KR20200105388A - 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. In the compound represented by chemical formula 1 of the present invention, n1 and n2 are each independently an integer of 0 to 5, but n1+n2 is an integer of 3 to 10.

Description

Novel compound and organic light emitting device using the same

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

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An 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 are being 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. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it 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. In the structure of such an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

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, but 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 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 of the following:

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 one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes a compound represented by Formula 1 do.

The compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an organic light-emitting device, and may improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light-emitting device. In particular, the compound represented by Chemical 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.

1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
2 is composed of 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 aid the understanding of the present invention.

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means a substituted or unsubstituted substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O and S atoms, or linked with two or more substituents among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" 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 it 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 ester group may be substituted with an oxygen of the ester group 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 the present specification, the number of carbon atoms of the imide group is not particularly limited, but it 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 specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, 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 a linear or branched chain, and the number of carbon atoms 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 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, cycloheptylmethyl, 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 a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. 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, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably 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 are 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 an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group 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. However, it 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 carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, 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, thiiadia There may be a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and 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 aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the description of the aforementioned heterocyclic group may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above. 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 aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or the cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that two substituents are bonded to each other.

When the compound represented by Chemical Formula 1 contains R ₁ (deuterium) and is used in an organic light-emitting device, the characteristics of the organic light-emitting device, especially the lifespan, can be improved compared to a compound not containing deuterium.

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

Preferably, L is any one of:

.

.

Preferably, R is any one of:

.

.

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 the compound represented by Formula 1, such as the following Scheme 1, Scheme 2, and the like.

[Scheme 1]

[Scheme 2]

In addition, the present invention provides an organic light-emitting device including the compound represented by Chemical Formula 1. For example, the present invention provides 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 of the organic material layers includes a compound represented by Formula 1 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 multilayer 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, and the like 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 an emission layer, and the emission layer includes the compound represented by Chemical Formula 1. In particular, the compound according to the present invention can be used as a dopant for a light emitting layer.

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

In addition, the hole blocking layer, the electron transport layer, the electron injection layer, or the layer that simultaneously transports electrons and injects electrons includes the compound represented by Formula 1 above.

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

1 shows an example of an organic light emitting device comprising 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 emission layer.

FIG. 2 is composed of 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 by materials and methods known in the art, except that at least one of the organic material layers 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, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be prepared by 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 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 coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to such a 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.

For 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 preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode 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); Combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is 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 are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer that injects holes from an electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for a light emitting layer or a light emitting material. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) 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 hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

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

The light-emitting material is a material capable of emitting light in a visible light region by transporting and bonding 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 of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

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

Dopant materials 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 pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of an aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. As an electron transport material, a material capable of injecting electrons from the cathode and transferring them to the emission layer, and a material having high mobility for electrons is suitable. 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 can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

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 that prevents migration to the layer and has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metals Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, 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-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double-sided 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.

Preparation of the compound represented by Formula 1 and an organic light emitting device including the same will be described in detail in the following examples. 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. 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 the dropwise addition, it 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. Keep the temperature of the reaction bath solution at 0 ℃ and slowly add 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 (20.6g, 2.0eq), Pd( A mixture of PPh ₃ ) ₄ (8.6g, 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, the column was separated with dichloromethane:hexane = 1:3 to obtain a white solid compound 2-1. (14.8g, 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 (20.6g, 2.0eq), Pd(PPh ₃ ) ₄ ( 8.6 g, 0.1 eq) 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, the column was separated with dichloromethane:hexane = 1:4 to obtain a white solid compound 2-2. (14.0g, 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 (20.6g, 2.0eq), Pd( A mixture of PPh ₃ ) ₄ (8.6g, 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, the column was separated with dichloromethane:hexane = 1:3 to obtain a white solid compound 2-3. (12.0g, 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 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 (Ethanol) was slowly added. The mixture obtained by distilling the mixture 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 conditions, 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 completion of the dropping, stirring was performed for 30 minutes, and then 22.8 g of triisopropyl borate was dissolved in 200 ml of purified tetrahydrofuran, and then slowly added dropwise. The reaction solution was kept at -78°C and stirred for about 1 hour, then raised to room temperature, and stirring was continued for 12 hours. Diluted hydrochloric acid was added to the reaction solution to complete the reaction, and then separated and extracted 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 for 12 hours. After completion of the reaction, the mixture was cooled to obtain a solid, and after filtration, 28.4 g of compound A-4 was obtained by column chromatography. A peak was confirmed at M/Z=246 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 / 100 ml of ethanol / 50 ml of H ₂ O was stirred at 100° C. for 8 hours. After extraction with dichloromethane, the column was separated with dichloromethane:hexane = 1:4 to obtain a white solid compound 2-4. (12.6g, 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, 0.1 eq) 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, the column was separated with dichloromethane:hexane = 1:4 to obtain a white solid compound 2-5. (14.0g, 40%)

Synthesis Example 8: Synthesis of Compound 3-1

Dissolve Intermediate 2-1 (20.2g, 53.3mmol) and Intermediate B-1 (23.9 g, 58.6mmol) in 300ml of toluene in a 3-neck flask and NaOtBu (sodium tert-butoxide, sodium tert-butoxide) (7.7g, 79.9 mmol), Pd(PtBu ₃ ) ₂ (bis(tri-tert-butylphosphine) palladium, bis(tri-tert-butylphosphine)palladium(0)) (0.3g, 0.5mmol) was added, followed by reflux condition in argon atmosphere Under stirring for 6 hours. When the reaction was completed, the mixture was cooled to room temperature, and water was added and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4, concentrated, and the sample was purified by silica gel column chromatography to obtain 6.0 g of compound 3-1. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at M/Z=751.

Synthesis Example 9: Synthesis of Compound 3-2

Dissolve Intermediate 2-2 (18.9g, 53.3mmol) and Intermediate B-1 (23.9 g, 58.6mmol) in 300ml of toluene in a 3-neck flask and NaOtBu (sodium tert-butoxide, sodium tert-butoxide) (7.7g, 79.9). mmol), Pd(PtBu ₃ ) ₂ (bis(tri-tert-butylphosphine) palladium, bis(tri-tert-butylphosphine)palladium(0)) (0.3g, 0.5mmol) was added, followed by reflux condition in argon atmosphere Under stirring for 6 hours. When the reaction was completed, the mixture was cooled to room temperature, and water was added and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4, concentrated, and the sample was purified by silica gel column chromatography to obtain 5.4 g of compound 3-2. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at M/Z=726.

Synthesis Example 10: Synthesis of Compound 3-3

In a three-necked flask, intermediate 2-3 (20.2g, 53.3mmol) and intermediate B-1 (23.9, 58.6mmol) were dissolved in 300ml of toluene, and NaOtBu (sodium tert-butoxide, 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 condition of argon atmosphere Stir for 6 hours. When the reaction was completed, the mixture was cooled to room temperature, and water was added and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4, concentrated, and the sample was purified by silica gel column chromatography to obtain 5.8 g of compound 3-3. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at M/Z=751.

Synthesis Example 11: Synthesis of Compound 3-4

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

Synthesis Example 12: Synthesis of Compound 3-5

Dissolve Intermediate 2-5 (18.9g, 53.3mmol) and Intermediate B-1 (23.9, 58.6mmol) in 300ml of toluene in a 3-neck flask and NaOtBu (sodium tert-butoxide, 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 condition of argon atmosphere Stir for 6 hours. When the reaction was completed, the mixture was cooled to room temperature, and water was added and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4, concentrated, and the sample was purified by silica gel column chromatography to obtain 4.0 g of compound 3-5. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at M/Z=726.

<Experimental Example>

Example 1

A glass substrate coated with a thin film of 1300Å of ITO (indium tin oxide) was put in distilled water dissolved in a detergent and washed with ultrasonic waves. In this case, Fischer Co. product was used as a detergent, and distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic cleaning 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 50Å to form a hole injection layer. The following compound HT-A 150Å was vacuum-deposited as a first hole transport layer thereon, and subsequently compound HT-B 100Å 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 a light emitting layer having a thickness of 400Å.

Then, 350Å of the following compound ET-A was deposited as a layer for simultaneous electron injection and electron transport, and lithium fluoride (LiF) at a thickness of 10Å and aluminum at a thickness of 1,000Å were sequentially deposited thereon to form a cathode. , An organic light emitting device was manufactured.

In the above process, the deposition rate of organic materials was maintained at 0.4 ~ 2.0 Å/sec, lithium fluoride at the cathode was maintained at a deposition rate of 1.0 Å/sec, and for aluminum 1.5 Å/sec, the vacuum degree during deposition was 1 × 10 Maintaining ^-7 to 5 × 10 ^-8 torr, an organic light emitting device was manufactured.

Examples 2 to 5

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the dopant compound shown in Table 1 below was used as the light emitting layer material in Example 1.

Comparative Examples 1 to 5

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the dopant compound shown in Table 1 below was used as the light emitting layer material in Example 1.

The organic light-emitting devices manufactured according to Examples 1 to 5 and Comparative Examples 1 to 5 were subjected to driving voltage and efficiency at a current density of 10 mA/cm ² , and The time (T95) to be 95% of the initial luminance was measured. The results are shown in Table 1 below.

Dopant
(Luminescent layer) 10mA / cm ² Driving voltage
(V) Luminous efficiency
(Cd/A) Life, 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 life characteristics 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)

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, but 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 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 of the following:

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.
The method of claim 1,
n1+n2 is 10,
compound.
The method of claim 1,
L is any one of the following,
compound:

.
The method of claim 1,
R is any one of the following,
compound:

.
The method of claim 1,
Ar ₁ is phenyl,
compound.
The method of claim 1,
Ar ₂ is phenyl,
compound.
The method of 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 one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the compound according to any one of claims 1 to 7 That is, an organic light-emitting device.

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