WO2020060288A1 - Novel compound and organic light emitting diode using same - Google Patents

Abstract

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

Description

Novel compound and organic light emitting device using same

Mutual citations with related applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0114406, issued on September 21, 2018, and Korean Patent Application No. 10-2019-0115563, issued on September 19, 2019. All content disclosed in the literature is incorporated as part of this specification.

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

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy 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, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.

The 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. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often formed of a multi-layered structure composed of different materials, for example, may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it will shine.

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

[Advanced technical literature]

[Patent Document]

(Patent Document 0001) Korean Patent Publication No. 10-2013-073537

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

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

[Formula 1]

In Chemical Formula 1,

X ₁ , X ₂ and X ₃ are each independently CH or N, provided that X ₁ , Two or more of X ₂ and X ₃ are N,

Y is S or O,

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

L ₁ is a direct bond, substituted or unsubstituted C _6-60 arylene, or C _5-60 heteroarylene comprising one or more hetero atoms selected from the group consisting of N, O and S,

L ₂ is a direct bond or a substituted or unsubstituted C _6-60 arylene,

R ₁ and R ₂ are each independently hydrogen or substituted or unsubstituted C _1-60 alkyl,

m and n are each independently an integer from 0 to 3.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer provides an organic light emitting device comprising the compound of the present invention described above.

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

FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.

FIG. 2 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is done.

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

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

[Formula 1]

In Chemical Formula 1,

X ₁ , X ₂ and X ₃ are each independently CH or N, provided that X ₁ , Two or more of X ₂ and X ₃ are N,

Y is S or O,

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

L ₁ is a direct bond, a substituted or unsubstituted C _6-60 arylene, or C _5-60 heteroarylene comprising one or more hetero atoms selected from the group consisting of N, O and S,

L ₂ is a direct bond or a substituted or unsubstituted C _6-60 arylene,

R ₁ and R ₂ are each independently hydrogen or substituted or unsubstituted C _1-60 alkyl,

m and n are each independently an integer from 0 to 3.

In this specification,

Means a linkage to another substituent.

The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; An alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above . For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the oxygen of the ester group may be substituted with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In this specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the boron group is specifically a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.

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

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

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, steelbenyl 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 cycloalkyl group has 3 to 20 carbon atoms. 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 is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may combine with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be back. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridil group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl 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, thiazolyl group, isooxazolyl Groups, oxadiazolyl groups, thiadiazolyl groups, benzothiazolyl groups, phenothiazinyl groups, and dibenzofuranyl groups, but are not limited thereto.

In the present specification, an aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group described above. In the present specification, the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described alkyl group. In the present specification, the description of the heteroaryl group among heteroarylamines may be applied. In the present specification, the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group. In the present specification, the description of the aryl group described above may be applied, except that the arylene is a divalent group. In the present specification, the description of the heterocyclic group described above may be applied, except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and a description of the aryl group or cycloalkyl group described above may be applied, except that two substituents are formed by bonding. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are formed by bonding.

Preferably, the compound represented by Formula 1 may be any one selected from the group consisting of compounds represented by Formulas 2 to 5 below:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Chemical Formulas 2 to 5,

X ₁ , X ₂ , X ₃ , Y, L ₁ , L ₂ , R ₁ , R ₂ , Ar ₁ , Ar ₂ , m and n are as defined above.

Preferably, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of:

Preferably, L ₁ may be a direct bond or phenylene.

Preferably, L ₂ may be a direct bond, phenylene or naphthylene.

Preferably, R ₁ and R ₂ are each independently hydrogen.

Preferably, m and n may each independently be 0 or 1.

Preferably, the compound represented by Formula 1 may be any one selected from the group consisting of:

The compound represented by Chemical Formula 1 according to the present invention includes a triazine group on the benzene ring side of benzoxazole (benzothiazole) and an N-substituted carbazole group on the hetero ring side, thereby significantly improving electron mobility, Accordingly, it is possible to have high efficiency, low driving voltage, high luminance and long life.

The compound represented by Chemical Formula 1 may be prepared through the following Reaction Schemes 1-1 to 1-2.

[Scheme 1-1]

[Scheme 1-2]

In Reaction Scheme 1, X is halogen, preferably bromo or chloro, and the description of the remaining substituents is as defined above.

The reaction is preferably performed in the presence of a palladium catalyst and a base as a Suzuki coupling reaction, and the reactants and catalysts for the reaction can be changed as known in the art. The manufacturing method may be more specific in the manufacturing examples to be described later.

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

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but 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 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 layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously performs hole injection and transport, and the hole injection layer, a hole transport layer, or a layer that simultaneously performs hole injection and transport is represented by Formula 1 It includes the compound displayed.

Further, the organic material layer may include a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1.

Further, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes a compound represented by Chemical Formula 1.

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously performs electron injection and electron transport includes the compound represented by Chemical Formula 1. In particular, the compound represented by Chemical Formula 1 according to the present invention has excellent thermal stability, has a deep HOMO level of 6.0 eV or higher, high triplet energy (ET), and hole stability. In addition, when the compound represented by Formula 1 is used in an organic material layer capable of electron injection and electron transport at the same time, an n-type dopant used in the art may be mixed and used.

In addition, the organic material layer includes a light emitting layer and an electron transport layer, and the electron transport layer may include a compound represented by Chemical Formula 1.

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

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

Figure 2 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is done. In such a structure, the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Chemical Formula 1. In addition, 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 a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a positive electrode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. Then, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed thereon, and a material that can be used as a cathode is deposited thereon. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

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

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

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode.

The positive electrode material is preferably a material having a large work function so that hole injection into the organic material layer is smooth. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide 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 material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There is 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 an electrode, and has the ability to transport holes as a hole injection material, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is produced in the light emitting layer. A compound which prevents migration of the excitons to the electron injection layer or the electron injection material, and which has excellent thin film formation ability is preferable. It is preferable that 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 matter, hexanitrile hexaazatriphenylene-based organic matter, quinacridone-based organic matter, and perylene-based Organic materials, anthraquinones, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer by receiving holes, and is a material that can transport holes to the light emitting layer by receiving holes from the anode or the hole injection layer as a hole transport material and has a high mobility for holes. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.

As the light-emitting material, a material capable of emitting light in the visible light region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly (p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes arylamino groups such as pyrene, anthracene, chrysene, periplanten, and the substituted or unsubstituted styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, examples of the metal complex include an iridium complex and a platinum complex, but are not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. Do. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

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

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.

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

Preparation Example 1 Preparation of Intermediate Compound A1

Preparation of compound A1-1

2,6-dichlorobenzo [d] thiazole (30 g, 0.147 mol), 9H-carbazole (24.6 g, 0.147 mol) and potassium phosphate (62.40 g, 0.294 mol) were added to dimethylacetamide (300 mL) and refluxed. After refluxing for 12 hours, when the reaction is completed, it is cooled to room temperature. After filtration, washed with water and ethanol and dried to obtain Compound A1-1. (37.9 g, Yield 77%; MS: [M + H] ⁺ = 335)

Preparation of compound A1

Compound A1-1 (37.9 g, 88.9 mmol) is dissolved in 1,4-dioxane (500 ml). Bis (pinacolato) diboron (33.9 g, 133.4 mmol), potassium acetate (26.2 g, 266.7 mmol) and Pd (dppf) Cl ₂ (1.9 g, 2.68 mmol) were added and then at 120 ° C Stir for 8 hours. After the reaction is completed, it is cooled to room temperature and filtered. The filtered solution is distilled to remove the solvent. After extraction with chloroform and water, the organic layer was dried over MgSO ₄ , concentrated, and recrystallized with ethyl acetate to obtain intermediate compound A1. (32.0 g, yield 85%; MS: [M + H] ⁺ = 503)

Preparation Example 2: Preparation of intermediate compound B1

Preparation of compound B1-1

(4- (9H-carbazol-9-yl) phenyl) boronic acid (25 g, 87.1 mmol), 2,6-dichlorobenzo [d] thiazole (17.8 g, 87.1 mmol) is added to dioxane (300 ml). And cesium carbonate (85.1 g, 261.2 mmol) was dissolved in water (100 mL), placed in a round bottom flask and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (1.4g, 2.6mmol) was added and refluxed for 3 hours, and when the reaction was completed, the mixture was cooled to room temperature. After filtration, washed with water and ethanol and dried to obtain compound B1-1. (28.5 g, yield 80%; MS: [M + H] ⁺ = 411)

Preparation of compound B1

B1-1 (18 g, 43.8 mmol) is dissolved in 1,4-dioxane (500 ml). Bis (pinacolato) diboron (16.7 g, 65.7 mmol), potassium acetate (12.9 g, 131.41 mmol) and Pd (PCy) 2. (OAc) 2 (1 g, 1.31 mmol) were added. Then, it was stirred at 120 ° C. for 8 hours. After the reaction is completed, it is cooled to room temperature and filtered. The filtered solution is distilled to remove the solvent. After extraction with chloroform and water, the organic layer was dried over MgSO ₄ , concentrated, and recrystallized from ethanol to obtain compound B1. (18.3 g, 83% yield; MS: [M + H] ⁺ = 411)

Preparation Example 3: Preparation of intermediate compound C1

Preparation of compound C1-1

(3- (9H-carbazol-9-yl) phenyl) boronic acid (20 g, 69.7 mmol), 2,6-dichlorobenzo [d] thiazole (14.2 g, 69.7 mmol) is added to dioxane (250 ml). Then, cesium carbonate (68.1 g, 209.0 mmol) was dissolved in water (100 mL), placed in a round bottom flask, and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (1.1 g, 2.1 mmol) was added and refluxed for 3 hours, and when the reaction was completed, the mixture was cooled to room temperature. After filtration, washed with water and ethanol and dried to obtain compound C1-1. (20 g, yield 70%; MS: [M + H] ⁺ = 395)

Preparation of compound C1

C1-1 (20 g, 48.7 mmol) is dissolved in 1,4-dioxane (500 ml). Bis (pinacolato) diboron (18.5 g, 73.0 mmol), potassium acetate (14.3 g, 146.0 mmol) and Pd (PCy) 2. (OAc) 2 (1.1 g, 1.46 mmol) were added. Then, it was stirred at 120 ° C. for 8 hours. After the reaction is completed, it is cooled to room temperature and filtered. The filtered solution is distilled to remove the solvent. After extraction with chloroform and water, the organic layer was dried over MgSO ₄ , concentrated, and recrystallized from ethanol to obtain compound C1. (18 g, yield 74%; MS: [M + H] ⁺ = 487)

Example 1: Preparation of compound 1

The intermediate compound 1A (15 g, 35.2 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (9.4 g, 35.2 mmol) synthesized in Preparation Example 1 was added to tetrahydrofuran (150 ml). . Then, calcium carbonate (19.5 g, 140.8 mmol) was dissolved in water (50 mL), placed in a round bottom flask, and refluxed. After that, tetrakis (triphenylphosmine) palladium (0) (1.2g, 3mol%) was added and refluxed for 3 hours, and when the reaction was completed, the mixture was cooled to room temperature. After filtration, washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried using magnesium sulfate. Thereafter, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound 1 (12.5 g, 67%, MS: [M + H] ⁺ = 532).

Example 2: Preparation of compound 2

Intermediate compound 1A (15 g, 35.2 mmol) synthesized in Preparation Example 1, 2-([1,1'-biphenyl] -4-yl) -4- (4-bromophenyl) -6-phenyl-1,3, 5-triazine (16.3 g, 35.2 mmol) was added to tetrahydrofuran (150 ml). Then, calcium carbonate (19.5 g, 140.8 mmol) was dissolved in water (50 mL), placed in a round bottom flask, and refluxed. After that, tetrakis (triphenylphosmine) palladium (0) (1.2g, 3mol%) was added and refluxed for 3 hours, and when the reaction was completed, the mixture was cooled to room temperature. After filtration, washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried using magnesium sulfate. Thereafter, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound 2 (17.6 g, 73%, MS: [M + H] ⁺ = 684).

Example 3: Preparation of compound 3

Intermediate compound 1A synthesized in Preparation Example 1 (15 g, 35.2 mmol), 2- (4-bromophenyl) -4- (dibenzo [b, d] furan-1-yl) -6-phenyl-1,3,5 -triazine (16.8 g, 35.2 mmol) is added to tetrahydrofuran (150 ml). Then, calcium carbonate (19.5 g, 140.8 mmol) was dissolved in water (50 mL), placed in a round bottom flask, and refluxed. After that, tetrakis (triphenylphosmine) palladium (0) (1.2g, 3mol%) was added and refluxed for 3 hours, and when the reaction was completed, the mixture was cooled to room temperature. After filtration, washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried using magnesium sulfate. Thereafter, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound 3 (10.3 g, 42%, MS: [M + H] ⁺ = 698).

Example 4: Preparation of compound 4

Intermediate Compound 1A synthesized in Preparation Example 1 (15 g, 35.2 mmol), 9- (4- (4-bromophenyl) -6-phenyl-1,3,5-triazin-2-yl) -9H-carbazole (16.8 g, 35.2 mmol) in tetrahydrofuran (150 ml). Then, calcium carbonate (19.5 g, 140.8 mmol) was dissolved in water (50 mL), placed in a round bottom flask, and refluxed. After that, tetrakis (triphenylphosmine) palladium (0) (1.2g, 3mol%) was added and refluxed for 3 hours, and when the reaction was completed, the mixture was cooled to room temperature. After filtration, washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried using magnesium sulfate. Thereafter, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound 4 (11.5 g, 47%, MS: [M + H] ⁺ = 697).

Example 5: Preparation of compound 5

Intermediate compound A1 synthesized in Preparation Example 1 (15 g, 35.2 mmol), 2- (4-bromophenyl) -4- (dibenzo [b, d] thiophen-4-yl) -6-phenyl-1,3,5 -triazine (17.4 g, 35.2 mmol) is added to tetrahydrofuran (150 ml). Then, calcium carbonate (19.5 g, 140.8 mmol) was dissolved in water (50 mL), placed in a round bottom flask, and refluxed. After that, tetrakis (triphenylphosmine) palladium (0) (1.2g, 3mol%) was added and refluxed for 3 hours, and when the reaction was completed, the mixture was cooled to room temperature. After filtration, washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried using magnesium sulfate. Thereafter, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound 5 (16.1 g, 64%, MS: [M + H] ⁺ = 714).

Example 6: Preparation of compound 6

The intermediate compound B1 (15 g, 29.9 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (8.0 g, 29.9 mmol) synthesized in Preparation Example 2 was added to tetrahydrofuran (150 ml). . Then, calcium carbonate (16.5 g, 119.5 mmol) was dissolved in water (40 mL), placed in a round bottom flask, and refluxed. After that, tetrakis (triphenylphosmine) palladium (0) (1.0g, 3mol%) was added and refluxed for 3 hours, and when the reaction was completed, the mixture was cooled to room temperature. After filtration, washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried using magnesium sulfate. Thereafter, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound 6 (12.7 g, 70%, MS: [M + H] ⁺ = 608).

Example 7: Preparation of compound 6

The intermediate compound C1 (15 g, 30.9 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (8.2 g, 30.9 mmol) synthesized in Preparation Example 3 was added to tetrahydrofuran (150 ml). . Then, calcium carbonate (17.1 g, 123.4 mmol) was dissolved in water (40 mL), placed in a round bottom flask, and refluxed. Then, tetrakis (triphenylphosmine) palladium (0) (1.1 g, 3 mol%) was added thereto, refluxed for 3 hours, and when the reaction was completed, the mixture was cooled to room temperature. After filtration, washed with water and ethanol, dissolved in chloroform, extracted with water, and the organic layer was dried using magnesium sulfate. Thereafter, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound 7 (6.0 g, 33%, MS: [M + H] ⁺ = 592).

[Experimental Example]

Experimental Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,300 에 was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer (Fischer Co.) was used as the detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and transporting to a plasma cleaner. In addition, after the substrate was cleaned for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum evaporator.

On the ITO transparent electrode prepared as above, the following HI-1 compound was thermally vacuum-deposited to a thickness of 50 Pa to form a hole injection layer. The following HT-1 compound was thermally vacuum-deposited to a thickness of 250 Pa on the hole injection layer to form a hole transport layer, and the following HT-2 compound was vacuum-deposited to a thickness of 50 Pa on the HT-1 deposition film to form an electron blocking layer. As a light emitting layer on the HT-2 deposited film, a compound 1 prepared in Example 1, the following YGH1 compound, and a phosphorescent dopant YGD-1 were co-deposited at 44:44:12 to form a 400 mm thick light emitting layer. The following ET-1 compound was vacuum-deposited on the light emitting layer to a thickness of 250 Pa, and further the following ET-2 compound was co-deposited with Li in a 2% weight ratio to a thickness of 100 Pa to form an electron transport layer and an electron injection layer. Aluminum was deposited on the electron injection layer to a thickness of 1000 MPa to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, and the aluminum was maintained at the deposition rate of 2 Å / sec, and the vacuum degree during deposition was maintained at 1 × 10 ^-7 to 5 × 10 ^-8 torr. Did.

Experimental Examples 2-7

An organic light emitting diode was manufactured according to the same method as Experimental Example 1-1 except for using the compound described in Table 1 below instead of the compound 1 of Example 1 in Experimental Example 1.

Comparative Experimental Examples 1-1 to 1-4

An organic light emitting diode was manufactured according to the same method as Experimental Example 1-1 except for using the compound described in Table 1 below instead of the compound 1 of Example 1 in Experimental Example 1. The compounds of CE1 and CE2 in Table 1 are as follows.

In the Experimental Example and Comparative Experimental Example, the driving voltage and luminous efficiency of the organic light emitting diode were measured at a current density of 10 mA / cm ² , and the time at which the luminance was 95% compared to the initial luminance at a current density of 50 mA / cm ² (LT95). Was measured. The results are shown in Table 1 below.

As shown in Table 1, when the compound of the present invention is used as a light emitting layer material, it was confirmed that it exhibits excellent efficiency and lifespan compared to Comparative Experimental Examples.

[Description of codes]

1: substrate 2: anode

3: light emitting layer 4: cathode

5: hole injection layer 6: hole transport layer

7: light emitting layer 8: electron transport layer

Claims (9)

1. Compound represented by the formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   X ₁ , X ₂ and X ₃ are each independently CH or N, provided that X ₁ , Two or more of X ₂ and X ₃ are N,

   Y is S or O,

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

   L ₁ is a direct bond, substituted or unsubstituted C _6-60 arylene, or C _5-60 heteroarylene comprising one or more hetero atoms selected from the group consisting of N, O and S,

   L ₂ is a direct bond, or a substituted or unsubstituted C _6-60 arylene,

   R ₁ and R ₂ are each independently hydrogen or substituted or unsubstituted C _1-60 alkyl,

   m and n are each independently an integer from 0 to 3.
2. According to claim 1,

   The compound represented by Chemical Formula 1 is any one selected from the group consisting of compounds represented by Chemical Formulas 2 to 4 below:

   [Formula 2]

   

   [Formula 3]

   

   [Formula 4]

   

   [Formula 5]

   

   In Chemical Formulas 2 to 5,

   X ₁ , X ₂ , X ₃ , Y, L ₁ , L ₂ , Ar ₁ , Ar ₂ , R ₁ , R ₂ , m and n are as defined in claim 1.
3. According to claim 1,

   Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of:

   
4. According to claim 1,

   L ₁ is a direct bond or phenylene.
5. According to claim 1,

   L ₂ is a direct bond, phenylene or naphthylene, a compound.
6. According to claim 1,

   R ₁ and R ₂ are each independently hydrogen, a compound.
7. According to claim 1,

   m and n are each independently 0 or 1, a compound.
8. According to claim 1,

   The compound represented by Formula 1 is any one selected from the group consisting of:

   

   

   

   

   

   

   
9. A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound according to any one of claims 1 to 8. That is, an organic light emitting device.

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