KR102479341B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel compound and organic light emitting device using the same

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

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

An organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, and may include, 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 are injected into the organic material layer, and when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.

The development of new materials for organic materials used in the organic light emitting device as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides a compound represented by Formula 1 below:

[Formula 1]

In Formula 1,

X is O or S;

A is a benzene ring fused with two adjacent rings,

Any one of R ₁ to R ₈ is represented by the following formula (2), and the others are each independently CH or CD;

Each R is independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl;

n is an integer from 0 to 6;

[Formula 2]

In Formula 2,

L is a single bond or a substituted or unsubstituted C _6-60 arylene;

Y is each independently N or CH, provided that at least two of Y are N,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl, or a substituted or unsubstituted C _5-60 hetero including any one or more selected from the group consisting of N, O and S; aryl,

Dotted lines indicate binding sites.

In addition, the present invention is a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Chemical Formula 1. to provide.

The compound represented by Chemical Formula 1 may be used as a material for an organic layer of an organic light emitting diode, and may improve efficiency, low driving voltage, and/or lifespan characteristics of an organic light emitting diode. In particular, the compound represented by Chemical Formula 1 may be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection.

1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, an organic layer 3, and a cathode 4.
2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 8, a hole blocking layer 9, an electron injection and transport layer ( 10), and an example of an organic light emitting element composed of a cathode 4 is shown.

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy groups; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl 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 a heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may have a structure as follows, but is not limited thereto.

In the present specification, the ester group may be substituted with an aryl group having 6 to 25 carbon atoms or a straight-chain, branched-chain or cyclic chain alkyl group having 1 to 25 carbon atoms in the ester group. Specifically, it may have a structure as follows, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. It may have a structure as follows, but is not limited thereto.

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

In the present specification, the boron group specifically includes a dimethyl boron group, a diethyl boron group, a t-butylmethyl boron group, a diphenyl boron group, a phenyl boron group, but is not limited thereto.

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

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

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

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms 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, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl 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, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. However, it is not limited thereto.

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

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

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

Preferably, Chemical Formula 1 may be any one of the following Chemical Formulas 1-1 to 1-3:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,

X, R ₁ to R ₈ , R and n are as previously defined.

In addition, in Formula 1, preferably, R may be hydrogen or deuterium, and when n is an integer of 2 or more, R may each independently be hydrogen or deuterium. More preferably, all R's may be hydrogen, wherein n is an integer of 6.

In addition, in Formula 1, preferably, one of R ₁ and R ₂ is represented by Formula 2, and the others are each independently CH or CD; any one of R ₃ and R ₄ is represented by Formula 2, and the others are each independently CH or CD; Alternatively, any one of R ₅ to R ₇ may be represented by Formula 2, and the others may be independently CH or CD.

In this case, in Formula 2, L is preferably a single bond; Or it may be deuterium substituted or unsubstituted C _6-20 arylene.

More preferably, L may be a single bond, phenylene, or naphthylene, and specifically, L may be a single bond or any one selected from the group consisting of the following formulas:

In each of the above formulas, the dotted line represents the bonding site.

Also, in Formula 2, preferably, two of Y's are N and the rest are CH, or all three of Y's may be N', more preferably, all of Y's are N's.

Also, in Formula 2, preferably, Ar ₁ and Ar ₂ are each independently C _6-30 aryl; Or C _5-30 heteroaryl containing N, O or S, wherein Ar ₁ and Ar ₂ are each independently one or more deuterium, C _1-20 alkyl, or C _6-20 aryl substituted or unsubstituted It can be.

In Formula 2, preferably, one of Ar ₁ and Ar ₂ is a C _6-20 aryl, and the other is a C _5-20 heteroaryl including N. O or S, or Ar ₁ and Ar ₂ may both be C _6-20 aryl, wherein Ar ₁ and Ar ₂ may each independently be substituted with one or more deuterium, C _1-18 alkyl, or C _6-18 aryl, or may be unsubstituted. .

More preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, (naphthyl)phenyl, (phenyl)naphthyl, flu orenyl, dibenzofuranyl, dibenzothiophenyl or carbazolyl, wherein Ar ₁ and Ar ₂ are each independently one or more deuterium; C _1-18 alkyl such as methyl; Or it may be unsubstituted or substituted with C _6-18 aryl such as phenyl.

More preferably, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of the following formulas:

In each of the above formulas,

Z is NR, O or S;

R, R ₁₁ and R ₁₂ are the same or different and each independently represent hydrogen, deuterium, C _1-18 alkyl or C _6-18 aryl, preferably R, R ₁₁ and R ₁₂ are the same or different, hydrogen, deuterium, methyl, or phenyl;

Dotted lines indicate binding sites.

Even more preferably, any one of Ar ₁ and Ar ₂ is phenyl, biphenyl or naphthyl, and the others are phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, (naph ethyl) phenyl, (phenyl) naphthyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl, wherein Ar ₁ and Ar ₂ are each independently one or more deuterium, methyl, or It may be substituted or unsubstituted with phenyl.

Also, in Chemical Formula 1, Ar ₁ and Ar ₂ may be identical to each other or may be different from each other.

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

.

.

On the other hand, the compound represented by Formula 1 can be prepared, for example, by a manufacturing method such as the following Reaction Scheme 1.

[Scheme 1]

In Reaction Scheme 1, A, Ar ₁ , Ar ₂ , R ₁ to R ₈ , X, Y, and n are as defined in Formula 1 above.

In Reaction Formula 1, W is a halogen group or a boron-containing organic group.

In addition, in Scheme 1, any one of R' ₁ to R' ₈ is a group capable of reacting with W and Suzuki coupling, and the others are each independently CH or CD. Specifically, the group capable of Suzuki coupling reaction with W may be a halogen group or a boron-containing organic group, which is different from W, so that when W is a halogen group, any one of R' ₁ to R' ₈ is boron It is a containing organic group, and when W is a boron-containing organic group, any one of R' ₁ to R' ₈ becomes a halogen group.

In Reaction Formula 1, W is a halogen group or a boron-containing organic group, and the halogen group is specifically chloro or boromo, and the boron-containing organic group is a boronic acid group, a boronic acid ester group, or a boronic acid pinacol ester (boronic acid pinacol ester).

Specifically, the compound represented by Formula 1 is obtained by combining a compound (i) having a parent core structure and a compound (ii) having a triazine structure bonded to the mother core structure in the presence of a base and a palladium-based catalyst, Ring reaction (Suzuki coupling reaction) can be prepared by a manufacturing method comprising the step.

As the palladium-based catalyst, bis(dibenzylideneacetone)palladium(0) (Bis(dibenzylideneacetone)palladium(0); (Pd(dba) ₂ )), bis(tri-tert-butylphosphine)palladium(0) )(bis(tri-tert-butylphosphine)palladium(0), Pd(P-tBuP ₃ ) ₂ ), tetrakis-(triphenylphosphine)palladium(0) (tetrakis(triphenylphosphine)palladium(0), Pd( PPh ₃ ) ₄ ), Tris (dibenzylideneacetone) dipalladium, Pd ₂ (dba) ₃ )), Bis (triphenylphosphine) palladium chloride, Pd ( PPh ₃ ) ₂ Cl ₂ ), bis(acetonitrile)palladium(II) chloride (Bis(acetonitrile)palladium(II) chloride, Pd(CH ₃ CN) ₂ Cl ₂ ), palladium(II) acetate (Palladium(II) acetate, Pd (OAc) ₂ ), Palladium(II) acetylacetonate (Pd(acac) ₂ ), Allylpalladium(II) chloride dimer, Pd(allyl)Cl] ₂ ) , Palladium on carbon (Pd/C), or palladium (II) chloride (Palladium (II) chloride, PdCl ₂ ), and the like, and any one or a mixture of two or more of them may be used.

In addition, as the base, sodium tert-butoxide (NaOtBu), potassium tert-butoxide, sodium tert-pentoxide, sodium ethoxide ( sodium ethoxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, lithium hydride or potassium hydride. inorganic bases; organic bases such as tetraethylammonium hydroxide ((Et ₄ NOH), bis(tetraethylammonium)carbonate, and triethylamine; and inorganic salts such as cesium fluoride, any one or a mixture of two or more of these may be used. can

In addition, the Suzuki coupling reaction may be carried out in water, an organic solvent, or a mixed solvent thereof, and the organic solvent includes diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol diethyl ether ether solvents such as dimethoxyethane, bis(2-methoxyethyl)ether, diethylene glycol diethyl ether, tetrahydrofuran or anisole; aromatic hydrocarbon-based solvents such as benzene, toluene or xylene; halogenated aromatic solvents such as chlorobenzene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylimidazolidone or acetonitrile; or a sulfoxide-based solvent such as dimethyl sulfoxide (DMSO), and any one or a mixture of two or more of these may be used.

Meanwhile, the reactants used in preparing compound (1) of Formula 1, compounds (i) and (ii), may be prepared using a conventional organic reaction or may be obtained and used commercially. The manufacturing method may be more specific in Preparation Examples to be described later.

In addition, the present invention provides an organic light emitting device including the compound represented by Formula 1 above. In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Chemical Formula 1. to provide.

In the organic light emitting device, the first electrode may be an anode and the second electrode may be a cathode, or the first electrode may be a cathode and the second electrode may be an anode.

Also, 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 including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron injection and transport layer as organic layers. However, the structure of the organic light emitting diode is not limited thereto and may include a smaller number of organic material layers.

In one embodiment, the organic material layer may include a light emitting layer, and in this case, the organic material layer including the compound may be a light emitting layer.

In another embodiment, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, and an electron injection and transport layer, wherein the organic material layer including the compound may be a light emitting layer.

In another embodiment, the organic material layer may include a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, and an electron injection and transport layer, wherein the organic material layer including the compound may be a light emitting layer.

In another embodiment, the organic material layer may include a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron injection and transport layer, wherein the organic material layer containing the compound may be a light emitting layer.

Also, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2 .

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

2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 8, a hole blocking layer 9, an electron injection and transport layer ( 10), and an example of an organic light emitting element composed of a cathode 4 is shown. In this structure, the compound represented by Formula 1 is the hole injection layer 5, the hole transport layer 6, the electron blocking layer 7, the light emitting layer 8, the hole blocking layer 9 and the electron injection and It may be included in one or more layers of the transport layer 10 .

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

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode After forming an organic material layer including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron injection and transport layer thereon, and depositing a material that can be used as a cathode thereon, it can be prepared. there is.

In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method means 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 may be manufactured by sequentially depositing an organic material layer and an anode material on a substrate from a cathode material (WO 2003/012890). However, the manufacturing method is not limited thereto.

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

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

The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation 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 layer. Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. As a hole transport material, a material capable of receiving holes from the anode or the hole injection layer and transferring them to the light emitting layer is a material having high hole mobility. this is suitable Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

The electron blocking layer is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons to increase hole-electron coupling probability, thereby increasing the efficiency of the organic light emitting device. means a layer that serves to improve The electron blocking layer includes an electron blocking material, and an arylamine-based organic material may be used as an example of the electron blocking material, but is not limited thereto.

The light emitting layer may include a host material and a dopant material. As the host material, the compound represented by Chemical Formula 1 may be used. In addition, as the host material, a condensed aromatic ring derivative or a compound containing a heterocyclic ring may be further used in addition to the compound represented by Formula 1 above. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.

In addition, examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc. having an arylamino group, and styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but is not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

More specifically, the dopant material may include compounds having the following structure, but is not limited thereto:

.

.

The hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to improve the efficiency of the organic light emitting device by controlling electron mobility and preventing excessive movement of holes to increase the probability of hole-electron coupling layers that play a role. The hole blocking layer includes a hole blocking material, and examples of the hole blocking material include azine derivatives including triazine; triazole derivatives; oxadiazole derivatives; phenanthroline derivatives; A compound having an electron withdrawing group such as a phosphine oxide derivative may be used, but is not limited thereto.

The electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting the received electrons to the light emitting layer, and is formed on the light emitting layer or the hole blocking layer. As such an electron injecting and transporting material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. Examples of specific electron injection and transport materials include Al complexes of 8-hydroxyquinoline; Complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes; triazine derivatives, etc., but are not limited thereto. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, etc. and their derivatives, metal complex compounds , or may be used together with nitrogen-containing 5-membered ring derivatives, etc., but is not limited thereto.

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

The electron injection and transport layer may also be formed as a separate layer such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the light emitting layer or the hole blocking layer, and the above-described electron injection and transport material may be used as an electron transport material included in the electron transport layer. In addition, the electron injection layer is formed on the electron transport layer, and examples of electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiophyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, etc. and their derivatives, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like can be used.

The organic light emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom emission device requiring relatively high light emitting efficiency.

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

Hereinafter, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited by the following examples.

Preparation Example 1

Preparation of Compound AA

In a nitrogen atmosphere, sub1 (10g, 27.5mmol) and sub2 (4.2g, 28.1mmol) were added to 200ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.4g, 82.6mmol) was dissolved in 34ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.9 g of AA_P1. (Yield 74%, MS: [M+H]+= 341)

In a nitrogen atmosphere, AA_P1 (10 g, 29.3 mmol) was added to 200 ml of AcOH, stirred and cooled to 0 ^° C. After this, Hydrazine monohydrate (1.6g, 32.2mmol) was slowly added, followed by stirring and refluxing. After reacting for 12 hours, the mixture was cooled to room temperature and the organic solvent was distilled under reduced pressure. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.1 g of AA_P2. (Yield 79%, MS: [M+H]+= 309)

AA_P2 (10g, 32.3mmol) and sub3 (6.7g, 35.5mmol) were added to 200ml of THF under a nitrogen atmosphere and stirred and refluxed. Thereafter, potassium carbonate (13.4g, 96.9mmol) was dissolved in 40ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.6 g of AA_P3. (Yield 80%, MS: [M+H]+= 373)

AA_P3 (10g, 26.8mmol) and potassium carbonate (11.1g, 80.5mmol) were added to 200ml of DMAc under a nitrogen atmosphere, followed by stirring and refluxing. After reacting for 9 hours, the mixture was cooled to room temperature and the organic solvent was distilled under reduced pressure. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.8 g of AA_P4. (Yield 61%, MS: [M+H]+= 353)

AA_P4 (15g, 42.5mmol) and bis(pinacolato)diboron (11.9g, 46.8mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. Then, potassium acetate (12.5g, 127.5mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7g, 1.3mmol) and tricyclohexylphosphine (0.7g, 2.6mmol) were added. After reacting for 5 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of Compound AA. (Yield 76%, MS: [M+H]+= 445)

Preparation Example 2

Preparation of Formula AB

11.8 g of Compound AB was prepared in the same manner as in Preparation Example 1, except that sub4 was used instead of sub1 as a starting material in Preparation Example 1. (Yield 80%, MS: [M+H]+= 445)

Preparation Example 3

Preparation of compound AC

In a nitrogen atmosphere, sub5 (10g, 30.4mmol) and sub2 (5g, 33.4mmol) were added to 200ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.6g, 91.2mmol) was dissolved in 38ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6 g of AC_P1. (Yield 65%, MS: [M+H]+= 307)

In a nitrogen atmosphere, AC_P1 (10 g, 32.6 mmol) was added to 200 ml of AcOH, stirred and cooled to 0 ^° C. Afterwards, Hydrazine monohydrate (1.8g, 35.8mmol) was slowly added, followed by stirring and refluxing. After reacting for 12 hours, the mixture was cooled to room temperature and the organic solvent was distilled under reduced pressure. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.4 g of AC_P2. (Yield 72%, MS: [M+H]+= 275)

AC_P2 (20g, 77.8mmol) and N-Chlorosuccinimide (10.6g, 79.3mmol) were added to 400ml of chloroform in a nitrogen atmosphere and stirred at room temperature. After reacting for 6 hours, the organic layer was separated after washing twice with water, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.7 g of AC_P3. (Yield 28%, MS: [M+H]+= 309)

AA_P3 (10g, 32.3mmol) and sub3 (6.7g, 35.5mmol) were added to 200ml of THF under a nitrogen atmosphere and stirred and refluxed. Thereafter, potassium carbonate (13.4g, 96.9mmol) was dissolved in 40ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.8 g of AC_P4. (Yield 65%, MS: [M+H]+= 373)

In a nitrogen atmosphere, AC_P4 (10g, 26.8mmol) and potassium carbonate (11.1g, 80.5mmol) were added to 200ml of DMAc and stirred and refluxed. After reacting for 9 hours, the mixture was cooled to room temperature and the organic solvent was distilled under reduced pressure. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.9 g of AC_P5. (Yield 63%, MS: [M+H]+= 353)

AC_P5 (15g, 42.5mmol) and bis(pinacolato)diboron (11.9g, 46.8mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. Then, potassium acetate (12.5g, 127.5mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7g, 1.3mmol) and tricyclohexylphosphine (0.7g, 2.6mmol) were added. After reacting for 5 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of Compound AC. (Yield 69%, MS: [M+H]+= 445)

Production Example 4

Preparation of compound AD

When AC_P3 was prepared from AC_P2 in Preparation Example 3, AD_P1 produced together with AC_P3 was purified and separated by silica gel column chromatography, and the same method as in Preparation Example 3 was performed, except that it was reacted with sub 3. Thus, 11.9 g of compound AD was prepared. (Yield 63%, MS: [M+H]+= 445)

Preparation Example 5

Preparation of compound AE

15.1 g of Compound AE was prepared in the same manner as in Preparation Example 1, except that sub5 was used instead of sub1 and sub6 was used instead of sub2 as the starting material in Preparation Example 1. (Yield 80%, MS: [M+H]+= 445)

Preparation Example 6

Preparation of Compound AF

12.1 g of Compound AF was prepared in the same manner as in Preparation Example 1, except that sub5 was used instead of sub1 and sub7 was used instead of sub2 as the starting material in Preparation Example 1. (Yield 64%, MS: [M+H]+= 445)

Preparation Example 7

Preparation of compound AG

14.7 g of Compound AG was prepared in the same manner as in Preparation Example 1, except that sub5 was used instead of sub1 and sub8 was used instead of sub2 as the starting material in Preparation Example 1. (Yield 78%, MS: [M+H]+= 445)

Preparation Example 8

Preparation of compound BA

AA_P2 (10g, 32.3mmol) and sub9 (6.7g, 35.5mmol) were added to 200ml of THF under a nitrogen atmosphere and stirred and refluxed. Thereafter, potassium carbonate (13.4g, 96.9mmol) was dissolved in 40ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.9 g of BA_P1. (Yield 66%, MS: [M+H]+= 373)

In a nitrogen atmosphere, BA_P1 (10g, 26.8mmol) and potassium carbonate (11.1g, 80.5mmol) were added to 200ml of DMAc and stirred and refluxed. After reacting for 9 hours, the mixture was cooled to room temperature and the organic solvent was distilled under reduced pressure. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.6 g of BA_P2. (Yield 70%, MS: [M+H]+= 353)

BA_P2 (15g, 42.5mmol) and bis(pinacolato)diboron (11.9g, 46.8mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. Then, potassium acetate (12.5g, 127.5mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7g, 1.3mmol) and tricyclohexylphosphine (0.7g, 2.6mmol) were added. After reacting for 5 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of Compound AA. (Yield 78%, MS: [M+H]+= 445)

Preparation Example 9

Preparation of Compound BB

11.8 g of compound BB was prepared in the same manner as in Preparation Example 9, except that AB_P2 was used instead of AA_P2 as a starting material in Preparation Example 9. (Yield 80%, MS: [M+H]+= 445)

Preparation Example 10

compound BC manufacturing

13 g of compound BC was prepared in the same manner as in Preparation Example 9, except that AC_P3 was used instead of AA_P2 as a starting material in Preparation Example 9. (Yield 69%, MS: [M+H]+= 445)

Preparation Example 11

compound BD manufacturing

14.5 g of compound BD was prepared in the same manner as in Preparation Example 9, except that AD_P1 was used instead of AA_P2 as a starting material in Preparation Example 9. (Yield 77%, MS: [M+H]+= 445)

Preparation Example 12

compound BE manufacturing

11.7 g of compound BE was prepared in the same manner as in Preparation Example 9, except that AE_P2 was used instead of AA_P2 as a starting material in Preparation Example 9. (Yield 62%, MS: [M+H]+= 445)

Preparation Example 13

Preparation of compound BF

13.6 g of compound BF was prepared in the same manner as in Preparation Example 9, except that AF_P2 was used instead of AA_P2 as a starting material in Preparation Example 9. (Yield 72%, MS: [M+H]+= 445)

Preparation Example 14

compound BG manufacturing

14.2 g of compound BG was prepared in the same manner as in Preparation Example 9, except that AG_P2 was used instead of AA_P2 as a starting material in Preparation Example 9. (Yield 75%, MS: [M+H]+= 445)

Preparation Example 15

compound CA preparation

11.3 g of compound CA was prepared in the same manner as in Preparation Example 9, except that sub10 was used instead of sub9 as a starting material in Preparation Example 9. (Yield 60%, MS: [M+H]+= 445)

Preparation Example 16

compound CB manufacturing

12.1 g of compound CB was prepared in the same manner as in Preparation Example 9, except that AB_P2 was used instead of AA_P2 and sub10 was used instead of sub9 in Preparation Example 9. (Yield 64%, MS: [M+H]+= 445)

Preparation Example 17

compound CC manufacturing

11.3 g of compound CC was prepared in the same manner as in Preparation Example 9, except that AC_P3 was used instead of AA_P2 as a starting material and sub10 was used instead of sub9 in Preparation Example 9. (Yield 60%, MS: [M+H]+= 445)

Preparation Example 18

compound CD manufacturing

14.4 g of compound CD was prepared in the same manner as in Preparation Example 9, except that AD_P1 was used instead of AA_P2 and sub10 was used instead of sub9 in Preparation Example 9. (Yield 76%, MS: [M+H]+= 445)

Preparation Example 19

compound CE manufacturing

14.7 g of compound CE was prepared in the same manner as in Preparation Example 9, except that AE_P2 was used instead of AA_P2 and sub10 was used instead of sub9 in Preparation Example 9. (Yield 78%, MS: [M+H]+= 445)

Production Example 20

compound CF manufacturing

14.4 g of compound CF was prepared in the same manner as in Preparation Example 9, except that AF_P2 was used instead of AA_P2 as a starting material and sub10 was used instead of sub9 in Preparation Example 9. (Yield 76%, MS: [M+H]+= 445)

Production Example 21

Compound CG Manufacturing

14g of compound CG was prepared in the same manner as in Preparation Example 9, except that AG_P2 was used instead of AA_P2 and sub10 was used instead of sub9 in Preparation Example 9. (Yield 74%, MS: [M+H]+= 445)

Production Example 22

compound DA preparation

In a nitrogen atmosphere, sub11 (10 g, 29 mmol) and sub2 (4.8 g, 31.9 mmol) were added to 200 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12g, 86.9mmol) was dissolved in 36ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6 g of DA_P1. (Yield 64%, MS: [M+H]+= 323)

In a nitrogen atmosphere, DA_P1 (10 g, 31.1 mmol) was added to 200 ml of AcOH, stirred and cooled to 0 ^° C. Afterwards, Hydrazine monohydrate (1.7g, 34.2mmol) was slowly added, followed by stirring and refluxing. After reacting for 12 hours, the mixture was cooled to room temperature and the organic solvent was distilled under reduced pressure. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.1 g of DA_P2. (Yield 79%, MS: [M+H]+= 291)

DA_P2 (10g, 34.3mmol) and sub12 (8.2g, 37.7mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (14.2g, 102.9mmol) was dissolved in 43ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.4 g of DA_P3. (Yield 64%, MS: [M+H]+= 385)

DA_P3 (10g, 26mmol) and Hydrogen Peroxide (1.8g, 52mmol) were added to 500ml of acetic acid in a nitrogen atmosphere and stirred and refluxed. After 3 hours, the reaction mixture was poured into water to drop crystals and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.3 g of DA_P4. (Yield 80%, MS: [M+H]+= 401)

DA_P4 (10g, 24.9mmol) was added to 200ml of H ₂ SO ₄ in a nitrogen atmosphere and stirred. When the reaction was completed after 2 hours, the reactant was poured into water to drop crystals and filtered. The filtered solid was dissolved again in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.1 g of DA_P5. (Yield 77%, MS: [M+H]+= 369)

DA_P5 (15g, 40.7mmol) and bis(pinacolato)diboron (11.4g, 44.7mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (12g, 122mmol) was added and sufficiently stirred, and then bis(dibenzylideneacetone)palladium(0) (0.7g, 1.2mmol) and tricyclohexylphosphine (0.7g, 2.4mmol) were added. After reacting for 5 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound DA. (Yield 64%, MS: [M+H]+= 461)

Production Example 23

Compound DB manufacturing

11.8g of Compound DB was prepared in the same manner as in Preparation Example 22, except that sub13 was used instead of sub11 as a starting material in Preparation Example 22. (Yield 63%, MS: [M+H]+= 461)

Production Example 24

Compound DC Preparation

In a nitrogen atmosphere, sub14 (10 g, 32.2 mmol) and sub2 (5.8 g, 38.6 mmol) were added to 200 ml of THF and stirred and refluxed. After that, potassium carbonate (13.3g, 96.5mmol) was dissolved in 40ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.6 g of DC_P1. (Yield 60%, MS: [M+H]+= 289)

In a nitrogen atmosphere, DC_P1 (10 g, 34.6 mmol) was added to 200 ml of AcOH, stirred and cooled to 0 ^° C. Afterwards, Hydrazine monohydrate (2.1g, 41.5mmol) was slowly added, followed by stirring and refluxing. After reacting for 12 hours, the mixture was cooled to room temperature and the organic solvent was distilled under reduced pressure. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.6 g of DC_P2. (Yield 74%, MS: [M+H]+= 257)

DC_P2 (20g, 77.8mmol) and N-Chlorosuccinimide (10.6g, 79.3mmol) were added to 400ml of chloroform in a nitrogen atmosphere and stirred at room temperature. After reacting for 6 hours, the organic layer was separated after washing twice with water, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.4 g of DC_P3. (Yield 28%, MS: [M+H]+= 293)

DA_P3 (10g, 34.3mmol) and sub12 (9g, 41.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (14.2g, 102.9mmol) was dissolved in 43ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.6 g of DA_P4. (Yield 73%, MS: [M+H]+= 385)

DC_P4 (10g, 26mmol) and Hydrogen Peroxide (1.8g, 52mmol) were added to 500ml of acetic acid in a nitrogen atmosphere and stirred and refluxed. After 3 hours, the reaction mixture was poured into water to drop crystals and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.3 g of DC_P5. (Yield 61%, MS: [M+H]+= 401)

In a nitrogen atmosphere, DC_P5 (10g, 24.9mmol) was added to 200ml of H ₂ SO ₄ and stirred. When the reaction was completed after 2 hours, the reactant was poured into water to drop crystals and filtered. The filtered solid was dissolved again in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.3 g of DA_P6. (Yield 79%, MS: [M+H]+= 369)

DC_P6 (15g, 40.7mmol) and bis(pinacolato)diboron (11.4g, 44.7mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (12g, 122mmol) was added and sufficiently stirred, and then bis(dibenzylideneacetone)palladium(0) (0.7g, 1.2mmol) and tricyclohexylphosphine (0.7g, 2.4mmol) were added. After reacting for 5 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound DC. (Yield 66%, MS: [M+H]+= 461)

Preparation Example 25

Preparation of compound DD

The same starting material as in Preparation Example 24 was used, but when the DD_P1 compound was synthesized, DC_P3 and DD_P1 of Preparation Example 24 were simultaneously produced and purified by silica gel column chromatography. Except for this, 12.2 g of compound DD was prepared using the same method as in Preparation Example 24. (Yield 65%, MS: [M+H]+= 461)

Production Example 26

Preparation of compound DE

11.8 g of compound DE was prepared in the same manner as in Preparation Example 22, except that sub14 was used instead of sub11 and sub6 was used instead of sub2 as the starting material in Preparation Example 22. (Yield 63%, MS: [M+H]+= 461)

Production Example 27

Preparation of compound DF

11.8 g of compound DF was prepared in the same manner as in Preparation Example 22, except that sub14 was used instead of sub11 and sub7 was used instead of sub2 as the starting material in Preparation Example 22. (Yield 63%, MS: [M+H]+= 461)

Production Example 28

Preparation of compound DG

13.7 g of compound DG was prepared in the same manner as in Preparation Example 22, except that sub14 was used instead of sub11 and sub8 was used instead of sub2 in Preparation Example 22. (Yield 73%, MS: [M+H]+= 461)

Production Example 29

Preparation of compound EA

DA_P2 (10g, 34.3mmol) and sub15 (8.2g, 37.7mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (14.2g, 102.9mmol) was dissolved in 43ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.4 g of EA_P1. (Yield 64%, MS: [M+H]+= 385)

EA_P1 (10g, 26mmol) and Hydrogen Peroxide (1.8g, 52mmol) were added to 500ml of acetic acid in a nitrogen atmosphere, followed by stirring and refluxing. After 3 hours, the reaction mixture was poured into water to drop crystals and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.3 g of EA_P2. (Yield 80%, MS: [M+H]+= 401)

EA_P2 (10g, 24.9mmol) was added to 200ml of H ₂ SO ₄ in a nitrogen atmosphere and stirred. When the reaction was completed after 2 hours, the reactant was poured into water to drop crystals and filtered. The filtered solid was dissolved again in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.1 g of EA_P3. (Yield 77%, MS: [M+H]+= 369)

EA_P3 (15g, 40.7mmol) and bis(pinacolato)diboron (11.4g, 44.7mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (12g, 122mmol) was added and sufficiently stirred, and then bis(dibenzylideneacetone)palladium(0) (0.7g, 1.2mmol) and tricyclohexylphosphine (0.7g, 2.4mmol) were added. After reacting for 5 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound EA. (Yield 78%, MS: [M+H]+= 461)

Production Example 30

Preparation of compound EB

13.8 g of compound EB was prepared in the same manner as in Preparation Example 29, except that DB_P2 was used instead of DA_P2 as a starting material in Preparation Example 29. (Yield 74%, MS: [M+H]+= 461)

Preparation Example 31

Preparation of compound EC

13.3 g of compound EC was prepared in the same manner as in Preparation Example 29, except that DC_P3 was used instead of DA_P2 as a starting material in Preparation Example 29. (Yield 71%, MS: [M+H]+= 461)

Preparation Example 32

Preparation of Compound ED

14.4 g of compound ED was prepared in the same manner as in Preparation Example 29, except that DD_P1 was used instead of DA_P2 as a starting material in Preparation Example 29. (Yield 77%, MS: [M+H]+= 461)

Preparation Example 33

Preparation of compound EE

13.5g of compound EE was prepared in the same manner as in Preparation Example 29, except that DE_P2 was used instead of DA_P2 as a starting material in Preparation Example 29. (Yield 72%, MS: [M+H]+= 461)

Preparation Example 34

Preparation of compound EF

12g of compound EF was prepared in the same manner as in Preparation Example 29, except that DF_P2 was used instead of DA_P2 as a starting material in Preparation Example 29. (Yield 64%, MS: [M+H]+= 461)

Production Example 35

Preparation of compound EG

13.3 g of compound EG was prepared in the same manner as in Preparation Example 29, except that DG_P2 was used instead of DA_P2 as a starting material in Preparation Example 29. (Yield 71%, MS: [M+H]+= 461)

Preparation Example 36

Preparation of compound FA

13.5 g of compound FA was prepared in the same manner as in Preparation Example 29, except that sub16 was used instead of sub15 as a starting material in Preparation Example 29. (Yield 72%, MS: [M+H]+= 461)

Preparation Example 37

Preparation of compound FB

13.8 g of compound FB was prepared in the same manner as in Preparation Example 29, except that DB_P2 was used instead of DA_P2 as a starting material and sub16 was used instead of sub15 in Preparation Example 29. (Yield 74%, MS: [M+H]+= 461)

Production Example 38

Preparation of compound FC

15 g of compound FC was prepared in the same manner as in Preparation Example 29, except that DC_P3 was used instead of DA_P2 as a starting material and sub16 was used instead of sub15 in Preparation Example 29. (Yield 80%, MS: [M+H]+= 461)

Preparation Example 39

Preparation of compound FD

14.6g of Compound FD was prepared in the same manner as in Preparation Example 29, except that DD_P1 was used instead of DA_P2 as a starting material and sub16 was used instead of sub15 in Preparation Example 29. (Yield 78%, MS: [M+H]+= 461)

Production Example 40

Preparation of compound FE

15 g of compound FE was prepared in the same manner as in Preparation Example 29, except that DE_P2 was used instead of DA_P2 as a starting material and sub16 was used instead of sub15 in Preparation Example 29. (Yield 80%, MS: [M+H]+= 461)

Preparation Example 41

Preparation of compound FF

12.5 g of compound FF was prepared in the same manner as in Preparation Example 29, except that DF_P2 was used instead of DA_P2 as a starting material and sub16 was used instead of sub15 in Preparation Example 29. (Yield 67%, MS: [M+H]+= 461)

Production Example 42

Preparation of compound FG

13.3 g of compound FG was prepared in the same manner as in Preparation Example 29, except that DG_P2 was used instead of DA_P2 as a starting material and sub16 was used instead of sub15 in Preparation Example 29. (Yield 71%, MS: [M+H]+= 461)

Synthesis Example 1

Formula AA (10g, 22.5mmol) and Trz1 (6.1g, 23mmol) were added to 200ml of THF under nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.6 g of Compound 1. (Yield 78%, MS: [M+H]+= 550)

Synthesis Example 2

Formula AA (10g, 22.5mmol) and Trz2 (11.3g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of Compound 2. (Yield 61%, MS: [M+H]+= 776)

Synthesis Example 3

Formula AB (10g, 22.5mmol) and Trz3 (7.3g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.3 g of Compound 3. (Yield 69%, MS: [M+H]+= 600)

Synthesis Example 4

Formula AB (10g, 22.5mmol) and Trz4 (8.6g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10 g of Compound 4. (Yield 68%, MS: [M+H]+= 656)

Synthesis Example 5

Formula AB (10g, 22.5mmol) and Trz5 (9g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of Compound 5. (Yield 79%, MS: [M+H]+= 676)

Synthesis Example 6

Formula AD (10g, 22.5mmol) and Trz1 (6.1g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.4 g of Compound 6. (Yield 76%, MS: [M+H]+= 550)

Synthesis Example 7

Formula AE (10g, 22.5mmol) and Trz6 (9g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.3 g of Compound 7. (Yield 61%, MS: [M+H]+= 676)

Synthesis Example 8

Formula AG (10g, 22.5mmol) and Trz1 (6.1g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.4 g of Compound 8. (Yield 76%, MS: [M+H]+= 550)

Synthesis Example 9

Formula BA (10g, 22.5mmol) and Trz7 (9.6g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere and stirred and refluxed. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of Compound 9. (Yield 77%, MS: [M+H]+= 702)

Synthesis Example 10

Formula BA (10g, 22.5mmol) and Trz8 (11.1g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of Compound 10. (Yield 72%, MS: [M+H]+= 766)

Synthesis Example 11

Chemical Formula BB (10g, 22.5mmol) and Trz1 (6.1g, 23mmol) were added to 200ml of THF under nitrogen atmosphere and stirred and refluxed. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.7 g of Compound 11. (Yield 70%, MS: [M+H]+= 550)

Synthesis Example 12

Chemical Formula BB (10g, 22.5mmol) and Trz9 (11.1g, 23mmol) were added to 200ml of THF under nitrogen atmosphere and stirred and refluxed. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of Compound 12. (Yield 75%, MS: [M+H]+= 766)

Synthesis Example 13

BB (10g, 22.5mmol) and Trz10 (9g, 23mmol) were added to 200ml of THF under nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9 g of Compound 13. (Yield 65%, MS: [M+H]+= 676)

Synthesis Example 14

Formula BD (10g, 22.5mmol) and Trz11 (7.9g, 23mmol) were added to 200ml of THF under nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.3 g of Compound 14. (Yield 73%, MS: [M+H]+= 626)

Synthesis Example 15

Formula BF (10g, 22.5mmol) and Trz12 (8.4g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of Compound 15. (Yield 74%, MS: [M+H]+= 650)

Synthesis Example 16

Chemical Formula BG (10g, 22.5mmol) and Trz13 (8.2g, 23mmol) were added to 200ml of THF and stirred and refluxed in a nitrogen atmosphere. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.5 g of Compound 16. (Yield 66%, MS: [M+H]+= 639)

Synthesis Example 17

Formula CA (10g, 22.5mmol) and Trz3 (7.3g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.5 g of Compound 17. (Yield 63%, MS: [M+H]+= 600)

Synthesis Example 18

Formula CA (10g, 22.5mmol) and Trz14 (8.2g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of Compound 18. (Yield 74%, MS: [M+H]+= 640)

Synthesis Example 19

Chemical formula CC (10g, 22.5mmol) and Trz15 (9g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of Compound 19. (Yield 80%, MS: [M+H]+= 676)

Synthesis Example 20

Chemical formula CC (10g, 22.5mmol) and Trz16 (9.9g, 23mmol) were added to 200ml of THF under nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of Compound 20. (Yield 80%, MS: [M+H]+= 715)

Synthesis Example 21

Chemical formula CD (10g, 22.5mmol) and Trz17 (10.2g, 23mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of Compound 21. (Yield 80%, MS: [M+H]+= 726)

Synthesis Example 22

Chemical formula CD (10g, 22.5mmol) and Trz18 (10.8g, 23mmol) were added to 200ml of THF under nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of Compound 22. (Yield 66%, MS: [M+H]+= 752)

Synthesis Example 23

Chemical Formula CE (10g, 22.5mmol) and Trz1 (6.1g, 23mmol) were added to 200ml of THF and stirred and refluxed in a nitrogen atmosphere. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.6 g of Compound 23. (Yield 78%, MS: [M+H]+= 550)

Synthesis Example 24

Chemical formula CE (10g, 22.5mmol) and Trz19 (9g, 23mmol) were added to 200ml of THF, stirred and refluxed in a nitrogen atmosphere. Thereafter, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5 g of Compound 24. (Yield 76%, MS: [M+H]+= 676)

Synthesis Example 25

Formula DA (10g, 21.7mmol) and Trz20 (9.6g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of Compound 25. (Yield 67%, MS: [M+H]+= 731)

Synthesis Example 26

Formula DA (10g, 21.7mmol) and Trz21 (8.7g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7 g of Compound 26. (Yield 71%, MS: [M+H]+= 692)

Synthesis Example 27

Formula DC (10g, 21.7mmol) and Trz21 (8.3g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.2 g of Compound 27. (Yield 63%, MS: [M+H]+= 672)

Synthesis Example 28

Formula DD (10g, 21.7mmol) and Trz11 (7.6g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.4 g of Compound 28. (Yield 60%, MS: [M+H]+= 642)

Synthesis Example 29

Formula DE (10g, 21.7mmol) and Trz23 (9.3g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3 g of Compound 29. (Yield 73%, MS: [M+H]+= 716)

Synthesis Example 30

DF (10 g, 21.7 mmol) and Trz3 (7 g, 22.2 mmol) were added to 200 ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.2 g of Compound 30. (Yield 61%, MS: [M+H]+= 616)

Synthesis Example 31

Formula DG (10g, 21.7mmol) and Trz24 (8.7g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.8 g of Compound 31. (Yield 65%, MS: [M+H]+= 692)

Synthesis Example 32

Formula EA (10g, 21.7mmol) and Trz1 (5.9g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.3 g of Compound 32. (Yield 76%, MS: [M+H]+= 566)

Synthesis Example 33

Formula EA (10g, 21.7mmol) and Trz25 (7.9g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.7 g of Compound 33. (Yield 68%, MS: [M+H]+= 656)

Synthesis Example 34

Formula EC (10g, 21.7mmol) and Trz26 (8.1g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11 g of Compound 34. (Yield 76%, MS: [M+H]+= 666)

Synthesis Example 35

Formula ED (10g, 21.7mmol) and Trz1 (5.9g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.8 g of Compound 35. (Yield 80%, MS: [M+H]+= 566)

Synthesis Example 36

Formula EF (10g, 21.7mmol) and Trz27 (7.6g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11 g of compound 36. (Yield 79%, MS: [M+H]+= 642)

Synthesis Example 37

Formula EG (10g, 21.7mmol) and Trz1 (5.9g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.9 g of Compound 37. (Yield 64%, MS: [M+H]+= 566)

Synthesis Example 38

Formula FB (10g, 21.7mmol) and Trz11 (7.6g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.3 g of Compound 38. (Yield 74%, MS: [M+H]+= 642)

Synthesis Example 39

Chemical formula FC (10g, 21.7mmol) and Trz1 (5.9g, 22.2mmol) were added to 200ml of THF, stirred and refluxed in a nitrogen atmosphere. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.7 g of Compound 39. (Yield 71%, MS: [M+H]+= 566)

Synthesis Example 40

Formula FE (10g, 21.7mmol) and Trz28 (9.3g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of Compound 40. (Yield 73%, MS: [M+H]+= 718)

Synthesis Example 41

Formula FE (10g, 21.7mmol) and Trz29 (9.3g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of Compound 41. (Yield 68%, MS: [M+H]+= 718)

Synthesis Example 42

Formula FG (10g, 21.7mmol) and Trz1 (5.9g, 22.2mmol) were added to 200ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.7 g of Compound 42. (Yield 79%, MS: [M+H]+= 566)

Example 1

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

The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 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 having a thickness of 800 Å. Subsequently, an electron blocking layer was formed on the hole transport layer by vacuum depositing the following EB-1 compound to a film thickness of 150 Å. Subsequently, Compound 1 prepared in Synthesis Example 1 as a host and the following Dp-7 compound as a dopant were vacuum deposited on the electron suppression layer at a weight ratio of 98:2 to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed on the light emitting layer by vacuum depositing the following HB-1 compound to a film thickness of 30 Å. Subsequently, the following ET-1 compound and the following LiQ compound were vacuum deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300 Å. A negative electrode 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 the organic material was maintained at 0.4 ~ 0.7Å / sec, the deposition rate of lithium fluoride on the cathode was 0.3Å / sec, and the deposition rate of aluminum was 2Å / sec, and the vacuum level during deposition was 2ⅹ10 ^-7 ~ While maintaining 5x10 ^-6 torr, an organic light emitting device was fabricated.

Examples 2 to 42

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

Comparative Examples 1 to 6

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

Experimental example

When a current of 10 mA/cm ² was applied to the organic light emitting devices prepared in Examples 1 to 42 and Comparative Examples 1 to 6, driving voltage and efficiency were measured, respectively, and the results are shown in Table 1 below. Also, the lifetime T95 means the time required for the luminance to decrease from the initial luminance (6000 nit) to 95%.

division host Driving voltage (V) Efficiency (cd/A) Lifetime T95(hr) luminescent color Example 1 compound 1 3.80 20.3 122 Red Example 2 compound 2 3.86 20.6 117 Red Example 3 compound 3 3.81 20.9 129 Red Example 4 compound 4 3.88 19.4 110 Red Example 5 compound 5 3.82 19.6 114 Red Example 6 compound 6 3.76 20.2 115 Red Example 7 compound 7 3.84 19.9 106 Red Example 8 compound 8 3.74 20.1 109 Red Example 9 compound 9 3.92 17.5 97 Red Example 10 compound 10 3.98 18.2 101 Red Example 11 compound 11 3.95 18.6 106 Red Example 12 compound 12 4.07 18.1 104 Red Example 13 compound 13 3.90 18.8 127 Red Example 14 compound 14 4.05 17.9 110 Red Example 15 compound 15 3.94 18.4 106 Red Example 16 compound 16 4.06 17.6 121 Red Example 17 compound 17 3.77 21.2 138 Red Example 18 compound 18 3.73 21.8 145 Red Example 19 compound 19 3.81 20.1 117 Red Example 20 compound 20 3.93 19.5 94 Red Example 21 compound 21 3.97 19.9 131 Red Example 22 compound 22 4.08 18.8 114 Red Example 23 compound 23 4.02 20.5 128 Red Example 24 compound 24 4.08 20.9 132 Red Example 25 compound 25 3.72 21.1 126 Red Example 26 compound 26 3.80 20.4 104 Red Example 27 compound 27 3.81 19.9 97 Red Example 28 compound 28 3.75 21.4 112 Red Example 29 compound 29 3.73 21.8 128 Red Example 30 compound 30 3.74 20.2 119 Red Example 31 compound 31 3.70 21.6 124 Red Example 32 compound 32 3.94 19.3 102 Red Example 33 compound 33 3.97 18.8 94 Red Example 34 compound 34 3.90 20.1 86 Red Example 35 compound 35 3.93 19.5 105 Red Example 36 compound 36 3.91 19.9 92 Red Example 37 compound 37 3.89 19.0 109 Red Example 38 compound 38 3.73 21.3 125 Red Example 39 compound 39 3.76 21.1 117 Red Example 40 compound 40 3.70 21.9 139 Red Example 41 compound 41 3.81 21.6 115 Red Example 42 compound 42 3.77 21.4 119 Red Comparative Example 1 C-1 4.16 16.1 81 Red Comparative Example 2 C-2 4.13 16.8 57 Red Comparative Example 3 C-3 4.26 15.3 43 Red Comparative Example 4 C-4 4.12 16.6 74 Red Comparative Example 5 C-5 4.34 14.2 49 Red Comparative Example 6 C-6 4.28 13.4 32 Red

As a result of the experiment, the organic light emitting devices of the examples using the compound according to the present invention in the light emitting layer had significantly lowered driving voltage and significantly increased efficiency compared to the comparative example. From this, it can be seen that energy transfer from the host to the red dopant was well performed. In addition, the organic light emitting device of Examples exhibited significantly improved lifespan characteristics while maintaining high efficiency compared to Comparative Examples, which is determined because the compounds of the present invention have higher stability to electrons and holes than the compounds used in Comparative Examples. do.

In conclusion, it can be confirmed that when the compound of the present invention is used as a host of a red light emitting layer, the driving voltage, luminous efficiency and lifespan characteristics of an organic light emitting device can be improved. Considering that they have a trade-off relationship with each other, it can be seen that the organic light emitting devices of Examples exhibit significantly improved device characteristics compared to the devices of Comparative Examples.

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

Claims (10)

A compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
X is O or S;
A is a benzene ring fused with two adjacent rings,
Any one of R ₁ to R ₈ is represented by the following formula (2), and the others are each independently CH or CD,
R are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 Alkyl; Or a substituted or unsubstituted C _6-60 aryl,
n is an integer from 0 to 6;
[Formula 2]

In Formula 2,
L is a single bond; Or a substituted or unsubstituted C _6-60 arylene,
Y is each independently N or CH, provided that at least two of Y are N,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted, C _5-60 heteroaryl containing at least one selected from the group consisting of N, O and S,
Dotted lines indicate binding sites.
According to claim 1,
Formula 1 is any one of the following Formulas 1-1 to 1-3,
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,
X, R ₁ to R ₈ , R, and n are as defined in claim 1.
According to claim 1,
L is a single bond, phenylene, or naphthylene;
compound.
According to claim 1,
Y is all N,
compound.
According to claim 1,
Ar ₁ and Ar ₂ are each independently C _6-30 aryl; or C _5-30 heteroaryl containing N, O or S;
Wherein Ar ₁ and Ar ₂ are each independently substituted with one or more deuterium, C _1-20 alkyl or C _6-20 aryl, or unsubstituted;
compound.
According to claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, (naphthyl)phenyl, (phenyl)naphthyl, fluorenyl, dibenzo furanyl, dibenzothiophenyl or carbazolyl;
Wherein Ar ₁ and Ar ₂ are each independently one or more deuterium, C _1-18 alkyl, or C _6-18 aryl unsubstituted or substituted,
compound.
According to claim 1,
Any one of Ar ₁ and Ar ₂ is phenyl, biphenyl or naphthyl;
The rest are phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, (naphthyl)phenyl, (phenyl)naphthyl, fluorenyl, dibenzofuranyl, dibenzothiophene one, or carbazolyl;
Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with one or more deuterium, methyl, or phenyl;
compound.
According to claim 1,
R are each independently hydrogen or deuterium,
compound.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
compound:

.
a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound according to any one of claims 1 to 9. That is, an organic light emitting element.

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