KR20220157681A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to a novel electroluminescent compound represented by [Formula I] that can be employed in an organic layer such as a hole transport layer in an organic light emitting device to realize light emitting characteristics such as low voltage driving and excellent light emitting efficiency of a device, and to an electroluminescent device comprising the same.

Description

An organic light emitting compound and an organic light emitting device comprising the same {An electroluminescent compound and an electroluminescent device comprising the same}

The present invention relates to an organic light-emitting compound, and more particularly, to an organic light-emitting compound characterized in that it is employed as an organic layer material in an organic light-emitting device, and organic light-emitting properties such as low-voltage driving of the device and excellent light-emitting efficiency are remarkably improved by employing the organic light-emitting compound. It is about light emitting devices.

Organic light emitting devices can not only be formed on a transparent substrate, but also can be driven at a low voltage of 10 V or less compared to plasma display panels or inorganic electroluminescent (EL) displays, and consume relatively little power. , It has the advantage of being excellent in color, and can show three colors of green, blue, and red, so it has recently become a subject of much interest as a next-generation display device.

However, in order for the organic light emitting device to exhibit the above characteristics, the materials constituting the organic layer in the device, such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, and electron injection materials, are supported by stable and efficient materials. However, the development of stable and efficient organic layer materials for organic light emitting devices has not yet been sufficiently accomplished.

Therefore, in order to implement a more stable organic light emitting device, and to achieve high efficiency, long lifespan, and large size of the device, further improvement in terms of efficiency and lifespan characteristics is required, and in particular, development of materials forming each organic layer of the organic light emitting device is required. It is desperately needed.

In this regard, studies have recently been actively conducted to improve the mobility of existing organic materials for the hole transport layer material in the structure of the organic light emitting device.

Therefore, the present invention is to provide a novel organic light emitting compound that can be employed in an organic layer such as a hole transport layer in an organic light emitting device to realize excellent light emitting characteristics such as low voltage driving of the device and improved light emitting efficiency, and an organic light emitting device including the same. .

In order to solve the above problems, the present invention provides an organic light emitting device including an organic light emitting compound represented by the following [Chemical Formula I] and an organic layer such as a hole transport layer in the device.

[Formula I]

The characteristic structure of [Chemical Formula I] and the definitions of Y, L, and Ar ₁ to Ar ₂ , which are realized by the compound, will be described later.

When the organic light-emitting compound according to the present invention is used as a material for an organic layer such as a hole transport layer in an organic light-emitting device, low-voltage driving of the device and light-emitting characteristics such as excellent light-emitting efficiency can be realized, so that it can be usefully used in various display devices.

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

The present invention relates to an organic light emitting compound represented by the following [Formula I] capable of achieving light emitting characteristics such as low voltage driving of an organic light emitting device and excellent light emitting efficiency, and structurally having a skeleton structure represented by [Formula I] , that is, it is characterized in that a characteristic substituent is introduced through an L linkage in the structure of an indenoquinoline derivative, and through this structural feature, low-voltage driving characteristics and luminous efficiency characteristics of an organic light emitting device can be improved.

[Formula I]

In the above [Formula I],

Y is O, S, CR ₁ R ₂ or NR ₃ .

Wherein R ₁ to R ₃ are each independently hydrogen, heavy hydrogen, a halogen group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted It is selected from an aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

In addition, R ₁ and R ₂ may combine with each other to form an alicyclic ring or an aromatic ring.

L is a single bond or is selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, n is an integer of 0 to 3, wherein n is 2 or more In this case, a plurality of L's are the same as or different from each other.

Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 30 carbon atoms. It is selected from an aryl group and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

Meanwhile, in the definition of R ₁ to R ₃ , L and Ar ₁ to Ar ₂ , 'substituted or unsubstituted' means that R ₁ to R ₃ , L and Ar ₁ to Ar ₂ are deuterium or a halogen group, respectively. , Cyano group, nitro group, hydroxyl group, alkyl group, halogenated alkyl group, deuterated alkyl group, cycloalkyl group, heterocycloalkyl group, alkoxy group, halogenated alkoxy group, deuterated alkoxy group, amine group, aryl group, heteroaryl group , It means that it is substituted with one or two or more substituents selected from the group consisting of an alkylsilyl group and an arylsilyl group, is substituted with a substituent in which two or more substituents are connected, or does not have any substituent.

For example, a substituted aryl group means that a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, and the like are substituted with other substituents. do.

In addition, the substituted heteroaryl group refers to a pyridyl group, a thiophenyl group, a triazine group, a quinoline group, a phenanthroline group, an imidazole group, a thiazole group, an oxazole group, a carbazole group, and condensed heterocyclic groups thereof, such as a benzquinoline group. , It means that a benzimidazole group, a benzoxazole group, a benzthiazole group, a benzcarbazole group, a dibenzothiophenyl group, a dibenzofuran group, and the like are substituted with other substituents.

In the present invention, examples of the substituents will be described in detail below, but are not limited thereto.

In the present invention, the alkyl group may be straight or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group and the like, but is not limited thereto.

In the present invention, the alkoxy group may be straight chain or branched chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20, which is a range that does not cause steric hindrance. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, i-propyloxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group , Neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group , benzyloxy group, p-methylbenzyloxy group, etc., but is not limited thereto.

In the present invention, a deuterated alkyl or alkoxy group, a halogenated alkyl or alkoxy group means an alkyl or alkoxy group in which the alkyl or alkoxy group is substituted with deuterium or a halogen group.

In the present invention, the aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 30, and also includes a polycyclic aryl group structure in which cycloalkyl or the like is fused, and a monocyclic aryl group Examples of include a phenyl group, a biphenyl group, a terphenyl group, a stilbene group, and the like, and examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a tetracenyl group, and a chrysenyl group. , fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthrene group, etc., but the scope of the present invention is not limited only to these examples.

,

,

등이 있다.In the present invention, the fluorenyl group is a structure in which two ring organic compounds are linked through one atom, for example

,

,

etc.

,

등이 있다.In the present invention, the fluorenyl group includes the structure of an open fluorenyl group, where the open fluorenyl group is a structure in which one ring compound is disconnected from a structure in which two ring organic compounds are connected through one atom. , for example

,

etc.

,

,

,

등이 있다.In addition, the carbon atom of the ring may be substituted with any one or more heteroatoms selected from N, S and O, for example

,

,

,

etc.

In the present invention, the heteroaryl group is a heterocyclic group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and is a polycyclic group in which cycloalkyl or heterocycloalkyl is fused. It includes a heteroaryl group structure, and specific examples thereof in the present invention 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, and a bipyridyl group. , pyrimidyl group, triazine group, triazole group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, Dibenzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, phenoxazine group, phenothiazine group, etc., but only these It is not limited.

In the present invention, the silyl group is an unsubstituted silyl group or a silyl group substituted with an alkyl group, an aryl group, etc., and specific examples of such a silyl group include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxy phenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl, and the like, but are not limited thereto.

Specific examples of the substituent halogen group used in the present invention include fluorine (F), chlorine (Cl), and bromine (Br).

In the present invention, the cycloalkyl group refers to and includes monocyclic, polycyclic and spiroalkyl radicals, preferably containing ring carbon atoms of 3 to 20 carbon atoms, cyclopropyl, cyclopentyl, cyclohexyl, bicyclo heptyl, spirodecyl, spirundecyl, adamantyl, and the like, and the cycloalkyl group may be optionally substituted.

In the present invention, heterocycloalkyl groups refer to and include aromatic and non-aromatic cyclic radicals containing one or more heteroatoms, one or more heteroatoms being O, S, N, P, B, Si, and Se , Preferably selected from O, N or S, specifically, when N is included, it may be aziridine, pyrrolidine, piperidine, azepane, azocan, and the like.

The organic light emitting compound according to the present invention represented by [Chemical Formula I] may be used as various organic layers including an electron transport layer in an organic light emitting device due to its structural specificity.

Preferred specific examples of the organic light-emitting compound represented by [Chemical Formula I] according to the present invention include the following compounds, but are not limited thereto.

As described above, the organic light emitting compound according to the present invention can synthesize organic light emitting compounds having various properties by using a characteristic skeleton exhibiting unique properties and a moiety having unique properties introduced thereto, As a result, the organic light emitting compound according to the present invention can be applied to various organic layer materials such as a light emitting layer, a hole transport layer, an electron transport layer, an electron blocking layer, and a hole blocking layer. can be further improved.

In addition, the compound of the present invention can be applied to a device according to a general organic light emitting device manufacturing method.

An organic light emitting device according to an embodiment of the present invention may have a structure including a first electrode, a second electrode, and an organic layer disposed therebetween, and the organic light emitting compound according to the present invention is used in the organic layer of the device. Except for this, it can be manufactured using conventional device manufacturing methods and materials.

The organic layer of the organic light emitting device according to the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic layers are stacked. For example, it may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, and the like, and a structure including a capping layer provided in an organic light emitting device. However, it is not limited thereto and may include fewer or more organic layers.

An organic layer structure of a preferred organic light emitting device according to the present invention will be described in more detail in Examples to be described later.

In addition, the organic light emitting device according to the present invention uses a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form a metal or conductive metal oxide or an alloy thereof on a substrate. It can be manufactured by depositing an anode, forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate. The organic layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic layer can be formed by using various polymer materials and using a solvent process rather than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. Can be made in layers.

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

The cathode material is preferably a material having a small work function so as to easily inject electrons 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 multilayers such as LiF/Al or LiO ₂ /Al. structural materials, etc., but are not limited thereto.

The hole injection material is a material capable of receiving holes well from the anode at a low voltage, and preferably has a highest occupied molecular orbital (HOMO) between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high hole mobility is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts. can be further improved.

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

As the electron 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, and the compound according to the present invention may be used, or may be used together with conventional compounds have. Specific examples of such conventional compounds include, but are not limited to, Al complexes of 8-hydroxyquinoline, complexes containing Alq ₃ , organic radical compounds, and hydroxyflavone-metal complexes.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

In addition, the organic light emitting compound according to the present invention may act in organic electronic devices including organic solar cells, organic photoreceptors, organic transistors, and the like, on a principle similar to that applied to organic light emitting devices.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are intended to explain the present invention in more detail, and the scope of the present invention is not limited thereto, and various changes and modifications are possible within the scope and spirit of the present invention. It will be self-evident to those who have knowledge.

synthesis example 1: Synthesis of Compound 1

(One) manufacturing example 1: synthesis of intermediate 1-1

5-Bromo-6-methoxyquinoline (10.0 g, 0.042 mol), 2-Fluoro-4-chlorophenylboronic acid (8.8 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), Pd(PPh ₃ ) ₄ ( 1.0 g, 0.0008 mol) into 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours. After completion of the reaction, 11.2 g (yield: 54.5%) of <Intermediate 1-1> was obtained by extraction, concentration, and column.

(2) manufacturing example 2: Synthesis of Intermediate 1-2

Intermediate 1-1 (10.0 g, 0.035 mol) was dissolved in anhydrous DCM, and BBr ₃ (in DCM) (21.8 g, 0.087 mol) was added dropwise at 0 °C. The mixture was stirred and reacted at room temperature for 16 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 7.8 g of <Intermediate 1-2> (yield: 82.0%).

(3) manufacturing example 3: synthesis of intermediates 1-3

500 mL of NMP was added to Intermediate 1-2 (10.0 g, 0.033 mol) and K ₂ CO ₃ (11.4 g, 0.083 mol), followed by stirring at 180 °C for 24 hours. After completion of the reaction, 6.8 g (yield 68.5%) of <Intermediate 1-3> was obtained by extraction, concentration, column and recrystallization.

(4) manufacturing example 4: Synthesis of Compound 1

Intermediate 1-3 (10.0 g, 0.039 mol), Diphenylamine (10.0 g, 0.059 mol), NaOtBu (7.6 g, 0.079 mol), Pd(dba) ₂ (1.1 g, 0.002 mol), t-Bu ₃ P (0.8 g, 0.004 mol) into 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, 11.8 g (yield 77.5%) of <Compound 1> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=386 [(M) ⁺ ]

synthesis example 2: Synthesis of Compound 10

(One) manufacturing example 1: Synthesis of Compound 10

Intermediate 1-3 (10.0 g, 0.039 mol), N-([1,1'-Biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (21.4 g, 0.059 mol), 150 mL of Toluene was added to NaOtBu (7.6 g, 0.079 mol), Pd(dba) ₂ (1.1 g, 0.002 mol), and t-Bu ₃ P (0.8 g, 0.004 mol), followed by stirring at 70 °C for 4 hours. . After completion of the reaction, 17.1 g (yield 75.0%) of <Compound 10> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=578 [(M) ⁺ ]

synthesis example 3: synthesis of compound 19

(One) manufacturing example 1: synthesis of compound 19

Intermediate 1-3 (10.0 g, 0.039 mol), N-[1,1'-Biphenyl]-2-yl-9,9-diphenyl-9H-fluoren-2-amine (28.7 g, 0.059 mol), NaOtBu ( Toluene 150 mL was added to 7.6 g, 0.079 mol), Pd(dba) ₂ (1.1 g, 0.002 mol), and t-Bu ₃ P (0.8 g, 0.004 mol), followed by stirring at 70 °C for 4 hours. After completion of the reaction, 20.1 g (yield 72.9%) of <Compound 10> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=702 [(M) ⁺ ]

synthesis example 4: synthesis of compound 37

(One) manufacturing example 1: synthesis of intermediate 37-1

5-Bromo-6-methoxyquinoline (10.0 g, 0.042 mol), 2-Fluoro-5-chlorophenylboronic acid (8.8 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), Pd(PPh ₃ ) ₄ ( 1.0 g, 0.0008 mol) into 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 7.5 g of <Intermediate 37-1> (yield: 62.1%).

(2) manufacturing example 2: synthesis of intermediate 37-2

Intermediate 37-1 (10.0 g, 0.035 mol) was dissolved in anhydrous DCM, and BBr ₃ (in DCM) (21.8 g, 0.087 mol) was added dropwise at 0 °C. The mixture was stirred and reacted at room temperature for 16 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 7.7 g of <Intermediate 37-2> (yield: 81.0%).

(3) manufacturing example 3: synthesis of intermediate 37-3

500 mL of NMP was added to Intermediate 37-2 (10.0 g, 0.037 mol) and K ₂ CO ₃ (12.6 g, 0.091 mol), followed by stirring at 180 °C for 24 hours. After completion of the reaction, 5.7 g (yield: 61.5%) of <Intermediate 37-3> was obtained by extraction and concentration, followed by column and recrystallization.

(4) manufacturing example 4: synthesis of compound 37

Intermediate 37-3 (10.0 g, 0.039 mol), N-([1,1'-Biphenyl]-2-yl)dibenzo[b,d]furan-4-amine (19.8 g, 0.059 mol), NaOtBu (7.6 g, 0.079 mol), Pd(dba) ₂ (1.1 g, 0.002 mol), and t-Bu ₃ P (0.8 g, 0.004 mol) were added with 150 mL of toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, after extraction and concentration, 13.3 g of <Compound 37> was obtained by column and recrystallization (yield: 61.1%).

LC/MS: m/z = 552 [(M) ⁺ ]

synthesis example 5: synthesis of compound 75

(One) manufacturing example 1: synthesis of intermediate 75-1

1-bromo-4-iodonaphthalene (10.0 g, 0.030 mol), Bis(9,9-dimethyl-9H-fluoren-2-yl)amine (18.1 g, 0.045 mol), NaOtBu (5.8 g, 0.060 mol), Pd Toluene (150 mL) was added to (dba) ₂ (0.9 g, 0.002 mol) and t-Bu ₃ P (0.6 g, 0.003 mol), followed by stirring at 70 °C for 4 hours. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 10.7 g of <Intermediate 75-1> (yield: 58.7%).

(2) manufacturing example 2: synthesis of intermediate 75-2

Intermediate 75-1 (10 g, 0.017 mol), Bis(pinacolato)diboron (5.0 g, 0.020 mol), KOAc (4.9 g, 0.050 mol), Pd(dppf)Cl ₂ (0.6 g, 0.001 mol) in dioxane 200 mL was added and reacted by stirring at 100 °C for 12 hours. After completion of the reaction, the mixture was extracted and concentrated, followed by column and recrystallization to obtain 8.1 g of <Intermediate 75-2> (yield: 75.2%).

(3) manufacturing example 3: Synthesis of Compound 75

Intermediate 37-3 (10.0 g, 0.039 mol), Intermediate 75-2 (30.9 g, 0.047 mol), K ₂ CO ₃ (16.3 g, 0.118 mol), catalyst Pd(OAc) ₂ (2.3 g, 0.002 mol), Ligand X-Phos (1.9 g, 0.004 mol), 200 mL of THF, and 50 mL of H ₂ O were added and reacted by stirring at 90 °C for 6 hours. After completion of the reaction, the mixture was extracted, concentrated, and recrystallized with a column to obtain 19.8 g of <Compound 75> (yield: 67.4%).

LC/MS: m/z=744 [(M) ⁺ ]

synthesis example 6: Synthesis of Compound 250

(One) manufacturing example 1: synthesis of intermediate 250-1

5-Bromoquinoline (10.0 g, 0.048 mol), [4-Chloro-2-(methoxycarbonyl)phenyl]boronic acid (12.4 g, 0.058 mol), K ₂ CO ₃ (19.9 g, 0.144 mol), Pd(PPh ₃ ) 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to ₄ (1.1 g, 0.001 mol), followed by stirring at 100 °C for 6 hours. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 9.5 g of <Intermediate 250-1> (yield: 67.8%).

(2) manufacturing example 2: synthesis of intermediate 250-2

A solution of Intermediate 250-1 (10.0 g, 0.034 mol) dissolved in 150 mL of THF was added drop wise to 72 mL of MeMgBr (1.4 M in THF) dropwise for 3 hours so that the reaction temperature did not exceed 20 °C. After cooling at room temperature for 1 hour, 200 g of 10% Aqueous ammonium chloride and 300 mL of Toluene were added and reacted by stirring at room temperature for 1 hour. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 7.2 g of <Intermediate 250-2> (yield: 71.9%).

(3) manufacturing example 3: synthesis of intermediate 250-3

Intermediate 250-2 (10.0 g, 0.034 mol) was added to 150 mL of AcOH, stirred at 0 °C for 30 minutes, and then 300 mL of H ₃ PO ₄ was added thereto and reacted by stirring at room temperature for 1 hour. After completion of the reaction, 7.1 g (yield 75.6%) of <Intermediate 250-3> was obtained by extraction and concentration, followed by column and recrystallization.

(4) manufacturing example 4: Synthesis of Compound 250

Intermediate 250-3 (10.0 g, 0.036 mol), Bis(4-biphenylyl)amine (17.2 g, 0.043 mol), NaOtBu (6.9 g, 0.072 mol), Pd(dba) ₂ (1.0 g, 0.002 mol), t 150 mL of Toluene was added to -Bu ₃ P (0.7 g, 0.004 mol), followed by stirring at 70 °C for 4 hours. After completion of the reaction, 14.5 g (yield 71.8%) of <Compound 250> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=564 [(M) ⁺ ]

synthesis example 7: Synthesis of Compound 274

(One) manufacturing example 1: Synthesis of Compound 274

Intermediate 250-3 (10.0 g, 0.034 mol), bis(dibenzo[b,d]furan-3-yl)amine (18.7 g, 0.050 mol), NaOtBu (6.5 g, 0.067 mol), Pd(dba) ₂ ( 1.0 g, 0.002 mol) and t-Bu ₃ P (0.7 g, 0.003 mol) were added with 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, 13.5 g (yield: 67.8%) of <Compound 274> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z = 592 [(M) ⁺ ]

synthesis example 8: synthesis of compound 309

(One) manufacturing example 1: synthesis of intermediate 309-1

3-Aminodibenzofuran (10.0 g, 0.055 mol), 4-Bromo-9,9-dimethyl-9H-fluorene (22.4 g, 0.082 mol), NaOtBu (10.5 g, 0.109 mol), Pd(dba) ₂ (1.6 g, 0.003 mol) and t-Bu ₃ P (1.1 g, 0.006 mol) were added with 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 11.2 g of <Intermediate 309-1> (yield: 54.7%).

(2) manufacturing example 2: synthesis of intermediate 309-2

2-Bromo-6-iodonaphthalene (10.0 g, 0.030 mol), intermediate 309-1 (16.9 g, 0.045 mol), NaOtBu (5.8 g, 0.060 mol), Pd(dba) ₂ (0.9 g, 0.002 mol), t Toluene 150 mL was added to -Bu ₃ P (0.6 g, 0.003 mol), followed by stirring at 70 °C for 4 hours. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 10.6 g of <Intermediate 309-2> (yield: 60.8%).

(3) manufacturing example 3: synthesis of intermediate 309-3

Intermediate 309-2 (10 g, 0.017 mol), Bis(pinacolato)diboron (5.3 g, 0.021 mol), KOAc (5.1 g, 0.052 mol), Pd(dppf)Cl ₂ (0.6 g, 0.001 mol) in dioxane 200 mL was added and reacted by stirring at 100 °C for 12 hours. After completion of the reaction, the mixture was extracted, concentrated, and recrystallized with a column to obtain 7.7 g of <Intermediate 309-3> (yield: 71.2%).

(4) manufacturing example 4: synthesis of compound 309

Intermediate 250-3 (10.0 g, 0.036 mol), Intermediate 309-3 (26.9 g, 0.043 mol), K ₂ CO ₃ (14.8 g, 0.107 mol), catalyst Pd(OAc) ₂ (2.1 g, 0.002 mol), Ligand X-Phos (1.7 g, 0.004 mol), 200 mL of THF, and 50 mL of H ₂ O were added and reacted by stirring at 90 °C for 6 hours. After completion of the reaction, the mixture was extracted, concentrated, and recrystallized with a column to obtain 17.5 g of <Compound 309> (yield: 65.7%).

LC/MS: m/z=744 [(M) ⁺ ]

synthesis example 9: synthesis of compound 351

(One) manufacturing example 1: Synthesis of compound 351

Intermediate 250-3 (10.0 g, 0.036 mol), N-(4-(phenyl-9H-carbazol-3-yl)phenyl)biphenyl-4-amine (22.0 g, 0.054 mol), NaOtBu (6.9 g, 0.072 mol ), Pd(dba) ₂ (1.0 g, 0.002 mol), and t-Bu ₃ P (0.7 g, 0.004 mol) were added with 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, 15.3 g (yield 65.5%) of <Compound 351> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=653 [(M) ⁺ ]

device Example ( HTL )

In an embodiment according to the present invention, the ITO transparent electrode is patterned on a glass substrate of 25 mm × 25 mm × 0.7 mm so that the light emitting area is 2 mm × 2 mm in size by using an ITO glass substrate to which the ITO transparent electrode is attached. After that, it was washed. After the substrate was mounted in a vacuum chamber and the base pressure was 1 × 10 ^-6 torr, an organic material and a metal were deposited on the ITO in the following structure.

device Example 1 to 60

After employing the compound implemented according to the present invention as a hole transport layer and manufacturing an organic light emitting device having the following device structure, emission and driving characteristics of the compound implemented according to the present invention were measured.

ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (100 nm) / electron blocking layer (EBL1, 10 nm) / light emitting layer (20 nm) / electron transport layer (ET1:Liq, 30 nm) / LiF (1 nm) / Al (100 nm)

[HAT-CN] was formed on top of the ITO transparent electrode to form a hole injection layer with a thickness of 5 nm, and then the compound according to the present invention described in [Table 1] was formed to a thickness of 100 nm to form a hole transport layer. Thereafter, [EBL1] was deposited to a thickness of 10 nm to form an electron blocking layer, and an emission layer was formed by co-evaporation to a thickness of 20 nm using [BH1] as a host compound and [BD1] as a dopant compound. Thereafter, an electron transport layer (the [ET1] compound Liq 50% doped) was deposited to a thickness of 30 nm, and then LiF was deposited to a thickness of 1 nm to form an electron injection layer. Thereafter, an Al film was formed to a thickness of 100 nm to fabricate an organic light emitting device.

device comparative example One

The organic light emitting device for Device Comparative Example 1 was manufactured in the same manner as in the device structures of Examples 1 to 30, except that α-NPB was used instead of the compound according to the present invention in the hole transport layer.

Experimental example 1: element Example Luminescence characteristics of 1 to 60

Driving voltage, current efficiency and color coordinates were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research) for the organic light emitting device manufactured according to the above Examples and Comparative Examples, 1,000 nit The standard result values are shown in [Table 1] below.

Example hole transport layer V cd/A CIEx CIEy One Formula 1 4.53 8.23 0.1312 0.1365 2 Formula 7 4.39 8.38 0.1351 0.1312 3 Formula 10 4.49 8.20 0.1323 0.1341 4 Formula 12 4.24 8.62 0.1314 0.1338 5 Formula 19 4.38 8.56 0.1329 0.1355 6 Formula 20 4.88 8.59 0.1363 0.1342 7 Formula 26 4.74 8.64 0.1312 0.1323 8 Formula 31 4.56 8.59 0.1346 0.1334 9 Formula 37 4.58 8.60 0.1338 0.1444 10 Formula 42 4.65 8.53 0.1301 0.1378 11 Formula 44 4.45 8.50 0.1353 0.1452 12 Formula 48 4.50 8.12 0.1312 0.1382 13 Formula 59 4.68 8.58 0.1331 0.1354 14 Formula 63 4.57 8.31 0.1337 0.1260 15 Formula 64 4.43 8.42 0.1314 0.1213 16 Formula 65 4.57 8.54 0.1377 0.1361 17 Formula 68 4.64 8.10 0.1324 0.1434 18 Formula 75 4.76 8.26 0.1338 0.1298 19 Formula 81 4.86 8.45 0.1354 0.1331 20 Formula 85 4.58 8.32 0.1334 0.1336 21 Formula 87 4.83 8.47 0.1353 0.1386 22 chemical formula 100 4.60 8.45 0.1312 0.1351 23 Formula 109 4.53 8.38 0.1358 0.1327 24 Formula 110 4.60 8.34 0.1343 0.1288 25 Formula 118 4.64 8.50 0.1358 0.1296 26 Formula 126 4.57 8.42 0.1330 0.1271 27 Formula 136 4.58 8.26 0.1327 0.1332 28 Formula 138 4.29 8.41 0.1335 0.1340 29 Formula 156 4.61 8.23 0.1342 0.1347 30 Formula 173 4.70 8.59 0.1364 0.1369 31 Formula 183 4.53 8.56 0.1330 0.1335 32 Formula 197 4.41 8.45 0.1366 0.1371 33 Formula 201 4.61 8.34 0.1319 0.1324 34 Formula 210 4.84 8.13 0.1344 0.1349 35 Formula 225 4.89 8.29 0.1334 0.1339 36 Formula 228 4.66 8.48 0.1315 0.1320 37 Formula 231 4.58 8.35 0.1358 0.1363 38 Formula 237 4.75 8.48 0.1319 0.1324 39 Formula 249 4.86 8.41 0.1336 0.1341 40 Formula 250 4.58 8.37 0.1334 0.1339 41 Formula 258 4.60 8.53 0.1321 0.1326 42 Formula 263 4.51 8.45 0.1365 0.1370 43 Formula 274 4.65 8.35 0.1334 0.1339 44 Formula 285 4.91 8.45 0.1332 0.1337 45 Formula 292 4.56 8.41 0.1363 0.1368 46 Formula 293 4.61 8.53 0.1317 0.1322 47 Formula 306 4.65 8.45 0.1343 0.1348 48 Formula 309 4.58 8.61 0.1367 0.1372 49 Formula 310 4.75 8.46 0.1346 0.1351 50 Formula 318 4.63 8.58 0.1374 0.1379 51 Formula 333 4.70 8.50 0.1315 0.1320 52 Formula 335 4.56 8.49 0.1323 0.1328 53 Formula 346 4.58 8.54 0.1350 0.1358 54 Formula 347 4.62 8.71 0.1336 0.1432 55 Formula 348 4.47 8.62 0.1387 0.1359 56 Formula 351 4.73 8.43 0.1369 0.1385 57 Formula 352 4.65 8.47 0.1357 0.1397 58 Formula 353 4.53 8.61 0.1367 0.1421 59 Formula 354 4.86 8.54 0.1398 0.1365 60 Formula 362 4.35 8.36 0.1342 0.1412 Comparative Example 1 α-NPB 5.12 7.70 0.1332 0.1243

Looking at the results shown in [Table 1], in the case of an organic light emitting device employing the compound according to the present invention in a hole transport layer in the device, a device employing α-NPB used as a conventional hole transport material (Comparative Example 1) In comparison, it can be confirmed that characteristics such as driving voltage and luminous efficiency are remarkably excellent.

[HAT_CN] [α-NPB] [BH1] [BD1] [ET1]

[EBL1]

Claims (6)

An organic light emitting compound represented by the following [Formula I]:
[Formula I]

In the above [Formula I],
Y is O, S, CR ₁ R ₂ or NR ₃ ;
Wherein R ₁ to R ₃ are each independently hydrogen, heavy hydrogen, a halogen group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted Any one selected from an aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms,
The R ₁ and R ₂ may combine with each other to form an alicyclic ring or an aromatic ring,
L is a single bond, or any one selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms,
n is an integer from 0 to 3, and when n is 2 or more, a plurality of L's are the same as or different from each other;
Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 30 carbon atoms. It is any one selected from an aryl group and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms. According to claim 1,
In the definition of R ₁ to R ₃ , L and Ar ₁ to Ar ₂ , 'substituted or unsubstituted' means that R ₁ to R ₃ , L and Ar ₁ to Ar ₂ are deuterium, a halogen group, or cyano, respectively. No group, nitro group, hydroxyl group, alkyl group, halogenated alkyl group, deuterated alkyl group, cycloalkyl group, heterocycloalkyl group, alkoxy group, halogenated alkoxy group, deuterated alkoxy group, amine group, aryl group, heteroaryl group, alkyl An organic light emitting compound characterized in that it is substituted with one or two or more substituents selected from the group consisting of a silyl group and an arylsilyl group, or is substituted with a substituent in which two or more substituents are connected, or does not have any substituents. According to claim 1,
[Formula I] is an organic light-emitting compound, characterized in that any one selected from the following [Compound 1] to [Compound 446]:

An organic light emitting device comprising a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode,
At least one of the organic layers comprises an organic light emitting compound of [Chemical Formula I] according to claim 1. According to claim 4,
The organic layer is selected from a hole injection layer, a hole transport layer, a layer that simultaneously performs hole injection and hole transport functions, an electron transport layer, an electron injection layer, a layer that simultaneously performs electron transport and electron injection functions, an electron blocking layer, a hole blocking layer, and a light emitting layer. Including one or more floors,
An organic light emitting device, wherein at least one of the layers includes the organic light emitting compound represented by [Chemical Formula I]. According to claim 5,
An organic light emitting device comprising the organic light emitting compound represented by the [Chemical Formula I] in any one of the hole transport layer, the hole injection layer, and the hole transport and hole injection layers.