KR101460361B1 - New imidazole derivatives and organic electronic device using the same - Google Patents

Abstract

The present invention provides a novel imidazole derivative and an organic electronic device using the same. The organic electronic device according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage and lifetime.

Imidazole, anthracene, pyrene, naphthalene, organic electronic devices, organic light emitting devices

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel imidazole derivative and an organic electronic device using the same.

The present invention relates to a novel imidazole derivative and an organic electronic device using the same.

In the present specification, an organic electronic device is an electronic device using an organic semiconductor material, and requires the exchange of holes and / or electrons between the electrode and the organic semiconductor material. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Is an electronic device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor material layer that interfaces with the electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of the organic electronic device include an organic light emitting device, an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor. These devices include an electron / hole injecting material, an electron / hole extracting material, Materials or luminescent materials. Hereinafter, the organic light emitting device will be described in detail, but in the organic electronic devices, the electron / hole injecting material, the electron / hole extracting material, the electron / hole transporting material, or the light emitting material all have a similar principle.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic layer between them. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected into the anode, electrons are injected into the organic layer, electrons are injected into the organic layer, excitons are formed when injected holes and electrons meet, When it falls to a state, it becomes a light. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material can be classified into blue, green and red light emitting materials and yellow and orange light emitting materials necessary for realizing better natural color depending on the luminescent color. Further, a host / dopant system can be used as a light emitting material in order to increase the color purity and increase the luminous efficiency through energy transfer. The principle is that when a small amount of dopant having a smaller energy band gap and a higher luminous efficiency than a host mainly constituting the light emitting layer is mixed with the light emitting layer in a small amount, the excitons generated in the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to sufficiently exhibit the excellent characteristics of the organic light emitting device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material is supported by a stable and efficient material Should be preceded.

Among them, organometallic complexes having a relatively high stability to electrons and an electron transfer rate as organic monomolecular materials are preferable as electron transporting materials. Among them, Alq ₃ having excellent stability and high electron affinity has been reported to be the most excellent, but when used in a blue light emitting device, there is a problem that the color purity drops due to exciton diffusion. Flavon derivatives of sanyo or germanium and silicon clopetadiene derivatives of Chisso are known (Japanese Patent Laid-Open Publication No. 1998-017860, Japanese Laid-Open Patent Publication No. 1999-087067 ).

As the organic monomolecular substance, a PBD (2-biphenyl-4-yl-5- (4-t-butylphenyl) -1,3,4-oxadiazole) derivative bonded to a Spiro compound and a hole blocking ability (2,2 ', 2 "- (benzene-1,3,5-triyl) -tris (1-phenyl-1H-benzimidazole) which has both excellent electron transporting ability , 1998, 1136 & Tao et al, Appl. Phys. Lett., 77, 2000, 1575), and benzoimidazole derivatives disclosed in LG Chem are widely known for their excellent durability.

Organic light emitting devices using the organic single molecular material as an electron transporting layer have short lifetime, low storage durability and low reliability. These problems are caused by physical or chemical changes of organic materials, photochemical or electrochemical changes of organic materials, oxidation and peeling of the cathodes, and durability.

Therefore, organic light emitting devices using a method of obtaining arbitrary luminescent color by changing the structure of an organic monomolecular material used in an organic luminescent device or obtaining various high efficiencies by a host dopant system have been proposed, Characteristics, life span and durability.

For example, Korean Patent Publication No. 2003-0067773 discloses a compound having a benzoimidazole ring and an anthracene skeleton.

However, there is a continuing need for the development of new materials having improved luminescence brightness, luminescence efficiency, and life span as compared with organic EL devices using such compounds.

The present inventors have found imidazole derivatives having a novel structure. In addition, when the organic imide layer of the organic electronic device is formed using the new imidazole derivative, it has been found that the efficiency of the device can be increased, the driving voltage can be lowered, the lifetime can be increased, and the stability can be increased.

Accordingly, it is an object of the present invention to provide a novel imidazole derivative and an organic electronic device using the same.

The present invention provides novel imidazole derivatives.

The present invention provides an organic electronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers comprises the novel imidazole derivative Wherein the organic electronic device is an organic electronic device.

The novel imidazole derivative according to the present invention can be used as a material for an organic material layer of an organic electronic device including an organic light emitting device, and an organic electronic device including the organic light emitting device using the same can be used for an organic semiconductor device, And the like.

The imidazole derivatives according to the present invention include compounds represented by the following Formula 1:

In Formula 1,

And R1 to compound at least one of R4 is represented by the formula (2), and the remainder are the same as or different from each other, each independently represent a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ C ₁ to C ₄₀ alkoxy groups, C ₃ to C ₄₀ cycloalkyl groups, C ₂ to C ₄₀ heterocycloalkyl groups, C ₆ to C ₄₀ aryl groups and C ₅ to C ₄₀ heteroaryl groups, A C ₆ -C ₄₀ aryl group substituted or unsubstituted with one or more groups selected from the group consisting of A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ cycloalkyl group of C ₄₀ of, C ₂ ~ C ₄₀ a heterocycloalkyl group, a heteroaryl group of C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C ₄₀ by at least one group selected from the heteroaryl group consisting of a substituted or unsubstituted C ₅ ~ C ₄₀ of; And a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ is selected from the group of one or more lines selected from a heteroaryl group the group consisting of C ₄₀ aryl group and a C ₅ ~ C ₄₀ group consisting of substituted or unsubstituted amino group of,

In Formula 2,

L ₁ is a direct bond; An alkoxy group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ of, C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C ₄₀ heteroaryl group with one or more groups selected from the group consisting of A C ₂ to C ₄₀ alkenylene group substituted or unsubstituted by a group; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ cycloalkyl group of C ₄₀ of, C ₂ ~ C ₄₀ a heterocycloalkyl group of the aryl group, C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C over one selected from the heteroaryl group consisting of ₄₀ group a substituted or unsubstituted C ₆ ~ C _40; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ cycloalkyl group of C ₄₀ of, C ₂ ~ C ₄₀ a heterocycloalkyl group, a heteroaryl group of C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C ₄₀ by at least one group selected from the heteroaryl group consisting of a substituted or unsubstituted C ₅ ~ C ₄₀ of; Heterocycloalkyl group of C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₂ ~ C ₄₀ of, C ₆ ~ C ₄₀ An aryl group of C ₆ to C ₄₀ , and a heteroaryl group of C ₅ to C ₄₀ ; or a C ₆ to C ₄₀ arylamine group which is unsubstituted or substituted with at least one group selected from the group consisting of C ₅ to C ₄₀ heteroaryl groups; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ cycloalkyl group of C ₄₀ of, C ₂ ~ C ₄₀ A C ₂₅ to C ₄₀ spiro group substituted or unsubstituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ to C ₄₀ aryl group and a C ₅ to C ₄₀ heteroaryl group; And a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C ₄₀ open is selected from the group consisting of a spiro of the heteroaryl group substituted or unsubstituted with one or more groups selected from the group consisting of C ₂₅ ~ C ₄₀ of ,

Ar ₁ is hydrogen; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ cycloalkyl group of C ₄₀ of, C ₂ ~ C ₄₀ A C ₁ to C ₄₀ alkyl group which is unsubstituted or substituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ to C ₄₀ aryl group and a C ₅ to C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ cycloalkyl group of C ₄₀ of, C ₂ ~ C ₄₀ a heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C ₄₀ cycloalkyl group with one or more groups selected from the heteroaryl group consisting of a substituted or unsubstituted C ₃ ~ C ₄₀ of; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ cycloalkyl group of C ₄₀ of, C ₂ ~ C ₄₀ A C ₂ to C ₄₀ alkenyl group which is unsubstituted or substituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ to C ₄₀ aryl group and a C ₅ to C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ cycloalkyl group of C ₄₀ of, C ₂ ~ C ₄₀ A C ₁ to C ₄₀ alkoxy group substituted or unsubstituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ to C ₄₀ aryl group and a C ₅ to C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ cycloalkyl group of C ₄₀ of, C ₂ ~ C ₄₀ An amino group substituted or unsubstituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ to C ₄₀ aryl group and a C ₅ to C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ cycloalkyl group of C ₄₀ of, C ₂ ~ C ₄₀ a heterocycloalkyl group, an aryl group, a C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C ₄₀ heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of a C ₆ ~ C _40; And a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C ₄₀ by at least one group selected from the heteroaryl group consisting of groups are selected from the group consisting of a heteroaryl, a substituted or unsubstituted C ₅ ~ C ₄₀ of the .

The compounds represented by Formula 1 include compounds represented by the following Formulas 1a, 1b, and 1c:

In the above formulas (1a), (1b) and (1c)

R1 to R4, L ₁ and Ar ₁ are as defined in formula (I).

In the imidazole derivative according to the present invention, it is preferable that at least one of R 1 to R 4 in the above formula (1) is a compound represented by the above formula (2), and the rest are the same aryl group.

In the imidazole derivative according to the present invention, it is preferable that at least one of R 1 to R 4 in the formula (1) is a compound represented by the formula (2), and the rest is the same heteroaryl group.

In the imidazole derivative according to the present invention, it is preferable that at least one of R 1 to R 4 in the formula (1) is a compound represented by the formula (2), and the remaining amino groups are substituted with the same aryl group or heteroaryl group.

In the imidazole derivative according to the present invention, it is preferable that at least one of R 1 to R 4 in Formula 1 is the compound represented by Formula 2, and at least one of the others is hydrogen.

In the imidazole derivative represented by Formula 1 according to the present invention, at least one of R 1 to R 4 is a compound represented by Formula 2, and the remainder is selected from the group consisting of:

Wherein Z 1 to Z 3 are the same or different from each other and each independently represents a halogen, an amino group, a nitrile group, a nitro group, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy Substituted or unsubstituted with at least one group selected from the group consisting of a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group and a C ₅ to C ₄₀ heteroaryl group, A C ₆ to C ₄₀ aryl group; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ cycloalkyl group of C ₄₀ of, C ₂ ~ C ₄₀ a heterocycloalkyl group, a heteroaryl group of C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C ₄₀ by at least one group selected from the heteroaryl group consisting of a substituted or unsubstituted C ₅ ~ C ₄₀ of; And a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₂ ~ C heterocycloalkyl group, at least one group selected from C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C ₄₀ heteroaryl group consisting of the ₄₀ groups are selected from the group consisting of substituted or unsubstituted amino group.

In the imidazole derivative according to the present invention, when Ar _{1 in} Formula 2 is an aryl group, it is preferably selected from the group consisting of the following formulas:

In the general formula Z4 is halogen, each independently, an amino group, a nitrile group, a nitro group, a C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ of the a cycloalkyl group, C ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C ₄₀ heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of C ₆ ~ C ₄₀ of the aryl group; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ cycloalkyl group of C ₄₀ of, C ₂ ~ C ₄₀ a heterocycloalkyl group, a heteroaryl group of C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C ₄₀ by at least one group selected from the heteroaryl group consisting of a substituted or unsubstituted C ₅ ~ C ₄₀ of; And a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₃ ~ C ₄₀ cycloalkyl group, C ₂ ~ C heterocycloalkyl group, at least one group selected from C ₆ ~ C ₄₀ aryl group and a C ₅ ~ C ₄₀ heteroaryl group consisting of the ₄₀ groups are selected from the group consisting of substituted or unsubstituted amino group.

In addition, it is preferable that L ₁ in the above formula (2) is selected from the group consisting of the following formulas:

In the present invention, it is preferable that the alkyl group does not give steric hindrance of 1 to 40 carbon atoms. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl.

It is preferable that the cycloalkyl group does not give a steric hinderance of 3 to 40 carbon atoms. As a specific example, a cyclopentyl group or a cyclohexyl group is more preferable.

The alkenyl group is preferably an alkenyl group having 2 to 40 carbon atoms, specifically, an alkenyl group substituted with an aryl group such as a stilbenyl group or a styrenyl group.

The alkoxy group is preferably an alkoxy group having 1 to 40 carbon atoms.

Examples of the aryl group include, but are not limited to, a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, a pyrenyl group, a perylene group, and derivatives thereof.

Examples of the arylamine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methyl-phenylamine, 4-methyl-naphthylamine, 2-methyl- Amine, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a carbazole and a triphenylamine group, but is not limited thereto.

Examples of the heterocyclic group include pyridyl group, bipyridyl group, triazine group, acridyl group, thiophene group, furan group, imidazole group, oxazole group, thiazole group, triazole group, quinolinyl group and isoquinoline group , But are not limited thereto.

Examples of the halogen group include fluorine, chlorine, bromine or iodine.

등이 있다. Spiro groups are structures in which two ring organic compounds are connected to one atom,

.

등이 있다. An open spiro group is a structure in which two ring compounds are disconnected in a structure in which two ring organic compounds are connected to one atom,

.

R 1 to R 4 in the above formula (1) are phenyl substituted with at least one member selected from naphthyl, phenyl, biphenyl and carbazolyl; Pyridyl substituted with phenanthryl or pyridyl; Two phenyl-substituted amino groups; Pyranyl substituted with two phenyl; Isoquinolyl substituted with two phenyls; Or an alkyl group.

L ₁ is preferably a direct bond, phenylene, naphthylene, pyridylene, biphenylene or thienylene.

Ar ₁ is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracene group, a substituted or unsubstituted pyrene group, a chrysene group or a tetracene group desirable.

Specific examples of the compound represented by the formula (1a) include, but are not limited to, the following compounds.

Specific preferred examples of the compound represented by the above formula (1b) include, but are not limited to, the following compounds.

Specific preferred examples of the compound represented by the formula (1c) include, but are not limited to, the following compounds.

Hereinafter, a method for producing the compounds represented by the above general formulas (1a), (1b) and (1c) will be described.

The compound of formula (Ia) can be prepared by introducing an Ar ₁ substituent into an imidazole derivative. Specifically, the compound of formula (Ia) can be prepared by using an acid catalyst, using a halide and aldehyde-substituted derivatives, ammonium acetate (NH ₄ OAc), amine derivatives, and ethanedione derivatives. The resulting imidazole halide derivative and an Ar ₁ -boranic acid or an Ar ₁ -borone ester derivative can be prepared by a Suzuki coupling reaction under a Pd catalyst.

Among the methods used in the preparation of the compound represented by the formula (Ia), the reactions other than the Suzuki coupling reaction can be carried out by a general method known in the art.

Specifically, the compound represented by the above formula (1a)

1) preparing an imidazole ring through an acid catalyst by mixing an L ₁ derivative substituted with a halogen group and an aldehyde group, an ethanedione derivative having an R1 and a R 2 substituent, an ammonium acetate, and an amine derivative having an R 3 substituent; And

2) Suzuki-coupling an imidazole derivative substituted with a halogen group and a boronic acid or boron ester compound having an Ar ₁ substituent under a Pd catalyst to prepare an imidazole derivative substituted with Ar _1. have.

Such a production method can be represented by the following Reaction Scheme 1.

In the above Reaction Scheme 1,

R1 to R3, L ₁ and Ar ₁ are as defined in formula (I).

Hereinafter, a method for producing the compound represented by the above formula (1b) will be described.

The compound represented by Formula 1b can be prepared by introducing an Ar ₁ substituent into an imidazole derivative. Specifically, the compound represented by Formula 1b can be prepared using an amine derivative substituted with a halide element, ammonium acetate, an aldehyde derivative, or an ethanedione derivative under an acid catalyst. The resulting imidazole halide derivative and an Ar ₁ -boranic acid or an Ar ₁ -borone ester derivative can be prepared by a Suzuki coupling reaction under a Pd catalyst.

The reactions other than the Suzuki coupling reaction among the methods used in the preparation of the compound represented by the formula (1b) can be performed by a general method known in the art.

Specifically, the compound of formula (Ib)

1) preparing an imidazole ring under acid catalyst by mixing an halide element and an amine derivative having an L ₁ substituent, an ethanedione derivative having an R1 and R2 substituent, ammonium acetate, and an aldehyde derivative having an R4 substituent; And

2) Suzuki-coupling an imidazole derivative substituted with a halogen group and a boronic acid or boron ester compound having an Ar ₁ substituent under a Pd catalyst to prepare an imidazole derivative substituted with Ar _1. have.

Such a preparation method can be represented by the following reaction formula (2).

In the above Reaction Scheme 2,

R1 to R4, L ₁ and Ar ₁ are as defined in formula (I).

Hereinafter, a method for producing the compound represented by the above formula (1c) will be described.

The compound represented by the above formula (1c) can be prepared by introducing an Ar ₁ substituent into an imidazole derivative. Specifically, the compound of formula (1c) can be prepared by using an ethanedione derivative, an amine derivative, ammonium acetate, or an aldehyde derivative as a halide element under an acid catalyst. The resulting imidazole halide derivative and an Ar ₁ -boranic acid or an Ar ₁ -borone ester derivative can be prepared by a Suzuki coupling reaction under a Pd catalyst.

The reactions other than the Suzuki coupling reaction among the methods used in the preparation of the compound of formula (1c) can be performed by a general method known in the art.

Specifically, the compound represented by the above formula (1c)

1) preparing an imidazole ring under acid catalyst by mixing an halide element and an ethanedione derivative having an L ₁ substituent, an amine derivative having an R 3 substituent, ammonium acetate, and an aldehyde derivative having an R 4 substituent; And

2) Suzuki coupling of an imidazole derivative substituted with a halogen group and a boronic acid or boron ester compound having an Ar ₁ substituent under a Pd catalyst to prepare an imidazole derivative substituted with Ar ₁ .

Such a preparation method can be represented by the following reaction formula (3).

In the above Reaction Scheme 3,

R3 and R4, L ₁ and Ar ₁ are as defined in formula (I).

Also, the present invention is an organic electronic 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 is a compound And an organic electroluminescent device.

The organic electronic device of the present invention can be produced by a conventional method and materials for producing an organic electronic device, except that one or more organic material layers are formed using the above-described compounds.

Hereinafter, the organic light emitting device will be described.

In one embodiment of the present invention, the organic light emitting device may have a structure including a first electrode, a second electrode, and an organic layer disposed therebetween. The organic layer in the organic light emitting device of the present invention may have a single layer structure of one layer or a multilayer structure of two or more layers including a light emitting layer. When the organic material layer of the organic light emitting diode of the present invention has a multilayer structure, it may have a structure in which, for example, a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer are stacked. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers. For example, the organic light emitting device of the present invention may have a structure as shown in FIG. 1, reference numeral 1 denotes a substrate, 2 denotes an anode, 3 denotes a hole injecting layer, 4 denotes a hole transporting layer, 5 denotes an organic light emitting layer, 6 denotes an electron transporting layer and 7 denotes a cathode. The organic light emitting device having the structure as shown in FIG. 1 is generally referred to as an organic light emitting device having a normal structure. However, the present invention is not limited to this and includes an organic light emitting device having a reverse structure. That is, the organic light emitting device of the present invention may have a structure in which a substrate, a cathode, an electron transport layer, an organic light emitting layer, a hole transport layer, a hole injection layer, and an anode are sequentially stacked.

In the case where the organic light emitting device according to the present invention has an organic layer having a multilayer structure, the compound of the general formula (1) includes a light emitting layer, a hole transporting layer, a layer simultaneously transporting and emitting light, a layer simultaneously emitting light and electron transporting, And / or an injection layer. In the present invention, it is particularly preferable that the compound of Formula 1 is included in the electron injecting and / or transporting layer or the light emitting layer.

The organic electroluminescent device according to the present invention can be manufactured using conventional organic electroluminescent device manufacturing methods and materials, except that the compound of Formula 1 is used for at least one layer of the organic electroluminescent device. 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 fabricated by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate in order to fabricate an organic light emitting device having a reverse structure as described above.

The organic material layer may be formed by using a variety of polymer materials in a smaller number of layers 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, Can be manufactured.

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-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (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 , Anthraquinone, polyaniline and polythiophene-based conductive polymers, 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; Bis-methyl-8-hydroxyquinoline paraphenyl phenol aluminum complex (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.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention and do not limit the scope of the present invention.

1. Preparation of the compound of formula (1a)

PREPARATION EXAMPLE 1 Synthesis of Compound of Formula 1-A

To a solution of 9-bromo-10- [naphthalene-2-yl] -anthracene (6.85 g, 17.9 mmol) in 150 ml of purified THF under nitrogen atmosphere, Was completely dissolved and then tert-butyllithium (31.5 mL, 1.7 M pentane solution) was added slowly at -78 ° C. After stirring at the same temperature for one hour, trimethyl borate (8 mL, 71.5 mmol) was added. The cooling vessel was removed and the reaction mixture was stirred at ambient temperature for 3 h. To the reaction mixture was added a 2 N aqueous hydrochloric acid solution (100 ml) and the mixture was stirred at room temperature for 1.5 hours. The resulting precipitate was filtered, washed sequentially with water and ethyl ether, and vacuum dried. Dried, dispersed in ethyl ether, stirred for 2 hours, filtered and dried to obtain the compound represented by the formula (1-A) (4.43 g, yield 71%) as white.

MS: [M + H] < ⁺ > = 349

PREPARATION EXAMPLE 2 Synthesis of Compound of Formula 1-B

The synthesis of the compound of the formula 1-A of Preparation Example 1 was repeated except that 9-bromo-10- [naphthalene-2-yl] -anthracene was used instead of 9- The same procedure as in the synthesis of the compound of the above formula (I-A) was repeated except for using bromo-10- [naphthalen-1-yl] -anthracene (9-bromo-10- [naphthalene- To prepare the compound of the above formula (1-B).

MS: [M + H] < ⁺ > = 557

PREPARATION EXAMPLE 3 Synthesis of Compounds of Formulas 1-C, 1-D and 1-E shown below

[Chemical Formula 1-C]

Under N ₂ stream, a 9-bromo-anthracene (8.2 g, 31.9 mmol), the by-phenylboronic acid (7.6 g, 38.6 mmol), Pd (PPh 3) 4 (0.7 g, 0.6 mmol) 2M K 2 CO 3 Was added to an aqueous solution (300 mL) and THF (300 mL), and the mixture was refluxed and stirred for about 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the organic layer was separated from the reaction mixture. The organic layer was dried over magnesium sulfate, distilled under reduced pressure, and recrystallized from THF / EtOH to obtain the compound of the formula 1-C (8.5 g, 81%).

MS: [M] ^< ⁺ & gt ^; = 330

[Chemical Formula 1-D]

The compound of the above formula (1-C) (8.0 g, 24.2 mmol) was dissolved in chloroform (150 mL) under N ₂ flow and acetic acid (150 mL) was added. Br ₂ (1.3 mL, 25.4 mmol) Respectively. The mixture was warmed to room temperature and stirred for 5 hours. After completion of the reaction, the reaction solution was concentrated and recrystallized with EtOH to obtain the compound of the above formula (1-D) (7 g, 71%).

MS: [M] ^< ⁺ & gt ^; = 408

[Chemical Formula 1-E]

Ether (80 mL) dehydrated and dehydrated toluene (80 mL) were added to the compound of the above formula (1-D) (7 g, 17.1 mmol) under N ₂ stream and cooled to -64 ° C in an ice bath. A 2.5 M butyllithium / hexane solution (9 mL) was added dropwise thereto over 30 minutes, and the mixture was reacted at -64 캜 for 2 hours. To this was added boric acid triisoste (12 mL) dropwise over 15 minutes. After the addition, the mixture was stirred at room temperature for 12 hours. The mixture was ice-cooled and 2N hydrochloric acid (70 mL) was added at 10 DEG C or lower, and toluene (30 mL) was added thereto. This was separated, dried over magnesium sulfate, concentrated under reduced pressure and recrystallized from hexane to obtain a yellow solid. To the solid was added concentrated hydrochloric acid (7 mL) and tetrabutylammonium bromide (0.04 g, 0.1 mmol), dissolved in THF (100 mL), and reacted at room temperature for 12 hours. After completion of the reaction, H ₂ O was added to the reaction solution to solidify it, followed by filtration to obtain the compound of Formula 1-E (3.2 g, 50%).

MS: [M] ^< ⁺ & gt ^; = 374

PREPARATION EXAMPLE 4 Synthesis of Compound of Formula 1-F

2-Naphthaleneboronic acid (10 g, 48.3 mmol) and 2-bromo-6-naphthol (10.8 g, 48.3 mmol) were completely dissolved in tetrahydrofuran (100 mL), 2M potassium carbonate aqueous solution was added, Phosphino palladium (1.11 g, 2 mol%) was added and the mixture was heated with stirring for 5 hours. The temperature was lowered to room temperature, and the water layer was removed. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and then subjected to column chromatography with tetrahydrofuran: hexane = 1: 6 to prepare the compound of Formula 1-F (8.5 g, 65%).

MS: [M + H] < ⁺ > = 271

PREPARATION EXAMPLE 5 Synthesis of Compound of Formula 1-G

The compound of Formula 1-F (7.2 g, 26.8 mmol) was dissolved in dichloromethane, triethylamine (7.47 mL, 53.6 mmol) was added, and the mixture was stirred for 10 minutes. After the temperature was lowered to 0 ° C, trifluoromethanesulfonic anhydride (4.4 mL, 40.2 mmol) was slowly added thereto, the temperature was raised to room temperature, and the mixture was stirred for 1 hour. The aqueous sodium bicarbonate solution was added, the water layer was removed, and water was removed with anhydrous magnesium sulfate. Filtered, concentrated under reduced pressure, and recrystallized with hexane to obtain the compound of the formula 1-G (8.74 g, 81%).

MS: [M + H] < ⁺ > = 403

PREPARATION EXAMPLE 6 Synthesis of Compound of Formula 1-H

(3.95 g, 9.82 mmol), bis (pinacolato) diboron (2.75 g, 10.9 mmol) and potassium acetate (2.89 g, 29.4 mmol) were suspended in dioxane (50 mL) . Palladium (diphenylphosphinoferrocene) chloride (0.24 g, 3 mol%) was added to the suspension. The resulting mixture was stirred at 80 < 0 > C for about 6 hours and cooled to room temperature. The mixture was diluted with water (50 mL) and extracted with dichloromethane (3 x 50 mL). The organic extracts were dried over magnesium sulfate and concentrated in vacuo. The crude product was washed with ethanol and dried in vacuo to give the compound of formula 1-H (3.36 g, 90%).

MS: [M + H] < ⁺ > = 381

PREPARATION EXAMPLE 7 Synthesis of Compound of Formula I-I

4-bromo-benzaldehyde (1.85 g, 10 mmol) was dissolved in acetic acid (20 mL, 20 mmol), benzyl chloride (2.1 g, 10 mmol), ammonium acetate (1.16 g, ). The resulting mixture was stirred at 100 < 0 > C for about 6 hours and cooled to room temperature. The mixture was diluted with water (50 mL), and the resulting solid was filtered, washed with water and ethyl ether to obtain the compound of the formula (I-I) (2.7 g, 62%).

MS: [M + H] < ⁺ > = 452

PREPARATION EXAMPLE 8 Synthesis of Compound of Formula 1-J

The compound of the formula (I-J) was prepared in the same manner as the compound of the formula (I-I) except that 3-bromo-benzaldehyde was used instead of 4-bromo-benzaldehyde.

MS: [M + H] < ⁺ > = 452

PREPARATION EXAMPLE 9 Synthesis of Compound of Formula 1-K

The compound of the formula 1-K was prepared in the same manner as the compound of the formula 1-I, except that? -Naphthyl was used instead of benzyl.

MS: [M + H] < ⁺ > = 552

PREPARATION EXAMPLE 10 Synthesis of Compound of Formula 1-L

Compound 1-L was prepared in the same manner as in the preparation of Compound 1-I except that 1-amino-naphthalene was used in place of aniline.

MS: [M + H] < ⁺ > = 502

PREPARATION EXAMPLE 11 Synthesis of Compound of Formula 1-M

Naphthalene aldehyde (2.56 g, 10 mmol) was dissolved in acetic acid (1.67 g, 10 mmol), benzyl (2.1 g, 10 mmol), ammonium acetate 20 mL). The resulting mixture was stirred at 100 < 0 > C for about 6 hours and cooled to room temperature. The mixture was diluted with water (50 mL), and the resulting solid was filtered and washed with water and ethyl to obtain the compound of the formula 1-M (3.6 g, 60%).

MS: [M + H] < ⁺ > = 602

PREPARATION EXAMPLE 12 Synthesis of Compound of Formula 1-N shown below

Except that 1-bromo-phenylene was used in place of 9-bromo-10- [naphthalen-2-yl] -anthracene instead of 9- Compound (1-N) was prepared in the same manner as in the preparation of Compound (1-A).

MS: [M] ^< ⁺ & gt ^; = 246

Example 1 Synthesis of Compound of Formula 1-8

The compound of Formula 1-A (2.79 g, 8.0 mmol) and the compound of Formula 1-I (2.84 g, 6.3 mmol) were completely dissolved in tetrahydrofuran (100 mL), and 2M aqueous potassium carbonate solution (20 mL) Tetrakistriphenylphosphinopalladium (155 mg, 0.013 mmol) 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 subjected to column chromatography with tetrahydrofuran: hexane = 1: 6 to prepare the compound of Formula 1-8 (2.55 g, 60%).

MS: [M + H] < ⁺ > = 675

Example 2 Synthesis of Compound of Formula 1-9

The compound of the above formula 1-9 was prepared in the same manner as the compound of the formula 1-8 except that the compound of the formula 1-K was used instead of the compound of the formula 1-I.

MS: [M + H] < ⁺ > = 775

Example 3 Synthesis of Compound of Formula 1-15

Compounds of the formula 1-15 were prepared in the same manner as the compound of the formula 1-8 except that the compound of the formula 1-I was used instead of the compound of the formula 1-I.

MS: [M + H] < ⁺ > = 675

Example 4 Synthesis of Compound of Formula 1-36

The compound of the formula 1-36 was prepared in the same manner as the compound of the formula 1-8 except that the compound of the formula 1-L was used instead of the compound of the formula 1-I.

MS: [M + H] < ⁺ > = 725

Example 5 Synthesis of Compound of the Following Formula 1-51

The compound of the formula 1-51 was prepared in the same manner as the compound of the formula 1-8 except that the compound of the formula 1-B was used instead of the compound of the formula 1-A.

MS: [M + H] < ⁺ > = 675

Example 6 Synthesis of Compound of Formula 1-55

The compound of Formula 1-55 was prepared in the same manner as the compound of Formula 1-8 except that the compound of Formula 1-E was used instead of the compound of Formula 1-A.

MS: [M + H] < ⁺ > = 701

Example 7 Synthesis of Compound of Formula 1-99

The compound of Formula 1-99 was prepared in the same manner as the compound of Formula 1-8 except that the compound of Formula 1-A was used instead of the compound of Formula 1-A.

MS: [M + H] < ⁺ > = 625

Example 8 Synthesis of Compound of the Following Formula 1-115

The compound of the formula 1-115 was prepared in the same manner as the compound of the formula 1-8 except that the compound of the formula 1-N was used instead of the compound of the formula 1-A.

MS: [M + H] < ⁺ > = 573

Example 9 Synthesis of Compound of Formula 1-127

2-Naphthalene-boronic acid (1.72 g, 10.0 mmol) and the compound of the formula 1-M (6.0 g, 10.0 mmol) were completely dissolved in tetrahydrofuran (100 mL), and 2M aqueous potassium carbonate solution (25 mL) And tetrakistriphenylphosphinopalladium (231 mg, 0.2 mmol) were added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, and the aqueous layer was removed. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and then subjected to column chromatography with tetrahydrofuran: hexane = 1: 6 to prepare the compound of Formula 1-127 (3.9 g, 60%).

MS: [M + H] < ⁺ > = 649

2. Production method of the compound represented by the formula (1b)

PREPARATION EXAMPLE 13 Synthesis of Compound of Formula 2-A

Aniline (20.47 g, 119 mmol) and acetic acid (40 mL) were added to a solution of benzyl (5 g, 23.8 mmol), ammonium acetate (2.75 g, 35.7 mmol), benzaldehyde (3.71 g, 23.7 mmol) ). The resulting mixture was stirred at 100 < 0 > C for about 8 hours and cooled to room temperature. The mixture was diluted with water (100 mL), and the resulting solid was filtered, washed with water and ethyl, to obtain the compound of Formula 2-A (5.9 g, 55%).

MS: [M + H] < ⁺ > = 452

PREPARATION EXAMPLE 14 Synthesis of Compound of Formula 2-B

The compound of the formula 2-B was prepared in the same manner as the compound of the formula 2-A except for using 3-bromo-aniline instead of 4-bromo-aniline.

MS: [M + H] < ⁺ > = 452

PREPARATION EXAMPLE 15 Synthesis of Compound of Formula 2-C

The compound of Formula 2-C was prepared in the same manner as in the preparation of Formula 2-A except that? -Naphthyl was used instead of benzyl.

MS: [M + H] < ⁺ > = 552

PREPARATION EXAMPLE 16 Synthesis of Compound of Formula 2-D

The compound of the above formula 2-D was prepared in the same manner as the compound of the above formula 2-A except for using 2-naphthalene aldehyde instead of benzaldehyde.

MS: [M + H] < ⁺ > = 502

PREPARATION EXAMPLE 17 Synthesis of Compound of Formula 2-E shown below

The compound of the above formula 2-E was prepared in the same manner as the compound of the above formula 2-A except for using 2-pyridine aldehyde instead of benzaldehyde.

MS: [M + H] < ⁺ > = 453

Example 10 Synthesis of Compound of Formula 2-8

The compound of Formula 1-A (2.79 g, 8.0 mmol) and the compound of Formula 2-A (2.84 g, 6.3 mmol) were completely dissolved in tetrahydrofuran (100 mL), and 2M aqueous potassium carbonate solution (20 mL) Tetrakistriphenylphosphinopalladium (155 mg, 0.013 mmol) was added thereto, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, and the water layer was removed. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and subjected to column chromatography with tetrahydrofuran: hexane = 1: 6 to prepare the compound of Formula 2-8 (2.76 g, 65%).

MS: [M + H] < ⁺ > = 675

Example 11 Synthesis of Compound of Formula 2-9

The compound of Formula 2-9 was prepared in the same manner as the compound of Formula 2-8 except that the compound of Formula 2-C was used instead of the compound of Formula 2-A.

MS: [M + H] < ⁺ > = 775

Example 12 Synthesis of Compound of Formula 2-15 below

The compound of Formula 2-15 was prepared in the same manner as the compound of Formula 2-8 except that the compound of Formula 2-B was used instead of the compound of Formula 2-A.

MS: [M + H] < ⁺ > = 675

Example 13 Synthesis of Compound of Formula 2-36

The compound of Formula 2-36 was prepared in the same manner as the compound of Formula 2-8 except for using the compound of Formula 2-D instead of the compound of Formula 2-A.

MS: [M + H] < ⁺ > = 725

Example 14 Synthesis of Compound of Formula 2-43

The compound of Formula 2-43 was prepared in the same manner as the compound of Formula 2-8 except for using the compound of Formula 2-E instead of the compound of Formula 2-A.

MS: [M + H] < ⁺ > = 725

Example 15 Synthesis of Compound of Formula 2-51

The compound of Formula 2-51 was prepared in the same manner as the compound of Formula 2-8 except that the compound of Formula 1-B was used instead of the compound of Formula 1-A.

MS: [M + H] < ⁺ > = 675

Example 16 Synthesis of Compound of Formula 2-55

The compound of Formula 2-55 was prepared in the same manner as the compound of Formula 2-8 except that the compound of Formula 1-E was used instead of the compound of Formula 1-A.

MS: [M + H] < ⁺ > = 701

Example 17 Synthesis of Compound of Formula 2-99

The compound of Formula 2-99 was prepared in the same manner as the compound of Formula 2-8 except for using the compound of Formula 1-H instead of the compound of Formula 1-A.

MS: [M] ^< ⁺ & gt ^; = 625.5

Example 18 Synthesis of Compound of Formula 2-115 shown below

The compound of Formula 2-115 was prepared in the same manner as the compound of Formula 2-8 except for using the above-mentioned 1-pyrene boronic acid instead of the above-mentioned Formula 1-A.

MS: [M + H] < ⁺ > = 573

3. Production method of the compound represented by the formula (1c)

Production Example 18 Synthesis of Compound of Formula 3-A shown below

(20 mL) was added 4,4'-dibromobenzyl (3.68 g, 10 mmol), ammonium acetate (1.16 g, 15 mmol), aniline (4.67 g, 50 mmol) and benzaldehyde (1.06 g, ≪ / RTI > The resulting mixture was stirred at 100 < 0 > C for about 6 hours and cooled to room temperature. The mixture was diluted with water (50 mL), and the resulting solid was filtered and washed with water and ethyl to obtain the compound of the formula (3-A) (3.2 g, 60%).

MS: [M + H] < ⁺ > = 531

PREPARATION EXAMPLE 19 Synthesis of Compound of Formula 3-B

The compound of the above formula 3-B was prepared in the same manner as the compound of the above formula 3-A except for using 3,3'-dibromobenzyl instead of 4,4'-dibromobenzyl.

MS: [M + H] < ⁺ > = 531

PREPARATION EXAMPLE 20 Synthesis of Compound of Formula 3-C

3-C was prepared in the same manner as in the preparation of the above-mentioned compound (3-A) except that 2-naphthalene aldehyde was used instead of benzaldehyde.

MS: [M + H] < ⁺ > = 581

PREPARATION EXAMPLE 21 Synthesis of Compound of Formula 3-D

3-D was prepared in the same manner as in the preparation of the compound of the formula 3-A except for using 2-aminonaphthalene instead of aniline.

MS: [M + H] < ⁺ > = 581

PREPARATION EXAMPLE 22 Synthesis of Compound of Formula 3-E shown below

(3-E) was prepared in the same manner as in the preparation of the compound of formula (3-A) except that 2-pyridinecarbaldehyde was used instead of benzaldehyde.

MS: [M + H] < ⁺ > = 532

Example 19 Synthesis of Compound of Formula 3-8

The compound of Formula 1-A (4.83 g, 13.9 mmol) and the compound of Formula 3-A (3.34 g, 6.3 mmol) were completely dissolved in tetrahydrofuran (100 mL), and 2M potassium carbonate aqueous solution (35 mL) Tetrakistriphenylphosphinopalladium (155 mg, 0.013 mmol) 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, and concentrated under reduced pressure. The residue was subjected to column chromatography with tetrahydrofuran: hexane = 1: 4 to prepare the compound of Formula 2-8 (3.08 g, 50%).

MS: [M + H] < ⁺ > = 978

Example 20 Synthesis of Compound of Formula 3-9

The compound of Formula 3-9 was prepared in the same manner as the compound of Formula 3-8 except that the compound of Formula 3-C was used instead of the compound of Formula 3-A.

MS: [M + H] < ⁺ > = 1028

Example 21 Synthesis of Compound of Formula 3-15 below

The compound of Formula 3-15 was prepared in the same manner as the compound of Formula 3-8 except that the compound of Formula 3-B was used instead of the compound of Formula 3-A.

MS: [M + H] < ⁺ > = 978

Example 22 Synthesis of Compound of Formula 3-36

The compound of Formula 3-36 was prepared in the same manner as the compound of Formula 3-8 except that the compound of Formula 3-D was used instead of the compound of Formula 3-A.

MS: [M + H] < ⁺ > = 1028

Example 23 Synthesis of Compound of Formula 3-14 below

The compound of Formula 3-14 was prepared in the same manner as the compound of Formula 3-8 except that the compound of Formula 3-E was used instead of the compound of Formula 3-A.

MS: [M + H] < ⁺ > = 979

Example 24 Synthesis of Compound of Formula 3-115 below

The compound of Formula 3-115 was prepared in the same manner as the compound of Formula 3-8 except for using the compound of Formula 1-N instead of the compound of Formula 1-A.

MS: [M + H] < ⁺ > = 773

<Experimental Example 1>

The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1500 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, a Fischer Co. product was used as a detergent, and distilled water, which was filtered with a filter of Millipore Co., was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

Hexanitrile hexaazatriphenylene (HAT) of the following chemical formula was thermally vacuum deposited on the ITO transparent electrode thus prepared to a thickness of 500 Å to form a hole injection layer.

4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (400 Å) of the following formula, which is a hole transporting material, was vacuum- deposited on the hole injection layer to form a hole transport layer .

Subsequently, GH and GD were vacuum deposited on the hole transport layer at a film thickness of 300 Å at a film thickness ratio of 20: 1 to form a light emitting layer.

The compound of Formula 1-8 prepared in Example 1 was vacuum deposited on the light emitting layer to a thickness of 200 Å to form an electron injection and transport layer.

Lithium fluoride (LiF) and aluminum having a thickness of 2000 Å were sequentially deposited on the electron injection and transport layer to a thickness of 12 Å to form a cathode.

The deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the lithium fluoride at the cathode was maintained at a deposition rate of 0.3 Å / sec and the deposition rate of aluminum was maintained at 2 Å / sec. ^-7 to 5 x 10 &lt; ^-8 &gt; torr.

As a result of applying a forward electric field of 4.8 V to the organic light emitting device manufactured above, 19 cd / A green light was observed at a current density of 5 mA / cm 2.

<Experimental Example 2>

An organic EL device was fabricated in the same manner as in Experimental Example 1 except that the compound of Formula 1-99 was used in place of the compound of Formula 1-8.

As a result of applying a forward electric field of 4.5 V to the organic light emitting device fabricated above, 20 cd / A green light was observed at a current density of 5 mA / cm 2.

<Experimental Example 3>

An organic EL device was prepared in the same manner as in Experimental Example 1 except that the compound of Formula 1-17 was used instead of the compound of Formula 1-8.

As a result of applying a forward electric field of 4.2 V to the organic light emitting device manufactured above, 21 cd / A of green light was observed at a current density of 5 mA / cm 2.

<Experimental Example 4>

An organic EL device was fabricated in the same manner as in Experimental Example 1 except that the compound of Formula 2-8 was used in place of the compound of Formula 1-8.

As a result of applying a forward electric field of 4.4 V to the organic light emitting device manufactured above, 20 cd / A green light was observed at a current density of 5 mA / cm 2.

<Experimental Example 5>

An organic EL device was produced in the same manner as in Experimental Example 1 except that the compound of Formula 2-99 was used in place of the compound of Formula 1-8.

As a result of applying a forward electric field of 4.1 V to the organic light emitting device manufactured above, 22 cd / A green light was observed at a current density of 5 mA / cm 2.

<Experimental Example 6>

An organic EL device was fabricated in the same manner as in Experimental Example 1, except that the compound of Formula 2-115 was used in place of the compound of Formula 1-8.

As a result of applying a forward electric field of 4.0 V to the organic light emitting device manufactured above, 22 cd / A of green light was observed at a current density of 5 mA / cm 2.

<Experimental Example 7>

An organic EL device was prepared in the same manner as in Experimental Example 1, except that the compound of Formula 3-9 was used in place of the compound of Formula 1-8.

As a result of applying a forward electric field of 3.8 V to the organic light emitting device manufactured above, 22 cd / A of green light was observed at a current density of 5 mA / cm 2.

&Lt; Comparative Example 1 &

(500 Å), 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) on the ITO electrode prepared in the same manner as in Experimental Example 1, (200 ANGSTROM), lithium fluoride (LiF) 12 ANGSTROM (400 ANGSTROM), GH: GD (film thickness ratio 20: 1) (300 ANGSTROM) and Korean Patent Laid- A hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer were formed in this order. A 2000 Å thick aluminum layer was deposited thereon to form a cathode and an organic light emitting device was fabricated.

As a result of applying a forward electric field of 4.8 V to the organic light emitting device, the green light was observed at 18 cd / A at a current density of 5 mA / cm 2.

1 shows an example of an organic light emitting device according to the present invention.

DESCRIPTION OF THE REFERENCE NUMERALS

1 substrate 2 anode

3 hole injection layer 4 hole transport layer

5 Organic light emitting layer 6 Electron transport layer

7 cathode

2 is a MS graph of the compound of Formula 2-99 of the present invention.

Claims (22)

delete delete delete delete delete delete delete delete delete delete delete An imidazole derivative represented by the following formula (1c): [Chemical Formula 1c]

In the general formula 1c, R4, L _1, R3 and Ar ₁ is selected from the following table, the formula 3-1 to 3-126.

An organic electronic 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 comprises the imidazole derivative of claim 12 Organic electronic device. 14. The organic electronic device according to claim 13, wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor. 14. The organic electronic device according to claim 13, wherein the organic electronic device is an organic light emitting device. 16. The organic electronic device according to claim 15, wherein the organic light emitting device is an organic light emitting device having a forward structure in which an anode, at least one organic material layer, and a cathode are sequentially stacked on a substrate. 16. The organic electronic device according to claim 15, wherein the organic light emitting device is an organic light emitting device having a reverse structure in which a cathode, one or more organic compound layers and an anode are sequentially stacked on a substrate. 16. The organic electroluminescent device according to claim 15, wherein the organic material layer of the organic light emitting device comprises at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron injecting layer, an electron transporting layer, . 16. The organic electronic device according to claim 15, wherein the organic material layer of the organic light emitting device comprises a light emitting layer, and the light emitting layer comprises the imidazole derivative. 16. The organic electronic device according to claim 15, wherein the organic material layer of the organic light emitting device comprises at least one layer selected from the group consisting of an electron transporting layer, an electron injecting layer, and an electron transporting and injecting layer. 16. The organic electronic device according to claim 15, wherein the organic material layer of the organic light emitting device includes a layer for simultaneous transport of holes and light emission. 16. The organic electronic device according to claim 15, wherein the organic material layer of the organic light emitting device comprises a layer simultaneously emitting light and electron.

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