4 mmol), and sodium tert-butoxide (5.5 g, 57.6 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 17.9 g of compound 27. (Yield 69%, MS: [M+H] ⁺ = 675)

Example 28

Compound sub14 (15 g, 38.4 mmol) and compound amine28 (20.9 g, 40.4 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (15.9 g, 115.3 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21 g of Compound 28. (Yield 70%, MS: [M+H] ⁺ = 783)

Example 29

In a nitrogen atmosphere, compound sub14 (15 g, 38.4 mmol), compound amine29 (14.7 g, 40.4 mmol), and sodium tert-butoxide (5.5 g, 57.6 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 15.3 g of compound 29. (Yield 55%, MS: [M+H] ⁺ = 725)

Example 30

Compound sub15 (15 g, 38.4 mmol) and compound amine30 (19 g, 40.4 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (15.9 g, 115.3 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 2 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.2 g of Compound 30. (Yield 68%, MS: [M+H] ⁺ = 737)

Example 31

In a nitrogen atmosphere, compound sub16 (15 g, 55.6 mmol), compound amine31 (15.1 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 17.5 g of compound 31. (Yield 64%, MS: [M+H] ⁺ = 493)

Example 32

In a nitrogen atmosphere, compound sub16 (15 g, 55.6 mmol), compound amine32 (21.1 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 21.1 g of compound 32. (Yield 64%, MS: [M+H] ⁺ = 595)

Example 33

In a nitrogen atmosphere, compound sub16 (15 g, 55.6 mmol), compound amine33 (20.5 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 20.1 g of compound 33. (Yield 62%, MS: [M+H] ⁺ = 585)

Example 34

Compound sub16 (15 g, 55.6 mmol) and compound amine34 (31 g, 58.4 mmol) were added to THF (300 ml), stirred, and refluxed. Afterwards, potassium carbonate (23.1 g, 166.8 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reaction for 2 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 32 g of compound 34. (Yield 80%, MS: [M+H] ⁺ = 720)

Example 35

In a nitrogen atmosphere, compound sub17 (15 g, 38.4 mmol), compound amine35 (11.9 g, 40.4 mmol), and sodium tert-butoxide (5.5 g, 57.6 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 15.6 g of compound 35. (Yield 67%, MS: [M+H] ⁺ = 605)

Example 36

In a nitrogen atmosphere, compound sub18 (15 g, 38.4 mmol), compound amine36 (18.6 g, 40.4 mmol), and sodium tert-butoxide (5.5 g, 57.6 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 18.6 g of compound 36. (Yield 63%, MS: [M+H] ⁺ = 770)

Example 37

In a nitrogen atmosphere, compound sub19 (15 g, 38.4 mmol), compound amine37 (16.6 g, 40.4 mmol), and sodium tert-butoxide (5.5 g, 57.6 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 16.9 g of compound 37. (Yield 61%, MS: [M+H] ⁺ = 720)

Example 38

Compound sub20 (15 g, 32.2 mmol) and compound amine38 (17.9 g, 33.8 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (13.3 g, 96.5 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.6 g of compound 38. (Yield 70%, MS: [M+H] ⁺ = 872)

Example 39

Compound sub21 (15 g, 38.4 mmol) and compound amine39 (21.4 g, 40.4 mmol) were added to THF (300 ml), stirred and refluxed. Afterwards, potassium carbonate (15.9 g, 115.3 mmol) was dissolved in water (100 ml), stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 2 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.8 g of compound 39. (Yield 78%, MS: [M+H] ⁺ = 796)

Example 40

In a nitrogen atmosphere, compound sub22 (15 g, 38.4 mmol), compound amine40 (16.6 g, 40.4 mmol), and sodium tert-butoxide (5.5 g, 57.6 mmol) were added to xylene (300 ml), stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, the reaction was 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 15.8 g of compound 40. (Yield 57%, MS: [M+H] ⁺ = 720)

[Experimental example]

Experimental Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000 Å was placed in distilled water with a detergent dissolved in it and washed ultrasonically. 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%. On the hole injection layer, the following HT-1 compound was vacuum deposited to form a hole transport layer with a film thickness of 800 Å. On the hole transport layer, the following EB-1 compound was vacuum deposited to form an electron blocking layer with a thickness of 150 Å. Next, on the electron blocking layer, Compound 1 prepared previously and the Dp-39 compound below were vacuum deposited at a weight ratio of 98:2 to form a light-emitting layer with a thickness of 400 Å. On the light emitting layer, the following HB-1 compound was vacuum deposited to form a hole blocking layer with a thickness of 30 Å. Next, 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. On the electron injection and transport layer, lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å were sequentially deposited to form a cathode, thereby manufacturing an organic light-emitting device.

In the above process, the deposition rate of organic matter 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 aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2×10 ^-7. An organic light emitting device was manufactured by maintaining ~5×10 ^-6 torr.

Experimental Examples 2 to 40

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 8

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 (based on 10 mA/cm ² ) was applied to the organic light-emitting device manufactured in the above experimental and comparative experimental examples, the voltage and efficiency were measured, and the results are shown in Tables 1 and 2 below. At this time, the lifespan T95 refers to the time (hr) required for the luminance to decrease from the initial luminance to 95%.

host material driving voltage
(V@10mA/cm ² ) Current efficiency
(cd/A@10mA/cm ² ) life span
(T95@10mA/ ^cm2 ) Example 1 Compound 1 4.10 23.98 185 Example 2 compound 2 4.21 24.10 199 Example 3 Compound 3 4.12 24.15 177 Example 4 Compound 4 4.10 23.13 191 Example 5 Compound 5 4.12 23.15 192 Example 6 Compound 6 4.15 23.26 176 Example 7 Compound 7 4.26 24.91 181 Example 8 Compound 8 4.15 25.28 185 Example 9 Compound 9 4.19 25.71 188 Example 10 Compound 10 4.18 23.51 189 Example 11 Compound 11 4.21 25.26 193 Example 12 Compound 12 4.33 25.05 190 Example 13 Compound 13 4.21 25.94 185 Example 14 Compound 14 4.26 26.83 182 Example 15 Compound 15 4.35 25.66 196 Example 16 Compound 16 4.21 24.15 191 Example 17 Compound 17 4.07 23.29 185 Example 18 Compound 18 4.09 23.42 208 Example 19 Compound 19 4.21 24.81 189 Example 20 Compound 20 4.23 25.09 182 Example 21 Compound 21 4.30 23.64 186 Example 22 Compound 22 4.15 25.15 183 Example 23 Compound 23 4.26 24.33 198 Example 24 Compound 24 4.17 24.67 192 Example 25 Compound 25 4.08 25.12 196 Example 26 Compound 26 4.26 25.61 203 Example 27 Compound 27 4.19 24.48 190 Example 28 Compound 28 4.20 26.90 195 Example 29 Compound 29 4.03 25.61 183 Example 30 Compound 30 4.23 24.33 197 Example 31 Compound 31 4.21 26.01 192 Example 32 Compound 32 4.30 25.81 185 Example 33 Compound 33 4.28 27.33 179 Example 34 Compound 34 4.18 26.31 188 Example 35 Compound 35 4.10 25.98 194 Example 36 Compound 36 4.32 26.07 199 Example 37 Compound 37 4.25 25.78 190 Example 38 Compound 38 4.15 26.44 204 Example 39 Compound 39 4.09 26.18 201 Example 40 Compound 40 4.23 25.67 197

host material driving voltage
(V@10mA/cm ² ) Current efficiency
(cd/A@10mA/cm ² ) life span
(T95@10mA/ ^cm2 ) Comparative Example 1 Compound RH-1 5.60 14.15 51 Comparative Example 2 Compound RH-2 5.62 13.93 60 Comparative Example 3 Compound RH-3 5.87 13.82 61 Comparative Example 4 Compound RH-4 5.71 13.76 59 Comparative Example 5 Compound RH-5 5.80 12.55 58 Comparative Example 6 Compound RH-6 5.75 12.39 53 Comparative Example 7 Compound RH-7 5.90 13.25 61 Comparative Example 8 Compound RH-8 5.81 13.67 51

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

Claims (10)

Compounds represented by Formula 1 or 2 below:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
X is O, or S,
R is substituted or unsubstituted C _6-60 aryl; One of R ₁ to R ₈ is a substituent represented by the following formula (3), and the remainder is hydrogen or deuterium; or
R is a substituent represented by Formula 3; R ₁ to R ₈ are each independently hydrogen or deuterium,
[Formula 3]

In Formula 3 above,
L is 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,
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 substituted or unsubstituted C _2-60 heteroaryl containing at least one selected from the group consisting of N, O, and S. ego,
However, when R is a substituent represented by Formula 3, the following structures are excluded from the substituent represented by Formula 3:

.
According to paragraph 1,
R is phenyl, biphenylyl, or naphthyl,
One of R ₁ to R ₈ is a substituent represented by Formula 3 above, and the remainder is hydrogen or deuterium,
compound.
According to paragraph 1,
When R is a substituent represented by Formula 3 above,
L is a single bond, phenylene, biphenyldiyl, or naphthylene;
L ₁ and L ₂ are each independently a single bond, phenylene, biphenyldiyl, or naphthylene;
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, phenanthrenyl, dimethylfluorenyl, diphenylfluorenyl, di benzofuranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-carbazolyl; However, Ar ₁ and Ar ₂ are not both phenyl and not both biphenyl-4-yl,
compound.
According to paragraph 1,
L is a single bond, phenylene, biphenyldiyl, or naphthylene,
compound.
According to paragraph 1,
L ₁ and L ₂ are each independently a single bond, phenylene, biphenyldiyl, or naphthylene,
compound.
According to paragraph 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, phenanthrenyl, dimethylfluorenyl, diphenylfluorenyl, di benzofuranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-carbazolyl,
compound.
According to paragraph 1,
Ar ₁ and Ar ₂ are different from each other,
compound.
According to paragraph 1,
The compound represented by Formula 1 or Formula 2 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 includes the compound according to any one of claims 1 to 8. An organic light-emitting device.
According to clause 9,
The organic material layer containing the compound is a light emitting layer,
Organic light emitting device.