KR101398711B1 - Nitrogen containing compound and organic electronic device using the same - Google Patents

Abstract

The present invention provides a nitrogen-containing heterocyclic compound 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.

Organic electronic element, imidazole, indole

Description

TECHNICAL FIELD [0001] The present invention relates to a nitrogen-containing heterocyclic compound and an organic electronic device using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a nitrogen-containing heterocyclic compound 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 benzimidazole derivatives disclosed by 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 benzimidazole ring and an anthracene skeleton.

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

The present inventors have revealed a nitrogen-containing heterocyclic compound. In addition, when a nitrogen-containing heterocyclic compound is used to form an organic material layer of an organic electronic device, it has been found that the efficiency of the device can be increased, the driving voltage can be lowered, the lifetime can be increased,

Accordingly, it is an object of the present invention to provide a nitrogen-containing heterocyclic compound and an organic electronic device using the same.

The present invention provides a nitrogen-containing heterocyclic compound represented by the following general formula (1).

In Formula 1,

At least one of X ₁ to X ₆ is C or N, at least one of X ₁ to X ₅ is N, at least one of R 1 to R 10 is a compound represented by the following general formula (2), and the others are the same or different, A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, _A C ₂ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group and a C ₂ to C ₄₀ heteroaryl group; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, an aryl group of ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of C ₆ ~ C ₄₀ of the; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a heteroaryl group of ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of C ₂ ~ C ₄₀ of the; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, ₂ ~ C ₄₀ heterocycloalkyl group, is selected from the group consisting of C ₆ ~ C ₄₀ aryl group and C ₂ ~ substituted or unsubstituted amino group by at least one group selected from the heteroaryl group consisting of C ₄₀ in an adjacent R1 to The substituent of R10 may form a bond to form a substituted condensed or non-condensed ring.

In Formula 2,

L ₁ is a direct bond; A C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy groups of, C ₆ ~ C ₄₀ aryl group and C ₂ ~ 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 ~ C40 aryl group and C ₂ ~ C ₄₀ heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of a 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 C ₂ ~ C ₄₀ by at least one group selected from the heteroaryl group consisting of a substituted or unsubstituted C ₂ ~ 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 A C ₆ to C ₄₀ arylamine group substituted or unsubstituted with at least one group selected from the group consisting of an aryl group of C ₁ to C ₄₀ and a heteroaryl group of C ₂ to 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 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 ₂ 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 C ₂ ~ 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; heavy hydrogen; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ heteroaryl substituted with an aryl group by at least one group selected from the group consisting of or unsubstituted alkyl group of C ₁ ~ C ₄₀ of; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ heteroaryl substituted with an aryl group by at least one group selected from the group consisting of or unsubstituted C ₃ ~ C ₄₀ cycloalkyl group of; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ heteroaryl substituted with an aryl group by at least one group selected from the group consisting of or unsubstituted C ₂ ~ C ₄₀ alkenyl group a; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, alkoxy groups of ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of C ₃ ~ C ₄₀ of the; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, ₂ ~ C ₄₀ of the heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ substituted by at least one group selected from the heteroaryl group consisting of C ₄₀ or unsubstituted amino group; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, an aryl group of ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of C ₆ ~ C ₄₀ of the; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a heteroaryl group of ₂ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ heteroaryl group unsubstituted or substituted with one or more groups selected from the group consisting of C ₂ ~ C ₄₀ of the; A C ₂₅ to C ₄₀ spiro group substituted or unsubstituted with at least one group selected from the group consisting of a C ₆ to C ₄₀ aryl group and a C ₂ 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 C ₂ ~ C at least one selected from the heteroaryl group consisting of the ₄₀ groups are selected from the open spiro group the group consisting of substituted or unsubstituted C ₂₅ ~ C ₄₀ of .

The present invention provides 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 contains the nitrogen-containing heterocyclic compound Wherein the organic electronic device is an organic electronic device.

The nitrogen-containing heterocyclic compound 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 increase in efficiency, a decrease in driving voltage, And the like.

The nitrogen-containing heterocyclic compound according to the present invention is characterized by being represented by the above formula (1).

Specifically, the compound represented by the formula (1) is preferably selected from the group consisting of compounds represented by the following formulas (1a) to (1f).

In the above general formulas (1a) to (1f)

R1 to R14 have the same definitions as R1 to R10 in formula (1).

In the nitrogen-containing heterocyclic compound represented by Formula 1 according to the present invention, at least one of R 1 to R 10 is a compound represented by Formula 2, and at least one of R 1 to R 10 is preferably an aryl group.

In the nitrogen-containing heterocyclic compound represented by Formula 1 according to the present invention, it is preferable that at least one of R 1 to R 10 is a compound represented by Formula 2, and at least one of R 1 to R 10 is a heteroaryl group.

In the nitrogen-containing heterocyclic compound represented by Formula 1 according to the present invention, at least one of R 1 to R 10 is a compound represented by Formula 2, and at least one of R 1 to R 10 is preferably an amino substituted with an aryl group or a heteroaryl group .

In the nitrogen-containing heterocyclic compound represented by Formula 1 according to the present invention, it is preferable that at least one of R1 to R10 is a compound represented by Formula 2 and at least one of the others is hydrogen.

In the nitrogen-containing heterocyclic compound represented by Formula 1 according to the present invention, at least one of R 1 to R 10 is a compound represented by Formula 2, and at least one of R 1 to R 10 is preferably selected from the group consisting of:

In the above formula, Z1 to Z3 are the same or different from each other and each independently hydrogen; heavy hydrogen; 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 group; A C ₃ to C ₄₀ cycloalkyl group; A C ₂ to C ₄₀ heterocycloalkyl group; A C ₆ to C ₄₀ aryl group; A C ₂ to C ₄₀ heteroaryl group; A C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a substituted or unsubstituted aryl group, an aryl group of C ₂ ~ C ₄₀ of the heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ heteroaryl group substituted with one or more groups selected from the group consisting of a C ₆ ~ C _40; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a heteroaryl group of ₂ ~ C ₄₀ of the heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ substituted with one or more groups selected from the heteroaryl group consisting of C ₂ ~ C _40; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, ₂ ~ C ₄₀ heterocycloalkyl group is selected from the group consisting of a C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ heteroaryl group substituted with an amino group with one or more groups selected from the group consisting of a.

In the nitrogen-containing heterocyclic compound 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 above formulas, Z4 is each independently hydrogen; heavy hydrogen; 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 group; A C ₃ to C ₄₀ cycloalkyl group; A C ₂ to C ₄₀ heterocycloalkyl group; A C ₆ to C ₄₀ aryl group; A C ₂ to C ₄₀ heteroaryl group; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, an aryl group of ₂ ~ C ₄₀ of the heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ heteroaryl group substituted with one or more groups selected from the group consisting of a C ₆ ~ C _40; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a heteroaryl group of ₂ ~ C ₄₀ of the heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ substituted with one or more groups selected from the heteroaryl group consisting of C ₂ ~ C _40; A C ₁ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₁ to C ₄₀ alkoxy group, ₂ ~ C ₄₀ heterocycloalkyl group is selected from the group consisting of a C ₆ ~ C ₄₀ aryl group and C ₂ ~ C ₄₀ heteroaryl group substituted with an amino group with one or more groups selected from the group consisting of a.

The L ₁ in the above formula (2) is preferably 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 a pyridyl group, bipyridyl group, triazine group, acridyl group, thiophene group, furan group, imidazole group, oxazole group, thiazole group, triazole group, quinolinyl group, isoquinoline group, A benzoxazole group, a benzoxazole group, and the like, 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 10 in the general formula (1) are phenyl, which is substituted with at least one member selected from the group consisting of hydrogen, deuterium, alkyl group, naphthyl, phenyl, biphenyl and carbazolyl; Pyridyl substituted with phenanthryl or pyridyl; An amino group substituted with two phenyls; Pyranyl substituted with two phenyl; More preferably, isoquinolyl substituted with two phenyls.

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.

Formula 1a-1 Formula la-2

Formula 1a-3 Formula 1a-4

(1a-5)

Formula 1a-7 Formula 1a-8

(1a-9)

(1a-11)

(1a-13)

(1a-15)

Formula 1a-17 Formula la-18

(1a-19)

(1a-21)

Formula 1a-23 Formula 1a-24

Formula 1a-25 Formula 1a-26

Formula 1a-27 Formula la-28

(1a-29)

Formula 1a-31 Formula 1a-32

(1a-33)

Formula 1a-35 Formula 1a-36

Formula 1a-37 Formula 1a-38

Formula 1a-39 Formula 1a-40

(1a-41)

Formula 1a-43 Formula 1a-44

(1a-45)

Formula 1a-47 Formula 1a-48

Formula 1a-49 Formula 1a-50

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

Formula 1b-1 Formula 1b-2

Formula 1b-3 < EMI ID =

Formula 1b-5 Formula 1b-6

Formula 1b-7 Formula 1b-8

Formula 1b-9 Formula 1b-10

1b-11 < EMI ID =

Formula 1b-13 Formula 1b-14

Formula 1b-15 Formula 1b-16

Formula 1b-17 Formula 1b-18

Formula 1b-19 Formula 1b-20

Formula 1b-21 Formula 1b-22

Formula 1b-23 Formula 1b-24

Formula 1b-25 Formula 1b-26

Formula 1b-27 Formula 1b-28

Formula 1b-29 Formula 1b-30

Formula 1b-31 Formula 1b-32

Formula 1b-33 Formula 1b-34

Formula 1b-35 Formula 1b-36

Formula 1b-37 Formula 1b-38

Formula 1b-39 Formula 1b-40

Formula 1b-41 Formula 1b-42

Formula 1b-43 Formula 1b-44

Formula 1b-45 Formula 1b-46

Formula 1b-47 Formula 1b-48

Formula 1b-49 Formula 1b-50

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

Formula 1c-1 Formula 1c-2

Formula 1c-3 Formula 1c-4

Formula 1c-5 Formula 1c-6

Formula 1c-7 Formula 1c-8

Formula 1c-9 Formula 1c-10

Formula 1c-11 Formula 1c-12

Formula 1c-13 Formula 1c-14

Formula 1c-15 Formula 1c-16

Formula 1c-17 Formula 1c-18

Formula 1c-19 Formula 1c-20

Formula 1c-21 Formula 1c-22

Formula 1c-23 Formula 1c-24

Formula 1c-25 Formula 1c-26

Formula 1c-27 Formula 1c-28

Formula 1c-29 Formula 1c-30

Formula 1c-31 Formula 1c-32

Formula 1c-33 Formula 1c-34

Formula 1c-35 Formula 1c-36

Formula 1c-37 Formula 1c-38

Formula 1c-39 Formula 1c-40

Formula 1c-41 Formula 1c-42

Formula 1c-43 Formula 1c-44

Formula 1c-45 Formula 1c-46

Formula 1c-47 Formula 1c-48

Formula 1c-49 Formula 1c-50

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

≪ RTI ID = 0.0 > 1d-1 &

≪ RTI ID = 0.0 > 1d-3 &

≪ RTI ID = 0.0 > 1d-5 &

≪ RTI ID = 0.0 > 1d-8 &

1d-9 < / RTI > <

≪ RTI ID = 0.0 > 1d-11 &

≪ RTI ID = 0.0 > 1d-13 &

≪ RTI ID = 0.0 > 1d-15 &

≪ RTI ID = 0.0 > 1d-17 &

1d-19 < EMI ID =

≪ RTI ID = 0.0 > 1d-22 &

Formula 1d-23 Formula 1d-24

Formula 1d-25 Formula 1d-26

≪ RTI ID = 0.0 > 1d-28 &

≪ RTI ID = 0.0 > 1d-29 &

Formula 1d-31 Formula 1d-32

1d-33 < RTI ID = 0.0 >

1d-35 < EMI ID =

(D-37)

1d-39 < EMI ID =

1d-41 < EMI ID =

1d-43 < RTI ID = 0.0 >

1d-45 < RTI ID = 0.0 >

≪ RTI ID = 0.0 > 1d-47 &

Formula 1d-49 Formula 1d-50

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

Formula (1e-1) Formula (1e-2)

Formula (1e-3) Formula (1e-4)

Formula (1e-5) Formula (1e-6)

Formula 1e-7 Formula 1e-8

Formula (1e-9) Formula (1e-10)

Formula (1e-11) Formula (1e-12)

Formula 1e-13 Formula 1e-14

Formula 1e-15 Formula 1e-16

Formula 1e-17 Formula 1e-18

Formula 1e-19 Formula 1e-20

Formula 1e-21 Formula 1e-22

Formula 1e-23 Formula 1e-24

Formula 1e-25 Formula 1e-26

Formula 1e-27 Formula 1e-28

Formula 1e-29 Formula 1e-30

Formula 1e-31 Formula 1e-32

Formula 1e-33 Formula 1e-34

Formula 1e-35 Formula 1e-36

Formula 1e-37 Formula 1e-38

Formula 1e-39 Formula 1e-40

(1e-41)

Formula 1e-43 Formula 1e-44

Formula 1e-45 Formula 1e-46

Formula 1e-47 Formula 1e-48

Formula 1e-49 Formula 1e-50

Preferable specific examples of the compound represented by the above formula (1f) include, but are not limited to, the following compounds.

1f-1 < / RTI > <

Formula (1f-3) Formula (1f-4)

Formula (1f-5) Formula (1f-6)

Formula 1f-7 Formula 1f-8

1f-9 < EMI ID =

(1f-11)

(1f-13)

(1f-15) < EMI ID =

Formula 1f-17 Formula 1f-18

Formula 1f-19 Formula 1f-20

Formula 1f-21 Formula 1f-22

Formula 1f-23 Formula 1f-24

Formula 1f-25 Formula 1f-26

Formula 1f-27 Formula 1f-28

Formula 1f-29 Formula 1f-30

Formula 1f-31 Formula 1f-32

(1f-33) < EMI ID =

Formula 1f-35 Formula 1f-36

Formula 1f-37 Formula 1f-38

Formula 1f-39 Formula 1f-40

(1f-41) < EMI ID =

Formula 1f-43 Formula 1f-44

Formula 1f-45 Formula 1f-46

Formula 1f-47 Formula 1f-48

Formula 1f-49 Formula 1f-50

The compound of formula (1) according to the present invention can be prepared by the same method as in Preparation Example 1 or 2, but is not limited thereto.

[Production Example 1]

Structure A Structure B Structure C Structure D

[Production Example 2]

Structure A Structure E Structure F Structure G

In Production Example 1 or 2,

R1 to R12 have the same definitions as R1 to R10 in the above formula (1).

Specifically, a structural formula A is prepared, which is a hetero five-membered ring compound having a benzene ring having R1 to R4 and containing a halogen group such as a chloride group at an ortho position. An aldehyde group or an acetyl group is introduced into the above structural formula A to prepare a material of the structural formula B or the structural formula E and a condensation reaction to prepare a material of the structural formula C or the structural formula F having a substituted imidazole or a substituted indole. The material of formula D or formula G can be prepared by amination reaction in the final palladium catalyst. The method for preparing the compound of Formula 1 is not limited thereto, and the substitution reaction or the condensation reaction may be carried out by a general technique known in the art.

A more specific method for preparing the compound of formula (1) according to the present invention is shown in the examples.

The present invention provides 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 contains the compound of the formula The organic electroluminescent device is provided.

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 having high mobility to holes is suitable for transporting holes from the anode or the hole injection layer to the light emitting layer. 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 (1a-2)

 Compound A Compound B Compound C Compound 1a-2

Production Example 1-1 Synthesis of Compound A

2'-Chloroacetophenone (20 g, 129.3 mmol), phenylhydrazine (15.4 g, 142.2 mmmol) and polyphosphoric acid (300 g) were added and stirred with heating. After completion of the reaction, the temperature was lowered to room temperature, poured into water, and then stirred. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound A (20 g, yield 68%; MS: [M + H] ⁺ = 228) was obtained by column purification with tetrahydrofuran: hexane = 1:

≪ Preparation Example 1-2 > Synthesis of Compound B

N-Methylformanilide (23.6 g, 175 mmol) and phosphoryl chloride (26.8 g, 175 mmol) were mixed and stirred at room temperature. After 15 minutes, ethylene dichloride (200 ml) was added and the mixture was cooled to 0 ° C, and Compound A (20 g, 87.8 mmol) of Preparation Example 1-1 was slowly added thereto. After 20 minutes, calcium carbonate (17.5 g, 175 mmol) was added and heated. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 6 to obtain Compound B (16 g, yield 71%; MS: [M + H] ⁺ = 256).

≪ Preparation Example 1-3 > Synthesis of Compound C

(16 g, 62.6 mmmol) and o-phenylenediamine (6.8 g, 62.9 mmol) were mixed, and N, N-dimethylacetamide and toluene were added thereto. Respectively. After the completion of the reaction, the reaction mixture was poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the product was purified by column chromatography with tetrahydrofuran: hexane = 1: 8 to obtain Compound C (11 g, yield 57%; MS: [M + H] ⁺ = 308).

Production Example 1-4 Synthesis of Compound (1a-2)

(11 g, 35.8 mmmol), bromobenzene (6.3 g, 40 mmol), bis (tritiated-butylphosphine) palladium (0.18 g, 0.36 mmol), sodium tertiary- Butoxide (4.5 g, 46.8 mmol) were mixed and refluxed with xylene (100 ml) while stirring. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 5 to obtain 9 g (Yield: 66%; MS: [M + H] ⁺ = 384).

PREPARATION EXAMPLE 2 Synthesis of Compound (1a-8)

   Compound A Compound B Compound 1a-8

≪ Preparation Example 2-1 > Synthesis of Compound A

(2.75 g, 10.8 mmol) and bis (pinacolato) diboron (2.89 g, 29.4 mmol) were added to a solution of 2-bromo-9,10- ) Was suspended in dioxane (50 ml). Palladium (diphenylphosphinoferrocene) chloride (0.24 g, 0.3 mmol) was added under reflux and stirred for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, poured into water, and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and distilled under reduced pressure. The resulting solid was filtered, washed with ethanol and dried in vacuo to give Compound A (4.46 g, 82% yield; MS: [M + H] ⁺ = 557).

PREPARATION EXAMPLE 2-2 Synthesis of Compound B

To a solution of Compound A (4 g, 7.2 mmol) of Preparation Example 2-1 and 1-bromo-4-iodobenzene (2.5 g, 8.8 mmol) in tetrahydrofuran (100 ml) was added 2M potassium carbonate aqueous solution And tetrakis (triphenylphosphine) palladium (0.16 g, 0.14 mmol) were added thereto, followed by heating with stirring for 5 hours. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from tetrahydrofuran and ethanol to obtain Compound B (3.2 g, yield 76%; MS: [M + H] ⁺ = 586).

Production Example 2-3 Synthesis of Compound (1a-8)

(1.7 g, 5.5 mmol) and bis (trityl-butylphosphine) palladium (0.03 g, 0.06 mmol) were added to a solution of the compound B (3 g, 5.1 mmol) And sodium tertiary-butoxide (0.63 g, 6.6 mmol) were mixed and refluxed with stirring in xylene (70 ml). After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform, acidic white clay was added and stirred, followed by filtration and distillation under reduced pressure. (2.8 g, yield 68%; MS: [M + H] ⁺ = 812) was obtained by recrystallization from tetrahydrofuran and ethanol.

PREPARATION EXAMPLE 3 Synthesis of Compound (1a-10)

    Compound A Compound B Compound C

    Compound D Compound E < RTI ID = 0.0 >

Production Example 3-1 Synthesis of Compound A

(15 g, 79.3 mmol), phenylhydrazine (11 g, 103 mmmol) and polyphosphoric acid (250 g) were added and the mixture was heated with stirring. After completion of the reaction, the temperature was lowered to room temperature and poured into water. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the product was purified by column chromatography with tetrahydrofuran: hexane = 1: 7 to obtain Compound A (13.1 g, yield 63%; MS: [M + H] ⁺ = 262).

<Production example 3-2> Synthesis of compound B

N-Methylformanilide (10.3 g, 76 mmol) and phosphoryl chloride (11.6 g, 76 mmol) were mixed and stirred at room temperature. Ethylene dichloride (200 ml) was added after 15 minutes, and the mixture was cooled to 0 ° C, and Compound A (10 g, 38 mmmol) of Preparation Example 3-1 was slowly added thereto. After 20 minutes, calcium carbonate (7.6 g, 76 mmol) was added and heated. After the completion of the reaction, the temperature was lowered to room temperature, and the reaction solution was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 5 to obtain Compound B (6.4 g, yield 58%; MS: [M + H] ⁺ = 290).

PREPARATION EXAMPLE 3-3 Synthesis of Compound C

N, N-dimethylacetamide and toluene were added to a solution of the compound B (6 g, 20.7 mmmol) of Preparation Example 3-2 and o-phenylenediamine (2.5 g, 23 mmol) Respectively. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 6 to obtain Compound C (3.4 g, yield 49%; MS: [M + H] ⁺ = 342).

<Production example 3-4> Synthesis of compound D

A mixture of the compound C (3.3 g, 9.7 mmol) of Preparation Example 3-3 and iodobenzene (4 g, 20 mmol), potassium carbonate (2.8 g, 20 mmol) and copper (0.7 g, -Dimethylacetamide (50 ml) was added and the mixture was heated with stirring. After completion of the reaction, the temperature was lowered to room temperature and then filtered, and the filtrate was poured into water. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound D (2.3 g, yield 57%; MS: [M + H] ⁺ = 418) was obtained by recrystallization from tetrahydrofuran and ethanol.

PREPARATION EXAMPLE 3-5 Synthesis of Compound E

(2.3 g, 5.5 mmmol), bis (pinacolato) diboron (1.8 g, 7.1 mmol) and potassium acetate (1.6 g, 16.3 mmol) in dioxane (60 ml) And heated with stirring. Bis (dibenzylidineacetone) palladium (0.1 g, 0.17 mmol) and tricyclohexylphosphine (0.1 g, 0.36 mmol) were placed in a refluxed state and heated. After completion of the reaction, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound E (2.1 g, yield 75%; MS: [M + H] ⁺ = 510) was obtained by recrystallization from tetrahydrofuran and ethanol.

PREPARATION EXAMPLE 3-6 Synthesis of Compound (1a-10)

To a solution of compound E (2 g, 3.9 mmol) of Preparation 3-5 and 2-bromo-9,10- (di-2-naphthyl) anthracene (2 g, 3.9 mmol) in tetrahydrofuran After dissolving, 2M aqueous potassium carbonate solution was added, tetrakis (triphenylphosphine) palladium (0.11 g, 0.1 mmol) was added, and the mixture was stirred under heating. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform and dried over anhydrous magnesium sulfate. The residue was subjected to vacuum distillation and recrystallized from tetrahydrofuran and ethanol to obtain the compound of formula 1a-10 (2.4 g, yield 76%; MS: [M + H] ⁺ = 812).

PREPARATION EXAMPLE 4 Synthesis of Compound (1a-14)

      Compound A Compound B Compound C Compound D

  Compound E &lt; RTI ID = 0.0 &gt;

Production Example 4-1 Synthesis of Compound A

Dichloromethane (100 ml) and saturated aqueous sodium hydrogencarbonate (100 ml) were added to a mixture of 2'-chloroacetophenone (15 g, 97 mmol) and 4-bromophenylhydrazine hydrochloride (22 g, 98 mmol) And the mixture was vigorously stirred at room temperature for 3 hours. The organic layer was separated, dried over sodium sulfate, distilled under reduced pressure, and zinc chloride (16.4 g, 120 mmol) was added thereto, followed by heating to 140 占 폚. After completion of the reaction, the reaction mixture was cooled to room temperature, and water and dichloromethane were added thereto and stirred. The organic layer was separated, dried over anhydrous sodium sulfate, and distilled under reduced pressure, followed by column purification with tetrahydrofuran: hexane = 1: 8 to obtain Compound A (19.3 g, yield 65%; MS: [M + H] ⁺ = 307).

<Production example 4-2> Synthesis of compound B

N-Methylformanilide (16.8 g, 124 mmol) and phosphoryl chloride (19 g, 124 mmol) were mixed and stirred at room temperature. After 15 minutes, ethylene dichloride (200 ml) was added and the mixture was cooled to 0 ° C, and then Compound A (19 g, 62 mmmol) of Preparation Example 4-1 was gradually added thereto. After 20 minutes, calcium carbonate (12.4 g, 124 mmol) was added and heated. After the completion of the reaction, the temperature was lowered to room temperature, and the reaction solution was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and distilled under reduced pressure, followed by column purification with tetrahydrofuran: hexane = 1: 6 to obtain Compound B (12.7 g, yield 61%; MS: [M + H] ⁺ = 335).

<Production example 4-3> Synthesis of compound C

N, N-dimethylacetamide and toluene were added to a mixture of the compound B (12 g, 35.9 mmmol) of Preparation Example 4-2 and o-phenylenediamine (3.9 g, 36 mmol) Respectively. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 6 to obtain Compound C (6.5 g, yield 47%; MS: [M + H] ⁺ = 387).

PREPARATION EXAMPLE 4-4 Synthesis of Compound D

60% sodium hydride (0.43 g, 18 mmol) and iodomethane (2.5 g, 18 mmol) were added to a solution of the compound C (6 g, 15.5 mmol) of Preparation Example 4-3 in anhydrous tetrahydrofuran, Respectively. After completion of the reaction, water was poured into the reaction solution, and the organic layer was separated and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound D (5.4 g, yield 87%; MS: [M + H] ⁺ = 401) was obtained by recrystallization from tetrahydrofuran and ethanol.

<Production example 4-5> Synthesis of compound E

Butyllithium (17 ml, 1.7 mmol) was added at -78 ° C to a solution of 9-bromo-10- (naphthalen-1-yl) anthracene (10 g, 26 mmol) in anhydrous tetrahydrofuran M pentane solution) was added slowly. After stirring at the same temperature for one hour, trimethyl borate (3.1 g, 30 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 (50 ml) and the mixture was stirred at room temperature for 1.5 hours. The resultant solid was filtered, washed with water and ethyl ether, and vacuum dried to obtain Compound E (6.4 g, yield 71%; MS: [M + H] ⁺ = 349).

&Lt; Preparation Example 4-6 > Synthesis of Compound (1a-14)

Compound D (5 g, 12.5 mmmol) of Preparation Example 4-4 and Compound E (4.9 g, 14 mmol) of Preparation Example 4-5 were dissolved in tetrahydrofuran (80 ml), 2M aqueous potassium carbonate solution was added, Kiss (triphenylphosphine) palladium (0.23 g, 0.25 mmol) was added thereto, followed by stirring while heating. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from tetrahydrofuran and ethanol to obtain Compound 1a-14 (5.4 g, yield 69%; MS: [M + H] ⁺ = 624).

PREPARATION EXAMPLE 5 Synthesis of Compound (1a-20)

  Compound A Compound B Compound C Compound D Compound E

  Compound F Compound G Compound 1a-20

Production Example 5-1 Synthesis of Compound A

(15 g, 79.3 mmol), phenylhydrazine (11 g, 103 mmmol) and polyphosphoric acid (250 g) were added to the solution, and the mixture was stirred with heating. After completion of the reaction, the temperature was lowered to room temperature and poured into water. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the product was purified by column chromatography with tetrahydrofuran: hexane = 1: 8 to obtain Compound A (12.4 g, yield 60%; MS: [M + H] ⁺ = 262).

<Production example 5-2> Synthesis of compound B

N-Methylformanilide (10.3 g, 76 mmol) and phosphoryl chloride (11.6 g, 76 mmol) were mixed and stirred at room temperature. Ethylene dichloride (200 ml) was added after 15 minutes, and the mixture was cooled to 0 ° C. Then, Compound A (10 g, 38 mmmol) of Preparation Example 5-1 was gradually added thereto. After 20 minutes, calcium carbonate (7.6 g, 76 mmol) was added and heated. After the completion of the reaction, the temperature was lowered to room temperature, and the reaction solution was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification using tetrahydrofuran: hexane = 1: 7 to obtain Compound B (6.9 g, yield 63%; MS: [M + H] ⁺ = 290).

<Production example 5-3> Synthesis of compound C

N, N-dimethylacetamide and toluene were added to a solution of the compound B (6 g, 20.7 mmmol) of Preparation Example 5-2 and o-phenylenediamine (2.5 g, 23 mmol) Respectively. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 6 to obtain Compound C (3.2 g, yield 45%; MS: [M + H] ⁺ = 342).

<Production example 5-4> Synthesis of compound D

A mixture of the compound C (3.2 g, 9.4 mmol) of Preparation 5-3 and iodobenzene (4 g, 20 mmol), potassium carbonate (2.8 g, 20 mmol) and copper (0.7 g, -Dimethylacetamide (50 ml) was added and the mixture was heated with stirring. After completion of the reaction, the temperature was lowered to room temperature and then filtered, and the filtrate was poured into water. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound D (2.4 g, yield 62%; MS: [M + H] ⁺ = 418) was obtained by recrystallization from tetrahydrofuran and ethanol.

<Production example 5-5> Synthesis of compound E

(2.3 g, 5.5 mmol), bis (pinacolato) diboron (1.8 g, 7.1 mmol) and potassium acetate (1.6 g, 16.3 mmol) in dioxane (60 ml) And heated with stirring. Bis (dibenzylidineacetone) palladium (0.1 g, 0.17 mmol) and tricyclohexylphosphine (0.1 g, 0.36 mmol) were placed in a refluxed state and heated. After completion of the reaction, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound E (2.3 g, yield 82%; MS: [M + H] ⁺ = 510) was obtained by recrystallization from tetrahydrofuran and ethanol.

<Production example 5-6> Synthesis of compound 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 aqueous potassium carbonate solution was added, tetrakis Triphenylphosphine) palladium (1.11 g, 0.97 mmol) were added and the mixture was heated and stirred for 5 hours. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was subjected to distillation under reduced pressure, followed by column chromatography with tetrahydrofuran: hexane = 1: 6 to obtain Compound A (8.5 g, 65%; MS: [M + H] ⁺ = 271).

<Production example 5-7> Synthesis of compound G

Compound (F) (7.2 g, 26.8 mmol) of Preparation 5-6 was dissolved in dichloromethane (80 ml), 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 added slowly and the temperature was raised to room temperature and stirred for 1 hour. An aqueous solution of sodium hydrogencarbonate was added thereto, and the water layer was removed and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was recrystallized with hexane to obtain Compound G (8.74 g, 81%; MS: [M + H] ⁺ = 403).

Production Example 5-8 Synthesis of Compound (1a-20)

Compound E (2.3 g, 5.3 mmol) of Preparation 5-5 and Compound G (2 g, 5 mmol) of Preparation 5-7 were dissolved in tetrahydrofuran (50 ml), 2M aqueous potassium carbonate solution was added, Kiss (triphenylphosphine) palladium (0.12 g, 0.1 mmol) was added thereto, followed by stirring while heating. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform, acidic white clay was added and stirred, followed by filtration and distillation under reduced pressure. The compound 1a-20 (2.2 g, yield 69%; MS: [M + H] ⁺ = 636) was obtained by column chromatography with tetrahydrofuran: hexane = 1:

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

Preparation Example 6 Synthesis of Compound (1b-1)

 Compound A Compound B Compound C Compound 1b-1

&Lt; Preparation Example 6-1 > Synthesis of Compound A

N, N-dimethylacetamide (15.2 g, 175 mmol) and phosphoryl chloride (26.8 g, 175 mmol) were mixed and stirred at room temperature. After 15 minutes, ethylene dichloride (200 ml) was added and the mixture was cooled to 0 ° C, and Compound A (20 g, 87.8 mmol) of Preparation Example 1-1 was slowly added thereto. After 20 minutes, calcium carbonate (17.5 g, 175 mmol) was added and heated. After the completion of the reaction, the temperature was lowered to room temperature, and the reaction solution was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 6 to obtain Compound A (15.2 g, yield 64%; MS: [M + H] ⁺ = 270).

<Production example 6-2> Synthesis of compound B

Compound A (15 g, 55.6 mmol) of Preparation Example 6-1, phenylhydrazine (6.3 g, 58 mmol) and polyphosphoric acid (250 g) were added and stirred under heating. After completion of the reaction, the temperature was lowered to room temperature and poured into water. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, column purification was carried out with tetrahydrofuran: hexane = 1: 8 to obtain Compound B (11.4 g, yield 60%; MS: [M + H] ⁺ = 343)

<Production example 6-3> Synthesis of compound C

(10 g, 29.2 mmmol), bis (triturated-butylphosphine) palladium (0.18 g, 0.36 mmol) and sodium tertiary-butoxide (4.5 g, 46.8 mmol) of Preparation Example 6-2 And the mixture was refluxed in xylene (100 ml) with stirring. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 7 to obtain Compound C (6.4 g, yield 72%; MS: [M + H] ⁺ = 307).

<Production example 6-4> Synthesis of compound of formula (1b-1)

(3.9 g, 24.8 mmol), bis (tritiated-butylphosphine) palladium (0.1 g, 0.2 mmol), sodium tertiary-butylphosphine Butoxide (2.5 g, 26 mmol) were mixed and refluxed with xylene (100 ml) while stirring. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 8 to obtain the compound of formula (Ib-1) (4.8 g, yield 64%; MS: [M + H] ⁺ = 383).

PREPARATION EXAMPLE 7 Synthesis of Compound (1b-6)

Compound A Compound B Compound 1b-6

&Lt; Preparation Example 7-1 > Synthesis of Compound A

(5 g, 19.4 mmol) and 4-hydroxyphenylboronic acid (2.8 g, 20.3 mmol) were dissolved in tetrahydrofuran (100 ml) and heated to dissolve Then, 2M aqueous potassium carbonate solution and tetrakis (triphenylphosphine) palladium (0.45 g, 0.39 mmol) were added and the mixture was heated and stirred for 4 hours. The temperature was lowered to room temperature and the organic layer was separated and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound A (6.5 g, yield 85%; MS: [M + H] ⁺ = 397) was obtained by column purification with tetrahydrofuran: hexane = 1:

PREPARATION EXAMPLE 7-2 Synthesis of Compound B

Dichloromethane (80 ml) was added to the compound A (5 g, 12.6 mmol) of Preparation Example 7-1, and triethylamine (1.3 g, 13 mmol) and trifluoromethanesulfonic anhydride (3.9 g, 14 mmol ) Was slowly added and stirred. After completion of the reaction, water and dichloromethane were added to separate the organic layer, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was purified by dichloromethane and ethanol to obtain Compound B (6 g, yield 90%; MS: [M + H] ⁺ = 529).

<Production example 7-3> Synthesis of compound of formula (1b-6)

(6.9 g, 13 mmol) and bis (trityl-butylphosphine) palladium (0.13 g, 0.26 mmol) in the same manner as in Production Example 7-3, Compound C (4 g, 13 mmmol) And sodium tertiary-butoxide (1.6 g, 17 mmol) were mixed and refluxed in xylene (60 ml) with stirring. After completion of the reaction, the temperature was lowered to room temperature, and the resulting solid was filtered. The filtered solid was dissolved in chloroform, acidic white clay was added and stirred, followed by filtration and distillation under reduced pressure. (5.5 g, yield 62%; MS: [M + H] ⁺ = 685) was obtained by recrystallization from tetrahydrofuran and ethanol.

PREPARATION EXAMPLE 8 Synthesis of Compound (1b-9)

    Compound A Compound B Compound C Compound D

    Compound E Compound F Compound 1b-9

<Production example 8-1> Synthesis of compound A

(15 g, 79.3 mmol), phenylhydrazine (11 g, 103 mmmol) and polyphosphoric acid (250 g) were added to the solution, and the mixture was stirred with heating. After completion of the reaction, the temperature was lowered to room temperature and poured into water. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the product was purified by column chromatography with tetrahydrofuran: hexane = 1: 7 to obtain Compound A (13.1 g, yield 63%; MS: [M + H] ⁺ = 262).

<Production example 8-2> Synthesis of compound B

N, N-dimethylacetamide (6.6 g, 76 mmol) and phosphoryl chloride (11.6 g, 76 mmol) were mixed and stirred at room temperature. Ethylene dichloride (200 ml) was added after 15 minutes, and the mixture was cooled to 0 캜, and Compound A (10 g, 38 mmmol) of Preparation Example 8-1 was slowly added thereto. After 20 minutes, calcium carbonate (7.6 g, 76 mmol) was added and heated. After the completion of the reaction, the temperature was lowered to room temperature, and the reaction solution was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and distilled under reduced pressure, followed by column purification with tetrahydrofuran: hexane = 1: 6 to obtain Compound B (6.2 g, yield: 54%; MS: [M + H] ⁺ = 304).

<Production example 8-3> Synthesis of compound C

(6 g, 20.7 mmmol), phenylhydrazine (2.4 g, 22 mmmol) and polyphosphoric acid (100 g) were added to the reaction mixture, and the mixture was heated with stirring. After completion of the reaction, the temperature was lowered to room temperature and poured into water. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was subjected to column purification using tetrahydrofuran: hexane = 1: 8 to obtain Compound C (5.6 g, yield 72%; MS: [M + H] ⁺ = 377).

<Production example 8-4> Synthesis of compound D

(5 g, 13.3 mmmol), bis (triturated-butylphosphine) palladium (0.07 g, 0.13 mmol) and sodium tertiary-butoxide (1.4 g, 15 mmol) in Preparation Example 8-3 And refluxed with xylene (60 ml) with stirring. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 7 to obtain Compound D (3.8 g, yield 84%; MS: [M + H] ⁺ = 341).

<Production example 8-5> Synthesis of compound E

(2.7 g, 13.2 mmol), potassium carbonate (2.8 g, 20 mmol) and copper (0.7 g, 11 mmol) were added to a solution of the compound D (3.5 g, 10.3 mmol) -Dimethylacetamide (50 ml) was added and the mixture was heated with stirring. After completion of the reaction, the temperature was lowered to room temperature and then filtered, and the filtrate was poured into water. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound E (3.1 g, yield 72%; MS: [M + H] ⁺ = 417) was obtained by recrystallization from tetrahydrofuran and ethanol.

<Production example 8-6> Synthesis of compound F

(2.3 g, 9.1 mmol) and potassium acetate (2.1 g, 21.6 mmol) were mixed with the compound E (3 g, 7.2 mmol) of Preparation Example 8-5 and dioxane (60 ml) And heated with stirring. Bis (dibenzylidineacetone) palladium (0.1 g, 0.17 mmol) and tricyclohexylphosphine (0.1 g, 0.36 mmol) were placed in a refluxed state and heated. After completion of the reaction, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound F (2.6 g, yield 71%; MS: [M + H] ⁺ = 509) was obtained by recrystallization from tetrahydrofuran and ethanol.

<Production example 8-7> Synthesis of compound of formula (1b-9)

(2.5 g, 4.9 mmol) of Preparation Example 8-6 and 2-bromo-9,10- (di-2-naphthyl) anthracene (2.5 g, 4.9 mmol) were dissolved in tetrahydrofuran After dissolving, 2M aqueous potassium carbonate solution was added, tetrakis (triphenylphosphine) palladium (0.11 g, 0.1 mmol) was added, and the mixture was stirred under heating. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was dissolved in chloroform and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was recrystallized from tetrahydrofuran and ethanol to obtain the compound of Formula 1b-9 (3.2 g, yield 81%; MS: [M + H] ⁺ = 811).

PREPARATION EXAMPLE 9 Synthesis of Compound (1b-47)

    Compound A Compound B Compound C Compound D

      Compound E Compound F Compound 1b-47

Production Example 9-1 Synthesis of Compound A

N, N-dimethylacetamide (10.8 g, 124 mmol) and phosphoryl chloride (19 g, 124 mmol) were mixed and stirred at room temperature. After 15 minutes, ethylene dichloride (200 ml) was added and the mixture was cooled to 0 ° C, and then Compound A (19 g, 62 mmmol) of Preparation Example 4-1 was gradually added thereto. After 20 minutes, calcium carbonate (12.4 g, 124 mmol) was added and heated. After the completion of the reaction, the temperature was lowered to room temperature, and the reaction solution was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 9 to obtain Compound A (12.7 g, yield 59%; MS: [M + H] ⁺ = 349).

<Production example 9-2> Synthesis of compound B

Compound A (10 g, 28.7 mmmol), phenylhydrazine (3.2 g, 30 mmmol) and polyphosphoric acid (100 g) were added to the reaction mixture and stirred under heating. After completion of the reaction, the temperature was lowered to room temperature and poured into water. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound B (8.6 g, yield 71%; MS: [M + H] ⁺ = 422) was obtained by column purification with tetrahydrofuran: hexane = 1:

<Manufacturing Example 9-3> Synthesis of Compound C

(8 g, 19 mmol), bis (triturated-butylphosphine) palladium (0.1 g, 0.19 mmol) and sodium tertiary-butoxide (2.4 g, 25 mmol) in Preparation Example 9-2 And the mixture was refluxed in xylene (100 ml) with stirring. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 7 to obtain Compound C (5.9 g, yield 81%; MS: [M + H] ⁺ = 386).

<Production example 9-4> Synthesis of compound D

(5 g, 13 mmol), iodobenzene (4 g, 20 mmol), potassium carbonate (2.8 g, 20 mmol) and copper (0.7 g, 11 mmol) -Dimethylacetamide (50 ml) was added and the mixture was heated with stirring. After completion of the reaction, the temperature was lowered to room temperature and then filtered, and the filtrate was poured into water. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound D (4.4 g, yield 73%; MS: [M + H] ⁺ = 461) was obtained by recrystallization from tetrahydrofuran and ethanol.

<Production Example 9-5> Synthesis of Compound E

6-Bromo-2-naphthoic acid (5 g, 20 mmol), thionyl chloride (20 ml) and N, N-dimethylformamide (1 ml) were stirred and heated for 4 hours. After the excess thionyl chloride was removed by distillation under reduced pressure, N-methylpyrrolidine (20 ml) and N-phenyl-1,2-diaminobenzene (3.7 g, 20 mmol) were added to the reaction mixture, Lt; / RTI &gt; After cooling to room temperature, excess water was added to form a solid. Filtered, washed sequentially with water and ethanol, and then dried to obtain Compound E (6.2 g, yield 78%; MS: [M + H] ⁺ = 400).

<Production example 9-6> Synthesis of compound F

A mixture of compound E (6 g, 15 mmol) of Preparation 9-5, bis (pinacolato) diboron (4.3 g, 17 mmol) and potassium acetate (2.9 g, 30 mmol) And stirred with heating. Palladium (diphenylphosphinoferrocene) chloride (0.37 g, 0.45 mmol) was added under reflux and stirred. After completion of the reaction, the temperature was lowered to room temperature and poured into water. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was recrystallized from tetrahydrofuran and ethanol to obtain Compound F (6.2 g, yield 93%; MS: [M + H] ⁺ = 447).

<Production example 9-7> Synthesis of compound of formula (1b-47)

Compound D (4 g, 8.7 mmol) of Preparation Example 9-4 and Compound F (3.9 g, 8.7 mmol) of Preparation Example 9-6 were dissolved in tetrahydrofuran (100 ml), 2M aqueous potassium carbonate solution was added, Kiss (triphenylphosphine) palladium (0.2 g, 0.17 mmol) was added thereto, followed by stirring with heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was recrystallized from tetrahydrofuran and ethanol to obtain the compound of Formula 1b-47 (4.7 g, yield 77%; MS: [M + H] ⁺ = 701).

PREPARATION EXAMPLE 10 Synthesis of Compound (1b-50)

      Compound A Compound 1b-50

PREPARATION EXAMPLE 10-1 Synthesis of Compound A

(5 g, 10.8 mmol), bis (pinacolato) diboron (3 g, 12 mmol) and potassium acetate (2.5 g, 25.5 mmol) were mixed in dioxane (80 ml) And stirred with heating. Palladium (diphenylphosphinoferrocene) chloride (0.26 g, 0.32 mmol) was added under reflux and stirred. After completion of the reaction, the temperature was lowered to room temperature and poured into water. The mixture was extracted with chloroform and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound A (4.9 g, yield 89%; MS: [M + H] ⁺ = 509) was obtained by recrystallization from tetrahydrofuran and ethanol.

Production Example 10-2 Synthesis of Compound (1b-50)

Compound A (4 g, 7.9 mmol) of Preparation Example 10-1 and 3-bromo-N-phenylcarbazole (2.6 g, 8.4 mmol) were dissolved in tetrahydrofuran (60 ml) and 2M aqueous potassium carbonate solution And tetrakis (triphenylphosphine) palladium (0.18 g, 0.16 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was subjected to distillation under reduced pressure and recrystallized from tetrahydrofuran and ethanol to obtain the compound of Formula 1b-50 (3.4 g, yield 69%; MS: [M + H] ⁺ = 624).

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

PREPARATION EXAMPLE 11 Synthesis of Compound (1c-2)

Compound A Compound 1c-2

PREPARATION EXAMPLE 11-1 Synthesis of Compound A

Ethylene glycol (15 ml) was added to the mixture of o-phenylenediamine dihydrochloride (3.6 g, 20 mmol) and diethyl oxalic acid (1.5 g, 10 mmol) and reacted in a microwave oven at 165 W for 2 minutes. After the reaction was completed, the reaction mixture was cooled to room temperature, poured into water and neutralized with calcium carbonate. The resulting solid was filtered and recrystallized from 90% ethanol to obtain Compound A (2.2 g, yield 92%; MS: [M + H] ⁺ = 235).

Production Example 11-2 Synthesis of Compound (1c-2)

Dibromobenzene (2 g, 8.5 mmol) and bis (tritiated-butylphosphine) palladium (0.09 g, 0.17 mmol) in the same manner as in Preparation Example 11-1, , Sodium tertiary-butoxide (2.1 g, 22.1 mmol) were mixed and refluxed in xylene (50 ml) with stirring. After the completion of the reaction, the reaction mixture was poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the product was subjected to column purification using tetrahydrofuran: hexane = 1: 7 to obtain Compound 1c-2 (1.3 g, yield 50%; MS: [M + H] ⁺ = 309).

PREPARATION EXAMPLE 12 Synthesis of Chemical Formula 1c-11

Compound A Compound 1c-11

Production Example 12-1 Synthesis of Compound A

Bromo-3,4-dichlorobenzene (2.8 g, 12.4 mmol) was dissolved in tetrahydrofuran (60 ml), and a 2M aqueous potassium carbonate solution was added to the solution of Compound G (5 g, 12.4 mmol) And tetrakis (triphenylphosphine) palladium (0.29 g, 0.25 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The compound A (3.7 g, yield 75%; MS: [M + H] ⁺ = 399) was obtained by distillation under reduced pressure and recrystallization from tetrahydrofuran and ethanol.

Production Example 12-2 Synthesis of Compound (1c-11)

Compound (A) (1.8 g, 7.7 mmol) and bis (trityl-butylphosphine) palladium (0.08 g, 0.15 mmol) were added to a solution of the compound A (3 g, 7.5 mmol) And sodium tertiary-butoxide (1.9 g, 19.8 mmol) were mixed and refluxed in xylene (60 ml) with stirring. After completion of the reaction, the temperature was lowered to room temperature, and the resulting solid was filtered. The filtered solid was dissolved in chloroform, acidic white clay was added and stirred, followed by filtration and distillation under reduced pressure. The compound 1c-11 (1.9 g, yield 45%; MS: [M + H] ⁺ = 561) was obtained by recrystallization from tetrahydrofuran and ethanol.

PREPARATION EXAMPLE 13 Synthesis of Compound (1c-13)

  Compound A Compound B Compound C Compound 1c-13

<Production example 13-1> Synthesis of compound A

Ethyleneglycol (15 ml) was added to the mixture of 4-chloro-1,2-phenylenediamine dihydrochloride (4.4 g, 20 mmol) and diethyloxalic acid (1.5 g, 10 mmol) Lt; / RTI &gt; After the reaction was completed, the reaction mixture was cooled to room temperature, poured into water and neutralized with calcium carbonate. The resulting solid was filtered and recrystallized from 90% ethanol to obtain Compound A (2.5 g, yield 83%; MS: [M + H] ⁺ = 303).

<Production example 13-2> Synthesis of compound B

Dibromobenzene (1.6 g, 6.8 mmol) and bis (tritiated-butylphosphine) palladium (0.09 g, 0.17 mmol) in the same manner as in Preparation Example 13-1, , Sodium tertiary-butoxide (2.1 g, 22.1 mmol) were mixed and refluxed in xylene (50 ml) with stirring. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 6 to obtain Compound B (1.2 g, yield 48%; MS: [M + H] ⁺ = 377).

<Production example 13-3> Synthesis of compound C

(1.2 g, 3.2 mmol), bis (pinacolato) diboron (1.8 g, 7 mmol) and potassium acetate (1.5 g, 15 mmol) were mixed in dioxane (40 ml) And stirred with heating. Bis (dibenzylidineacetone) palladium (0.07 g, 0.13 mmol) and tricyclohexylphosphine (0.07 g, 0.26 mmol) were added under reflux and heated. After completion of the reaction, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and recrystallized from tetrahydrofuran and ethanol to obtain Compound C (1.2 g, yield 67%; MS: [M + H] ⁺ = 561).

<Production example 13-4> Synthesis of compound of formula (1c-13)

Compound C (1 g, 1.8 mmol) of Preparation Example 13-3 and 3-bromoquinoline (0.8 g, 3.8 mmol) were dissolved in tetrahydrofuran (50 ml), 2M potassium carbonate aqueous solution was added, tetrakis Triphenylphosphine) palladium (0.08 g, 0.07 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was subjected to vacuum distillation and recrystallized from tetrahydrofuran and ethanol to obtain the compound of formula 1c-13 (0.8 g, yield 79%; MS: [M + H] ⁺ = 563).

PREPARATION EXAMPLE 14 Synthesis of Compound (1c-22)

        Compound A Compound 1c-22

Production Example 14-1 Synthesis of Compound A

Bromo-3,4-dichlorobenzene (2.5 g, 11.2 mmol) was dissolved in tetrahydrofuran (60 ml), and a 2M aqueous potassium carbonate solution was added to the solution of Compound F (5 g, 11.2 mmol) And tetrakis (triphenylphosphine) palladium (0.29 g, 0.25 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was distilled under reduced pressure, and recrystallized from tetrahydrofuran and ethanol to obtain Compound A (4 g, yield 77%; MS: [M + H] ⁺ = 465).

PREPARATION EXAMPLE 14-2 Synthesis of Compound (1c-22)

Compound (A) (1.5 g, 6.4 mmol) and bis (trityl-butylphosphine) palladium (0.08 g, 0.15 mmol) in the same manner as in Preparation Example 14-1, Compound A (3 g, And sodium tertiary-butoxide (1.9 g, 19.8 mmol) were mixed and refluxed in xylene (60 ml) with stirring. After completion of the reaction, the temperature was lowered to room temperature, and the resulting solid was filtered. The filtered solid was dissolved in chloroform, acidic white clay was added and stirred, followed by filtration and distillation under reduced pressure. The compound 1c-22 (1.9 g, yield 47%; MS: [M + H] ⁺ = 627) was obtained by recrystallization from tetrahydrofuran and ethanol.

PREPARATION EXAMPLE 15 Synthesis of Compound (1c-40)

Compound A Compound B Compound C Compound 1c-40

Production Example 15-1 Synthesis of Compound A

2-Naphthol (5 g, 22.4 mmol) was suspended in dichloromethane (80 ml), and triethylamine (2.5 g, 25 mmol) and trifluoromethanesulfonic anhydride (7.1 g, 25 mmol) Was added slowly and stirred. After completion of the reaction, water was added and the organic layer was separated and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was recrystallized from dichloromethane and ethanol to obtain Compound A (6.6 g, yield 83%; MS: [M + H] ⁺ = 356).

<Production example 15-2> Synthesis of compound B

Compound (A) (2.4 g, 6.8 mmol) and bis (trityl-butylphosphine) palladium (0.09 g, 0.17 mmol) of Preparation A- , Sodium tertiary-butoxide (2.1 g, 22.1 mmol) were mixed and refluxed in xylene (50 ml) with stirring. After the completion of the reaction, the reaction mixture was poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound B (1.4 g, yield 50%; MS: [M + H] ⁺ = 426) was obtained by column purification with tetrahydrofuran: hexane = 1:

Production Example 15-3 Synthesis of Compound C

(1.4 g, 3.3 mmol), bis (pinacolato) diboron (1.8 g, 7 mmol) and potassium acetate (1.5 g, 15 mmol) were mixed in dioxane (40 ml) And stirred with heating. Bis (dibenzylidineacetone) palladium (0.07 g, 0.13 mmol) and tricyclohexylphosphine (0.07 g, 0.26 mmol) were added under reflux and heated. After completion of the reaction, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then recrystallized from tetrahydrofuran and ethanol to obtain Compound C (1.4 g, yield 71%; MS: [M + H] ⁺ = 611).

Production Example 15-4 Synthesis of Compound (1c-40)

The compound C (1.3 g, 2.1 mmmol) and 2-bromonaphthalene (1 g, 4.8 mmol) in Preparation Example 15-3 were dissolved in tetrahydrofuran (50 ml), and a 2M aqueous potassium carbonate solution was added thereto. Triphenylphosphine) palladium (0.09 g, 0.08 mmol) were added thereto, followed by stirring with heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was subjected to vacuum distillation and recrystallized from tetrahydrofuran and ethanol to obtain the compound of formula 1c-40 (0.9 g, yield 70%; MS: [M + H] ⁺ = 611).

4. Preparation of the compound represented by the formula (1d)

PREPARATION EXAMPLE 16 Synthesis of Compound (1d-1)

Compound A Compound B Compound C

  Compound D Compound E Compound 1d-1

<Production example 16-1> Synthesis of compound A

(7.2 g, 180 mmol) and iodomethane (25.5 g, 180 mmol) were added at 0 ° C, and stirred at 0 ° C. To the mixture was added dropwise a solution of benzimidazole (20 g, 169.2 mmmol) in anhydrous tetrahydrofuran Respectively. After completion of the reaction, water was poured into the reaction solution, and the organic layer was separated and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the product was purified by column chromatography with tetrahydrofuran: hexane = 1: 8 to obtain Compound A (32 g, yield 91%; MS: [M + H] ⁺ = 209).

<Production example 16-2> Synthesis of compound B

Compound A (30 g, 144 mmol) of Preparation 16-1 and 2-chlorobenzimidazole (7.3 g, 48 mmol) were mixed and stirred while being heated to 135 캜. After completion of the reaction, the reaction mixture was cooled to room temperature, suspended in chloroform, filtered, and then subjected to the following reaction without purification.

Production Example 16-3 Synthesis of Compound C

Compound B of Preparation Example 16-2 was suspended in methanol, 10 wt% of palladium / carbon (10.2 g, 9.6 mmol) was added, and the mixture was stirred under 1 atm of hydrogen. After completion of the reaction, the reaction mixture was filtered, and the filtered solid was dissolved in chloroform. The organic layer was washed with water and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound C (2.8 g, yield 25%; MS: [M + H] ⁺ = 235) was obtained by recrystallization from tetrahydrofuran and ethanol.

<Production example 16-4> Synthesis of compound D

Compound C (2.5 g, 10.7 mmol) of Preparation 16-3 was dissolved in chloroform (70 ml), N-bromosuccinimide (2 g, 11.2 mmol) was added and stirred. After completion of the reaction, water was poured and the organic layer was separated and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was recrystallized from tetrahydrofuran and ethanol to obtain Compound D (2.8 g, yield 76%; MS: [M + H] ⁺ = 314).

<Production example 16-5> Synthesis of compound E

Compound D (2.5 g, 8 mmmol) of Preparation 16-4 and 2-chlorophenylboronic acid (1.4 g, 9 mmol) were dissolved in tetrahydrofuran (60 ml), 2M aqueous potassium carbonate solution was added, tetrakis (Triphenylphosphine) palladium (0.18 g, 0.16 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was subjected to vacuum distillation and recrystallization from tetrahydrofuran and ethanol gave Compound E (1.9 g, yield 69%; MS: [M + H] ⁺ = 345).

<Production example 16-6> Synthesis of compound of formula (1d-1)

(1.5 g, 4.4 mmol) of Preparation 16-5, bis (tritiated-butylphosphine) palladium (0.03 g, 0.05 mmol) and sodium tertiary-butoxide (0.5 g, 5.2 mmol) And refluxed with xylene (40 ml) with stirring. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 9 to obtain the compound of formula (1d-1) (1.1 g, yield 81%; MS: [M + H] ⁺ = 309).

PREPARATION EXAMPLE 17 Synthesis of Compound (d-3)

   Compound A Compound B Compound C

      Compound D Compound E Compound 1d-3

<Production example 17-1> Synthesis of compound A

A suspension of benzyl (20 g, 186.7 mmol), ammonium acetate (21.6 g, 280 mmol), benzylamine (60 g, 560.1 mmol) and 37 wt% formaldehyde (15.2 g, 186.7 mmol) was suspended in acetic acid . After the completion of the reaction, the temperature was lowered to room temperature, water was poured, and the resulting solid was filtered. The filtered solid was washed successively with water and ethyl ether and dried under vacuum to obtain Compound A (35.9 g, 62%; MS: [M + H] ⁺ = 311).

<Production example 17-2> Synthesis of compound B

Compound A (20 g, 64.4 mmol) of Preparation 17-1 and 2-chlorobenzimidazole (3.3 g, 21.6 mmol) were mixed and stirred while being heated to 135 캜. After completion of the reaction, the temperature was lowered to room temperature and suspended in chloroform. After filtration, the following reaction was carried out without purification.

Production Example 17-3 Synthesis of Compound C

Compound B of Preparation Example 17-2 was suspended in methanol, palladium / carbon 10 wt% (4 g, 4.3 mmol) was added, and the mixture was stirred under 1 atm of hydrogen. After completion of the reaction, the solid was filtered, and the filtered solid was dissolved in chloroform. The organic layer was washed with water and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound C (1.5 g, yield 21%; MS: [M + H] ⁺ = 337) was obtained by recrystallization from tetrahydrofuran and ethanol.

<Production example 17-4> Synthesis of compound D

Compound C (1.5 g, 4.5 mmol) of Preparation 17-3 was dissolved in chloroform (50 ml), N-bromosuccinimide (0.89 g, 5 mmol) was added and stirred. After completion of the reaction, water was poured and the organic layer was separated and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound D (1.5 g, yield 80%; MS: [M + H] ⁺ = 416) was obtained by recrystallization from tetrahydrofuran and ethanol.

<Production Example 17-5> Synthesis of Compound E

Compound D (1.5 g, 3.6 mmol) of Preparation 17-4 and 2-chlorophenylboronic acid (0.63 g, 4 mmol) were dissolved in tetrahydrofuran (50 ml), 2M aqueous potassium carbonate solution was added, tetrakis (Triphenylphosphine) palladium (0.09 g, 0.08 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound E was recrystallized from tetrahydrofuran and ethanol to obtain Compound E (1.2 g, yield 75%; MS: [M + H] ⁺ = 447).

<Production example 17-6> Synthesis of compound of formula (1d-3)

(1.2 g, 2.7 mmmol), palladium (0.03 g, 0.05 mmol) and sodium tertiary-butoxide (0.4 g, 4.1 mmol) were added to a solution of the compound E And refluxed with xylene (40 ml) with stirring. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 8 to obtain the compound of formula (1d-3) (0.8 g, yield 72%; MS: [M + H] ⁺ = 411).

Production Example 18 Synthesis of Compound (d-20)

      Compound A Compound B Compound C Compound 1d-20

Production Example 18-1 Synthesis of Compound A

Compound D (1.5 g, 3.6 mmol) of Preparation 17-4 and 2,4-dichlorophenylboronic acid (0.76 g, 4 mmol) were dissolved in tetrahydrofuran (50 ml), 2M aqueous potassium carbonate solution was added, Tetrakis (triphenylphosphine) palladium (0.09 g, 0.08 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The mixture was distilled under reduced pressure, and recrystallized from tetrahydrofuran and ethanol to obtain Compound A (1.3 g, yield 75%; MS: [M + H] ⁺ = 481).

<Production example 18-2> Synthesis of compound B

(Tert-butylphosphine) palladium (0.03 g, 0.05 mmol) and sodium tertiary-butoxide (0.4 g, 4.1 mmol) were added to a mixture of the compound A (1.3 g, 2.7 mmmol) And refluxed with xylene (40 ml) with stirring. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 7 to obtain Compound B (0.97 g, yield 81%; MS: [M + H] ⁺ = 445).

Production Example 18-3 Synthesis of Compound C

(0.9 g, 2 mmol), bis (pinacolato) diboron (0.6 g, 2.4 mmol) and potassium acetate (0.59 g, 6 mmol) were mixed in dioxane (40 ml) And stirred with heating. Bis (dibenzylidineacetone) palladium (0.02 g, 0.04 mmol) and tricyclohexylphosphine (0.02 g, 0.08 mmol) were added under reflux and heated. After completion of the reaction, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was recrystallized from tetrahydrofuran and ethanol to obtain Compound C (0.97 g, yield 90%; MS: [M + H] ⁺ = 537).

<Production example 18-4> Synthesis of compound of formula (1d-20)

(0.91 g, 1.7 mmmol) and 9-bromo-10- (naphthalene-2-yl) anthracene (0.76 g, 2 mmol) in Preparation Example 18-3 were dissolved in 40 ml of tetrahydrofuran, Potassium carbonate aqueous solution was added, and tetrakis (triphenylphosphine) palladium (0.05 g, 0.04 mmol) was added thereto, followed by stirring with heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was subjected to vacuum distillation and recrystallized from tetrahydrofuran and ethanol to obtain the compound of formula (1d-20) (0.9 g, yield 74%; MS: [M + H] ⁺ = 713).

Production Example 19 Synthesis of Compound (1d-22)

   Compound A Compound B Compound C Compound 1d-22

Production Example 19-1 Synthesis of Compound A

Compound D (1.5 g, 4.8 mmol) and 2, 5-dichlorophenylboronic acid (0.76 g, 4 mmol) in Preparation Example 16-4 were dissolved in tetrahydrofuran (50 ml), 2M aqueous potassium carbonate solution was added, Tetrakis (triphenylphosphine) palladium (0.09 g, 0.08 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was subjected to vacuum distillation and recrystallized from tetrahydrofuran and ethanol to obtain Compound A (1.4 g, yield 77%; MS: [M + H] ⁺ = 379).

<Production example 19-2> Synthesis of compound B

(1.4 g, 3.7 mmmol), bis (triturated-butylphosphine) palladium (0.04 g, 0.07 mmol) and sodium tertiary-butoxide (0.5 g, 5.2 mmol) in Preparation Example 19-1 And refluxed with xylene (40 ml) with stirring. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification using tetrahydrofuran: hexane = 1: 7 to obtain Compound B (0.96 g, yield 76%; MS: [M + H] ⁺ = 343).

Production Example 19-3 Synthesis of Compound C

(0.9 g, 2.6 mmol), bis (pinacolato) diboron (0.8 g, 3 mmol) and potassium acetate (0.76 g, 7.8 mmol) were mixed in dioxane (40 ml) And stirred with heating. Bis (dibenzylidineacetone) palladium (0.02 g, 0.04 mmol) and tricyclohexylphosphine (0.02 g, 0.08 mmol) were added under reflux and heated. After completion of the reaction, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the compound C (0.99 g, yield 88%; MS: [M + H] ⁺ = 435) was obtained by recrystallization from tetrahydrofuran and ethanol.

Production Example 19-4 Synthesis of Compound (d-22)

To a solution of the compound C (0.9 g, 2.1 mmmol) of Preparation 19-3 and 2-bromo-9,10- (di-2-naphthyl) anthracene (1.1 g, 2.1 mmol) in tetrahydrofuran After dissolving, 2M aqueous potassium carbonate solution was added, and tetrakis (triphenylphosphine) palladium (0.05 g, 0.04 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was subjected to distillation under reduced pressure and recrystallized from tetrahydrofuran and ethanol to obtain the compound of formula (1d-22) (1.1 g, yield 71%; MS: [M + H] ⁺ = 737).

PREPARATION EXAMPLE 20 Synthesis of Compound (1d-35)

    Compound A Compound B Compound C Compound 1d-35

Production Example 20-1 Synthesis of Compound A

Compound D (1.5 g, 3.6 mmol) of Preparation 17-4 and 2,5-dichlorophenylboronic acid (0.76 g, 4 mmol) were dissolved in tetrahydrofuran (50 ml), 2M aqueous potassium carbonate solution was added, Tetrakis (triphenylphosphine) palladium (0.09 g, 0.08 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was distilled under reduced pressure, and recrystallized from tetrahydrofuran and ethanol to obtain Compound A (1.4 g, yield 81%; MS: [M + H] ⁺ = 481).

<Production example 20-2> Synthesis of compound B

(1.4 g, 2.9 mmmol), bis (triturated-butylphosphine) palladium (0.04 g, 0.07 mmol) and sodium tertiary-butoxide (0.5 g, 5.2 mmol) in Preparation Example 20-1 And refluxed with xylene (40 ml) with stirring. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification using tetrahydrofuran: hexane = 1: 7 to obtain Compound B (0.9 g, yield 70%; MS: [M + H] ⁺ = 445).

Production Example 20-3 Synthesis of Compound C

(0.9 g, 2 mmol), bis (pinacolato) diboron (0.6 g, 2.4 mmol) and potassium acetate (0.59 g, 6 mmol) were mixed in dioxane (40 ml) And stirred with heating. Bis (dibenzylidineacetone) palladium (0.02 g, 0.04 mmol) and tricyclohexylphosphine (0.02 g, 0.08 mmol) were added under reflux and heated. After completion of the reaction, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the residue was recrystallized from tetrahydrofuran and ethanol to obtain Compound C (0.97 g, yield 90%; MS: [M + H] ⁺ = 537).

Production Example 20-4 Synthesis of Compound (1d-35)

Compound C (0.9 g, 1.7 mmol) of Preparation 20-3 and 3-bromo-N-phenylcarbazole (0.58 g, 1.8 mmol) were dissolved in tetrahydrofuran (40 ml), and a 2M aqueous potassium carbonate solution And tetrakis (triphenylphosphine) palladium (0.05 g, 0.04 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was subjected to distillation under reduced pressure and recrystallized from tetrahydrofuran and ethanol to obtain the compound of formula (1d-35) (0.77 g, yield 69%; MS: [M + H] ⁺ = 652).

5. Production method of the compound represented by the formula (1e)

PREPARATION EXAMPLE 21 Synthesis of Compound (e-2)

      Compound A Compound B Compound C

       Compound D &lt; RTI ID = 0.0 &gt;

<Production example 21-1> Synthesis of compound A

Phenylhydrazine hydrochloride (30 g, 207.5 mmol) and ethyl pyruvate (24.4 g, 210 mmol) were mixed, and ethanol (300 ml) was added thereto and stirred. After 12 hours, gaseous hydrogen chloride was added to saturate and the mixture was stirred for 12 hours. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove ethanol and pour water. The organic layer was extracted with dichloromethane and dried over anhydrous magnesium sulfate. The crude product was purified by column chromatography with tetrahydrofuran: hexane = 1: 8 to obtain Compound A (18.3 g, yield 47%; MS: [M + H] ⁺ = 190).

<Production example 21-2> Synthesis of compound B

Compound A (18 g, 95.1 mmol) of Preparation 21-1 was dissolved in anhydrous tetrahydrofuran (400 ml) and lithium aluminum hydride (10.8 g, 285 mmol) was gradually added at 0 ° C. After completion of the reaction, water (11 ml), 25% aqueous sodium hydroxide solution (11 ml) and water (30 ml) were added successively and stirred. The resulting solid was filtered and washed with tetrahydrofuran, and the filtrate was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the following reaction was carried out without purification.

<Manufacturing Example 21-3> Synthesis of Compound C

Compound B of Preparation Example 21-2 was dissolved in dichloromethane (300 ml), pyridinium chlorochromate (20.5 g, 95 mmol) and Celite 545 (10 g) were added and stirred at room temperature. After completion of the reaction, the mixture was distilled off under reduced pressure, and the residue was purified by column chromatography with tetrahydrofuran: hexane = 1: 7 to obtain Compound C (5.8 g, yield 42%; MS: [M + H] ⁺ = 146).

<Production example 21-4> Synthesis of compound D

Compound C (5.5 g, 37.9 mmol) of Preparation Example 21-3 and o-phenylenediamine (4.1 g, 38 mmol) were dissolved in N, N-dimethylacetamide (50 ml) and refluxed with stirring. After completion of the reaction, the temperature was lowered to room temperature and poured into water. The organic layer was extracted with dichloromethane and dried over anhydrous magnesium sulfate. The residue was purified by column chromatography with tetrahydrofuran: hexane = 1: 6 to obtain compound D (5.1 g, yield 58%; MS: [M + H] ⁺ = 234).

<Production example 21-5> Synthesis of compound of formula (1e-2)

Dibromobenzene (5.2 g, 22 mmol) and bis (tritiated-butylphosphine) palladium (0.22 g, 0.43 mmol) in the same manner as in Preparation Example 21-4, , Sodium tertiary-butoxide (5.3 g, 55.1 mmol) were mixed and refluxed with xylene (100 ml) while stirring. After the completion of the reaction, the reaction mixture was poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the product was purified by column chromatography with tetrahydrofuran: hexane = 1: 5 to obtain Compound 1e-2 (3.2 g, yield 49%; MS: [M + H] ⁺ = 308).

PREPARATION EXAMPLE 22 Synthesis of Compound (1e-5)

       Compound A Compound B Compound C Compound D

       Compound E Compound 1e-5

<Production example 22-1> Synthesis of compound A

4-Bromophenylhydrazine hydrochloride (40 g, 179 mmol) and ethyl pyruvate (20.8 g, 180 mmol) were mixed, and ethanol (400 ml) was added and stirred. After 12 hours, gaseous hydrogen chloride was added to saturate and the mixture was stirred for 12 hours. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove ethanol and pour water. The organic layer was extracted with dichloromethane and dried over anhydrous magnesium sulfate. The residue was subjected to vacuum distillation and column purification with tetrahydrofuran: hexane = 1: 6 to obtain Compound A (21.5 g, yield 45%; MS: [M + H] ⁺ = 269).

<Production example 22-2> Synthesis of compound B

Compound A (21 g, 78.3 mmol) of Preparation Example 22-1 was dissolved in anhydrous tetrahydrofuran (400 ml), and lithium aluminum hydride (8.9 g, 235 mmol) was slowly added thereto at 0 ° C. After completion of the reaction, water (9 ml), 25% aqueous sodium hydroxide solution (9 ml) and water (27 ml) were added successively and stirred. The resulting solid was filtered and washed with tetrahydrofuran, and then the filtrate was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the following reaction was carried out without purification.

<Manufacturing Example 22-3> Synthesis of Compound C

Compound B of Preparation Example 22-2 was dissolved in dichloromethane (300 ml), pyridinium chlorochromate (17.2 g, 80 mmol) and Celite 545 (10 g) were added and stirred at room temperature. After completion of the reaction, the mixture was distilled off under reduced pressure, and the obtained product was purified by column chromatography with tetrahydrofuran: hexane = 1: 7 to obtain Compound C (6.8 g, yield 39%; MS: [M + H] ⁺ = 225).

<Production example 22-4> Synthesis of compound D

Compound C (6.5 g, 29 mmmol) of Preparation 22-3 and phenylboronic acid (4 g, 33 mmol) were dissolved in tetrahydrofuran (80 ml), 2M aqueous potassium carbonate solution was added, tetrakis Phosphine) palladium (0.67 g, 0.58 mmol) was added thereto, followed by heating with stirring. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The mixture was distilled under reduced pressure, and recrystallized from tetrahydrofuran and ethanol to obtain Compound D (5.3 g, yield 83%; MS: [M + H] ⁺ = 222).

<Production example 22-5> Synthesis of compound E

Chloro-aniline (11.5 g, 90.4 mmol) and compound D (5 g, 22.6 mmol) of Preparation 22-4 were dissolved in acetic acid (130 g, ml). After completion of the reaction, the temperature was lowered to room temperature and the reaction solution was poured into water. The resulting solid was filtered and the filtered solid was column-purified with tetrahydrofuran: hexane = 1: 6 to obtain Compound E (8.4 g, yield 71%; MS: [M + H] ⁺ = 522).

<Production Example 22-6> Synthesis of Compound (e-5)

(Tert-butylphosphine) palladium (0.05 g, 0.12 mmol) and sodium tertiary-butoxide (1.4 g, 14.6 mmol) in a mixture of the compound E (6 g, 11.5 mmol) And the mixture was refluxed in xylene (100 ml) with stirring. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 5 to obtain Compound 1e-5 (3.7 g, yield 66%; MS: [M + H] ⁺ = 486).

PREPARATION EXAMPLE 23 Synthesis of Compound (1e-18)

  Compound A Compound B Compound 1e-18

Production Example 23-1 Synthesis of Compound A

Compound C (5 g, 22.3 mmmol) of Preparation 22-3 and Compound E (8.4 g, 24 mmol) of Preparation 4-5 were dissolved in tetrahydrofuran (100 ml), followed by the addition of a 2M aqueous potassium carbonate solution, Tetrakis (triphenylphosphine) palladium (0.52 g, 0.45 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was subjected to vacuum distillation and recrystallization from tetrahydrofuran and ethanol gave Compound A (7.6 g, yield 76%; MS: [M + H] ⁺ = 448).

<Production example 23-2> Synthesis of compound B

Chloroaniline (7.9 g, 61.9 mmol) and the compound A of Preparation 23-1 (7 g, 15.6 mmol) were dissolved in acetic acid (130 g, ml). After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from tetrahydrofuran and ethanol to obtain Compound B (8.1 g, yield 69%; MS: [M + H] ⁺ = 748).

Production Example 23-3 Synthesis of Compound (e-18)

Palladium (0.06 g, 0.12 mmol) and sodium tertiary-butoxide (1.3 g, 13.9 mmol) were added to a solution of the compound B (8 g, 10.7 mmol) of Preparation Example 23-2, bis (tri- tert- butylphosphine) palladium And the mixture was refluxed in xylene (100 ml) with stirring. After completion of the reaction, the temperature was lowered to room temperature, and the resulting solid was filtered. The filtered solid was recrystallized from tetrahydrofuran and ethanol to obtain the compound of formula 1e-18 (4.6 g, yield 60%; MS: [M + H] ⁺ = 712).

6. A process for producing a compound represented by the formula (1f)

Production Example 24 Synthesis of Compound (1f-1)

     Compound A Compound B Compound 1f-1

Production Example 24-1 Synthesis of Compound A

N-phenylsulfonylindole (50 g, 194.3 mmol) was dissolved in anhydrous tetrahydrofuran (900 ml) and tertiary-butyl lithium (171 ml, 1.7 M pentane solution) was added and stirred at room temperature. After 1 hour, anhydrous copper (II) chloride (53.8 g, 400 mmol) was added and refluxed with stirring. After completion of the reaction, the reaction solution was poured into water, and the organic layer was separated and dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the reaction mixture was stirred in methanol and the resultant solid was filtered. The filtrated solid was subjected to column purification by column chromatography with dichloromethane: methanol = 20: 1 to obtain Compound A (11.9 g, yield 24%; MS: [M + H] ⁺ = 513).

<Production example 24-2> Synthesis of compound B

Compound A (10 g, 19.5 mmol) of Preparation 24-1 was dissolved in methanol (200 ml), sodium hydroxide (2 g, 50 mmol) was added and the mixture was heated with stirring. After completion of the reaction, the reaction mixture was distilled under reduced pressure and poured into water. The resulting solid was filtered and the filtered solid was purified by column chromatography with dichloromethane: methanol = 20: 1 to obtain Compound B (2.7 g, yield 60%; MS: [M + H] ⁺ = 233).

Production Example 24-3 Synthesis of Compound (1f-1)

(2.5 g, 10.8 mmol), 1,2-dibromobenzene (2.6 g, 11 mmol) and bis (tritiated-butylphosphine) palladium (0.11 g, 0.22 mmol) And sodium tertiary-butoxide (2.7 g, 28.1 mmol) were mixed and refluxed with stirring in xylene (80 ml). After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification using tetrahydrofuran: hexane = 1: 7 to obtain Compound 1f-1 (1.9 g, yield 57%; MS: [M + H] ⁺ = 307).

PREPARATION EXAMPLE 25 Synthesis of Compound (1f-22)

Compound A Compound 1f-22

Production Example 25-1 Synthesis of Compound A

1f-1 (2 g, 6.5 mmol) of Preparation Example 24-3 was dissolved in chloroform (60 ml), N-bromosuccinimide (1.2 g, 6.7 mmol) was added and stirred. After the completion of the reaction, the reaction mixture was poured into water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and then subjected to column purification with tetrahydrofuran: hexane = 1: 6 to obtain Compound A (1.8 g, yield 72%; MS: [M + H] ⁺ = 386).

Production Example 25-2 Synthesis of Compound (1f-22)

Compound A (1.5 g, 3.9 mmol) of Preparation Example 25-1 and Compound A (2.2 g, 4 mmol) of Preparation Example 2-1 were dissolved in tetrahydrofuran (80 ml), followed by the addition of 2M aqueous potassium carbonate solution, Kiss (triphenylphosphine) palladium (0.09 g, 0.08 mmol) was added thereto, followed by heating and stirring for 8 hours. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was subjected to distillation under reduced pressure and recrystallized from tetrahydrofuran and ethanol to obtain the compound of the formula 1f-22 (2.1 g, yield 73%; MS: [M + H] ⁺ = 735).

PREPARATION EXAMPLE 26 Synthesis of Compound (1f-24)

Compound A Compound 1f-24

Production Example 26-1 Synthesis of Compound A

1-Bromopyrrene (10 g, 35.6 mmol) was completely dissolved in anhydrous tetrahydrofuran (120 ml) and then tert-butyllithium (23 ml, 1.7 M pentane solution) was added slowly at -78 deg. After stirring for one hour, trimethyl borate (4.8 g, 46.2 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 (50 ml) and the mixture was stirred at room temperature for 2 hours. The organic layer was separated, dried over anhydrous magnesium sulfate, and distilled under reduced pressure. And recrystallized with hexane to obtain Compound A (5.3 g, yield 60%; MS: [M + H] ⁺ = 247).

Production Example 26-2 Synthesis of Compound (1f-24)

Compound A (1.4 g, 5.7 mmol) of Preparation Example 26-1 and Compound A (2.1 g, 5.5 mmol) of Preparation Example 25-1 were dissolved in tetrahydrofuran (70 ml), 2M aqueous potassium carbonate solution was added, Kiss (triphenylphosphine) palladium (0.13 g, 0.11 mmol) was added thereto, followed by stirring while heating. After the completion of the reaction, the temperature was lowered to room temperature, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue was subjected to distillation under reduced pressure and recrystallized from tetrahydrofuran and ethanol to obtain Compound 1f-24 (2 g, yield 72%; MS: [M + H] ⁺ = 507).

<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.

[LINE]

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 .

[NPB]

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.

  [GH] [GD]

The compound of Formula 1a-2 prepared in Preparation 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, 20 cd / A green light was observed at a current density of 5 mA / cm 2.

<Experimental Example 2>

An organic light emitting device was prepared in the same manner as in Example 1 except that the compound of Formula 1a-8 prepared in Preparation Example 2 was used instead of the compound of Formula 1a-2.

As a result of applying a forward electric field of 4.4 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 3>

An organic light emitting device was prepared in the same manner as in Example 1 except that the compound of Formula 1a-10 prepared in Preparation Example 3 was used instead of the compound of Formula 1a-2.

As a result of applying a forward electric field of 4.1 V to the organic light emitting device manufactured above, 23 cd / A green light was observed at a current density of 5 mA / cm 2.

<Experimental Example 4>

An organic light emitting device was prepared in the same manner as in Example 1 except that the compound of Formula 1a-20 prepared in Preparation Example 5 was used instead of the compound of Formula 1a-2.

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 light emitting device was prepared in the same manner as in Experimental Example 1, except that the compound 1b-6 prepared in Preparation Example 7 was used in place of the compound represented by Formula 1a-2.

As a result of applying a forward electric field of 4.3 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 light emitting device was prepared in the same manner as in Experimental Example 1 except that the compound of Formula 1b-10 prepared in Preparation Example 8 was used instead of the compound of Formula 1a-2.

As a result of applying a forward electric field of 4.3 V to the organic light emitting device fabricated above, 23 cd / A of green light was observed at a current density of 5 mA / cm 2.

<Experimental Example 7>

An organic light emitting device was prepared in the same manner as in Experimental Example 1, except that the compound 1b-47 prepared in Preparation Example 9 was used in place of the compound represented by Formula 1a-2.

As a result of applying a forward electric field of 3.9 V to the organic light emitting device manufactured above, 23 cd / A green light was observed at a current density of 5 mA / cm 2.

<Experimental Example 8>

An organic light emitting device was prepared in the same manner as in Experimental Example 1, except that the compound 1c-11 prepared in Preparation Example 12 was used in place of the compound represented by Formula 1a-2.

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.

<Experimental Example 9>

An organic light emitting device was prepared in the same manner as in Experimental Example 1, except that the compound 1c-13 prepared in Preparation Example 13 was used in place of the compound represented by Formula 1a-2.

As a result of applying a forward electric field of 3.7 V to the organic light emitting device fabricated above, 23 cd / A green light was observed at a current density of 5 mA / cm 2.

<Experimental Example 10>

An organic light emitting device was prepared in the same manner as in Experimental Example 1, except that the compound 1d-20 prepared in Preparation Example 18 was used in place of the compound represented by Formula 1a-2.

As a result of applying a forward electric field of 4.1 V to the organic light emitting device manufactured above, 24 cd / A green light was observed at a current density of 5 mA / cm 2.

&Lt; Experimental Example 11 &

An organic light emitting device was prepared in the same manner as in Experimental Example 1, except that the compound 1d-22 prepared in Preparation Example 19 was used in place of the compound represented by Formula 1a-2.

As a result of applying a forward electric field of 3.9 V to the organic light emitting device fabricated above, green light was observed at 25 cd / A at a current density of 5 mA / cm 2.

<Experimental Example 12>

An organic light emitting device was prepared in the same manner as in Experimental Example 1, except that the compound 1e-18 prepared in Preparation Example 23 was used in place of the compound represented by Formula 1a-2.

As a result of applying a forward electric field of 3.8 V to the organic light emitting device manufactured above, 23 cd / A green light was observed at a current density of 5 mA / cm 2.

<Experimental Example 13>

An organic light emitting device was prepared in the same manner as in Experimental Example 1, except that the compound 1f-22 prepared in Preparation Example 25 was used in place of the compound represented by Formula 1a-2.

As a result of applying a forward electric field of 3.9 V to the organic light emitting device manufactured above, 24 cd / A 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.

[Electron transport material]

As a result of applying a forward electric field of 4.6 V to the organic light emitting device, green light was observed at 19 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

Claims (25)

A nitrogen-containing heterocyclic compound represented by any one of the following formulas (1a) to (1f): [Chemical Formula 1a] [Chemical Formula 1b]

[Chemical Formula 1c] [Chemical Formula 1d]

[Formula 1e] [Formula 1f]

At least one of R1 to R11 in the above formulas (1a) and (1e); At least one of R1 to R14 in the above formulas (1b) and (1f); At least one of R 1 to R 8 in the above formulas (1c) and (1d) is a compound represented by the following formula (2) The remaining R in the above formulas (1a) to (1f) are the same or different from each other, and each independently hydrogen; Methyl group; A C ₆ to C ₄₀ aryl group substituted or unsubstituted with a C ₆ to C ₄₀ aryl group; Or a quinolinyl group, In the above general formulas (1a) to (1f), two closest substituents in one ring in each formula are bonded to each other to form a hydrogen; Methyl group; A C ₆ to C ₄₀ aryl group substituted or unsubstituted with a C ₆ to C ₄₀ aryl group; Or a benzene ring substituted with a quinoline group, (2)

In Formula 2, L ₁ is a direct bond; Aryl of C ₆ ~ C ₄₀ aryl groups substituted or unsubstituted divalent C ₆ ~ C ₄₀ ring; Or a divalent carbazole, Ar ₁ is hydrogen; Methyl group; A C ₆ to C ₄₀ aryl group substituted or unsubstituted with a C ₆ to C ₄₀ aryl group; A quinoline group; Or a phenylbenzimidazonyl group. delete delete delete delete The method according to claim 1, At least one of R1 to R11 in the above formulas (1a) and (1e); At least one of R1 to R14 in the above formulas (1b) and (1f); At least one of R 1 to R 8 in the formulas (1c) and (1d) is a compound represented by the formula (2) And at least one of the remaining R's is hydrogen. The method according to claim 1, At least one of R1 to R11 in the above formulas (1a) and (1e); At least one of R1 to R14 in the above formulas (1b) and (1f); At least one of R 1 to R 8 in the formulas (1c) and (1d) is a compound represented by the formula (2) And at least one of the remaining R's is selected from the group consisting of:

In the above formula, Z1 to Z3 are the same or different from each other and each independently hydrogen; Or a C ₆ to C ₄₀ aryl group. The method according to claim 1, Wherein Ar &lt; ₁ &gt; in the formula (2) is an aryl group selected from the group consisting of the following formulas:

In the above formulas, Z4 is each independently hydrogen; Or a C ₆ to C ₄₀ aryl group. The method according to claim 1, Wherein L &lt; ₁ &gt; in the general formula (2) is selected from the group consisting of the following formulas:

The method according to claim 1, Wherein the compound represented by the formula (1a) is selected from the group consisting of a nitrogen-containing heterocyclic compound represented by the following formula: Formula 1a-1 Formula la-2

Formula 1a-3 Formula 1a-4

(1a-5)

Formula 1a-7 Formula 1a-8

(1a-9)

(1a-11)

(1a-13)

(1a-15)

Formula 1a-17 Formula la-18

(1a-19)

Formula 1a-23 Formula 1a-24

Formula 1a-25 Formula 1a-26

Formula 1a-27 Formula la-28

(1a-29)

Formula 1a-31 Formula 1a-32

Formula 1a-36

(1a-41)

Formula 1a-47 Formula 1a-48

The method according to claim 1, Wherein the compound represented by Formula 1b is selected from the group consisting of a nitrogen-containing heterocyclic compound: Formula 1b-1 Formula 1b-2

Formula 1b-3 &lt; EMI ID =

Formula 1b-5 Formula 1b-6

Formula 1b-7 Formula 1b-8

Formula 1b-9 Formula 1b-10

1b-11 &lt; EMI ID =

 1b-18

Formula 1b-19 Formula 1b-20

Formula 1b-21 Formula 1b-22

Formula 1b-29 Formula 1b-30

Formula 1b-33 Formula 1b-34

Formula 1b-39 Formula 1b-40

1b-45

1b-47

Formula 1b-49 Formula 1b-50

The method according to claim 1, Wherein the compound represented by Formula 1c is selected from the group consisting of a nitrogen-containing heterocyclic compound represented by the following formula: Formula 1c-1 Formula 1c-2

Formula 1c-5 Formula 1c-6

Formula 1c-7 Formula 1c-8

Formula 1c-9 Formula 1c-10

Formula 1c-11 Formula 1c-12

1c-13

Formula 1c-15 Formula 1c-16

Formula 1c-17 Formula 1c-18

1c-19

1c-22

1c-23

Formula 1c-29 Formula 1c-30

Formula 1c-31 Formula 1c-32

1c-34

1c-35

Formula 1c-39 Formula 1c-40

Formula 1c-41 Formula 1c-42

1c-44

1c-45

1c-48

Formula 1c-49 Formula 1c-50

The method according to claim 1, Wherein the compound represented by the formula (1d) is selected from the group consisting of a nitrogen-containing heterocyclic compound represented by the following formula: &Lt; RTI ID = 0.0 &gt; 1d-1 &

1d-3

&Lt; RTI ID = 0.0 &gt; 1d-5 &

1d-7

1d-9 &lt; / RTI &gt; &lt;

1d-11

&Lt; RTI ID = 0.0 &gt; 1d-13 &

1d-19 &lt; EMI ID =

&Lt; RTI ID = 0.0 &gt; 1d-22 &

Formula 1d-23 Formula 1d-24

Formula 1d-25 Formula 1d-26

&Lt; RTI ID = 0.0 &gt; 1d-28 &

1d-31

1d-34

1d-35

1d-37

1d-39 &lt; EMI ID =

1d-41

1d-43

1d-45

1d-47

Formula 1d-49 Formula 1d-50

The method according to claim 1, Wherein the compound represented by Formula 1e is selected from the group consisting of a nitrogen-containing heterocyclic compound: Formula (1e-1) Formula (1e-2)

1e-4

Formula (1e-5) Formula (1e-6)

Formula 1e-7 Formula 1e-8

Formula (1e-9) Formula (1e-10)

Formula (1e-11) Formula (1e-12)

1e-13

Formula 1e-15 Formula 1e-16

Formula 1e-17 Formula 1e-18

1e-19

1e-22

1e-23

Formula 1e-25 Formula 1e-26

Formula 1e-29 Formula 1e-30

Formula 1e-31 Formula 1e-32

1e-34

(1e-35)

(1e-37)

Formula 1e-39 Formula 1e-40

1e-42

1e-44

1e-45

1e-48

Formula 1e-49 Formula 1e-50

The method according to claim 1, The nitrogen-containing heterocyclic compound represented by the formula (1f) is selected from the group consisting of: 1f-1 &lt; / RTI &gt; &lt;

Formula (1f-3) Formula (1f-4)

Formula (1f-5) Formula (1f-6)

Formula 1f-7 Formula 1f-8

(1f-13)

(1f-15) &lt; EMI ID =

1f-18

1f-20

Formula 1f-21 Formula 1f-22

Formula 1f-23 Formula 1f-24

Formula 1f-27 Formula 1f-28

1f-29

1f-32

1f-33

1f-36

Formula 1f-39 Formula 1f-40

(1f-41) &lt; EMI ID =

1f-45

Formula 1f-47 Formula 1f-48

Formula 1f-49 Formula 1f-50

An organic electronic device comprising an anode, a cathode, and at least one organic layer disposed between the anode and the cathode, wherein at least one of the organic layers comprises the nitrogen-containing heterocyclic compound of any one of claims 1 to 6 to 15 Lt; / RTI &gt; 18. The method of claim 16, 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. 18. The method of claim 16, Wherein the organic electronic device is an organic light emitting device. 19. The method of claim 18, 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. 19. The method of claim 18, Wherein the organic light emitting device is an organic light emitting device having a reverse structure in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate. 19. The method of claim 18, Wherein the organic material layer of the organic light emitting device comprises at least one of a hole injecting layer, a hole transporting layer, a light emitting layer, an electron injecting layer, a transferring transporting layer, and a layer simultaneously injecting electrons and transporting electrons. 19. The method of claim 18, Wherein the organic compound layer of the organic light emitting element comprises a light emitting layer, and the light emitting layer comprises the nitrogen containing heterocyclic compound. 19. The method of claim 18, Wherein the organic material layer of the organic light emitting device comprises at least one of an electron transport layer, an electron injection layer, and a layer simultaneously performing electron injection and electron transport, and the layer includes the nitrogen containing heterocyclic compound. 19. The method of claim 18, Wherein the organic material layer of the organic light emitting device includes a layer that simultaneously transports holes and emits light. 19. The method of claim 18, Wherein the organic material layer of the organic light emitting device comprises a layer simultaneously emitting light and transporting electrons.

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