KR102288990B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel compound and organic light emitting device comprising the same

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

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

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

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

Korean Patent Publication No. 10-2000-0051826

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

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

[Formula 1]

In Formula 1,

R ₁ is deuterium,

n1 and n2 are each independently an integer of 0 to 5, n1+n2 is an integer of 3 to 10,

L is any one of the following,

above,

X ₁ is N-(Ar ₁ ), O, or S,

Ar ₁ is a substituted or unsubstituted C _6-60 aryl,

each R ₂ is independently hydrogen, cyano, or 4,6-diphenyl-1,3,5-triazin-2-yl,

R is any one of:

above,

A is a benzene ring fused with adjacent rings,

X ₂ and X ₃ are each independently N-(Ar ₂ ), O, or S,

Ar ₂ is substituted or unsubstituted C _6-60 aryl.

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

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

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

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

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

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

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

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

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, 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 are 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 an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

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

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

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

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

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

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

When the compound represented by Formula 1 includes R ₁ (deuterium), when used in an organic light emitting device, characteristics of the organic light emitting device, in particular, lifespan can be improved compared to the compound without deuterium.

Preferably, in Formula 1, n1+n2 is 10.

Preferably, L is any of the following:

.

.

Preferably, R is any of the following:

.

.

Preferably, Ar ₁ is phenyl.

Preferably, Ar ₂ is phenyl.

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

.

.

In addition, the present invention provides a method for preparing a compound represented by Formula 1, such as Scheme 1 and Scheme 2 below.

[Scheme 1]

[Scheme 2]

In addition, the present invention provides an organic light emitting device including the compound represented by the formula (1). In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Formula 1 above. 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, a hole blocking layer, an electron transport layer, an electron injection layer, etc. 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 layer may include an emission layer, and the emission layer includes the compound represented by Formula 1 above. In particular, the compound according to the present invention can be used as a dopant in the light emitting layer.

In addition, the organic material layer may include a hole blocking layer, an electron transport layer, or an electron injection layer, the hole blocking layer, the electron transport layer, or the electron injection layer includes the compound represented by the formula (1).

In addition, the hole blocking layer, the electron transport layer, the electron injection layer, or the layer for transporting and injecting electrons at the same time includes the compound represented by the formula (1).

Also, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Also, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of 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 Formula 1 may be included in the light emitting layer.

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

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

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. and forming an organic material 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 material layer, and an anode material on a substrate.

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

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

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.

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

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

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

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

The 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-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

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

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

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. do. Specific examples include Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the 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 which prevents movement to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, 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) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

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

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

The compound represented by Formula 1 and the preparation of an organic light emitting device including the same will be described in detail in Examples below. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

<Synthesis example>

Synthesis Example 1: Synthesis of Intermediate 1-1

Magnesium 39.5 g (1.7 mol), iodine 10 g and tetrahydrofuran 100 mL were added, and refluxed for 2 hours under nitrogen condition. After cooling to room temperature, 226.9 g (1.4 mol) of bromobenzene-d5 was dissolved in 200 mL of tetrahydrofuran and slowly added dropwise. After dropwise addition, the mixture was refluxed for 2 hours and cooled to room temperature. In another flask, 100 g (0.54 mol) of cyanuric chloride was dissolved in 200 Ml of tetrahydrofuran, and the reaction solution was cooled to 0 °C. While maintaining the temperature of the previous reaction bath solution at 0 °C, it is slowly added dropwise. After completion of the reaction, the reaction was terminated with a 4 M aqueous salt ginseng solution, extracted, and the organic layer was concentrated under reduced pressure, recrystallized with hexane, and dried to obtain 80 g of the compound represented by Formula 1-1.

Synthesis Example 2: Synthesis of Intermediate 2-1

Compound 1-1 (20.8g, 1.0eq), (4-chloro-3-cyanophenyl)boronic acid A-1 ( _{15.0g, 1.1eq), K 2} CO ₃ (20.6 g, 2.0eq), Pd ( A mixture of PPh ₃ ) ₄ (8.6 g, 0.1eq) of 400 ml of toluene / 100 ml of ethanol / _{50 ml of H 2} O was stirred at 100° C. for 12 hours. After extraction with dichloromethane, column separation was performed using dichloromethane: hexane = 1:3 to obtain a white solid compound 2-1. (14.8 g, 52%)

Synthesis Example 3: Synthesis of Intermediate 2-2

Compound 1-1 (20.8g, 1.0eq), (4-chlorophenyl)boronic acid A-2 ( _{12.9g, 1.1eq), K 2} CO ₃ (20.6 g, 2.0eq), Pd(PPh ₃ ) ₄ ( 8.6 g, 0.1eq) of 400 ml of toluene / 100 ml of ethanol / _{50 ml of H 2} O was stirred at 100° C. for 8 hours. After extraction with dichloromethane, column separation was performed using dichloromethane: hexane = 1:4 to obtain a white solid compound 2-2. (14.0 g, 40%)

Synthesis Example 4: Synthesis of Intermediate 2-3

Compound 1-1 (20.8g, 1.0eq), (2-chloro-5-cyanophenyl)boronic acid A-3 ( _{15.0g, 1.1eq), K 2} CO ₃ (20.6 g, 2.0eq), Pd ( A mixture of PPh ₃ ) ₄ (8.6 g, 0.1eq) of 400 ml of toluene / 100 ml of ethanol / _{50 ml of H 2} O was stirred at 100° C. for 8 hours. After extraction with dichloromethane, column separation was performed using dichloromethane:hexane = 1:3 to obtain white solid compound 2-3. (12.0 g, 42%)

Synthesis Example 5: Synthesis of Intermediate A-4

2-bromo-3-chloro-6-iodophenol (42 g, 299.99 mmol) and 2-fluorophenylboronic acid (100 g, 299.99 mmol) was dissolved in 800 ml of tetrahydrofuran (THF). Sodium carbonate (Na ₂ CO ₃ ) 2 M solution (500 mL) and tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] (10.4 g, 9 mmol) were added thereto, and refluxed for 12 hours. . After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. The toluene layer was separated, dried over magnesium sulfate, and the filtered filtrate was distilled under reduced pressure. The resulting mixture was recrystallized twice using chloroform and ethanol to obtain 46.1 g.

Next, 40 g of the prepared compound is dissolved in dimethylformamide (DMF) (400 ml). Potassium carbonate (55 g, 397.96 mmol) was added thereto, followed by stirring at 100° C. for 1 hour. After the reaction was completed, it was cooled to room temperature, and 100 ml of ethanol was slowly added thereto. The mixture obtained by distillation under reduced pressure was recrystallized from chloroform and ethyl acetate to obtain 29.9 g.

Next, 28.2 g (100 mmol) of the prepared compound was dissolved in 300 ml of anhydrous tetrahydrofuran under nitrogen condition, and the ambient temperature of the reactor was maintained at -78°C. Next, 40 ml of 2.5M-butyl lithium was slowly added dropwise. After stirring for 30 minutes after completion of the dropping, 22.8 g of triisopropyl borate was dissolved in 200 ml of purified tetrahydrofuran, and then slowly added dropwise. The reaction solution was stirred for about 1 hour while maintaining at -78°C, and then raised to room temperature and stirring was continued for 12 hours. After the reaction was terminated by adding diluted hydrochloric acid to the reaction solution, liquid separation was performed using methylene chloride. The obtained organic layer was dried over magnesium sulfate, filtered and distilled under reduced pressure. Next, after putting in 400 ml of acetic acid, a catalytic amount of hydrochloric acid was added dropwise, followed by stirring at reflux temperature for 12 hours. After completion of the reaction, a solid was obtained by cooling, and 28.4 g of Compound A-4 was obtained by using column chromatography after filtration. A peak at M/Z = 246 was confirmed by measurement of the mass spectrum of the obtained solid.

Synthesis Example 6: Synthesis of Intermediate 2-4

Toluene of compound 1-1 (20.8g, 1.0eq), A-4 ( _{20.3g, 1.1eq), K 2} CO ₃ (20.6g, 2.0eq), Pd(PPh ₃ ) ₄ (8.6g, 0.1eq) A mixture of 400 ml / ethanol 100 ml / H ₂ O 50 ml was stirred at 100° C. for 8 hours. After extraction with dichloromethane, column separation was performed using dichloromethane:hexane = 1:4 to obtain a white solid compound 2-4. (12.6 g, 38%)

Synthesis Example 7: Synthesis of Intermediate 2-5

Compound 1-1 (20.8g, 1.0eq), (2-chlorophenyl)boronic acid A-5 ( _{12.9g, 1.1eq), K 2} CO ₃ (20.6g, 2.0eq), Pd(PPh ₃ ) ₄ ( 8.6 g, 0.1eq) of 400 ml of toluene / 100 ml of ethanol / _{50 ml of H 2} O was stirred at 100° C. for 8 hours. After extraction with dichloromethane, column separation was performed using dichloromethane: hexane = 1:4 to obtain a white solid compound 2-5. (14.0 g, 40%)

Synthesis Example 8: Synthesis of compound 3-1

Dissolve Intermediate 2-1 (20.2 g, 53.3 mmol) and Intermediate B-1 (23.9 g, 58.6 mmol) in 300 ml of toluene in a 3-neck flask, and NaOtBu (sodium tert-butoxide) (7.7 g, 79.9) mmol), Pd(PtBu ₃ ) ₂ (bis(tri-tert-butylphosphine)palladium, bis(tri-tert-butylphosphine)palladium(0)) (0.3g, 0.5mmol) was added, and argon atmosphere reflux conditions under stirring for 6 hours. Upon completion of the reaction, after cooling to room temperature, water was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4, concentrated, and the sample was purified by silica gel column chromatography to obtain 6.0 g of Compound 3-1. As a result of mass spectrum measurement of the obtained solid, a peak was confirmed at M/Z=751.

Synthesis Example 9: Synthesis of compound 3-2

In a three-necked flask, dissolve Intermediate 2-2 (18.9 g, 53.3 mmol) and Intermediate B-1 (23.9 g, 58.6 mmol) in 300 ml of toluene, and NaOtBu (sodium tert-butoxide) (7.7 g, 79.9) mmol), Pd(PtBu ₃ ) ₂ (bis(tri-tert-butylphosphine)palladium, bis(tri-tert-butylphosphine)palladium(0)) (0.3g, 0.5mmol) was added, and argon atmosphere reflux conditions under stirring for 6 hours. Upon completion of the reaction, after cooling to room temperature, water was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4, concentrated, and the sample was purified by silica gel column chromatography to obtain 5.4 g of compound 3-2. As a result of mass spectrum measurement of the obtained solid, a peak was confirmed at M/Z=726.

Synthesis Example 10: Synthesis of compound 3-3

Dissolve Intermediate 2-3 (20.2g, 53.3mmol) and Intermediate B-1 (23.9, 58.6mmol) in 300ml of toluene in a 3-neck flask, and NaOtBu (sodium tert-butoxide) (7.7g, 79.9mmol) ), Pd(PtBu ₃ ) ₂ (bis(tri-tert-butylphosphine)palladium, bis(tri-tert-butylphosphine)palladium(0)) (0.3g, 0.5mmol) was added, and then under reflux conditions under argon atmosphere. Stirred for 6 hours. Upon completion of the reaction, after cooling to room temperature, water was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4, concentrated, and the sample was purified by silica gel column chromatography to obtain 5.8 g of compound 3-3. As a result of mass spectrum measurement of the obtained solid, a peak was confirmed at M/Z=751.

Synthesis Example 11: Synthesis of compound 3-4

In a 3-neck flask, dissolve Intermediate 2-4 (23.7 g, 53.3 mmol) and Intermediate B-1 (23.9 g, 58.6 mmol) in 300 ml of toluene, and NaOtBu (sodium tert-butoxide) (7.7 g, 79.9) mmol), Pd(PtBu ₃ ) ₂ (bis(tri-tert-butylphosphine)palladium, bis(tri-tert-butylphosphine)palladium(0)) (0.3g, 0.5mmol) was added, and argon atmosphere reflux conditions under stirring for 6 hours. Upon completion of the reaction, after cooling to room temperature, water was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4, concentrated, and the sample was purified by silica gel column chromatography to obtain 3.8 g of Compound 3-4. As a result of mass spectrum measurement of the obtained solid, a peak was confirmed at M/Z=816.

Synthesis Example 12: Synthesis of compound 3-5

In a 3-neck flask, dissolve Intermediate 2-5 (18.9 g, 53.3 mmol) and Intermediate B-1 (23.9, 58.6 mmol) in 300 ml of toluene, and NaOtBu (sodium tert-butoxide) (7.7 g, 79.9 mmol) ), Pd(PtBu ₃ ) ₂ (bis(tri-tert-butylphosphine)palladium, bis(tri-tert-butylphosphine)palladium(0)) (0.3g, 0.5mmol) was added, and then under reflux conditions under argon atmosphere. Stirred for 6 hours. Upon completion of the reaction, after cooling to room temperature, water was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4, concentrated, and the sample was purified by silica gel column chromatography to obtain 4.0 g of compound 3-5. As a result of mass spectrum measurement of the obtained solid, a peak was confirmed at M/Z=726.

<Experimental example>

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1300 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following compound HAT was thermally vacuum deposited to a thickness of 50 Å to form a hole injection layer. On it, the following compound HT-A 150 Å was vacuum-deposited as a first hole transport layer, and subsequently, the following compound HT-B 100 Å was deposited as a second hole transport layer. T-Host as a host and compound 3-1 as a dopant were vacuum-deposited at a weight ratio of 45:55 to form an emission layer with a thickness of 400 Å.

Then, 350 Å of the following compound ET-A was deposited as a layer that simultaneously injects and transports electrons, and lithium fluoride (LiF) and aluminum were deposited to a thickness of 1,000 Å to a thickness of 10 Å on this sequentially to form a cathode. , an organic light emitting device was manufactured.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 2.0 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 1.0 Å/sec, and the deposition rate of aluminum was maintained at 1.5 Å/sec, and the vacuum degree during deposition was 1 × 10 ^{By maintaining -7} to 5 × 10 ^-8 torr, an organic light emitting diode was manufactured.

Examples 2 to 5

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the dopant compounds shown in Table 1 were used as the light emitting layer material in Example 1.

Comparative Examples 1 to 5

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the dopant compounds shown in Table 1 were used as the light emitting layer material in Example 1.

The organic light emitting diodes manufactured by Examples 1 to 5 and Comparative Examples 1 to 5 were subjected to a driving voltage and efficiency at a current density of ^{10 mA/cm 2 , and also} The time (T95) at which it becomes 95% of the initial luminance was measured. The results are shown in Table 1 below.

dopant
(light emitting layer) 10mA/cm ² drive voltage
(V) Luminous Efficiency
(Cd/A) Lifetime, T95
(time) Example 1 3-1 3.42 46.76 120 Comparative Example 1 TD-1 3.43 46.55 107 Example 2 3-2 3.65 44.48 83 Comparative Example 2 TD-2 3.66 44.12 74 Example 3 3-3 3.64 47.41 79 Comparative Example 3 TD-3 3.64 47.32 70 Example 4 3-4 3.68 43.59 44 Comparative Example 4 TD-4 3.67 43.55 39 Example 5 3-5 3.72 45.97 54 Comparative Example 5 TD-5 3.72 45.88 48

As shown in Table 1, the devices of Examples 1 to 5 using the compound having the structure of Formula 1 have longer lifespan than the devices of Comparative Examples 1 to 5.

1: Substrate 2: Anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: hole blocking layer
9: electron transport layer

Claims (8)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ is deuterium,
n1 and n2 are each independently an integer of 0 to 5, n1+n2 is an integer of 3 to 10,
L is

ego,
above,
X ₁ is O or S,
R ₂ are each independently hydrogen or cyano;
R is

ego,
above,
X ₂ is N-(Ar ₂ ), O, or S,
Ar ₂ is substituted or unsubstituted C _6-60 aryl.
According to claim 1,
n1+n2 is 10,
compound.
According to claim 1,
L is any one of the following,
compound:

.
According to claim 1,
R is

sign,
compound.
delete According to claim 1,
Ar ₂ is phenyl,
compound.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
compound:

.
a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers is any one of claims 1 to 4, 6 and 7 An organic light-emitting device comprising the compound according to one of the claims.

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