KR20120083241A - New hetero-cyclic compound and organic light emitting device using the same - Google Patents

Abstract

PURPOSE: A heterocyclic compound and an organic light-emitting device using the same are provided to lower driving voltage and enhance luminous efficiencies and lifetime properties. CONSTITUTION: A heterocyclic compound is represented by chemical formula 1. Here, x is -(A)m-(B)n, and Y indicates -(B')p. Ar is substituted or non-substituted C6-40 arylene or substituted or non-substituted divalent heterocycle. A indicates substituted or non-substituted arylene. B and B' respectively indicate substituted or non-substituted arylamine or substituted or non-substituted hetero ring. m and p are integers of 1-10. n is an integer of 0-10. R1-R5 are respectively selected from hydrogen, deuterium, substituted or non-substituted alkyl group, substituted or non-substituted alkoxy group, substituted or non-substited alkenyl, substituted or non-substituted aryl, substituted silicone, substituted boron, substituted or non-substituted hetero ring, and substituted amino, nitrile, nitro, halogen, amide and ester.

Description

New heterocyclic compound and organic light emitting device using the same {NEW HETERO-CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME}

The present invention relates to a novel compound and an organic light emitting device using the same. In particular, the present invention relates to novel compounds that can greatly improve the lifetime, efficiency, electrochemical stability and thermal stability of organic light emitting devices, and to organic light emitting devices in which such compounds are contained in an organic compound layer.

The organic light emitting phenomenon is an example of converting an electric current into visible light by an internal process of a specific organic molecule. The principle of the organic light emitting phenomenon is as follows. When the organic layer is placed between the anode and the cathode, a voltage is applied between the two electrodes to inject electrons and holes from the cathode and the anode into the organic layer, respectively. The electrons and holes injected into the organic layer recombine to form excitons, which then fall back to the ground to shine. An organic light emitting device using this principle may generally be composed of an organic material layer including a cathode, an anode, and an organic material layer disposed therebetween, such as a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.

Most of the materials used in the organic light emitting device are pure organic materials or complex compounds in which organic materials and metals are complexed, and depending on the purpose, hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. It can be divided into. Here, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material which is easily oxidized and has an electrochemically stable state during oxidation, is mainly used. On the other hand, as an electron injection material or an electron transport material, organic materials having n-type properties, that is, organic materials that are easily reduced and have an electrochemically stable state at the time of reduction are mainly used. As the light emitting layer material, a material having a p-type property and an n-type property at the same time, that is, a material having a stable form in both oxidation and reduction states, and a material having high luminous efficiency that converts it to light when excitons are formed desirable.

In addition to the above, it is preferable that the material used in the organic light emitting device additionally have 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 diode. NPB, which is mainly used as a hole transport layer material, has a glass transition temperature of less than 100 ^° C., and therefore, it is difficult to use in an organic light emitting device requiring a high current.

Second, in order to obtain a high-efficiency organic light emitting device capable of driving a low voltage, holes or electrons injected into the organic light emitting device should be smoothly transferred to the light emitting layer, and the injected holes and electrons should not escape out of the light emitting layer. For this purpose, the material used for the organic light emitting device should have an appropriate band gap and HOMO or LUMO energy level. PEDOT: PSS, which is currently used as a hole transport material in organic light emitting devices manufactured by the solution coating method, has a low LUMO energy level compared to the LUMO energy level of the organic material used as the light emitting layer material. There is difficulty.

In addition, the material used in the organic light emitting device should be excellent in chemical stability, charge mobility, interface characteristics between the electrode and the adjacent layer. That is, the material used in the organic light emitting device should be less deformation of the material by moisture or oxygen. In addition, by having an appropriate hole or electron mobility it should be able to maximize the exciton formation by balancing the density of holes and electrons in the light emitting layer of the organic light emitting device. In addition, for the stability of the device should be able to improve the interface with the electrode containing a metal or metal oxide. Therefore, there is a demand in the art for the development of organic materials having the above requirements.

Accordingly, the present inventors can satisfy the conditions required for the materials that can be used in the organic light emitting device, such as appropriate energy level, electrochemical stability and thermal stability, and the chemistry that can play various roles required in the organic light emitting device depending on the substituent. An object of the present invention is to provide a heterocyclic compound having a structure and an organic light emitting device including the same.

The present invention provides a compound of Formula 1 below.

In Formula 1,

X _is- (A) _m- (B) _n ,

Y is-(B ') _p ,

Ar is an arylene group having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, alkyl, alkoxy and amino groups; Or a divalent heterocyclic group unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, alkyl, alkoxy and amino groups,

A is a halogen group, an alkyl group, an alkenyl group alkoxy group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, a substituted or unsubstituted Arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group,

B and B 'are each independently a halogen group, an alkyl group, an alkenyl group alkoxy group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalke An arylamine group unsubstituted or substituted with one or more substituents selected from the group consisting of a silyl group, a substituted or unsubstituted heterocyclic group, a nitrile group, and an acetylene group; Or a halogen group, an alkyl group, an alkenyl group alkoxy group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, a substituted or unsubstituted Is a heterocyclic group which is unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group and contains O, N or S as a hetero atom,

m is an integer from 1 to 10, n is an integer from 0 to 10, p is an integer from 1 to 10,

R1 to R5 are each independently hydrogen; heavy hydrogen; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted heterocyclic groups, nitrile groups and acetylene groups An alkyl group unsubstituted or substituted with one or more substituents selected from the group consisting of; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted heterocyclic groups, nitrile groups and acetylene groups An alkoxy group unsubstituted or substituted with one or more substituents selected from the group consisting of; A halogen group, an alkyl group, an alkenyl group alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted aryl alkenyl group, a substituted or unsubstituted heterocyclic group, a nitrile group and an acetylene group Alkenyl groups unsubstituted or substituted with one or more substituents selected from the group; A halogen group, an alkyl group, an alkenyl group alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted aryl alkenyl group, a substituted or unsubstituted heterocyclic group, a nitrile group and an acetylene group An aryl group unsubstituted or substituted with one or more substituents selected from the group; A silicone group substituted with a substituted or unsubstituted aryl group; A boron group substituted with a substituted or unsubstituted aryl group; Halogen group, alkyl group, alkenyl group alkoxy group, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted arylalkenyl group, substituted or unsubstituted hetero A heterocyclic group which is unsubstituted or substituted with one or more substituents selected from the group consisting of a cyclic group, a nitrile group and an acetylene group and contains O, N or S as a hetero atom; An amino group substituted with one or more substituents selected from the group consisting of an alkyl group, an alkenyl group substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group; Nitrile group; A nitro group; Halogen group; Amide group; And it is selected from the group consisting of ester groups.

In addition, the present invention is an organic light emitting device comprising a first electrode, at least one organic material layer and a second electrode in a stacked form, wherein at least one of the organic material layer comprises a compound of Formula 1 To provide.

The compound of the present invention can be used as an organic layer material, especially a hole injection material and / or a hole transport material in the organic light emitting device, when the compound is used in the organic light emitting device to lower the driving voltage of the device, improve the light efficiency, the compound Thermal stability of the device can improve the life characteristics of the device.

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG.
FIG. 2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is.

When explaining the substituent of Formula 1 in detail.

In Chemical Formula 1, the alkyl group, the alkoxy group, and the alkenyl group are not particularly limited in carbon number, but preferably have 1 to 20 carbon atoms, and may be linear or branched.

The length of the alkyl group contained in the compound does not affect the conjugated length of the compound, but may incidentally affect the method of applying the compound to the organic light emitting device, such as vacuum deposition or solution coating.

In the formula (1), the aryl group preferably has 6 to 40 carbon atoms, and more preferably 6 to 20 carbon atoms. Specific examples of the aryl group include monocyclic aromatics such as phenyl group, biphenyl group, terphenyl group, stilbene and polycyclic aromatic rings such as naphthyl group, anthracenyl group, phenanthrene group, pyrenyl group, and perrylenyl group. It is not limited only to these

In the formula (1), the heterocyclic group is preferably 2 to 40 carbon atoms, more preferably 3 to 20 containing S, O or N. Specific examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, pyrazine group, quinolinyl group, isoquinoline group, ah Although there are creedyl groups and the like, they are not limited thereto.

In Chemical Formula 1, an amine group substituted with one or more aryl groups exemplified above may be used as the arylamine group.

In Formula 1, a divalent arylene group and a divalent heterocyclic group may be used divalent groups having the same structure as the structures exemplified above as the monovalent aryl group and heterocyclic group.

A of the formula (1) is preferably an arylene group, preferably a monocyclic aromatic and naphthylene group such as phenylene group, biphenylene group, terphenylene group, stilbenylene group, anthracenylene group, phenathrenylene group, pyrenylene group, and Although there exist polycyclic aromatic rings, such as a leilenylene group, it is not limited only to these.

When B or B 'of the general formula (1) is a heterocyclic group, thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, pyrazine group, qui Nolinyl group, isoquinoline group, acridil group, carbazole group and the like, but is not limited thereto.

In addition, when B or B 'of the general formula (1) is an arylamine group, there are preferably the following groups, but is not limited thereto.

In Formula 1, Ar is more preferably a phenylene group.

In Formula 1, R1 and R2 are phenyl groups, and R3 to R5 are preferably hydrogen.

In the present specification, 'substituted or unsubstituted' means a halogen group, an alkyl group, an alkoxy group, an alkenyl group, an alkoxy group, an arylamine group, an aryl group, an arylalkyl group, an aryl alkenyl group, a heterocyclic group, a nitrile group, a nitro group, It means unsubstituted or substituted with one or more substituents selected from the group consisting of an amino group and an acetylene group. The substituents may be further substituted as necessary.

The compound of Formula 1 is preferably a compound represented by the following Formula 2 to Formula 8, but is not limited thereto.

The compound of Chemical Formula 1 is a core structure represented by Chemical Formula 1, that is, a structure in which arylene or a divalent heterocyclic group is substituted as a substituent Ar at a carbon position between R3 and R4 of indole as a core structure. Hydrogen as substituents R1 to R5; heavy hydrogen; Substituted or unsubstituted aliphatic hydrocarbons; Substituted or unsubstituted aromatic hydrocarbons; A silicone group substituted with a substituted or unsubstituted aryl group; A boron group substituted with a substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; Amino group; Nitrile group; A nitro group; Halogen group; Amide group; And by introducing a variety of substituents, such as ester groups may have properties suitable for use as an organic material layer used in the organic light emitting device.

In general, the conjugation length and energy bandgap of a compound are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy bandgap. As described above, since the core of the compound of Formula 1 contains limited conjugation, it has a large energy band gap.

In the present invention, a compound having various energy band gaps may be synthesized by introducing various substituents into R 1 to R 5, X, and Y positions of Formula 1 having a large energy band gap. In general, it is easy to control the energy band gap by introducing a substituent into the core structure having a large energy band gap, but when the core structure has a small energy band gap, it is difficult to largely control the energy band gap by introducing a substituent. In addition, in the present invention, the HOMO and LUMO energy levels of the compound may be adjusted by introducing various substituents at the R 1 to R 5, X, and Y positions of Formula 1 having a large energy band gap.

Moreover, the compound which has the intrinsic characteristic of the introduced substituent can be synthesize | combined by introducing various substituents into the core structure represented by said Formula (1). For example, by incorporating a substituent mainly used in the hole injection layer material, the hole transporting material, the light emitting layer material, and the electron transporting layer material used in the manufacture of the organic light emitting device into the core structure, a material satisfying the conditions required for each organic material layer is synthesized. can do.

In particular, since the compound of Formula 1 may include an aryl amine structure in the core structure, it may have an appropriate energy level as a hole injection and / or hole transport material in the organic light emitting device. In the present invention, a device having a low driving voltage and high light efficiency may be realized by selecting a compound having an appropriate energy level among the compounds of Formula 1 and using the compound in an organic light emitting device.

In addition, by introducing a variety of substituents in the core structure it is possible to finely control the energy band gap, on the other hand to improve the properties at the interface between the organic material and to vary the use of the material.

In particular, it is possible to finely control the HOMO, LUMO energy level and energy band gap by controlling the number of amines containing substituents B and B ', while improving the properties at the interface between organic materials and various uses of the material I can let you

On the other hand, the compound of Formula 1 has a high glass transition temperature (Tg) is excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.

In addition, the compound of Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of an organic electronic device. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spray method, roll coating and the like, but is not limited thereto.

Specific methods for preparing the compound of formula 1 according to the present invention are described in the Examples, and those skilled in the art can prepare the compounds according to the present invention based on the examples.

In addition, the present invention is an organic light emitting device comprising a first electrode, at least one organic layer and a second electrode in a stacked form, wherein at least one layer of the organic layer comprises a compound of formula (1) To provide.

The organic electronic device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electronic device, except that at least one organic material layer is formed using the above-described compounds.

Hereinafter, an organic light emitting diode will be described.

The compounds of the present invention described above may serve as a hole injection, hole transport, electron injection, electron transport, or a light emitting material in the organic light emitting device, and when the compounds of the present invention are used as a light emitting material, it alone serves as a light emitting material. In addition, it may serve as a light emitting host with an appropriate light emitting dopant or a light emitting dopant with a suitable light emitting host. In particular, the compounds of the present invention are preferably used as a hole transport material in the organic light emitting device.

In addition, in the organic light emitting device including the first electrode, at least one organic layer, and the second electrode of the present invention in a stacked form, the organic layer includes a hole transport layer, the hole transport layer comprises the compound of Formula 1 can do.

In addition, in an organic light emitting device including a first electrode, at least one organic layer, and a second electrode of the present invention in a stacked form, the organic layer includes a hole injection layer, and the hole injection layer is a compound of Formula 1 It may include.

In addition, in an organic light emitting device including a first electrode, at least one organic layer, and a second electrode of the present invention in a stacked form, the organic layer includes a layer for simultaneously injecting holes and transporting holes. At the same time, the hole transport layer may include the compound of Formula 1.

In addition, in the organic light emitting device including the first electrode, one or more organic material layers and the second electrode of the present invention in a stacked form, the organic material layer includes an electron injection or electron transport layer, the electron injection or electron transport layer is It may include a compound of formula (1).

In addition, in the organic light emitting device including the first electrode, one or more organic material layers, and the second electrode of the present invention in a stacked form, the organic material layer may include a light emitting layer, and the light emitting layer may include the compound of Formula 1 In one exemplary embodiment of the present invention, the organic light emitting diode may have a structure including a first electrode, a second electrode, and an organic material layer disposed therebetween. Except that it is used in at least one layer of the organic material of the can be prepared using a conventional method and material for manufacturing an organic light emitting device. The structure of the organic light emitting device according to the present invention is illustrated in FIGS. 1 and 2. FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG. FIG. 2 shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is. However, the scope of the present invention is not limited to the structure shown in FIG. 1 or FIG.

For example, the organic light emitting device according to the present invention is a metal oxide or a metal oxide or alloy thereof having a conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation It can be prepared by depositing an anode to form an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to the above 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 (see International Patent Application Publication No. 2003/012890).

The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.

As the cathode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode 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-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

It is preferable that the negative electrode 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; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably 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 porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

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

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

As the electron transport material, a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including 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 top emission type, a bottom emission type or a double-sided emission type according to the material used.

The preparation method of the compound of Formula 1 and the preparation of the organic light emitting device using the same will be described in detail in the following Preparation Examples and Examples. However, the following Preparation Examples and Examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

The synthesis method of the organic compound represented by Chemical Formula 1 and the manufacture of the organic electroluminescent device using the same will be described in more detail by the following Examples and Comparative Examples. However, these examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1 Synthesis of Compound of Formula 1-A

[Formula 1-A]

Benzyl phenyl ketone (36.6 g, 186 mmol), 4-bromo hydrazine hydrochloride (50.0 g, 223 mmol) and 4M hydrochloric acid (solution diluted with 1,4-dioxane, 14 mL, 0.3 equiv) were suspended in 300 mL of ethanol. . The resulting mixture was stirred for about 18 hours, refluxed and cooled to room temperature. The mixture was diluted with water (200 mL) and extracted with dichloromethane (3 x 100 mL). The organic extract was dried over magnesium sulfate and distilled under reduced pressure. The product was recrystallized with hexane to give the compound of formula 1-A (61.8 g, 95%).

MS: [M] < + > 348

Preparation Example 2 Synthesis of Compound of Formula 1-B

[Formula 1-B]

4-Bromo-iodinebenzene (3.4 g, 12 mmol) and bisdiphenylamine (3.86 g, 12 mmol) were dissolved in 50 ml of N, N-dimethylacetamide and copper chloride (CuCl) (164 mg, 1.2 mmol), 2,2'-bipyridyl (187 mg, 1.2 mmol) was added and then refluxed under nitrogen stream for 12 hours. After cooling to room temperature, distilled water (200 mL) was added to the reaction solution to terminate the reaction, and extracted with chloroform (3 × 100 mL). The organic layer was dried over magnesium sulfate and distilled under reduced pressure. The product was recrystallized through ethyl ether and hexane to prepare the formula 1-B (3.7g, 65%).

MS: [M] + = 476

Preparation Example 3 Synthesis of Compound of Formula 1-C

[Formula 1-C]

4-Bromo-iodinebenzene (3.4 g, 12 mmol) and bisdiphenylamine (3.86 g, 12 mmol) were dissolved in 50 ml of N, N-dimethylacetamide and copper chloride (CuCl) (164 mg, 1.2 mmol), 2,2'-bipyridyl (187 mg, 1.2 mmol) was added and then refluxed under nitrogen stream for 12 hours. After cooling to room temperature, distilled water (200 mL) was added to the reaction solution to terminate the reaction, and extracted with chloroform (3 × 100 mL). The organic layer was dried over magnesium sulfate and distilled under reduced pressure. The product was recrystallized through ethyl ether and hexane to prepare the formula 1-B (3.7g, 65%).

MS: [M] + = 476

Preparation Example 4 Synthesis of Compound of Formula 1-D

[Formula 1-D]

Except for using naphthyl phenyl amine instead of bisdiphenylamine in the preparation method of the compound of Formula 1-B of Preparation Example 2, the same method as the preparation method of the compound of Formula 1-B Was prepared.

MS: [M] < + > 375

Preparation Example 5 Synthesis of Compound of Formula 1-E

[Formula 1-E]

Except for using the compound of Formula 1-D instead of the compound of Formula 1-B in the method for preparing a compound of Formula 1-C of Preparation Example 3 in the same manner as the preparation method of the compound of Formula 1-C The compound of formula 1-E was prepared.

MS: [M] + = 339

Preparation Example 6 Synthesis of Compound of Formula 1-F

[Formula 1-F]

Except that 3-bromo-N-phenyl carbazole was used instead of the compound of Formula 1-B in the method of preparing the compound of Formula 1-C of Preparation Example 3, and In the same manner to prepare a compound of Formula 1-F.

MS: [M] < + > = 287

Preparation Example 7 Synthesis of Compound of Formula 1-G

[Formula 1-G]

After completely dissolving the compound of Formula 1-A (5 g, 14.3 mmol) and the compound of Formula 1-C (6.3 g, 14.3 mmol) in tetrahydrofuran (50 mL), 2M aqueous potassium carbonate solution (20 mL) was added. Tetrakistriphenylphosphinopalladium (495 mg, 3 mol%) was added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and tetrahydrofuran: hexane = 1: 10 to prepare a compound of Chemical Formula 1-G (6.64 g, 70%).

MS: [M] ⁺ = 664

Preparation Example 8 Synthesis of Compound of Formula 1-H

[Formula 1-H]

Except for using the compound of Formula 1-E instead of the compound of Formula 1-C in the method for preparing a compound of Formula 1-G of Preparation Example 7 in the same manner as the method for producing a compound of Formula 1-C The compound of formula 1-H was prepared.

MS: [M] ⁺ = 562

Preparation Example 9 Synthesis of Compound of Formula 1-I

                                                   [Formula 1-I]

After completely dissolving the compound of Formula 1-A (5 g, 14.3 mmol) and the amine compound (7.23 g, 14.3 mmol) in tetrahydrofuran (50 mL), 2M aqueous potassium carbonate solution (20 mL) was added thereto and tetrakistriphenyl Phosphinopalladium (495 mg, 3 mol%) was added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and tetrahydrofuran: hexane = 1: 10 to prepare a compound of Chemical Formula 1-I (6.77 g, 65%).

MS: [M] ⁺ = 729

Example 1 Preparation of a Compound Represented by Formula 2

[Formula 2]

The compound of formula 1-G (2 g, 3 mmol), iodine benzene (1.22 g, 6 mmol) was dissolved in 20 mL of xylene, sodium-tertiary-butoxide (578 mg, 6 mmol), Pd [P ( t-Bu) ₃ ] ₂ (46 mg, 3 mol%) was added and then refluxed under nitrogen stream for 5 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. Normal hexane / tetrahydrofuran = 10/1 to obtain a compound of formula 2 (1.2g, 54%) by column separation.

MS: [M] ⁺ = 740

Example 2 Synthesis of Compound of Formula 3

(3)

The compound of Chemical Formula 3 was prepared by the same method as the method of preparing the compound of Chemical Formula 2, except that 4-bromo biphenyl compound was used instead of the iodine benzene compound in the method of preparing Chemical Formula 2 of Example 1. It was.

MS: [M] ⁺ = 817

Example 3 Synthesis of Compound of Formula 4

[Formula 4]

Except for using the 2- (3-bromophenyl) -5-phenylthiophene compound instead of the iodine benzene compound in the preparation method of the compound of formula 2 of Example 1, The compound of formula 4 was prepared by the method.

MS: [M] ⁺ = 899

Example 4 Synthesis of Compound of Formula 5

[Chemical Formula 5]

Except for using the 2- (4-bromophenyl) -5-phenylthiophene compound instead of the iodine benzene compound in the method for preparing a compound of Formula 2 of Example 1, The compound of Formula 5 was prepared by the method.

MS: [M] ⁺ = 899

Example 5 Preparation of a Compound Represented by Chemical Formula 6

[Formula 6]

The compound of Formula 1-H (1.69 g, 3 mmol), iodine benzene (1.22 g, 6 mmol) was dissolved in 20 mL of xylene, sodium-tertiary-butoxide (578 mg, 6 mmol), Pd [P (t-Bu) ₃ ] ₂ (46 mg, 3 mol%) was added and then refluxed under nitrogen stream for 5 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. Normal hexane / tetrahydrofuran = 10/1 to obtain a compound of Formula 6 (1.15 g, 60%) by column separation.

MS: [M] ⁺ = 638

Example 6 Synthesis of Compound of Formula 7

[Formula 7]

The compound of Chemical Formula 7 was prepared by the same method as the method of preparing the compound of Chemical Formula 6, except that 4-bromo biphenyl compound was used instead of the iodine benzene compound in the method of preparing Chemical Formula 6 of Example 5. It was.

MS: [M] ⁺ = 714

Example 7 Synthesis of Compound of Formula 8

[Formula 8]

The compound of Chemical Formula 8 in the same manner as the method for preparing the compound of Chemical Formula 2, except that the compound of Chemical Formula 1-I was used instead of the compound of Chemical Formula 1-G in the method of preparing the compound of Chemical Formula 2 of Example 1 Was prepared.

MS: [M] ⁺ = 806

<Experimental Example 1>

A glass substrate (corning 7059 glass) coated with a thin film of ITO (Indium Tin Oxide) at a thickness of 1000 Å was placed in distilled water in which a dispersant was dissolved, and washed with ultrasonic waves. Fischer Co. products were used for the detergent, and Millipore Co. Secondly filtered distilled water was used as a filter of the product. After washing ITO for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, the ultrasonic washing in the order of isopropyl alcohol, acetone, methanol solvent and dried.

The hexanitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. After vacuum depositing Chemical Formula 2 (400 kPa) synthesized in Preparation Example, which is a material for transporting holes thereon, the host H1 and the dopant D1 compound were vacuum deposited to a thickness of (300 kPa) as a light emitting layer. The E1 compound was then thermally vacuum deposited (300 kPa) sequentially into the electron injection and transport layer. 12 음극 thick lithium fluoride (LiF) and 2000 Å thick aluminum were sequentially deposited on the electron transport layer to form a cathode, thereby manufacturing an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at the deposition rate of 3-7 Å / sec.

[Hexanitrile hexaazatriphenylgiene] [NPB]

      [H1] [D1] [E1]

<Experimental Example 2>

Except for using the formula 3 instead of the formula 2 synthesized in Preparation Example 1 as the hole transport layer in the experiment was the same.

<Experimental Example 3>

Except for using the formula 4 instead of the formula 2 synthesized in Preparation Example 1 as the hole transport layer in the experiment was the same.

<Experimental Example 4>

Except for using the formula 5 instead of the formula 2 synthesized in Preparation Example 1 as the hole transport layer in the experiment was the same.

<Experimental Example 5>

Except for using the formula 6 instead of the formula 2 synthesized in Preparation Example 1 as the hole transport layer in the experiment was the same.

<Experimental Example 6>

Except for using the formula 7 instead of the formula 2 synthesized in Preparation Example 1 as the hole transport layer in the experiment was the same.

Experimental Example 7

Except for using the formula 8 instead of the formula 2 synthesized in Preparation Example 1 as the hole transport layer in the experiment was the same.

Comparative Example

Except for using NPB instead of the formula 2 synthesized in Preparation Example 1 as the hole transport layer in the experiment was the same.

Table 1 shows the results of experimenting with the organic light emitting device manufactured by using each compound as the hole transporting material as in the above embodiment.

The compound derivative of the formula according to the present invention may serve as hole injection, hole transport, electron injection and transport, or a light emitting material in an organic electric device including an organic light emitting device, and the device according to the present invention has efficiency, driving voltage, and stability. Excellent properties in terms of appearance.

1: substrate
2: anode
3: light emitting layer
4: cathode
5: hole injection layer
6: hole transport layer
7: light emitting layer
8: electron transport layer

Claims (14)

A compound of formula
[Formula 1]

In Chemical Formula 1,
X _is- (A) _m- (B) _n ,
Y is-(B ') _p ,
Ar is an arylene group having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, alkyl, alkoxy and amino groups; Or a divalent heterocyclic group unsubstituted or substituted with one or more substituents selected from the group consisting of nitro, nitrile, halogen, alkyl, alkoxy and amino groups,
A is a halogen group, an alkyl group, an alkenyl group alkoxy group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, a substituted or unsubstituted Arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group,
B and B 'are each independently a halogen group, an alkyl group, an alkenyl group alkoxy group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalke An arylamine group unsubstituted or substituted with one or more substituents selected from the group consisting of a silyl group, a substituted or unsubstituted heterocyclic group, a nitrile group, and an acetylene group; Or a halogen group, an alkyl group, an alkenyl group alkoxy group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, a substituted or unsubstituted Is a heterocyclic group which is unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group and contains O, N or S as a hetero atom,
m is an integer from 1 to 10, n is an integer from 0 to 10, p is an integer from 1 to 10,
R1 to R5 are each independently hydrogen; heavy hydrogen; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted heterocyclic groups, nitrile groups and acetylene groups An alkyl group unsubstituted or substituted with one or more substituents selected from the group consisting of; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted heterocyclic groups, nitrile groups and acetylene groups An alkoxy group unsubstituted or substituted with one or more substituents selected from the group consisting of; A halogen group, an alkyl group, an alkenyl group alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted aryl alkenyl group, a substituted or unsubstituted heterocyclic group, a nitrile group and an acetylene group Alkenyl groups unsubstituted or substituted with one or more substituents selected from the group; A halogen group, an alkyl group, an alkenyl group alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted aryl alkenyl group, a substituted or unsubstituted heterocyclic group, a nitrile group and an acetylene group An aryl group unsubstituted or substituted with one or more substituents selected from the group; A silicone group substituted with a substituted or unsubstituted aryl group; A boron group substituted with a substituted or unsubstituted aryl group; Halogen group, alkyl group, alkenyl group alkoxy group, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted arylalkenyl group, substituted or unsubstituted hetero A heterocyclic group which is unsubstituted or substituted with one or more substituents selected from the group consisting of a cyclic group, a nitrile group and an acetylene group and contains O, N or S as a hetero atom; An amino group substituted with one or more substituents selected from the group consisting of an alkyl group, an alkenyl group substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group; Nitrile group; A nitro group; A halogen group; Amide group; And it is selected from the group consisting of ester groups. The method according to claim 1, A of Formula 1 in the group consisting of phenylene group, biphenylene group, terphenylene group, stilbenylene group, naphthylene group, anthracenylene group, phenanthrenylene group, pyrenylene group and peryleneylene group The compound selected. The thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, pyrazine when the B or B 'of Formula 1 is a heterocyclic group A compound selected from the group consisting of a group, a quinolinyl group, an isoquinoline group, an acridyl group and a carbazole group. The compound according to claim 1, wherein when B or B ′ of Formula 1 is an arylamine, the compound is one of the following groups:

The compound of claim 1, wherein B or B ′ of Formula 1 is phenylene. The compound of claim 1, wherein Ar in Formula 1 is a phenylene group. The compound of claim 1, wherein R 1 and R 2 in Formula 1 are phenyl groups, and R 3 to R 5 are hydrogen. The compound of Formula 1 according to claim 1, wherein the compound of Formula 1 is any one of Formulas 2 to 8.
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In an organic light emitting device comprising a first electrode, at least one organic layer and the second electrode in a stacked form, at least one of the organic layer comprises a compound of formula 1 of any one of claims 1 to 8. The organic light emitting device. The organic light emitting device of claim 9, wherein the organic material layer includes a hole transport layer, and the hole transport layer includes the compound represented by Chemical Formula 1. The organic light emitting device of claim 9, wherein the organic material layer includes a hole injection layer, and the hole injection layer includes the compound of Chemical Formula 1. The organic light emitting device of claim 9, wherein the organic material layer includes a layer for simultaneously injecting holes and transporting holes, and the layer includes the compound of Formula 1. The organic light emitting device of claim 9, wherein the organic material layer includes an electron injection or electron transport layer, and the electron injection or electron transport layer includes the compound of Formula 1. The organic light emitting device of claim 9, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the compound of Chemical Formula 1.

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