KR20210139185A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same. The present invention provides a compound represented by chemical formula 1. The compound represented by chemical formula 1 described above can be used as a material for an organic layer of the organic light emitting device, and can improve efficiency, lower driving voltage, and/or improve lifespan characteristics in the organic light emitting device.

Description

Novel compound and organic light emitting device using the same

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

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

An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, and for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.

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

Korean Patent Publication No. 10-2000-0051826

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

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

[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), the rest 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 substituted or unsubstituted C _{6-60 aryl, or substituted or unsubstituted, C 5-60} hetero comprising at least one selected from the group consisting of N, O and S aryl,

The dotted line indicates the bonding position.

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

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

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

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents . 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 in the carbonyl group is not particularly limited, but preferably 1 to 40 carbon atoms. Specifically, it may have a structure as follows, but is not limited thereto.

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

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

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

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, 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, and the like.

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

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

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

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

etc. can be However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 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, an acridyl group , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia and a jolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

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

The present invention provides a compound represented by the above formula (1).

Preferably, Formula 1 may be any one of Formulas 1-1 to 1-3 below:

[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 above.

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 may be hydrogen, where n is an integer of 6.

In addition, in Formula 1, preferably _{, any one of R 1} and R ₂ is represented by Formula 2, and the rest 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 remainder may be each independently CH or CD.

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

More preferably, L may be a single bond, phenylene, or naphthylene, 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 indicates the bonding position.

In addition, in Formula 2, preferably, two of Y may be N and the rest may be CH, or all three Ys may be N, and more preferably, all of Y may be N.

In addition, in Formula 2, preferably, Ar ₁ and Ar ₂ are each independently C _6-30 aryl; _{or C 5-30} heteroaryl including 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 can be

In addition, in Formula 2, preferably, one of _{Ar 1} and Ar _{2 is C 6-20} aryl, and the other is C _5-20 heteroaryl including N. O or S, or Ar ₁ and Ar ₂ Both _{may be C 6-20} aryl, wherein Ar ₁ and Ar ₂ may each independently be unsubstituted or substituted with one or more deuterium, C _1-18 alkyl, or C _{6-18 aryl.} .

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, each independently 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;

The dotted line indicates the bonding position.

Even more preferably _{, any one of Ar 1} and Ar ₂ is phenyl, biphenyl or naphthyl, and the remainder is phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, (naph tyl)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 unsubstituted or substituted with phenyl.

In addition, in Formula 1, Ar ₁ and Ar ₂ may be the same as or 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 may be prepared by, for example, a preparation method as shown in Scheme 1 below.

[Scheme 1]

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

Also, in Scheme 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, and when W is a halogen group, any one of _{R′ 1} to R′ _{8 is boron.} It becomes 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 addition, in Scheme 1, W is a halogen group or a boron-containing organic group, and the halogen group is specifically chloro or boromo, etc., 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) group and the like.

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

Examples of the palladium-based catalyst include 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 (Bis (triphenylphosphine) palladium chloride, Pd ( PPh ₃ ) ₂ Cl ₂ ), bis(acetonitrile)palladium(II) chloride, Pd(CH ₃ CN) ₂ Cl ₂ ), 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 (PdCl ₂ ), and the like, and any one or a mixture of two or more thereof may be used.

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

In addition, the Suzuki coupling reaction may be performed in water, an organic solvent, or a mixed solvent thereof. Examples of the organic solvent include 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) may be used, and any one or a mixture of two or more thereof may be used.

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

In addition, the present invention provides an organic light emitting device including the compound represented by the formula (1). In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound represented by Formula 1; to provide.

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

In addition, 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 an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.

In one embodiment, the organic material layer may include a light emitting 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, 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 suppression 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 suppression 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. Also, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting diode 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 including a substrate 1 , an anode 2 , an organic material layer 3 , and a cathode 4 . In such a structure, the compound represented by Formula 1 may be included in the organic layer 3 .

2 is 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 device including 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 of the transport layers 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 layer of the organic material layer includes the compound represented by Formula 1 above. Also, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

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

In addition, the compound represented by Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

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

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

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

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

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

The electron suppression layer is formed on the hole transport layer, preferably provided in contact with the light emitting layer, adjusts hole mobility, prevents excessive movement of electrons, and increases the probability of hole-electron coupling by increasing the efficiency of the organic light emitting device layer that plays a role in improving 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 emission 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, in addition to the compound represented by Formula 1, a condensed aromatic ring derivative or a hetero ring-containing compound may be additionally used. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Further, examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is a substituted or unsubstituted derivative. It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

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

.

.

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 hole-electron coupling probability layer that plays 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 into which an electron withdrawing group is introduced, such as a phosphine oxide derivative, may be used, but the present invention 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 the electrode and transporting the received electrons to the emission layer, and is formed on the emission layer or the hole blocking layer. As the electron injection and transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Examples of specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes; and triazine derivatives, but is not limited thereto. or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metal complex compounds , or may be used together with a nitrogen-containing 5-membered ring derivative, and the like, 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) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. The present invention is not limited thereto.

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 electron injection and transport material described above may be used as the electron transport material included in the electron transport layer. In addition, the electron injection layer is formed on the electron transport layer, and the electron injection material included in the electron injection layer is LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone and the like may 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 luminous efficiency.

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

Hereinafter, preferred embodiments are presented to help the 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 placed in 200ml of THF, stirred and refluxed. After that, potassium carbonate (11.4g, 82.6mmol) was dissolved in 34ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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 o C.} After that, Hydrazine monohydrate (1.6g, 32.2mmol) was slowly added, followed by stirring and reflux. After reaction 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.1 g of AA_P2. (yield 79%, MS: [M+H]+=309)

In a nitrogen atmosphere, AA_P2 (10g, 32.3mmol) and sub3 (6.7g, 35.5mmol) were added to 200ml of THF, followed by stirring and reflux. After that, potassium carbonate (13.4g, 96.9mmol) was dissolved in 40ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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)

In a nitrogen atmosphere, AA_P3 (10g, 26.8mmol) and potassium carbonate (11.1g, 80.5mmol) were added to 200ml of DMAc, stirred and refluxed. After reaction for 9 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.8 g of AA_P4. (Yield 61%, MS: [M+H]+= 353)

In a nitrogen atmosphere, AA_P4 (15g, 42.5mmol) and bis(pinacolato)diboron (11.9g, 46.8mmol) were refluxed in 300ml of 1,4-dioxane and stirred. After that, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of compound AA. (Yield 76%, MS: [M+H]+= 445)

Preparation 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 3

Preparation of compound AC

In a nitrogen atmosphere, sub5 (10g, 30.4mmol) and sub2 (5g, 33.4mmol) were added to 200ml of THF, stirred and refluxed. After that, potassium carbonate (12.6g, 91.2mmol) was dissolved in 38ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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 o C.} After that, Hydrazine monohydrate (1.8g, 35.8mmol) was slowly added, followed by stirring and reflux. After reaction 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.4 g of AC_P2. (Yield 72%, MS: [M+H] + = 275)

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

In a nitrogen atmosphere, AA_P3 (10g, 32.3mmol) and sub3 (6.7g, 35.5mmol) were placed in 200ml of THF, stirred and refluxed. After that, potassium carbonate (13.4g, 96.9mmol) was dissolved in 40ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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)

AC_P4 (10g, 26.8mmol) and potassium carbonate (11.1g, 80.5mmol) were added to 200ml of DMAc in a nitrogen atmosphere, and stirred and refluxed. After reaction for 9 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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 in 300ml of 1,4-dioxane in a nitrogen atmosphere and stirred. After that, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound AC. (yield 69%, MS: [M+H]+= 445)

Preparation 4

Preparation of compound AD

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

Preparation 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 as a starting material in Preparation Example 1, and sub6 was used instead of sub2. (Yield 80%, MS: [M+H]+= 445)

Preparation 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 as a starting material in Preparation Example 1, and sub7 was used instead of sub2. (Yield 64%, MS: [M+H]+= 445)

Preparation 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 as a starting material in Preparation Example 1, and sub8 was used instead of sub2. (Yield 78%, MS: [M+H]+= 445)

Preparation 8

Preparation of compound BA

In a nitrogen atmosphere, AA_P2 (10g, 32.3mmol) and sub9 (6.7g, 35.5mmol) were placed in 200ml of THF, stirred and refluxed. After that, potassium carbonate (13.4g, 96.9mmol) was dissolved in 40ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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, stirred and refluxed. After reaction for 9 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.6 g of BA_P2. (Yield 70%, MS: [M+H]+= 353)

In a nitrogen atmosphere, BA_P2 (15g, 42.5mmol) and bis(pinacolato)diboron (11.9g, 46.8mmol) were refluxed in 300ml of 1,4-dioxane and stirred. After that, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound AA. (Yield 78%, MS: [M+H]+= 445)

Preparation 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 10

Compound BC Preparation

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 11

Compound BD preparation

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 12

Compound BE preparation

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 13

Compound BF preparation

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 14

Compound BG preparation

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 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 16

Compound CB preparation

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 as a starting material in Preparation Example 9, and sub10 was used instead of sub9. (Yield 64%, MS: [M+H]+= 445)

Preparation 17

Compound CC preparation

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 in Preparation Example 9, and sub10 was used instead of sub9. (Yield 60%, MS: [M+H]+= 445)

Preparation 18

Compound CD Preparation

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 as a starting material in Preparation Example 9, and sub10 was used instead of sub9. (Yield 76%, MS: [M+H]+= 445)

Preparation 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 as a starting material in Preparation Example 9, and sub10 was used instead of sub9. (Yield 78%, MS: [M+H]+= 445)

Preparation 20

Compound CF preparation

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 in Preparation Example 9, and sub10 was used instead of sub9. (Yield 76%, MS: [M+H]+= 445)

Preparation 21

Compound CG preparation

14 g of compound CG 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, and sub10 was used instead of sub9. (Yield 74%, MS: [M+H]+= 445)

Preparation 22

Compound DA preparation

In a nitrogen atmosphere, sub11 (10g, 29mmol) and sub2 (4.8g, 31.9mmol) were added to 200ml of THF, stirred and refluxed. After that, potassium carbonate (12g, 86.9mmol) was dissolved in 36ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 o C.} After that, Hydrazine monohydrate (1.7g, 34.2mmol) was slowly added, followed by stirring and reflux. After reaction 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.1 g of DA_P2. (yield 79%, MS: [M+H] + = 291)

In a nitrogen atmosphere, DA_P2 (10g, 34.3mmol) and sub12 (8.2g, 37.7mmol) were added to 200ml of THF and stirred and refluxed. After that, potassium carbonate (14.2g, 102.9mmol) was dissolved in 43ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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, stirred and refluxed. After 3 hours, the reaction product was poured into water to drop crystals and filtered. The filtered solid was dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.3 g of DA_P4. (yield 80%, MS: [M+H]+= 401)

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

In a nitrogen atmosphere, DA_P5 (15g, 40.7mmol) and bis(pinacolato)diboron (11.4g, 44.7mmol) were refluxed in 300ml of 1,4-dioxane and stirred. After that, potassium acetate (12g, 122mmol) was added, and after sufficient stirring, 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 again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound DA. (Yield 64%, MS: [M+H] + = 461)

Preparation 23

Compound DB preparation

11.8 g 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)

Preparation 24

Compound DC Preparation

In a nitrogen atmosphere, sub14 (10g, 32.2mmol) and sub2 (5.8g, 38.6mmol) were added to 200ml of THF, stirred and refluxed. After that, potassium carbonate (13.3g, 96.5mmol) was dissolved in 40ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 o C.} After that, Hydrazine monohydrate (2.1g, 41.5mmol) was slowly added, followed by stirring and reflux. After reaction 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.6 g of DC_P2. (Yield 74%, MS: [M+H] + = 257)

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

In a nitrogen atmosphere, DA_P3 (10g, 34.3mmol) and sub12 (9g, 41.2mmol) were added to 200ml of THF and stirred and refluxed. After that, potassium carbonate (14.2g, 102.9mmol) was dissolved in 43ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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)

In a nitrogen atmosphere, DC_P4 (10g, 26mmol) and Hydrogen Peroxide (1.8g, 52mmol) were added to 500ml of acetic acid, stirred and refluxed. After 3 hours, the reaction product was poured into water to drop crystals and filtered. The filtered solid was dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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 reaction product was poured into water to drop crystals and filtered. The filtered solid was dissolved again in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.3 g of DA_P6. (yield 79%, MS: [M+H]+=369)

In a nitrogen atmosphere, DC_P6 (15g, 40.7mmol) and bis(pinacolato)diboron (11.4g, 44.7mmol) were refluxed in 300ml of 1,4-dioxane and stirred. After that, potassium acetate (12g, 122mmol) was added, and after sufficient stirring, 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 again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound DC. (Yield 66%, MS: [M+H]+= 461)

Preparation 25

Preparation of compound DD

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

Preparation 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 as a starting material in Preparation 22, and sub6 was used instead of sub2. (Yield 63%, MS: [M+H] + = 461)

Preparation 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 as a starting material in Preparation 22, and sub7 was used instead of sub2. (Yield 63%, MS: [M+H] + = 461)

Preparation 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 as a starting material in Preparation 22, and sub8 was used instead of sub2. (Yield 73%, MS: [M+H] + = 461)

Preparation 29

Preparation of compound EA

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

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

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

In a nitrogen atmosphere, EA_P3 (15g, 40.7mmol) and bis(pinacolato)diboron (11.4g, 44.7mmol) were refluxed in 300ml of 1,4-dioxane and stirred. After that, potassium acetate (12g, 122mmol) was added, and after sufficient stirring, 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 again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound EA. (Yield 78%, MS: [M+H] + = 461)

Preparation 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 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 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 33

Preparation of compound EE

13.5 g 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 34

Preparation of compound EF

12 g 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)

Preparation 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 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 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 in Preparation Example 29, and sub16 was used instead of sub15. (Yield 74%, MS: [M+H] + = 461)

Preparation 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 in Preparation Example 29, and sub16 was used instead of sub15. (Yield 80%, MS: [M+H] + = 461)

Preparation 39

Preparation of compound FD

14.6 g 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 in Preparation Example 29, and sub16 was used instead of sub15. (Yield 78%, MS: [M+H] + = 461)

Preparation 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 in Preparation Example 29, and sub16 was used instead of sub15. (Yield 80%, MS: [M+H] + = 461)

Preparation 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 in Preparation Example 29, and sub16 was used instead of sub15. (Yield 67%, MS: [M+H] + = 461)

Preparation 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 in Preparation Example 29, and sub16 was used instead of sub15. (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 in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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 placed in 200ml of THF in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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

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

Synthesis Example 11

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

Synthesis Example 12

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

Synthesis Example 13

Formula BB (10g, 22.5mmol) and Trz10 (9g, 23mmol) were placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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

Formula BG (10g, 22.5mmol) and Trz13 (8.2g, 23mmol) were placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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

Chemical formula CA (10g, 22.5mmol) and Trz3 (7.3g, 23mmol) were placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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

Chemical formula CA (10g, 22.5mmol) and Trz14 (8.2g, 23mmol) were placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9.3g, 67.5mmol) was dissolved in 28ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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

Chemical formula DA (10g, 21.7mmol) and Trz20 (9.6g, 22.2mmol) were placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7 g of compound 26. (Yield 71%, MS: [M+H]+=692)

Synthesis Example 27

Chemical formula DC (10g, 21.7mmol) and Trz21 (8.3g, 22.2mmol) were placed in 200ml of THF in a nitrogen atmosphere, stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.4 g of compound 28. (Yield 60%, MS: [M+H]+= 642)

Synthesis Example 29

Chemical formula DE (10g, 21.7mmol) and Trz23 (9.3g, 22.2mmol) were placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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

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

Synthesis Example 31

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

Synthesis Example 32

Chemical formula EA (10g, 21.7mmol) and Trz1 (5.9g, 22.2mmol) were placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.7 g of compound 33. (Yield 68%, MS: [M+H] + = 656)

Synthesis Example 34

Chemical formula EC (10g, 21.7mmol) and Trz26 (8.1g, 22.2mmol) were placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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

Chemical formula EG (10g, 21.7mmol) and Trz1 (5.9g, 22.2mmol) were placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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

Chemical formula FE (10g, 21.7mmol) and Trz29 (9.3g, 22.2mmol) were placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 placed in 200ml of THF in a nitrogen atmosphere, and stirred and refluxed. After that, potassium carbonate (9g, 65.2mmol) was dissolved in 27ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 indium tin oxide (ITO) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. In this case, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

The following HI-1 compound was formed as a hole injection layer on the prepared ITO transparent electrode to a thickness of 1150 Å, but the following A-1 compound was p-doped at a concentration of 1.5%. The following HT-1 compound was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Next, the following EB-1 compound was vacuum-deposited to a thickness of 150 Å on the hole transport layer to form an electron blocking layer. Then, on the electron suppression layer, the compound 1 prepared in Synthesis Example 1 as a host and the following Dp-7 compound as a dopant were vacuum-deposited in a weight ratio of 98:2 to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed by vacuum-depositing the following HB-1 compound to a thickness of 30 Å on the light emitting layer. Then, on the hole blocking layer, the following ET-1 compound and the following LiQ compound were vacuum-deposited in a weight ratio of 2:1 to form an electron injection and transport layer to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

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

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. In addition, the lifetime T95 means the time it takes for the luminance to decrease from the initial luminance (6000 nit) to 95%.

division host Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous 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 diodes of Examples in which the compound according to the present invention was used for the light emitting layer had significantly lower driving voltages and greatly increased efficiency compared to Comparative Examples. 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 the example exhibited greatly improved lifespan characteristics while maintaining high efficiency compared to the comparative example, which is determined because the compound of the present invention has higher stability to electrons and holes than the compound used in the comparative example. do.

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

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 the following formula (1):
[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), the rest are each independently CH or CD,
each R is 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 substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted, C 5-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,
The dotted line indicates the bonding position.
According to claim 1,
Formula 1 is any one of 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 are 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 unsubstituted or substituted with one or more deuterium, C _1-18 alkyl, or C _{6-18 aryl,}
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,
wherein Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with one or more deuterium, methyl, or phenyl;
compound.
According to claim 1,
each R is 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 at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the compound according to any one of claims 1 to 9 which is an organic light emitting device.

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