KR101586531B1 - New compounds and organic light emitting device using the same - Google Patents

Abstract

The present invention provides a novel compound capable of greatly improving the lifetime, efficiency, electrochemical stability, and thermal stability of an organic light emitting device, and an organic light emitting device in which the compound is contained in an organic compound layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a novel compound and an organic light-

This application claims the benefit of the filing date of Korean Patent Application No. 10-2012-0058939 filed on May 31, 2012, the entire contents of which are incorporated herein by reference.

The present invention relates to an organic light emitting device in which a novel compound capable of significantly improving lifetime, efficiency, electrochemical stability, and thermal stability of an organic light emitting device is contained in an organic compound layer.

The organic light emission phenomenon is one example in which current is converted into visible light by an internal process of a specific organic molecule. The principle of organic luminescence phenomenon is as follows. When an organic layer is positioned between an anode and a cathode, when a voltage is applied between the two electrodes, electrons and holes are injected into the organic layer from the cathode and the anode, respectively. Electrons and holes injected into the organic material layer recombine to form an exciton, and the exciton falls back to the ground state to emit light. An organic light emitting device using such a principle may be generally composed of an organic material layer including a cathode, an anode, and an organic material layer disposed therebetween, for example, a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.

As a material used in an organic light emitting device, a pure organic material or a complex in which an organic material and a metal form a complex is mostly used. Depending on the application, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, . As the hole injecting material and the hole transporting material, an organic material having a p-type property, that is, an organic material that is easily oxidized and electrochemically stable at the time of oxidation is mainly used. On the other hand, as an electron injecting material or an electron transporting material, an organic material having an n-type property, that is, an organic material that is easily reduced and electrochemically stable when being reduced is mainly used. As the light emitting layer material, a material having both a p-type property and an n-type property, that is, a material having both a stable form in oxidation and in a reduced state is preferable, and a material having a high luminous efficiency for converting an exciton into light desirable.

In addition to the above, it is preferable that the material used in the organic light emitting device further has the following properties.

First, the material used in the organic light emitting device is preferably excellent in thermal stability. This is because joule heating occurs due to the movement of charges in the organic light emitting device. At present, NPB, which is mainly used as a hole transporting layer material, has a glass transition temperature of 100 DEG C or less, which makes it difficult to use in an organic light emitting device requiring a high current.

Secondly, in order to obtain a highly efficient organic light emitting device capable of driving at a low voltage, holes or electrons injected into the organic light emitting element should be smoothly transferred to the light emitting layer, and injected holes and electrons should not escape from the light emitting layer. For this purpose, the material used in the organic light emitting device should have an appropriate band gap and a HOMO or LUMO energy level. At present, in the case of PEDOT: PSS used as a hole transport material in an organic light emitting device manufactured by a solution coating method, since the LUMO energy level is lower than the LUMO energy level of an organic material used as a light emitting layer material, There is a difficulty in.

In addition, materials used in organic light emitting devices should have excellent chemical stability, charge mobility, and interface characteristics with electrodes or adjacent layers. That is, the material used in the organic light emitting device should have little deformation of the material due to moisture or oxygen. In addition, by having appropriate hole or electron mobility, it is necessary to maximize the formation of excitons by balancing the density of holes and electrons in the light emitting layer of the organic light emitting device. And, for the stability of the device, the interface with the electrode including the metal or the metal oxide should be good.

Accordingly, there is a need in the art to develop organic materials having the above-mentioned requirements.

Korean Patent Publication No. 10-2011-0027635

A compound having a chemical structure capable of satisfying the conditions required for a material usable in an organic light emitting device, for example, an appropriate energy level, electrochemical stability and thermal stability, The organic light-emitting device is required to be studied.

The present invention provides novel compounds.

The present invention also provides an organic light emitting device comprising a first electrode, a second electrode, and at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the compound An organic light emitting device is provided.

The compound of the present invention can be used as an organic material layer in an organic light emitting device. When the compound is used in an organic light emitting device, the driving voltage of the device is lowered, the light efficiency is improved, and the lifetime characteristics of the device are improved .

Fig. 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. Fig.
2 shows an example of an organic light emitting element made up of a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is.

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

The novel compounds according to the present invention can be represented by the following general formula (1) or (2).

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

R1 and R2 each independently represent an alkyl group having 1 to 10 carbon atoms; And an aryl group having 6 to 30 carbon atoms, R 1 and R 2 may each independently form an aliphatic or aromatic ring by bonding with adjacent functional groups,

L is a direct bond or an arylene group having 6 to 30 carbon atoms,

Ar is hydrogen; A halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an arylamine group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted with at least one member selected from the group consisting of aryl groups; An arylamine group having 6 to 30 carbon atoms; A halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an arylamine group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, A carbazolyl group substituted or unsubstituted with at least one member selected from the group consisting of aryl groups; And an alkoxy group having 1 to 10 carbon atoms, an arylamine group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aryl group having 5 to 30 carbon atoms, And a substituted or unsubstituted benzocarbazole group substituted by at least one member selected from the group consisting of a heteroaryl group.

In the compounds according to the present invention, the substituents of the above formulas (1) and (2) will be described in more detail as follows.

The alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 12. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl.

The alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 12. Specific examples thereof include, but are not limited to, an alkenyl group having an aryl group such as a stilbenyl group or a styrenyl group.

The alkoxy group preferably has 1 to 12 carbon atoms, more specifically, methoxy, ethoxy, isopropyloxy, and the like, but is not limited thereto.

The aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 40. Examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group and a stilbene group. Examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthrene group, a pyrenyl group, a perylenyl group, A benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group,

The heterocyclic group is a ring group containing heteroatoms O, N or S, and the number of carbon atoms is not particularly limited, but preferably 3 to 30 carbon atoms. Examples of the heterocyclic group include carbazole group, thiophene group, furan group, pyrrolyl group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, pyrazazinyl group, quinolinyl group, isoquinoline group , Acridyl groups, and the like, but are not limited thereto.

Specific examples of the arylamine group include, but are not limited to, the following structural formulas.

The term "substituted or unsubstituted" in the present specification means a group selected from the group consisting of deuterium, halogen, alkyl, alkenyl, alkoxy, silyl, arylalkenyl, aryl, Substituted or unsubstituted fluorenyl group and a nitrile group, or has no substituent group.

Examples of substituents which may additionally substitute for R 1, R 2, L and Ar in the above formulas 1 and 2 include halogen, alkyl, alkenyl, alkoxy, silyl, arylalkenyl, aryl, heterocyclic, An arylamine group, a fluorenyl group substituted or unsubstituted with an aryl group, a nitrile group, and the like, but are not limited thereto.

The compound represented by Formula 1 may be selected from the group consisting of the following structural formulas, but is not limited thereto.

The compound represented by Formula 2 may be selected from the group consisting of the following structural formulas, but is not limited thereto.

The conjugation length of the compound and the energy band gap are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy bandgap. Since the core of the compound of Formula 1 contains a limited conjugation, it has a large energy band gap.

In the present invention, compounds having various energy bandgaps can be synthesized by introducing various substituent groups into the core structure having a large energy band gap as described above. Usually, it is easy to control the energy band gap by introducing a substituent to a core structure having a large energy band gap. However, when the core structure has a small energy band gap, it is difficult to control the energy band gap by introducing a substituent. In the present invention, the HOMO and LUMO energy levels of the compound can be controlled by introducing various substituents to the core structure.

In addition, compounds having intrinsic properties of the substituent introduced by introducing various substituents into the structure of the above formula (1) or (2) can be synthesized. For example, by introducing a substituent mainly used in a hole injecting layer material, a hole transporting material, a light emitting layer material, and an electron transporting layer material used in manufacturing an organic light emitting device into the core structure, a material meeting the requirements of each organic layer is synthesized .

Since the compound of Formula 1 or 2 may include an amine structure in the core structure, it may have an appropriate energy level as a hole injecting and / or hole transporting material in the organic light emitting device. In the present invention, a compound having a suitable energy level according to the substituent among the compounds of the formula (1) or (2) is selected and used in an organic light emitting device, thereby realizing a device having a low driving voltage and a high light efficiency.

In addition, by introducing various substituents into the structure of the formula (1) or (2), it is possible to finely control the energy band gap, and the characteristics at the interface between the organic materials can be improved, .

On the other hand, the compound has a high glass transition temperature (Tg) and is excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.

The compounds according to the present invention can be prepared by methods such as the following Reaction Schemes 1 and 2, but are not limited thereto. More specific details are described in the following examples.

[Reaction Scheme 1]

[Reaction Scheme 2]

Also, the organic light emitting device according to the present invention is an organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers (1) or (2).

The organic light emitting device of the present invention can be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that one or more organic compound layers are formed using the above-described compounds.

The compound may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

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 injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting 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.

Therefore, in the organic light emitting device of the present invention, the organic material layer may include at least one of a hole injection layer, a hole transport layer, and a layer simultaneously injecting holes and transporting holes, .

In addition, the organic layer may include a light emitting layer, and the light emitting layer may include the compound.

In addition, the organic material layer may include at least one of an electron transporting layer, an electron injecting layer, and a layer that simultaneously performs electron transport and electron injection, and at least one of the layers may include the compound.

In such an organic layer having a multi-layer structure, the compound may be included in a light emitting layer, a layer that simultaneously transports holes and holes, a layer that simultaneously transports light and electrons, or a layer that simultaneously transports electrons and emits light.

In the organic light emitting device according to the present invention, it is particularly preferable that the compound represented by Formula 1 is contained in the hole injection layer and / or the hole transport layer.

The structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 and 2, but the present invention is not limited thereto.

1 illustrates the structure of an organic light emitting device in which an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated on a substrate 1. In FIG. In such a structure, the compound may be included in the light emitting layer (3).

2 shows an organic light emitting device in which an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 are sequentially laminated on a substrate 1 Structure is illustrated. In such a structure, the compound may be included in the hole injecting layer 5, the hole transporting layer 6, the light emitting layer 7, or the electron transporting layer 8.

For example, the organic light emitting device according to the present invention may be formed by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form a metal oxide or a metal oxide having conductivity on the substrate, To form an anode, an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, and an electron transporting layer is formed on the anode, and a material which can be used as a cathode is deposited thereon. In addition to such a 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.

The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. The organic material layer may be formed using a variety of polymeric materials by a method such as a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, Layer.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention 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); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methyl compounds), poly [3,4- (ethylene-1,2-dioxy) compounds] (PEDT), polypyrrole and polyaniline.

The negative electrode 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; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene , An anthraquinone, and a conductive polymer of polyaniline and a poly-compound, but the present invention is not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injecting layer to the light emitting layer and having high mobility to holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and 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-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is suitable for electrons, is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

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

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

The present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.

< Example >

< Manufacturing example  1> Preparation of the substance represented by the formula 1-10

1) Preparation of Compound 1

A 2 L round bottom flask was charged with 5,5,9,9-tetramethyl-9H-quino [3,2,1-de] acridine (5,5,9,9-tetramethyl-9H- Quino [ 1-de] acridine, CAS No. 52066-62-3, 100 g, 307.3 mmol), and 1 L of chloroform was added thereto, followed by cooling to 0 캜 with stirring. N-Bromosuccinimide (50 g, 280.9 mmol) was slowly added thereto, followed by stirring for 2 hours. After completion of the reaction, 200 ml of an aqueous sodium thiosulfate solution was added and stirred for 20 minutes, and then an organic layer was separated. The separated organic layer was washed with 200 ml of aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The solution was filtered, concentrated under reduced pressure and subjected to column purification to obtain Compound 1 (67.4 g, 166.7 mmol) in a yield of 59.3%.

MS: [M + H] &lt; ⁺ &gt; = 405

2) Preparation of compound 2

Compound 1 (60 g, 148.4 mmol) and 500 ml of anhydrous tetrahydrofuran were placed in a 1 L round bottom flask and cooled to -78 캜 with stirring. N-butyl lithium (2.5 M hexane solution; 62.3 ml, 155.8 mmol) was slowly added thereto and stirred for 1 hour. Trimethylborate (19.8 ml, 177.6 mmol) was slowly added thereto. After 30 minutes, 300 ml of 1N hydrogen chloride aqueous solution was added and the temperature was raised to room temperature while stirring. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. Distilled under reduced pressure, and recrystallized from chloroform and hexane to obtain Compound 2 (42.6 g, 115.4 mmol) in a yield of 77.8%.

3) Preparation of Compound 3

To a 500 ml round-bottomed flask was added the compound 2 (40 g, 108.3 mmol) and methyl 2-bromo-5-chlorobenzoate (CAS No. 27007-53-0, 27.1 g, 108.6 potassium carbonate (60 g, 434.1 mmol), tetrakis (triphenylphosphine) palladium (2.5 g, 2.16 mmol), 240 ml of tetrahydrofuran and 120 ml of water were added and refluxed with stirring for 8 hours. The mixture was cooled to room temperature and the organic layer was separated. Concentrated under reduced pressure, and subjected to column purification to obtain Compound 3 (39.1 g, 79.1 mmol) in a yield of 73%.

MS: [M + H] &lt; ⁺ &gt; = 494

4) Preparation of Compound 4

Compound 3 (35 g, 70.8 mmol) and 350 ml of anhydrous tetrahydrofuran were placed in a 500 ml round bottom flask and stirred. Methyl magnesium bromide (3.0 M ether solution; 59 ml, 177 mmol) was slowly added and refluxed with stirring for 12 hours. After cooling to room temperature, the reaction solution was slowly poured into 400 ml of a 2N aqueous solution of hydrogen chloride at 0 ° C and stirred for 30 minutes. The organic layer was separated, concentrated under reduced pressure, and then purified by column. Compound 4 (21.8 g, 44.1 mmol) was obtained in a yield of 62.3%.

MS: [MH ₂ O] &lt; ^{+ &} gt ^; = 475

5) Preparation of Compound 5

Compound (4) (35 g, 70.8 mmol) and 300 ml of glacial acetic acid were added to a 500 ml round-bottomed flask, and 0.2 ml of concentrated sulfuric acid was slowly added thereto and stirred for 3 hours. After completion of the reaction, the resulting solid was filtered and washed with 500 ml of water. A solution of the filtered solid in 400 ml of chloroform was washed twice with 100 ml of an aqueous solution of sodium chloride. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Recrystallization from chloroform and ethanol gave Compound 5 (27.5 g, 57.8 mmol) in a yield of 81.6%.

MS: [M + H] &lt; ⁺ &gt; = 476

6) Preparation of Formulas 1-10

(9-phenyl-9H-carbazol-3-yl) boronic acid, CAS No (5 g, 10.5 mmol) (0.06 g, 0.1 mmol), tricyclohexylphosphine (0.06 g, 0.2 mmol), potassium carbonate (5.8 g, 42 mmol), bis (dibenzylidineacetone) palladium , Dioxane (40 ml) and water (20 ml) were added, and the mixture was refluxed with stirring for 8 hours. The mixture was cooled to room temperature and the organic layer was separated. Concentrated under reduced pressure, and purified by column to obtain the compound of formula 1-10 (3.4 g, 5.0 mmol) in a yield of 47.4%.

MS: [M + H] &lt; ⁺ &gt; = 683

< Manufacturing example  2> Preparation of the substance represented by the formula 1-12

(5 g, 10.5 mmol) of the above Preparation Example 1 and 4- (diphenylamino) phenyl boronic acid, CAS No. 201802-67-7, 3 g, (0.06 g, 0.1 mmol), tricyclohexylphosphine (0.06 g, 0.2 mmol), dioxane (40 ml) and water (20 ml) And refluxed with stirring for 8 hours. The mixture was cooled to room temperature and the organic layer was separated. Concentrated under reduced pressure, and purified by column to obtain the compound of Formula 1-12 (3.1 g, 4.5 mmol) in a yield of 42.9%.

MS: [M + H] &lt; ⁺ &gt; = 685

< Manufacturing example  3> Preparation of the substance represented by the formula 1-21

To a 250 ml round-bottomed flask was charged the compound 5 (10 g, 21 mmol), diphenylamine (3.9 g, 23 mmol), sodium tert-butoxide (2.6 g, 27 mmol), bis (tri- butylphosphine) palladium (0.11 g, 0.22 mmol) and 100 ml of xylene were added, and the mixture was refluxed with stirring for 8 hours. The mixture was cooled to room temperature, 10 g of Celite 545 was added, and the mixture was stirred for 30 minutes. The reaction solution is filtered and concentrated under reduced pressure. The column was purified to obtain the compound of Formula 1-21 (7.2 g, 11.8 mmol) in a yield of 56.2%.

MS: [M + H] &lt; ⁺ &gt; = 609

< Manufacturing example  4> Preparation of the substance represented by the formula 1-23

To a 250 ml round-bottomed flask was added the compound 5 (10 g, 21 mmol) and N- [1,1'-biphenyl] -4-yl- [1,1'-biphenyl] -4- (1,1'-biphenyl] -4-yl- [1,1'-biphenyl] -4-amine, CAS No. 102113-98-4, 7.4 g, 23 mmol), sodium tert- (Trimethyl-butylphosphine) palladium (0.11 g, 0.22 mmol) and 100 ml of xylene were put into the flask and refluxed with stirring for 8 hours. The mixture was cooled to room temperature, 10 g of Celite 545 was added, and the mixture was stirred for 30 minutes. The reaction solution was filtered and concentrated under reduced pressure. The column was purified to obtain the compound of Formula 1-23 (9.7 g, 12.7 mmol) in a yield of 60.5%.

MS: [M + H] &lt; ⁺ &gt; = 761

< Manufacturing example  5> Preparation of the substance represented by the formula 2-21

1) Preparation of Compound 1

A 2 L round bottom flask was charged with 4,4,8,8,12,12-hexamethyl-4H, 8H, 12H-benzo [1,9] quinolizano [3,4,5,6,7- (4,4,8,8,12,12-hexamethyl-4H, 8H, 12H-benzo [1,9] quinolizino [3,4,5,6,7-def] acridine, 40 g, 109.4 mmol) 1 L of chloroform was added and the mixture was cooled to 0 캜 with stirring. N-Bromosuccinimide (19.5 g, 109.4 mmol) was slowly added thereto, followed by stirring at room temperature for 5 hours. After completion of the reaction, 200 ml of an aqueous sodium thiosulfate solution was added and stirred for 20 minutes, and then an organic layer was separated. The separated organic layer was washed with 200 ml of aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The solution was filtered, concentrated under reduced pressure, and subjected to column purification to obtain Compound 1 (33.4 g, 75.2 mmol) in a yield of 68.7%.

MS: [M + H] &lt; ⁺ &gt; = 445

2) Preparation of compound 2

The above compound 1 (32 g, 72 mmol) and 300 ml of anhydrous tetrahydrofuran were placed in a 500 ml round bottom flask and cooled to -78 캜 with stirring. N-butyllithium (2.5 M hexane solution; 31.6 ml, 79 mmol) was slowly added thereto and stirred for 1 hour. Trimethylborate (10.4 ml, 93.6 mmol) was slowly added thereto. After 30 minutes, 150 ml of a 1N hydrogen chloride aqueous solution was added and the temperature was raised to room temperature while stirring. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. Distilled under reduced pressure, and recrystallized from chloroform and hexane to obtain Compound 2 (21.2 g, 51.8 mmol) in a yield of 71.9%.

3) Preparation of Compound 3

(21 g, 51.3 mmol) and methyl 2-bromo-5-chlorobenzoate (CAS No. 27007-53-0, 12.8 g, 51.3 mmol) were added to a 500 ml round bottom flask. mmol), potassium carbonate (28.4 g, 205.5 mmol), tetrakis (triphenylphosphine) palladium (1.2 g, 1 mmol), tetrahydrofuran (200 ml) and water (100 ml) were added and refluxed with stirring for 8 hours. The mixture was cooled to room temperature and the organic layer was separated. The residue was distilled under reduced pressure, followed by column purification to obtain Compound 3 (19.2 g, 35.9 mmol) in a yield of 70%.

MS: [M + H] &lt; ⁺ &gt; = 534

4) Preparation of Compound 4

Compound (3) (15 g, 28.1 mmol) and 200 ml of anhydrous tetrahydrofuran were placed in a 500 ml round bottom flask and stirred. Methyl magnesium bromide (3.0 M ether solution; 24 ml, 72 mmol) was slowly added and refluxed with stirring for 12 hours. After cooling to room temperature, the reaction solution was slowly poured into 300 ml of a 2N aqueous solution of hydrogen chloride at 0 ° C and stirred for 30 minutes. The organic layer was separated, concentrated under reduced pressure, and then subjected to column purification to obtain Compound 4 (10.8 g, 20.2 mmol) in a yield of 71.9%.

MS: [MH ₂ O] &lt; ^{+ &} gt ^; = 515

5) Preparation of Compound 5

Compound (4) (10 g, 18.7 mmol) and glacial acetic acid (200 ml) were added to a 500 ml round bottom flask, and 0.2 ml of concentrated sulfuric acid was slowly added thereto and stirred for 3 hours. After completion of the reaction, the resulting solid was filtered and washed with 500 ml of water. A solution of the filtered solid in 300 ml of chloroform was washed twice with 100 ml of aqueous sodium chloride solution. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Recrystallization from chloroform and ethanol gave Compound 5 (7.5 g, 14.5 mmol) in a yield of 77.5%.

MS: [M + H] &lt; ⁺ &gt; = 516

6) Preparation of the compound of the formula 2-21

To a 250 ml round-bottomed flask was added the compound 5 (5 g, 9.7 mmol), diphenylamine (1.7 g, 10 mmol), sodium tert-butoxide (1.2 g, 12.6 mmol), bis (tri-butylphosphine) palladium g, 0.1 mmol) and 100 ml of xylene, and the mixture was refluxed with stirring for 8 hours. The mixture was cooled to room temperature, 7 g of Celite 545 was added, and the mixture was stirred for 30 minutes. The reaction solution was filtered and concentrated under reduced pressure. The column was purified to obtain the compound of Formula 2-21 (4.1 g, 6.3 mmol) in a yield of 65.1%.

MS: [M + H] &lt; ⁺ &gt; = 649

< Manufacturing example  6> Preparation of the substance represented by the formula 2-22

Phenyl-1-naphthylamine (2.7 g, 12.3 mmol), sodium tert-butoxide (1.5 g, 15.6 mmol), bis (Tri-tert-butylphosphine) palladium (0.05 g, 0.1 mmol) and 100 ml of xylene were placed and refluxed with stirring for 8 hours. The mixture was cooled to room temperature, 6 g of Celite 545 was added, and the mixture was stirred for 30 minutes. The reaction solution was filtered and concentrated under reduced pressure. Column purification afforded the compound of Formula 2-22 (4.7 g, 6.7 mmol) in 58% yield.

MS: [M + H] &lt; ⁺ &gt; = 699

< Manufacturing example  7> Preparation of the substance represented by the formula 2-24

Compound 5 (10 g, 19.4 mmol) and N-phenyl-4-biphenylamine (CAS No. 32228-99-2, 4.9 g, 20 mmol) were added to a 250 ml round- ), Sodium tert-butoxide (2.5 g, 26 mmol), bis (tri-tert-butylphosphine) palladium (0.1 g, 0.2 mmol) and 100 ml of xylene were placed and refluxed with stirring for 8 hours. The mixture was cooled to room temperature, 10 g of Celite 545 was added, and the mixture was stirred for 30 minutes. The reaction solution was filtered and concentrated under reduced pressure. Column purification afforded the compound of Formula 2-24 (8.6 g, 11.9 mmol) in 61.3% yield.

MS: [M + H] &lt; ⁺ &gt; = 725

< Example  1>

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) with a thickness of 1,000 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. As a detergent, a product of Fischer Co. was used. As a distilled water, Millipore Co. Distilled water, which was filtered by the filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, it was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and transferred to a plasma cleaner. Further, the substrate was dry-cleaned using oxygen plasma for 5 minutes, and then the substrate was transferred to a vacuum evaporator.

A hexanitrile hexaazatriphenylene (HAT) compound of the following formula was thermally vacuum deposited on the ITO transparent electrode prepared above to form a thin film. This thin film can improve the interface characteristics between the substrate and the hole injection layer. Next, a hole transporting layer was formed by depositing a film of Formula 1-10 on the thin film to a thickness of 200 ANGSTROM, and a compound of the following Formula HT1 was deposited thereon to a thickness of 100 ANGSTROM to form an electron blocking layer. Subsequently, CBP was doped with Ir (ppy) 3 in an amount of 10 wt% to form a light emitting layer having a thickness of 300 ANGSTROM. A hole blocking layer having a thickness of 50 ANGSTROM was formed thereon, and then an electron transport layer material having the following formula was deposited to a thickness of 300 ANGSTROM to form an electron transport layer. Lithium fluoride (LiF) 12 Å thick and aluminum 2,000 Å thick were sequentially deposited on the electron transport layer to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.3 to 0.8 Å / sec. The deposition rate of lithium fluoride at the cathode was maintained at 0.3 A / sec and aluminum at the deposition rate was maintained at 1.5 to 2.5 A / sec. The degree of vacuum during the deposition was maintained at 1 to 3 × 10 ^-7 .

The fabricated device exhibited an electric field of 5.49 V at a forward current density of 10 mA / cm ² and a spectrum exhibiting a current efficiency of 54.6 cd / A.

< Example  2>

The same device was prepared except that the compound of the formula 1-10 used as the hole transport layer in Example 1 was substituted with the compound of the formula 1-12.

The fabricated device exhibited an electric field of 5.56 V at a forward current density of 10 mA / cm ² and a spectrum exhibiting a current efficiency of 55.8 cd / A.

< Example  3>

The same device was fabricated except that the compound of the formula 1-10 used as the hole transport layer in Example 1 was substituted with the compound of the formula 1-21.

The fabricated device exhibited an electric field of 5.49 V at a forward current density of 10 mA / cm ² and a spectrum exhibiting a current efficiency of 56.0 cd / A.

< Example  4>

The same device was prepared except that the compound of the formula 1-10 used as the hole transport layer in Example 1 was substituted with the compound of the formula 1-23.

The fabricated device exhibited an electric field of 5.60 V at a forward current density of 10 mA / cm ² , and a spectrum exhibiting a current efficiency of 54.2 cd / A was observed.

< Example  5>

The same device was prepared except that the compound of the formula 1-10 used as the hole transport layer in Example 1 was substituted with the compound of the formula 2-21.

The fabricated device exhibited an electric field of 5.44 V at a forward current density of 10 mA / cm ² and a spectrum exhibiting a current efficiency of 53.9 cd / A.

< Example  6>

The same device was prepared except that the compound of the formula 1-10 used as the hole transport layer in Example 1 was substituted with the compound of the formula 2-22.

The fabricated device exhibited an electric field of 5.39 V at a forward current density of 10 mA / cm ² , and a spectrum exhibiting a current efficiency of 55.2 cd / A was observed.

< Example  7>

The same device was fabricated except that the compound of the formula 1-10 used as the hole transport layer in Example 1 was substituted with the compound of the formula 2-24.

The fabricated device exhibited an electric field of 5.50 V at a forward current density of 10 mA / cm ² and a spectrum exhibiting a current efficiency of 55.9 cd / A.

< Comparative Example >

The same device was fabricated except that the compound of the formula 1-10 used as the hole transport layer in Example 1 was replaced with NPB.

The fabricated device exhibited an electric field of 5.51 V at a forward current density of 10 mA / cm ² and a spectrum exhibiting a current efficiency of 53.2 cd / A.

[NPB]

Claims (8)

A compound represented by the following formula (1) or (2):
[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,
R1 and R2 each independently represent an alkyl group having 1 to 10 carbon atoms; Or a phenyl group, or R1 and R2 may combine to form a fluorene ring,
L is a direct bond or a phenylene group,
Ar is hydrogen; A phenyl group; A terphenyl group; Naphthyl group; A carbazolyl group in which the phenyl group is substituted or unsubstituted; A benzocarbazolyl group in which the phenyl group is substituted or unsubstituted; Pyrene; Triphenylene group; Or an arylamine group. The compound of claim 1, wherein the arylamine group is selected from the group consisting of:

The compound according to claim 1, wherein the compound represented by Formula 1 is selected from the group consisting of:

The compound according to claim 1, wherein the compound represented by Formula 2 is selected from the group consisting of:

1. An organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is provided in any one of claims 1 to 4 (1) or (2) as described above. 6. The organic electroluminescent device according to claim 5, wherein the organic material layer comprises at least one of an electron injection layer and an electron transport layer, and at least one of the electron injection layer and the electron transport layer comprises the compound of the above formula device. [6] The organic light emitting device of claim 5, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the compound of Formula 1 or 2. [ 6. The organic electroluminescent device according to claim 5, wherein the organic material layer includes at least one of a hole injecting layer, a hole transporting layer, and a layer simultaneously injecting holes and transporting holes, wherein one of the layers contains the compound of the above formula Wherein the organic light-emitting layer is a transparent conductive layer.

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