KR20230000475A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to a novel organic light emitting compound represented by chemical formula I, which 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 operation and excellent light-emitting efficiency of a device, and an organic light emitting 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 1] and the definitions of the compounds implemented thereby, X, Y, R ₁ and Ar ₁ to Ar ₂ 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 low-voltage driving of an organic light emitting device and light emitting properties such as excellent light emitting efficiency, structurally (1) represented by the following [Formula I] It is characterized by having a skeletal structure, that is, a fluorene-fluorenoxazole (thiazole/imidazole) spiro structure as a skeletal structure, and (2) introducing at least one aryl (heteroaryl) amine group into such a skeletal structure. Through its structural characteristics, it can be employed in a transport layer in an organic light emitting device to improve low-voltage driving characteristics and luminous efficiency characteristics of the device.

[Formula I]

In the above [Formula I],

X and Y are the same as or different from each other, and are each independently O, S or NR, and at least one of X and Y is NR.

Wherein R is hydrogen, heavy hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted halogenated group having 1 to 20 carbon atoms Alkyl group, substituted or unsubstituted halogenated alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms and substituted or unsubstituted 2 carbon atoms to 30 heteroaryl groups.

R ₁ is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

Ar ₁ to Ar ₄ are the same as or different from each other, and are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

n is 0 or 1;

According to an embodiment of the present invention, the structure including X and Y in [Formula I], that is, the oxazole, thiazole, and imidazole structure may be selected from the following [Structural Formula 1] (the entire skeleton structure is omitted ), R and R ₁ are the same as defined in [Formula I].

[Structural Formula 1]

Meanwhile, in the definition of R, R ₁ and Ar ₁ to Ar ₄ , 'substituted or unsubstituted' means that R, R ₁ and Ar ₁ to Ar ₄ are deuterium, a halogen group, a cyano group, a nitro group, Hydroxy 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, alkylsilyl group and arylsilyl It means substituted with one or two or more substituents selected from the group consisting of, substituted with a substituent in which two or more substituents are connected, or not having any substituents.

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.

In the present invention, the amine group may be -NH ₂ , an alkylamine group, an arylamine group, an arylheteroarylamine group, etc., the arylamine group refers to an amine substituted with an aryl, and the alkylamine group refers to an amine substituted with an alkyl. The arylheteroarylamine group refers to an amine substituted with aryl and heteroaryl groups, and examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted diarylamine group. There is an unsubstituted triarylamine group, and the aryl group and heteroaryl group in the arylamine group and the arylheteroarylamine group may be a monocyclic aryl group or a monocyclic heteroaryl group, or may be a polycyclic aryl group or a polycyclic heteroaryl group. And, the aryl group and heteroaryl group including two or more arylamine groups and arylheteroarylamine groups are monocyclic aryl groups (heteroaryl groups), polycyclic aryl groups (heteroaryl groups), or monocyclic aryl groups (heteroaryl groups). aryl group) and polycyclic aryl group (heteroaryl group) may be included at the same time. In addition, the aryl group and heteroaryl group of the arylamine group and the arylheteroarylamine group may be selected from examples of the aryl group and heteroaryl group described above.

The organic light-emitting compound according to the present invention represented by [Formula I] can be used in various organic layers in an organic light-emitting device due to its structural specificity, and preferably can be used in a hole transport layer.

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, and an organic light emitting device according to an embodiment of the present invention includes a first electrode and a second electrode and an organic layer disposed therebetween. It can be made of a structure, and can be manufactured using conventional device manufacturing methods and materials, except that the organic light emitting compound according to the present invention is used in the organic layer of the device.

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 light efficiency improvement layer (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 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 receiving holes transported from the anode or the hole injection layer and transferring them to the light emitting layer, and a material 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, and a material having high electron mobility is suitable. Specific examples include Al complexes of 8-hydroxyquinoline, complexes containing Alq ₃ , organic radical compounds, hydroxyflavone-metal complexes, etc., but are not limited thereto.

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

7-Bromo-2-phenyl-benzoxazole (10.0 g, 0.037 mol), Bis(pinacolato)diboron (11.1 g, 0.044 mol), KOAc (10.7 g, 0.109 mol), Pd(dppf)Cl ₂ (1.3 g, 0.002 mol) into 200 mL of Dioxane and reacted by stirring at 100 °C for 12 hours. After completion of the reaction, 9.1 g (yield 77.7%) of <Intermediate 1-1> was obtained by extraction, concentration, and column.

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

Methyl 2-bromobenzoate (10.0 g, 0.047 mol), intermediate 1-1 (17.9 g, 0.056 mol), K ₂ CO ₃ (19.3 g, 0.140 mol), Pd(PPh ₃ ) ₄ (1.1 g, 0.001 mol) 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O were added and reacted by stirring at 100 °C for 6 hours. After completion of the reaction, after extraction and concentration, 11.5 g (yield 75.1%) of <Intermediate 1-2> was obtained by column.

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

Intermediate 1-2 (10.0 g, 0.030 mol) was dissolved in 60 mL of Anhydrous DCM. Then, BBr ₃ (in DCM, 19.0 g, 0.076 mol) was added dropwise while maintaining at 0 °C, and reacted by stirring at 25 °C for 16 hours. After completion of the reaction, after extraction and concentration, 7.7 g (yield 80.4%) of <Intermediate 1-3> was obtained by column.

(4) manufacturing example 4: synthesis of intermediates 1-4

Intermediate 1-3 (10.0 g, 0.032 mol) and methanesulfonic acid (152.4 g, 1.586 mol) were stirred at 60 °C, cooled to 0 °C, and 25 mL of H ₂ O was added thereto, followed by stirring. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 5.4 g of <Intermediate 1-4> (yield: 57.3%).

(5) manufacturing example 5: synthesis of intermediates 1-5

After adding 2-Bromo-4-chloro-1,1'-biphenyl (10.0 g, 0.037 mol) and 100 mL of THF, 1.6 M n-BuLi (2.6 g, 0.041 mol) was slowly added dropwise while stirring at -78 °C. After stirring for 1 hour and adding intermediate 1-4 (12.1 g, 0.041 mol), the mixture was stirred at room temperature for 3 hours. Then, after adding a small amount of water and concentrating, H ₂ O: After layer separation using MC, Methanesulfonic acid (3.6 g, 0.037 mol) and 200 mL of MC were added to the obtained intermediate, followed by reflux stirring for 2 hours. reacted After completion of the reaction, 8.8 g (yield: 50.3%) of <Intermediate 1-5> was obtained by extraction and concentration, followed by column and recrystallization.

(6) manufacturing example 6: Synthesis of Compound 1

Intermediate 1-5 (10.0 g, 0.021 mol), Diphenylamine (5.4 g, 0.032 mol), NaOtBu (6.2 g, 0.064 mol), Pd (dba) ₂ (0.5 g, 0.0009 mol), t-Bu ₃ P (0.4 g, 0.0017 mol) into 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, 9.2 g (yield: 71.7%) of <Compound 1> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=600 [(M) ⁺ ]

synthesis example 2: synthesis of compound 6

(One) manufacturing example 1: synthesis of compound 6

Intermediate 1-5 (10.0 g, 0.021 mol), 2-(4-Biphenylyl)amino-9,9-dimethylfluorene (11.6 g, 0.032 mol), NaOtBu (6.2 g, 0.064 mol), Pd(dba) ₂ (0.5 g, 0.0009 mol) and t-Bu ₃ P (0.4 g, 0.0017 mol) were added with 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, 12.7 g (yield 74.9%) of <Compound 6> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=792 [(M) ⁺ ]

synthesis example 3: Synthesis of Compound 21

(One) manufacturing example 1: synthesis of intermediate 21-1

1-Bromo-3,5-diphenylbenzene (10.0 g, 0.032 mol), 3-Aminodibenzofuran (8.9 g, 0.049 mol), NaOtBu (9.3 g, 0.097 mol), Pd(dba) ₂ (0.7 g, 0.0013 mol), 150 mL of Toluene was added to t-Bu ₃ P (0.5 g, 0.0026 mol), followed by stirring at 70 °C for 4 hours. After completion of the reaction, 8.5 g (yield: 63.9%) of <Intermediate 21-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) manufacturing example 2: synthesis of compound 21

Intermediate 1-5 (10.0 g, 0.021 mol), Intermediate 21-1 (13.2 g, 0.032 mol), NaOtBu (6.2 g, 0.064 mol), Pd(dba) ₂ (0.5 g, 0.0009 mol), t-Bu ₃ 150 mL of Toluene was added to P (0.4 g, 0.0017 mol) and reacted by stirring at 70 °C for 4 hours. After completion of the reaction, 13.4 g (yield: 74.4%) of <Compound 21> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=842 [(M) ⁺ ]

synthesis example 4: synthesis of compound 27

(One) manufacturing example 1: synthesis of intermediate 27-1

After adding 2-Bromo-5-chloro-1,1-biphenyl (10.0 g, 0.037 mol) and 100 mL of THF, 1.6 M n-BuLi (2.6 g, 0.041 mol) was slowly added dropwise while stirring at -78 ° C. After stirring for 3 hours and adding intermediate 1-4 (12.1 g, 0.041 mol), the mixture was stirred at room temperature for 3 hours. Then, after adding a small amount of water and concentrating, H ₂ O: After layer separation using MC, Methanesulfonic acid (3.6 g, 0.037 mol) and 200 mL of MC were added to the obtained intermediate, followed by reflux stirring for 2 hours. reacted After completion of the reaction, 9.1 g (yield: 52.0%) of <Intermediate 27-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) manufacturing example 2: synthesis of compound 27

Intermediate 27-1 (10.0 g, 0.021 mol), 3-Dibenzofuranamine (10.8 g, 0.032 mol), NaOtBu (6.2 g, 0.064 mol), Pd(dba) ₂ (0.5 g, 0.0009 mol), t-Bu ₃ P (0.4 g, 0.0017 mol) into Toluene 150 mL was reacted by stirring at 70 ℃ for 4 hours. After completion of the reaction, 11.7 g (yield 71.4%) of <Compound 27> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=766 [(M) ⁺ ]

synthesis example 5: Synthesis of Compound 41

(One) manufacturing example 1: synthesis of intermediate 41-1

4-Bromo-2-phenylbenzo[d]oxazole (10.0 g, 0.037 mol), Bis(pinacolato)diboron (11.1 g, 0.044 mol), KOAc (10.7 g, 0.109 mol), Pd(dppf)Cl ₂ (1.3 g , 0.002 mol) into 200 mL of Dioxane and reacted by stirring at 100 °C for 12 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 8.7 g of <Intermediate 41-1> (yield: 74.3%).

(2) manufacturing example 2: synthesis of intermediate 41-2

Methyl 2-bromobenzoate (10.0 g, 0.047 mol), intermediate 41-1 (17.9 g, 0.056 mol), K ₂ CO ₃ (19.3 g, 0.140 mol), Pd(PPh ₃ ) ₄ (1.1 g, 0.001 mol) 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O were added and reacted by stirring at 100 °C for 6 hours. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 10.8 g of <Intermediate 41-2> (yield: 70.5%).

(3) manufacturing example 3: synthesis of intermediate 41-3

Intermediate 41-2 (10.0 g, 0.030 mol) is dissolved in 60 mL of Anhydrous DCM. Then, BBr ₃ (in DCM, 19.0 g, 0.076 mol) was added dropwise while maintaining at 0 °C, and reacted by stirring at 25 °C for 16 hours. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 7.2 g of <Intermediate 41-3> (yield: 75.2%).

(4) manufacturing example 4: synthesis of intermediate 41-4

Intermediate 41-3 (10.0 g, 0.032 mol) and methanesulfonic acid (152.4 g, 1.586 mol) were stirred at 60 °C, cooled to 0 °C, and 25 mL of H ₂ O was added thereto, followed by stirring. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 4.8 g of <Intermediate 41-4> (yield: 50.9%).

(5) manufacturing example 5: synthesis of intermediate 41-5

After adding 2-Bromo-4-chloro-1,1'-biphenyl (10.0 g, 0.037 mol) and 100 mL of THF, 1.6 M n-BuLi (2.6 g, 0.041 mol) was slowly added dropwise while stirring at -78 °C. After stirring for 3 hours and adding intermediate 41-4 (12.1 g, 0.041 mol), the mixture was stirred at room temperature for 3 hours. Then, after adding a small amount of water and concentrating, H ₂ O: After layer separation using MC, methanesulfonic acid (3.6 g, 0.037 mol) and 200 mL of MC were added to the obtained intermediate, followed by stirring at reflux for 2 hours. reacted After completion of the reaction, 10.4 g (yield 59.5%) of <Intermediate 41-5> was obtained by extraction and concentration, followed by column and recrystallization.

(6) manufacturing example 6: Synthesis of Compound 41

Intermediate 41-5 (10.0 g, 0.021 mol), 2-(2-Biphenylyl)amino-9,9-dimethylfluorene (11.6 g, 0.032 mol), NaOtBu (6.2 g, 0.064 mol), Pd(dba) ₂ (0.5 g, 0.0009 mol) and t-Bu ₃ P (0.4 g, 0.0017 mol) were added with 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, 12.3 g (yield 72.6%) of <Compound 41> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=792 [(M) ⁺ ]

synthesis example 6: synthesis of compound 46

(One) manufacturing example 1: synthesis of intermediate 46-1

4-Bromo-9,9'-spirobi[9H-fluorene] (10.0 g, 0.025 mol), 4-Aminobiphenyl (6.4 g, 0.038 mol), NaOtBu (7.3 g, 0.076 mol), Pd(dba) ₂ (0.6 g, 0.001 mol) and t-Bu ₃ P (0.4 g, 0.002 mol) were added with 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, 8.4 g (yield 68.7%) of <Intermediate 46-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) manufacturing example 2: synthesis of compound 46

Intermediate 41-6 (10.0 g, 0.021 mol), Intermediate 46-1 (15.5 g, 0.032 mol), NaOtBu (6.2 g, 0.064 mol), Pd(dba) ₂ (0.5 g, 0.0009 mol), t-Bu ₃ 150 mL of Toluene was added to P (0.4 g, 0.0017 mol) and reacted by stirring at 70 °C for 4 hours. After completion of the reaction, 14.7 g (yield 75.2%) of <Compound 46> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=914 [(M) ⁺ ]

synthesis example 6: synthesis of compound 60

(One) manufacturing example 1: synthesis of intermediate 60-1

After adding 2-Bromo-6-chloro-1,1'-biphenyl (10.0 g, 0.037 mol) and 100 mL of THF, 1.6 M n-BuLi (2.6 g, 0.041 mol) was slowly added dropwise while stirring at -78 °C. After stirring for 3 hours and adding intermediate 41-5 (12.1 g, 0.041 mol), the mixture was stirred at room temperature for 3 hours. Then, after adding a small amount of water and concentrating, H ₂ O: After layer separation using MC, Methanesulfonic acid (3.6 g, 0.037 mol) and 200 mL of MC were added to the obtained intermediate, followed by reflux stirring for 2 hours. reacted After completion of the reaction, 9.2 g (yield: 52.6%) of <Intermediate 60-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) manufacturing example 2: synthesis of compound 60

Intermediate 60-1 (10.0 g, 0.021 mol), N-(Biphenyl-2-yl)dibenzo[b,d]furan-3-amine (10.8 g, 0.032 mol), NaOtBu (6.2 g, 0.064 mol), Pd Toluene (150 mL) was added to (dba) ₂ (0.5 g, 0.0009 mol) and t-Bu ₃ P (0.4 g, 0.0017 mol), followed by stirring at 70 °C for 4 hours. After completion of the reaction, 11.6 g (yield: 70.8%) of <Compound 60> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=766 [(M) ⁺ ]

synthesis example 7: synthesis of compound 65

(One) manufacturing example 1: synthesis of intermediate 65-1

5-Bromo-2-phenylbenzothiazole (10.0 g, 0.035 mol), Bis(pinacolato)diboron (10.5 g, 0.041 mol), KOAc (10.2 g, 0.103 mol), Pd(dppf)Cl ₂ (1.3 g, 0.002 mol) 200 mL of Dioxane was added thereto and reacted by stirring at 100 °C for 12 hours. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 9.0 g of <Intermediate 65-1> (yield: 77.4%).

(2) manufacturing example 2: synthesis of intermediate 65-2

Methyl 2-bromobenzoate (10.0 g, 0.047 mol), intermediate 65-1 (18.8 g, 0.056 mol), K ₂ CO ₃ (19.3 g, 0.140 mol), Pd(PPh ₃ ) ₄ (1.1 g, 0.001 mol) 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O were added and reacted by stirring at 100 °C for 6 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 11.7 g of <Intermediate 65-2> (yield: 72.8%).

(3) manufacturing example 3: synthesis of intermediate 65-3

Intermediate 65-2 (10.0 g, 0.029 mol) is dissolved in 60 mL of Anhydrous DCM. Thereafter, BBr ₃ (in DCM, 18.1 g, 0.072 mol) was added dropwise while maintaining the temperature at 0 °C and reacted by stirring at 25 °C for 16 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 7.8 g of <Intermediate 65-3> (yield: 81.3%).

(4) manufacturing example 4: synthesis of intermediate 65-4

Intermediate 65-3 (10.0 g, 0.030 mol) and methanesulfonic acid (145.0 g, 1.509 mol) were stirred at 60 °C, cooled to 0 °C, and 25 mL of H ₂ O was added thereto, followed by stirring. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 5.2 g of <Intermediate 65-4> (yield: 55.0%).

(5) manufacturing example 5: synthesis of intermediate 65-5

After adding 2-Bromo-4-chloro-1,1'-biphenyl (10.0 g, 0.037 mol) and 100 mL of THF, 1.6 M n-BuLi (2.6 g, 0.041 mol) was slowly added dropwise while stirring at -78 °C. After stirring for 3 hours and adding intermediate 65-4 (12.8 g, 0.041 mol), the mixture was stirred at room temperature for 3 hours. Then, after adding a small amount of water and concentrating, H ₂ O: After layer separation using MC, Methanesulfonic acid (3.6 g, 0.037 mol) and 200 mL of MC were added to the obtained intermediate, followed by reflux stirring for 2 hours. reacted After completion of the reaction, 9.2 g (yield: 50.9%) of <Intermediate 65-5> was obtained by extraction and concentration, followed by column and recrystallization.

(6) manufacturing example 6: synthesis of compound 65

Intermediate 65-5 (10.0 g, 0.021 mol), N-Phenyl-1-naphthylamine (6.8 g, 0.031 mol), NaOtBu (6.0 g, 0.062 mol), Pd(dba) ₂ (0.5 g, 0.0008 mol), t Toluene 150 mL was added to -Bu ₃ P (0.3 g, 0.0017 mol) and reacted by stirring at 70 °C for 4 hours. After completion of the reaction, 9.7 g (yield 70.4%) of <Compound 65> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=666 [(M) ⁺ ]

synthesis example 8: synthesis of compound 123

(One) manufacturing example 1: synthesis of intermediate 123-1

Methyl 5-bromo-2-iodobenzoate (10.0 g, 0.029 mol), intermediate 1-1 (11.3 g, 0.035 mol), K ₂ CO ₃ (12.2 g, 0.088 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.001 mol) into Toluene 200 mL, EtOH 50 mL, H ₂ O 50 mL was reacted by stirring at 100 ℃ for 6 hours. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 8.6 g of <Intermediate 123-1> (yield: 71.8%).

(2) manufacturing example 2: synthesis of intermediate 123-2

Intermediate 123-1 (10.0 g, 0.025 mol) is dissolved in 60 mL of Anhydrous DCM. Thereafter, BBr ₃ (in DCM, 15.3 g, 0.061 mol) was added dropwise while maintaining 0 °C, and reacted by stirring at 25 °C for 16 hours. After completion of the reaction, after extraction and concentration, 7.2 g (yield 74.6%) of <Intermediate 123-2> was obtained by column.

(3) manufacturing example 3: synthesis of intermediate 123-3

Intermediate 123-2 (10.0 g, 0.025 mol) and methanesulfonic acid (121.9 g, 1.268 mol) were stirred at 60 °C, cooled to 0 °C, and 25 mL of H ₂ O was added thereto, followed by stirring. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 5.7 g of <Intermediate 123-3> (yield: 59.7%).

(4) manufacturing example 4: synthesis of intermediate 123-4

Intermediate 123-3 (10.0 g, 0.027 mol), 2-(4-Biphenylyl)amino-9,9-dimethylfluorene (14.4 g, 0.040 mol), NaOtBu (7.7 g, 0.080 mol), Pd(dba) ₂ (0.6 g, 0.0011 mol) and t-Bu ₃ P (0.4 g, 0.0021 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 columnized to obtain 13.4 g of <Intermediate 123-4> (yield: 76.8%).

(5) manufacturing example 5: synthesis of intermediate 123-5

2-Bromo-4-chloro-1,1' (10.0 g, 0.037 mol) and 100 mL of THF were added, and 1.6 M n-BuLi (2.6 g, 0.041 mol) was slowly added dropwise while stirring at -78 ° C for 1 hour. After stirring and adding intermediate 123-4 (26.8 g, 0.041 mol), the mixture was stirred at room temperature for 3 hours. Then, after adding a small amount of water and concentrating, H ₂ O: After layer separation using MC, methanesulfonic acid (3.6 g, 0.037 mol) and 200 mL of MC were added to the obtained intermediate, followed by stirring at reflux for 2 hours. reacted After completion of the reaction, 15.3 g (yield 49.5%) of <Intermediate 123-5> was obtained by extraction and concentration, followed by column and recrystallization.

(6) manufacturing example 6: Synthesis of Compound 123

Intermediate 123-5 (10.0 g, 0.012 mol), 2-(4-Biphenylyl)amino-9,9-dimethylfluorene (6.6 g, 0.018 mol), NaOtBu (3.5 g, 0.036 mol), Pd(dba) ₂ (0.3 g, 0.0005 mol) and t-Bu ₃ P (0.2 g, 0.001 mol) were added with 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, 9.7 g (yield: 69.6%) of <Compound 123> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z = 1151 [(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 63

After employing the compound implemented according to the present invention as a hole transport layer and fabricating 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 63, 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 63

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 3.63 7.63 0.1334 0.1363 2 formula 6 3.59 7.74 0.1295 0.1329 3 Formula 13 4.05 7.56 0.1311 0.1397 4 Formula 21 3.44 7.56 0.1285 0.1347 5 Formula 27 3.73 7.95 0.1307 0.1392 6 Formula 30 3.72 7.30 0.1303 0.1311 7 Formula 34 3.98 7.67 0.1333 0.1348 8 Formula 39 3.49 7.31 0.1329 0.1335 9 Formula 41 3.89 7.68 0.1315 0.1379 10 Formula 46 3.74 7.41 0.1285 0.1363 11 Formula 60 3.96 7.59 0.1325 0.1404 12 Formula 65 4.05 7.62 0.1341 0.1360 13 Formula 66 3.67 7.78 0.1311 0.1341 14 Formula 70 3.59 7.60 0.1285 0.1382 15 Formula 74 3.42 7.41 0.1307 0.1408 16 Formula 75 3.83 7.38 0.1330 0.1335 17 Formula 82 4.08 7.52 0.1294 0.1299 18 Formula 93 3.58 7.58 0.1320 0.1379 19 Formula 95 3.63 7.30 0.1309 0.1335 20 Formula 98 3.98 7.61 0.1334 0.1339 21 Formula 99 3.52 7.78 0.1307 0.1335 22 chemical formula 100 3.79 7.34 0.1341 0.1376 23 Formula 102 3.69 7.48 0.1320 0.1382 24 Formula 104 3.61 7.30 0.1298 0.1392 25 Formula 109 3.52 7.67 0.1325 0.1400 26 Formula 110 4.07 7.30 0.1314 0.1311 27 Formula 111 3.85 7.81 0.1320 0.1360 28 Formula 116 3.73 7.30 0.1296 0.1335 29 Formula 117 3.49 7.12 0.1307 0.1348 30 Formula 123 3.96 8.12 0.1311 0.1375 31 Formula 124 3.73 7.48 0.1333 0.1385 32 Formula 127 3.67 7.34 0.1334 0.1363 33 Formula 129 3.42 8.01 0.1285 0.1345 34 Formula 132 3.67 7.59 0.1307 0.1401 35 Formula 133 3.77 7.86 0.1298 0.1375 36 Formula 134 3.85 7.48 0.1341 0.1341 37 Formula 138 3.81 7.88 0.1309 0.1348 38 Formula 140 4.05 7.95 0.1298 0.1382 39 Formula 141 3.85 7.64 0.1307 0.1299 40 Formula 145 3.66 7.78 0.1315 0.1329 41 Formula 147 3.67 8.12 0.1330 0.1375 42 Formula 149 3.69 7.87 0.1296 0.1347 43 Formula 151 3.89 7.56 0.1314 0.1332 44 Formula 153 3.62 7.79 0.1334 0.1341 45 Formula 154 3.73 7.52 0.1325 0.1347 46 Formula 155 3.42 7.78 0.1316 0.1335 47 Formula 156 3.95 7.87 0.1295 0.1311 48 Formula 159 3.93 7.79 0.1315 0.1341 49 Formula 160 4.28 7.56 0.1311 0.1320 50 Formula 163 3.52 8.18 0.1309 0.1296 51 Formula 165 3.83 7.60 0.1341 0.1316 52 Formula 168 3.77 7.82 0.1303 0.1307 53 Formula 169 3.48 7.48 0.1325 0.1325 54 Formula 170 4.02 7.61 0.1285 0.1329 55 Formula 171 3.75 7.79 0.1317 0.1296 56 Formula 174 3.53 7.93 0.1320 0.1340 57 Formula 175 3.96 7.79 0.1341 0.1325 58 Formula 192 3.67 7.38 0.1294 0.1323 59 Formula 190 3.48 7.63 0.1313 0.1335 60 Formula 198 3.59 8.02 0.1286 0.1311 61 Formula 201 3.34 7.67 0.1311 0.1335 62 Formula 202 3.61 7.94 0.1333 0.1369 63 Formula 203 3.95 7.63 0.1317 0.1382 Comparative Example 1 α-NPB 4.67 6.65 0.1353 0.1517

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 for 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 seen that the driving voltage is reduced and the current efficiency is improved.

[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],
X and Y are the same as or different from each other, and are each independently O, S or NR, and at least one of X and Y is NR,
Wherein R is hydrogen, heavy hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted halogenated group having 1 to 20 carbon atoms Alkyl group, substituted or unsubstituted halogenated alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms and substituted or unsubstituted 2 carbon atoms to any one selected from 30 heteroaryl groups;
R ₁ is any one selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms;
Ar ₁ to Ar ₄ are the same as or different from each other, and are each independently any one selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms,
n is 0 or 1; According to claim 1,
In the definition of R, R ₁ and Ar ₁ to Ar ₄ , 'substituted or unsubstituted' means that R, R ₁ and Ar ₁ to Ar ₄ are deuterium, a halogen group, a cyano group, a nitro group, a hydroxy group, respectively. , 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, alkylsilyl group and arylsilyl group An organic light emitting compound characterized in that it is substituted with one or two or more substituents selected from the group consisting of, substituted with a substituent connected to two or more substituents among the substituents, or not having 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 203]:

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.