KR20120118563A - Cyclopentafluorene compound and organic light emitting device including the same - Google Patents

Abstract

PURPOSE: A cyclopentafluorene-based compound is provided to have excellent quantum efficiency when applied to a fluorescent device of phosphorescence device, etc, and to prevent crystallization when forming a membrane, thereby capable of providing thermal stailbity. CONSTITUTION: A cyclopentafluorene-based compound is represented by chemical formula 1. An organic electroluminescence device comprises a first electrode, a second electrode formed to face with the first electrode, and an organic material layer formed between the first electrode and the second electrode. The organic material layer comprises the cyclopentafluorene-based compound. The organic electroluminescence device comprises the first electrode, the second electrode, a light-emitting layer, a hole transport layer, and an electron transport layer. The light-emitting layer comprises host and dopant and the hole transport layer comprises the cyclopentafluorene-based compound.

Description

Cyclopentafluorene compound and organic light emitting device including the same {CYCLOPENTAFLUORENE COMPOUND AND ORGANIC LIGHT EMITTING DEVICE INCLUDING THE SAME}

The present invention relates to a cyclopentafluorene-based compound, and more particularly, to a cyclopentafluorene-based compound exhibiting high quantum efficiency and excellent thermal stability and an organic light emitting device including the same.

The organic light emitting device has a simpler structure, has various advantages in manufacturing process, and has high luminance and viewing angle compared to other flat panel display devices such as a liquid crystal display (LCD), a plasma display panel (PDP), and a field emission display (FED). Due to its excellent characteristics, fast response speed and low driving voltage, development is being actively conducted to be used as a light source for a flat panel display such as a wall-mounted TV or a back light of a display, an illumination, a billboard.

In general, an organic light emitting diode recombines holes injected from an anode and electrons injected from a cathode when a DC voltage is applied to form an exciton, an electron-hole pair, and the excitons return to a stable ground state to emit corresponding energy. It is converted to light by transmitting it to the material.

In order to increase the efficiency and stability of organic light emitting devices, a low-voltage driving organic light emitting device is reported by forming a stacked organic thin film between two opposite electrodes by CW Tang of Eastman Kodak Corporation (CW Tang, SA Vanslyke, Applied Physics). Letters, Vol. 51, p. 913, 1987), studies on organic materials for multilayer thin film structured organic light emitting diodes have been actively conducted. The efficiency and lifespan of such stacked organic light emitting diodes is deeply related to the molecular structure of the material of the thin film. For example, the quantum efficiency is greatly influenced by the structure of the host material, the hole transport layer material, or the electron transport layer material among the materials constituting the thin film, and when the thermal stability is poor, the material is crystallized at a high temperature or a driving temperature, and thus the lifetime of the device. It is a cause of shortening.

Various compounds are known as conventional fluorene-based compounds that can be used in organic electroluminescent devices. However, conventional fluorene-based compounds have a problem of low quantum efficiency and thermal stability.

Therefore, the first technical problem to be achieved by the present invention is to solve the problems of the prior art, the hole transport material of the organic EL device, the host material of the light emitting layer, the electron transport material, the host of the fluorescent material, the fluorescent device and the phosphorescent device, etc. It is to provide a cyclopentafluorene-based compound exhibiting excellent quantum efficiency when applied.

The second technical problem to be achieved by the present invention is a more rigid structure than the fluorene structure, and has a structure that is difficult to crystallize, which can prevent crystallization during film formation, thereby improving thermal stability. It is to provide a cyclopentafluorene-based compound.

The third technical problem to be achieved by the present invention is to provide an organic electroluminescent device comprising the cyclopentafluorene-based compound having a high quantum efficiency of the device, a long driving life and high thermal stability.

One embodiment of the present invention provides a cyclopentafluorene compound for an organic light emitting device represented by the following formula (1).

[Formula 1]

In Formula 1,

X ¹ to X ⁴ may be the same or different from each other, each independently represent a valence bond, a C _{6 -30} An aryl group or a C _{5 -30} Hetero arylene group,

,

,

,

,

, C_{1 -9}의 알킬기, C_{6 -30}의 아릴기 또는 C_{5 -30}의 헤테로 아릴기이거나, 이웃한 벤젠고리의 탄소원자와 결합하여 함께 C_6-30의 접합된 방향족 고리 또는 C_5-30의 접합된 헤테로 방향족 고리를 형성할 수 있으며, Y¹은 산소원자 또는 황원자이고,R ¹ to R ⁴ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

, Or a heteroaryl group of the alkyl group of C _{1 -9,} C _{6 -30} aryl group or a C _{5 -30,} of a C _6-30 together in combination with the carbon atom of the adjacent benzene ring bonded aromatic ring or a _5- C ₃₀ may form a conjugated heteroaromatic ring, Y ¹ is an oxygen atom or a sulfur atom,

,

,

,

,

, C_{1 -9}의 알킬기, C_{6 -30}의 아릴기 또는 C_5-30의 헤테로 아릴기이거나, 이웃한 벤젠고리의 탄소원자와 결합하여 함께 C_{6 -30}의 접합된 방향족 고리 또는 C_{5 -30}의 접합된 헤테로 방향족 고리를 형성할 수 있으며, Y²는 산소원자 또는 황원자이고,R ⁵ and R ⁶ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

, An alkyl group of C _{1 -9,} or a heteroaryl group of C _{6 -30} aryl group or a C _5-30 of the bonded aromatic of C _{6 -30} in combination with the carbon atom of the adjacent benzene ring or ring C _{5 - 30} may form a conjugated heteroaromatic ring, Y ² is an oxygen atom or a sulfur atom,

Wherein Ar ¹ to Ar ⁸ may be the same or different from each other, and each independently represents a hydrogen atom, a heterocyclic aryl group of C _{6 -30} aryl group or a C _{5 -30,}

Wherein R ⁷ to R ¹⁶ may be the same or different from each other, each independently represent a hydrogen atom or an alkyl group C _{1 -9.}

 Another aspect of the invention, the first electrode; A second electrode formed to face the first electrode; And an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer comprises the cyclopentafluorene-based compound.

Another aspect of the invention, the organic electroluminescent device comprising a first electrode, a second electrode, a light emitting layer, a hole transport layer and an electron transport layer, the light emitting layer comprises a host and a dopant, the hole transport layer is the cyclopentaflu It provides an organic electroluminescent device comprising an orene-based compound.

In another aspect of the present invention, an organic electroluminescent device comprising a first electrode, a second electrode, a light emitting layer, a hole transport layer, and an electron transport layer, wherein the light emitting layer comprises a host and a dopant, wherein the electron transport layer is the cyclopentaflu. It provides an organic electroluminescent device comprising an orene-based compound.

In another aspect of the present invention, an organic electroluminescent device comprising a first electrode, a second electrode, a light emitting layer, a hole transport layer, and an electron transport layer, wherein the light emitting layer comprises a host and a dopant, wherein the host is the cyclopentafluorene. It provides an organic electroluminescent device comprising a compound.

The present invention can provide a cyclopentafluorene-based compound exhibiting excellent quantum efficiency when applied to the hole transport material of the organic EL device, the host material of the light emitting layer, the electron transport material, the host of the fluorescent material, the fluorescent device and the phosphorescent device. .

In addition, the present invention has a more rigid structure than the fluorene structure, and has a structure that is difficult to crystallize, which prevents crystallization during film formation, thereby improving thermal stability, and thus cyclopentafluorene-based compound. Can be provided.

In another aspect, the present invention can provide an organic light emitting device comprising the cyclopentafluorene-based compound having a high quantum efficiency of the device, a long driving life and high thermal stability.

1 is a view schematically showing the structure of an organic light emitting device according to the present invention.
2 is a view showing a relationship between quantum efficiency and luminance of Example 1 and Comparative Example 1 according to the present invention.
3 is a view showing a relationship between quantum efficiency and luminance of Example 2 and Comparative Example 2 according to the present invention.
4 is a view showing a relationship between quantum efficiency and luminance of Example 3 and Comparative Example 3 according to the present invention.

Hereinafter, a preferred embodiment of the cyclopentafluorene-based compound for an organic light emitting device and the organic light emitting device including the same according to the present invention will be described in detail with reference to the formula and the accompanying drawings, the same as in the accompanying drawings Corresponding components are given the same reference numerals and redundant description thereof will be omitted.

However, the following description is not intended to limit the present invention to specific embodiments, and it is to be understood that the present invention includes all conversions, equivalents, and substitutes included in the spirit and technical scope of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Furthermore, terms including an ordinal number such as first, second, etc. to be used below can be used to describe various elements, but the constituent elements are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

In addition, when a component is referred to as being "formed" or "laminated" on another component, it may be directly attached to, or laminated to, the front or one side on the surface of the other component, but the intermediate It will be understood that other components may exist in the.

Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

As a technical means for achieving the above technical problem, one aspect of the present invention provides a cyclopentafluorene-based compound for an organic light emitting device represented by the following formula (1).

[Formula 1]

In Formula 1,

X ¹ to X ⁴ may be the same as or different from each other, and each independently a valence bond, C _6-30 Arylene group or C _5-30 Hetero arylene group, preferably a valence bond, C _6-14 Arylene groups or C _5-14 Hetero arylene group, more preferably a valence bond, C _6-10 Arylene group or C _5-10 Heteroaryl group, still more preferably a valence bond or a C _{6 -10} Arylene group, even more preferably a valence bond or a phenylene group,

,

,

,

,

, C_{1 -9}의 알킬기, C_{6 -30}의 아릴기 또는 C_{5 -30}의 헤테로 아릴기, 바람직하게는 수소원자,

,

,

,

,

, C_{1 -6}의 알킬기, 보다 바람직하게는 수소원자,

,

,

,

,

, 또는 C_{1 -3}의 알킬기이거나, 이웃한 벤젠고리의 탄소원자와 결합하여 함께 C_{6 -30}의 접합된 방향족 고리 또는 C_5-30의 접합된 헤테로 방향족 고리를 형성할 수 있으며, Y¹은 산소원자 또는 황원자, 바람직하게는 황원자이고,R ¹ to R ⁴ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

, A heteroaryl group of the alkyl group of C _{1 -9,} C _{6 -30} aryl group, or C _{5 -30,} preferably a hydrogen atom,

,

,

,

,

, An alkyl group of C _{1 -6,} more preferably a hydrogen atom,

,

,

,

,

, Or is an alkyl group of C _{1 -3,} may form a conjugated heteroaromatic ring of C _{6 -30} bonded aromatic ring or a C _5-30 together in combination with the carbon atom of the adjacent benzene ring, Y ¹ is Oxygen atom or sulfur atom, preferably sulfur atom,

,

,

,

,

, C_{1 -9}의 알킬기, C_{6 -30}의 아릴기 또는 C_{5 -30}의 헤테로 아릴기, 바람직하게는 수소원자,

,

,

,

,

, 또는 C_{1 -6}의 알킬기, 보다 바람직하게는 수소원자,

,

,

,

,

, 또는 C_{1 -3}의 알킬기이거나, 이웃한 벤젠고리의 탄소원자와 결합하여 함께 C_{6 -30}의 접합된 방향족 고리 또는 C_{5 -30}의 접합된 헤테로 방향족 고리를 형성할 수 있으며, Y²는 산소원자 또는 황원자, 보다 바람직하게는 황원자이고,R ⁵ and R ⁶ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

, A heteroaryl group of the alkyl group of C _{1 -9,} C _{6 -30} aryl group, or C _{5 -30,} preferably a hydrogen atom,

,

,

,

,

, Or an alkyl group of C _{1 -6,} more preferably a hydrogen atom,

,

,

,

,

, Or is an alkyl group of C _{1 -3,} may form a conjugated heteroaromatic ring of C _{6 -30} bonded aromatic ring or C _{5 -30} with the combination with the carbon atom of the adjacent benzene ring, Y ² is Oxygen atom or sulfur atom, more preferably sulfur atom,

Wherein Ar ¹ to Ar ⁸ is the same as or different from each other, and each independently represents a hydrogen atom, a heteroaryl group of C _{6 -30} aryl group, or C _{5 -30} of the group, preferably a hydrogen atom, an aryl group of C _{6 -14} or C _{5 -14} heteroaryl group, more preferably a hydrogen atom, an aryl group of C _{6 -10} aryl group, or C _{5 -10} membered heteroaryl group, more preferably a hydrogen atom or a C _6-10 more of, Even more preferably a hydrogen atom or a phenyl group,

Wherein R ⁷ to R ¹⁶ may be the same or different from each other and each independently represents a hydrogen atom or a C _{1 -9,} preferably represents a hydrogen atom or a C _{1 -6,} more preferably a hydrogen atom or C _{1 - And} an alkyl group of ₃ , even more preferably a hydrogen atom or a C _{1 -2} alkyl group, even more preferably a hydrogen atom.

Specific examples of the C _6-30 aryl group of R ¹ to R ⁶ and Ar ¹ to Ar ⁸ include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group and 9- Anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacene Diary, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, p-terphenyl-4-yl, p-terphenyl-3 -Yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p -Tolyl group, p-tert-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4 -Methylbiphenylyl group, 4-tert-butyl-p-terphenyl-4-yl group, etc. are mentioned.

In addition, specific examples of the C _6-30 heteroaryl group of the R ¹ to R ⁶ and Ar ¹ to Ar ⁸ are 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, pyrimidyl group, pyridazyl group , 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group , 1-isoindoleyl group, 2-isoindoleyl group, 3-isoindoleyl group, 4-isoindoleyl group, 5-isoindoleyl group, 6-isoindoleyl group, 7-isoindoleyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzo Furanyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 1-dibenzofuranyl group, 2-dibenzofuran Diary, 3-dibenzofuranyl group, 6-dibenzo Lanyl group, 7-dibenzofuranyl group, 8-dibenzofuranyl group, 9-dibenzofuranyl group, 2-benzothiophene, 3-benzothiophene, 4-benzothiophene, 5-benzothiophene, 6- Benzothiophene, 7-benzothiophene, 1-dibenzocyiophene, 2-dibenzocyiophene, 3-dibenzocyiophene, 4-dibenzocyiophene, 6-dibenzothiophene, 7-dibenzosai Offen, 8-dibenzothiophene, 9-dibenzothiophene, 2-benzophosphole, 3-benzophosphole, 4-benzophosphole, 5-benzophosphole, 6-benzophosphole, 7-benzophosphate Pole, 1-dibenzophosphole, 2-dibenzophosphole, 3-dibenzophosphole, 4-dibenzophosphole, 6-dibenzophosphole, 7-dibenzophosphole, 8-dibenzophosphole, 9 Ibenzophosphole, 2-benzophosphole oxide, 3-benzophosphole oxide, 4-benzophosphole oxide, 5-benzophosphole oxide, 6-benzophosphole oxide, 7-benzophosphole oxide, 1-di Benzophospholioxide, 2-dibenzoforce Poloxide, 3-dibenzophospholeoxide, 4-dibenzophospholeoxide, 6-dibenzophospholeoxide, 7-dibenzophospholeoxide, 8-dibenzophospholeoxide, 9-dibenzophospholeoxide , Quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3- Isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalinyl, 5-quinoxaline Diary, 6-quinoxalinyl, 1-phenanthridine, 2-phenanthridine, 3-phenanthridine, 4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9 -Acridinyl, 1,7-phenanthroline-2-yl, 1,7-phenanthroline-3-yl, 1,7-phenant Lin-4-yl, 1,7-phenanthroline-5-diary, 1,7-phenanthroline-6-diary, 1,7-phenanthroline-8-diary, 1,7-phenanthroline- 9-diary, 1,7-phenanthroline-10-diary, 1,8-phenanthroline-2-yl, 1,8-phenanthroline-3-yl, 1,8-phenanthroline-4- Diary, 1,8-phenanthroline-5-diary, 1,8-phenanthroline-6-diary, 1,8-phenanthroline-7-diary, 1,8-phenanthroline-9-diary, 1,8-phenanthroline-10- diary, 1,9-phenanthroline-2-yl, 1,9-phenanthroline-3-yl, 1,9-phenanthroline-4-yl, 1, 9-phenanthroline-5-diary, 1,9-phenanthroline-6-diary, 1,9-phenanthroline-7-diary, 1,9-phenanthroline-8-diary, 1,9- Phenanthroline-10-diary, 1,10-phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1,10-phenanthroline-4-yl, 1,10-phenanthrole Lin-5-di, 2,9-phenanthroline-1-yl, 2,9-phenanthroline-3-yl, 2,9-phenanthroline-4-yl, 2,9-phenanthroline- 5-diary, 2,9-phenanthroline-6-diary, 2,9-phenanthroline-7-diary, 2,9-phenanthroline-8-diary, 2,9-phenanthrole -10- diary, 2,8-phenanthroline-1-yl, 2,8-phenanthroline-3-yl, 2,8-phenanthroline-4-yl, 2,8-phenanthroline-5 -Diary, 2,8-phenanthroline-6-diary, 2,8-phenanthroline-7-diary, 2,8-phenanthroline-9-diary, 2,8-phenanthrolineyl group, 2, 7-phenanthroline-1-yl, 2,7-phenanthroline-3-yl, 2,7-phenanthroline-4-yl, 2,7-phenanthroline-5-yl, 2,7- Phenanthroline-6-diary, 2,7-phenanthroline-8-diary, 2,7-phenanthroline-9-diary, 2,7-phenanthroline-10-diary, 1-phenazinezin, 2-phenazinyl group, 1-phenothiazine group, 2-phenothiazine group, 3-phenothiazine group, 4-phenothiazine group, 10-phenothiazine group, 1-phenoxazine group, 2-phenoxyl group Photo diary, 3-phenoxazine diary, 4-phenoxazine diary, 10-phenoxazine diary, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadia Zolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrole-1-yl group, 2-methylpyrrole-3-yl group , 2-methylpyrrole-4-yl group, 2-methylpyrrole-5-yl group, 3-methylpyrrole-1-yl group, 3-methylpyrrole-2-yl group, 3-methylpyrrole-4-yl group, 3-methylpyrrole -5-yl group, 2-tert-butylpyrrole-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2- Methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-tert-butyl-1-indolyl group, 4-tert-butyl-1-indolyl group, 2-tert-butyl-3-indolyl group or 4 -tert-butyl-3- indolyl group, etc. are mentioned.

In addition, the R ¹ to R ⁶ and specific examples include methyl, ethyl of the alkyl group of C _{1 -9,} n- propyl, n- pentyl, n- butyl, n- hexyl, n- heptyl, n- octyl, iso A propyl group, sec-butyl group, isobutyl group, tert- butyl group, etc. are mentioned.

In order to improve the problems of the fluorene-based compound including the existing fluorene structure, the present invention has the advantages of fluorene structure and exhibits excellent quantum efficiency, cyclopenta as a new material with improved thermal stability and film stability An organic compound having a fluorene structure was prepared. The cyclopentafluorene structure has a more rigid structure than the fluorene structure, and has a structure that is difficult to crystallize, thereby preventing crystallization during film formation, thereby improving thermal stability and excellent quantum efficiency. Indolence.

Hereinafter, structural formulas of the cyclopentafluorene-based compounds 1 to 737 of the present invention are illustrated in Tables 1 to 8, but the present invention is not limited to these compounds.

compound Chemical structural formula compound Chemical structure One

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compound Chemical structure compound Chemical structure 101

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compound Chemical structure compound Chemical structure 201

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compound Chemical structure compound Chemical structure 301

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compound Chemical structure compound Chemical structure 401

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An organic EL device according to the present invention will be described with reference to the accompanying drawings. 1 is a view schematically showing the structure of an organic EL device of the present invention. The organic light emitting device including the cyclopentafluorene-based compound represented by Chemical Formula 1 may be realized in various structures.

Referring to FIG. 1, an embodiment of the present invention includes a first electrode 110; A second electrode 150 formed to face the first electrode; And organic material layers 120, 130, and 140 formed between the first electrode 110 and the second electrode 150, wherein the organic material layers 120, 130, and 140 include the cyclopentafluorene-based compound. An organic electroluminescent device is provided.

Another embodiment of the present invention includes a first electrode 110, a second electrode 150, a light emitting layer 130, a hole transport layer 120 and an electron transport layer 140, the light emitting layer 130 is a host and a dopant In the organic light emitting device comprising a, the hole transport layer 120 may include the cyclopentafluorene-based compound. The electron transport layer 140 or the host may include the cyclopentafluorene-based compound.

Another embodiment of the present invention also includes a first electrode 110, a second electrode 150, a light emitting layer 130, a hole transport layer 120 and an electron transport layer 140, the light emitting layer 130 is a host In the organic light emitting device including a dopant, the electron transport layer 140 may provide an organic light emitting device comprising the cyclopentafluorene-based compound.

Another embodiment of the present invention also includes a first electrode 110, a second electrode 150, a light emitting layer 130, a hole transport layer 120 and an electron transport layer 140, the light emitting layer 130 is a host In the organic light emitting device including a dopant, the host may provide an organic light emitting device comprising the cyclopentafluorene-based compound.

In addition, according to another embodiment of the present invention, the organic light emitting device may further include a hole injection layer or an electron injection layer.

The organic electroluminescent device is preferably supported by a transparent substrate. The material of the transparent substrate is not particularly limited as long as it has good mechanical strength, thermal stability and transparency. For example, glass, a transparent plastic film, etc. can be used.

As the anode material of the organic EL device of the present invention, a metal, an alloy, an electrically conductive compound having a work function of 4 eV or more, or a mixture thereof can be used. Specifically, transparent conductive materials such as Au or CuI, ITO (indium tin oxide), SnO ₂ and ZnO which are metals are mentioned. The thickness of the positive electrode film is preferably 10 to 200 nm.

As a negative electrode material of the organic EL device of the present invention, a metal, an alloy, an electrically conductive compound or a mixture thereof having a work function of less than 4 eV can be used. Specifically, Na, Na-K alloy, calcium, magnesium, lithium, lithium alloy, indium, aluminum, magnesium alloy, aluminum alloy is mentioned. In addition, aluminum / AlO ₂ , aluminum / lithium, magnesium / silver or magnesium / indium may be used. The thickness of the negative electrode film is preferably 10 to 200 nm. In order to increase the luminous efficiency of the organic EL device, at least one electrode preferably has a light transmittance of 10% or more. The sheet resistance of the electrode is preferably several hundred Ω / mm or less. The thickness of the electrode is 10 nm to 1 m, more preferably 10 to 400 nm. Such an electrode may be manufactured by forming the above electrode material into a thin film through vapor deposition or sputtering such as chemical vapor deposition (CVD), physical vapor deposition (PVD), or the like.

The hole transport layer or the hole injection layer of the present invention is a material commonly used as a hole transport material among photoconductive materials as a hole transport material and a hole injection material, and a known material used for the formation of a hole transport layer or a hole injection layer of an organic EL device. It may include. For example, N, N-dicarbazolyl-3,5-benzene (mCP), poly (3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS), N, N'-di (1-naphthyl) -N, N '-diphenylbenzidine (NPD), N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diaminobiphenyl (TPD), N, N'-diphenyl-N, N'-Dinaphthyl-4,4'-diaminobiphenyl, N, N, N'N'-tetra-p-tolyl-4,4'-diaminobiphenyl, N, N, N'N ' Porphyrin compound derivatives such as tetraphenyl-4,4'-diaminobiphenyl, copper (II) 1,10,15,20-tetraphenyl-21H, 23H-porphyrin, aromatic tertiary in the main chain or side chain Polymer with amine, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N-tri (p-tolyl) amine, 4, 4 ', 4'-tris [N- Triarylamine derivatives such as (3-methylphenyl) -N-phenylamino] triphenylamine, carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, phthalocyanine derivatives such as metal-free phthalocyanine, copper phthalocyanine, starburst Amine May be a conductor, enamine stilbene derivatives, derivatives of aromatic tertiary amines and styrylamine compounds, polysilane and the like.

The electron transport layer of the present invention is a known electron transport material, for example diphenylphosphine oxide-4- (triphenylsilyl) phenyl (TSPO1), Alq ₃ , 2,5-diaryl silol derivative (PyPySPyPy), perfluorinated compound (PF -6P), Octasubstituted cyclooctatetraene compounds (COTs).

In the organic light emitting device of the present invention, the electron injection layer, the electron transport layer, the hole transport layer and the hole injection layer may be formed of a single layer containing one or more kinds of the above-mentioned compounds, or may be stacked on different kinds of compounds. It may consist of a plurality of layers to contain.

The light emitting layer of the organic electroluminescent device of the present invention may include a known light emitting material, for example, a phosphorescent fluorescent material, a fluorescent brightener, a laser dye, an organic scintillator and a reagent for fluorescence analysis. Specifically, a carbazole compound, a phosphine oxide compound, a carbazole phosphine oxide compound, bis ((3,5-difluoro-4-cyanophenyl) pyridine) iridium picolinate (FCNIrpic), tris (8-hydroxyquinoline) aluminum ( Alq ₃ ), polyaromatic compounds such as anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene and quinacridone, oligophenylene compounds such as quiterphenyl, 1,4-bis (2-methyl Styryl) benzene, 1,4-bis (4-methylstyryl) benzene, 1,4-bis (4-methyl-5-phenyl-2-oxazolyl) benzene, 1,4-bis (5-phenyl- 2-oxazolyl) benzene, 2,5-bis (5-t-butyl-2-benzoxazolyl) thiophene, 1,4-diphenyl-1,3-butadiene, 1,6-diphenyl-1, Scintillators for liquid scintillation such as 3,5-hexatriene, 1,1,4,4-tetraphenyl-1,3-butadiene, metal complexes of auxin derivatives, coumarin pigments, dicyano methylene pyran pigments and dicyano methylene Thiopyran pigment, polymethine pigment, oxobenzanthracene Pigments, xanthene pigments, carbostyryl pigments, perylene pigments, oxazine compounds, stilbene derivatives, spiro compounds, oxadiazole compounds and the like.

Each layer constituting the organic EL device of the present invention can be formed into a thin film through a known method such as vacuum deposition, spin coating or casting, or can be produced using a material used in each layer. The thickness of each of these layers is not particularly limited and may be appropriately selected according to the characteristics of the material, but may be determined usually in the range of 2 nm to 5,000 nm.

Since the compound of Chemical Formula 1 according to the present invention may be formed by a vacuum deposition method, the thin film forming process is simple and has an advantage of being easily obtained as a homogeneous thin film having little pin holes.

Hereinafter, the cyclopentafluorene compound according to the present invention and an organic electroluminescent device including the same according to the present invention will be described in more detail. However, this is for illustrative purposes and the scope of the present invention is not limited thereby.

[Example]

According to the present invention, first, the cyclopentafluorene-based compound of the present invention was prepared, and an organic electroluminescent device was manufactured using this compound. The following Preparation Examples and Examples are intended to specifically illustrate the present invention, whereby the present invention should not be limited.

Manufacturing example  1.Intermediate 2,2'- Dibromo biphenyl  Synthesis of compounds

10.00 g of 1,2-dibromobenzene was dissolved in 100 ml of tetrahydrofuran and the temperature was made to -78 ° C. Thereafter, 8.86 ml of butyllithium was slowly added dropwise. Slowly raised to room temperature. The reaction was terminated by distilled water and extracted with dichloromethane to dry the solvent. The reaction was purified by recrystallization from nucleic acid to afford the intermediate 2,2'-dibromobiphenyl compound.

Manufacturing example  2. Intermediate (1) 4, 8- Vis (4- Bromophenyl ) -4,8- Diphenyl -4,8- Dihydrocyclopentafluorene  Synthesis of Compounds.

After dissolving 3 g of 2,2′-dibromobiphenyl in 25 mL of tetrahydrofuran, the temperature was made to -78 ° C. Thereafter, 8.84 mL of 2.5 mol butyllithium was slowly added dropwise. After stirring for 2 hours, 5.77 g 4-bromo-benzophenone dissolved in 35 mL tetrahydrofuran was slowly added dropwise. Heavenly warms up to room temperature. 50 mL of a 2% sodium bicarbonate aqueous solution was added thereto, followed by stirring. Extract with dichloromethane and dry the solvent. 30 mL of acetic acid is added to this solid and the temperature is dissolved. 3 mL of sulfuric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the compound intermediate (1) 4,8-bis (4-bromophenyl) -4,8-diphenyl-4,8-dihydrocyclopentafluorene.

Manufacturing example  3. Synthesis of Compound 1

0.70 g of compound intermediate (1), 0.46 g of diphenylamine, and a palladium catalyst were added and dissolved in 20 mL of toluene. When the reagents were dissolved, 0.26 g of 1 mol solution sodium-tert-butoxide and 0.22 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtered to obtain Compound 1 as a pale yellow powder.

Compound 1 showed a high glass transition temperature of 143 ℃.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl3): δ 7.75 (d, 2H), 7.50 (d, 2H), 7.35-7.16 (m, 22H), 6.81 (t, 4H), 6.63 (m, 8H), 6.55 (s, 2H), 6.39 (d, 2H)

MS (FAB) m / z 814 [(M + 1) ⁺ ].

Manufacturing example  4. Synthesis of Compound 14

0.80 g of compound intermediate (1), 0.52 g of 9H-carbazole, and a palladium catalyst were added and dissolved in 30 mL of toluene. When the reagents were dissolved, 0.30 g of 1 mol solution sodium-tert-butoxide and 0.25 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtrated to obtain Compound 14 as a pale yellow powder.

Compound 2 showed a high glass transition temperature of 151 ℃.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 Hz, CDCl3): 7.77-7.75 (m, 12H), 7.45 (m, 12H), 7.27 (d, 4H), 7.16-7.14 (m, 6H), 6.98-6.95 (m, 6H)

MS (FAB) m / z 878 [(M + l) ⁺ ]

Preparation Example 5 Synthesis of Compound 3

Dissolve 1.00 g of intermediate 2,2'-dibromobiphenyl in 20 ml of tetrahydrofuran and lower the temperature to -78 ° C. 2.94 mL of 2.5 mol butyllithium was slowly added dropwise. After stirring for 2 hours while maintaining the temperature, di-2-pyridyl-ketone dissolved in tetrahydrofuran was slowly added dropwise. Slowly raise the temperature. Add 2% sodium bicarbonate aqueous solution and stir for 2 hours.

Extract with dichloromethane and distilled water and then dry the solvent. 30mL of acetic acid was dissolved and 3mL of sulfuric acid was added and the temperature was raised to reflux. After completion of the reaction, the mixture was extracted with dichloromethane, the solvent was dried and the solid was filtered and purified to obtain the compound 3 in the crystalline state.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 Hz, CDCl3): 7.77-7.75 (m, 7H), 7.50-7.35 (m, 10H), 7.20-7.14 (m, 12H), 6.98-6.95 (m, 3H), 6.81 (m, 2H ), 6.63-6.55 (m, 5H), 6.39 (d, 1H)

MS (FAB) m / z 845 [(M + l) ⁺ ]

Preparation Example 6 Synthesis of Intermediate

3 g of 2,2′-dibromobiphenyl was dissolved in 15 mL of tetrahydrofuran, and the temperature was set to −78 ° C. 4.61 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 2 g of benzophenone in 25 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 40 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate 4-bromo-9,9′-diphenyl-9H-fluorene.

Preparation Example 7 Synthesis of Intermediate (2)

6.0 g of 4-bromo-9,9'-diphenyl-9H-fluorene was dissolved in 76 mL of tetrahydrofuran, and the temperature was set to -78 ° C. 7.4 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 6.0 g of 4,4′-dibromobenzophenone in 120 mL of tetrahydrofuran, it was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 mL of acetic acid is added to this solid and the temperature is dissolved. 10 mL of hydrochloric acid was added and the temperature was kept at 120 ° C. to reflux. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered and obtained to obtain the compound intermediate (2).

Preparation Example 8 Synthesis of Compound 10

1 g of compound intermediate (2), 0.66 g of diphenylamine, and 0.021 g of palladium acetate (2) are added and dissolved in 30 mL of toluene. When the reagents were dissolved, 0.37 g of 1 mol solution sodium-tert-butoxide and 0.3 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtrated to obtain Compound 10 as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 Hz, CDCl ₃ ): δ 7.33-7.11 (m, 22H), 6.81-6.76 (m, 8H), 6.63 (d, 8H), 6.51 (d, 4H)

MS (FAB) m / z 817 [(M + H) ⁺ ].

Manufacturing example  9. Synthesis of Compound 216

30 mL of tetrahydrofuran was added to 1.5 g of the compound intermediate (2) to make the temperature at -78 ° C. Thereafter, 2.35 mL of butyllithium was slowly added dropwise. After stirring for 2 hours while maintaining the temperature, 1.3 g of chlorodiphenylphosphine was slowly added dropwise and raised to room temperature. After completion of the reaction, 10 mL of methanol was added thereto and stirred, and after extraction, the solvent was dried. Dichloromethane was added to this solid, and a small amount of hydrogen peroxide was added, stirring, and the compound 216 which has the above-mentioned typical compound structure of white phosphine oxide was obtained.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 Hz, CDCl ₃ ): δ 7.77 (d, 8H), 7.65 (d, 4H), 7.45 (t, 12H), 7.36-7.11 (m, 20H)

MS (FAB) m / z 883 [(M + H) ⁺ ].

Manufacturing example  10. Synthesis of Compound 217

1.4 g of compound intermediate (2), 0.46 g of diphenylamine, and 0.015 g of palladium acetate (2) were added and dissolved in 30 mL of toluene. When the reagents were dissolved, 0.26 g of 1 mol solution sodium-tert-butoxide and 1.10 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. This solid is dissolved in 30 mL of tetrahydrofuran and the temperature is lowered to -78 ° C. 1.5 mL of butyllithium was slowly added dropwise and stirred while maintaining the temperature for 2 hours. 0.5 g of chlorodiphenylphosphine was slowly added dropwise and the temperature was raised to room temperature. After completion of the reaction, 10 mL of methanol was added to the mixture, followed by stirring. After extraction, the solvent was dried. Dichloromethane was added to this solid, and a small amount of hydrogen peroxide was added while stirring to obtain compound 16 which is a white phosphine oxide.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200Hz, CDCl ₃ ): δ7.77 (d, 4H), 7.65 (d, 2H), 7.45-7.11 (m, 28H), 6.81-6.76 (m, 4H), 6.63 (d, 4H) , 6.51 (d, 2H)

MS (FAB) m / z 845 [(M + H) ⁺ ].

Manufacturing example  11. Synthesis of Intermediates

10 g of 1,2-dibromo-4-methylbenzene was dissolved in 100 mL of tetrahydrofuran. The temperature was lowered to −78 ° C. and 9 mL of butyllithium was slowly added dropwise with stirring.

The temperature was slowly raised to room temperature. Extraction was performed with dichloromethane and pure water. The solvent was dried and then recrystallized with nucleic acid to obtain an intermediate 2,2′-dibromo-4,4′-dimethylbiphenyl compound in a crystalline state.

Preparation Example 12 Synthesis of Intermediate (3)

2 g of 2,2′-dibromo-4,4′-dimethylbiphenyl was dissolved in 15 mL of tetrahydrofuran and the temperature was made to -78 ° C. Then 5.6 mL of butyllithium was slowly added dropwise. It was stirred for 2 hours as it was and 3.6 g 4-bromobenzonphenone dissolved in 35 mL tetrahydrofuran was slowly added dropwise. Slowly raised to room temperature. 50 mL of a 2% sodium bicarbonate aqueous solution was added to the solution and stirred. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of sulfuric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the compound intermediate (3).

Manufacturing example  13. Synthesis of Compound 5

2 g of compound intermediate (3), 1.9 g of diphenylamine and 0.064 g of palladium acetate (2) were added, and dissolved in 30 mL of toluene. When the reagents were dissolved, 1.3 g of 1 mol solution sodium-tert-butoxide and 4.8 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtrated to obtain Compound (5) as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 7.75 (d, 2H), 7.50 (d, 2H), 7.35 (d, 2H), 7.20-7.16 (m, 12H), 7.07 (s, 4H), 6.81 (t, 4H), 6.63 (m, 8H), 6.55 (s, 2H), 6.39 (d, 2H), 2.34 (s, 6H)

MS (FAB) m / z 845 [(M + H) ⁺ ].

Preparation Example 14 Synthesis of Intermediate

After dissolving 3 g of 2,2′-dibromo-4,4′-dimethylbiphenyl in 15 mL of tetrahydrofuran, the temperature was set to -78 ° C. 4.61 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 2 g of benzophenone in 25 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 40 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate 4-bromo-2,7-dimethyl-9,9′-diphenyl-9H-fluorene.

Manufacturing example  15. Synthesis of Intermediate (4)

5.7 g of 4-bromo-2,7-dimethyl-9,9'-diphenyl-9H-fluorene was dissolved in 76 mL of tetrahydrofuran and the temperature was set to -78 ° C. 7.4 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 6.3 g of 4,4′-dibromobenzophenone in 123 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 mL of acetic acid is added to this solid and the temperature is dissolved. 10 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered and obtained to obtain the compound intermediate (4).

Manufacturing example  16. Synthesis of Compound 6

2 g of compound intermediate (4), 1.9 g of diphenylamine and 0.064 g of palladium acetate (2) were added, and dissolved in 50 mL of toluene. When the reagents were dissolved, 1.3 g of 1 mol solution sodium-tert-butoxide and 4.8 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtered to obtain Compound 6 as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 7.33-7.11 (m, 20H), 6.98 (d, 2H), 6.81-6.76 (m, 8H), 6.63 (d, 8H), 6.51 (d, 4H ) 2.34 (s, 6H)

MS (FAB) m / z 845 [(M + H) ⁺ ].

Manufacturing example  17. Synthesis of Intermediates

2 g of 4,4′-dibromobenzophenone, 1.5 g of phenylboronic acid, and 0.68 g of tetrakis (phenylphosphine) palladium (0) were dissolved in 30 mL of tetrahydrofuran. 30 mL of 2 molar potassium carbonate solution was added to the reactor and refluxed while maintaining the temperature at 120 ° C. After the reaction was extracted with dichloromethane and the solvent was dried. This solid was filtered to obtain an intermediate 4,4'-diphenylbenzophenone compound.

Manufacturing example  18.Synthesis of Intermediates

3 g of 2,2′-dibromobiphenyl was dissolved in 15 mL of tetrahydrofuran, and the temperature was set to −78 ° C. 4.61 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 2 g of 4,4`-diphenylbenzophenone in 25 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 40 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain intermediate 9,9-di ([1,1′-biphenyl] -3-yl) -4-bromo-9H-fluorene.

Manufacturing example  19.Synthesis of Intermediate (5)

5.7 g of 9,9-di ([1,1′-biphenyl] -3-yl) -4-bromo-9H-fluorene was dissolved in 76 mL of tetrahydrofuran and the temperature was set to -78 ° C. 4.9 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 4.2 g of 4,4′-dibromobenzophenone in 123 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 mL of acetic acid is added to this solid and the temperature is dissolved. 10 mL of hydrochloric acid was added and the temperature was kept at 120 ° C. to reflux. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate compound (5).

Manufacturing example  20. Synthesis of Compound 11

2 g of compound intermediate (5), 2.1 g of diphenylamine and 0.075 g of palladium acetate (2) were added and dissolved in 30 mL of toluene. When the reagents were dissolved, 1.9 g of 1 mole solution sodium-tert-butoxide and 6.5 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtrated to obtain Compound (11) as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 7.79 (s, 2H), 7.52-7.07 (m, 30H), 6.81-6.76 (m, 8H), 6.63 (d, 8H), 6.51 (d, 4H )

MS (FAB) m / z 969 [(M + H) ⁺ ].

Preparation Example 21 Synthesis of Intermediate

2 g of 4,4′-dibromobenzophenone, 1.2 g of bromomethane, and 0.03 g of aluminum trichloride were dissolved in 30 mL of acetonitrile. The temperature was maintained at 100 ° C. and refluxed. Filtration and purification with dichloromethane gave the intermediate 4,4`-dimethylbenzophenone compound.

Manufacturing example  22. Synthesis of Intermediates

3 g of 2,2′-dibromobiphenyl was dissolved in 15 mL of tetrahydrofuran, and the temperature was set to −78 ° C. 4.61 mL of butyllithium was slowly added dropwise and stirred for 2 hours. 2 g of 4,4`-dimethylbenzophenone was dissolved in 25 ml of tetrahydrofuran, and slowly added dropwise thereto, and the temperature was raised to room temperature. After the reaction, 40 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered and purified to obtain intermediate 4-bromo-9,9-di-p-tolyl-9H-fluorene.

Preparation Example 23 Synthesis of Intermediate (6)

5.7 g of 4-bromo-9,9-di-p-tolyl-9H-fluorene was dissolved in 76 mL of tetrahydrofuran, and the temperature was -78 ° C. 7.4 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 6.3 g of 4,4′-dibromobenzophenone in 123 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 mL of acetic acid is added to this solid and the temperature is dissolved. 10 mL of hydrochloric acid was added and the temperature was kept at 120 ° C. to reflux. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate compound (6).

Preparation Example 24 Synthesis of Compound 9

2 g of compound intermediate (6), 1.9 g of diphenylamine, and 0.064 g of palladium acetate (2) were added and dissolved in 30 mL of toluene. When the reagents were dissolved, 1.3 g of 1 mol solution sodium-tert-butoxide and 4.8 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtered and purified to obtain Compound (9) as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 7.36 (d, 2H), 7.20-7.11 (m, 20H), 6.81-6.76 (m, 8H), 6.63 (d, 8H), 6.51 (d, 4H ), 2.34 (s, 6 H).

MS (FAB) m / z 845 [(M + H) ⁺ ].

Preparation Example 25 Synthesis of Intermediate

2 g of 1,2,4-tribromobenzene, 0.92 g of phenylboronic acid, and 0.36 g of tetrakis (phenylphosphine) palladium (0) were dissolved in 30 mL of tetrahydrofuran. 30 mL of 2 mol aqueous potassium carbonate solution was put in a reactor and refluxed while maintaining the temperature at 120 ° C. After the reaction was extracted with dichloromethane and the solvent was dried. This solid was filtered to give the intermediate 3,4-dibromobiphenyl compound.

Manufacturing example  26. Synthesis of Intermediates

10 g of 3,4-dibromobiphenyl was dissolved in 100 mL of tetrahydrofuran. The temperature was lowered to −78 ° C. and 6.6 mL of butyllithium was slowly added dropwise and stirred.

The temperature was slowly raised to room temperature. Extraction was performed with dichloromethane and pure water. The solvent was dried and then recrystallized with nucleic acid to obtain the intermediate 2``, 3`-dibromo-para-quaterphenyl compound in the crystalline state.

Manufacturing example  27. Synthesis of Intermediate (7)

2 g of 2``, 3`-dibromo-para-quaterphenyl was dissolved in 15 mL of tetrahydrofuran and the temperature was made to -78 ° C. Thereafter, 4.3 mL of butyllithium was slowly added dropwise. After stirring for 2 hours, 2.8 g 4-bromobenzophenone dissolved in 35 mL tetrahydrofuran was slowly added dropwise. Slowly raised to room temperature. 50 mL of a 2% sodium bicarbonate aqueous solution was added to the solution and stirred. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of sulfuric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered and obtained to obtain the compound intermediate (7).

Manufacturing example  28. Synthesis of Compound 7

2 g of compound intermediate (7), 2.1 g of diphenylamine and 0.075 g of palladium acetate (2) were added and dissolved in 30 mL of toluene. When the reagents were dissolved, 1.9 g of 1 mole solution sodium-tert-butoxide and 6.5 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtered to obtain compound (7) as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ7.75 (d, 2H), 7.52-7.35 (m, 18H), 7.20-7.16 (m, 12H), 6.81 (t, 4H), 6.63 (m, 8H ), 6.55 (s, 2H), 6.39 (d, 2H)

MS (FAB) m / z 964 [(M + H) ⁺ ].

Manufacturing example  29. Synthesis of Intermediates

After dissolving 3 g of 2``, 3`-dibromo-para-quaterphenyl in 15 mL of tetrahydrofuran, the temperature was set to -78 ° C. 3.1 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 1.39 g of benzophenone in 25 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 40 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered to afford the intermediate 4-bromo-2,7,9,9-tetraphenyl-9H-fluorene.

Manufacturing example  30. Synthesis of Intermediate (8)

5.7 g of 4-bromo-2,7,9,9-tetraphenyl-9H-fluorene was dissolved in 76 mL of tetrahydrofuran and the temperature was set to -78 ° C. 4.99 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 4.22 g of 4,4′-dibromobenzophenone in 123 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 mL of acetic acid is added to this solid and the temperature is dissolved. 10 mL of hydrochloric acid was added and the temperature was kept at 120 ° C. to reflux. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate compound (8).

Manufacturing example  31. Synthesis of Compound 8

2 g of compound intermediate (8), 2.1 g of diphenylamine, and 0.075 g of palladium acetate (2) were added and dissolved in 30 mL of toluene. When the reagents were dissolved, 1.9 g of 1 mole solution sodium-tert-butoxide and 6.5 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtrated to obtain Compound (8) as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 7.52-7.11 (m, 32H), 6.81-6.76 (m, 8H), 6.63 (d, 8H), 6.51 (d, 4H)

MS (FAB) m / z 969 [(M + H) ⁺ ].

Manufacturing example  32. Synthesis of Compound 13

2 g of compound intermediate (1), 0.84 g of pyridin-3-ylboronic acid and 0.36 g of tetrakis (phenylphosphine) palladium (0) are dissolved in 30 mL of tetrahydrofuran. 30 mL of a 2 molar potassium carbonate aqueous solution was added dropwise and refluxed while maintaining the temperature at 120 ° C. The reaction solution was extracted with dichloromethane, the solvent was dried and the solid was filtered to give compound 13.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 9.24 (s, 2H), 8.70 (d, 2H), 8.42 (d, 2H), 7.57 (t, 2H), 7.33-7.11 (m, 24H)

MS (FAB) m / z 637 [(M + H) ⁺ ].

Preparation Example 33 Synthesis of Intermediate

2 g of 2,2`-dibromobiphenyl was dissolved in 15 mL of tetrahydrofuran and the temperature was made to -78 ° C. Then 5.6 mL of butyllithium was slowly added dropwise. It was stirred for 2 hours as it was and 3.6 g benzphenone dissolved in 35 mL tetrahydrofuran was slowly added dropwise. Slowly raised to room temperature. 50 mL of a 2% sodium bicarbonate aqueous solution was added to the solution and stirred. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of sulfuric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the compound intermediate 4,4,8,8, -tetraphenyl-4,8-dihydrocyclopenta [def] fluorene.

Manufacturing example  34. Synthesis of Intermediate (9)

Dissolve 2 g of 4,4,8,8, -tetraphenyl-4,8-dihydrocyclopenta [def] fluorene in a DMF solvent, add 1.8 g of N-bromosuccinimide, and stir at room temperature. Extract with dichloromethane and dry the solvent. This solid was filtered and synthesized to synthesize compound intermediate (9).

Manufacturing example  35. Synthesis of Compound 4

1 g of compound intermediate (9), 0.65 g of diphenylamine, and 0.02 g of palladium acetate (2) were added and dissolved in 30 mL of toluene. When the reagents were dissolved, 0.3 g of 1 mol solution sodium-tert-butoxide and 0.31 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtered and purified to obtain Compound 4 as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 7.33-7.11 (m, 28H), 6.81 (t, 4H), 6.63 (d, 8H), 6.47 (s, 4H).

MS (FAB) m / z 817 [(M + H) ⁺ ].

Preparation Example 36 Synthesis of Intermediate

3 g of 2,2′-dibromobiphenyl was dissolved in 15 mL of tetrahydrofuran, and the temperature was set to −78 ° C. 4.61 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 2 g of benzophenone in 25 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 40 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered to obtain the intermediate 4-bromo-9,9-diphenyl-9H-fluorene.

Manufacturing example  37.Synthesis of Intermediates

5.7 g of 4-bromo-9,9 diphenyl-9H-fluorene was dissolved in 76 mL of tetrahydrofuran, and the temperature was -78 ° C. 4.9 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 1.4 g of propane-2-one in 123 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 mL of acetic acid is added to this solid and the temperature is dissolved. 10 mL of hydrochloric acid was added and the temperature was kept at 120 ° C. to reflux. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate 4,4-dimethyl-8,8-diphenyl-4,8-dihydrocyclopenta [def] fluorene.

Preparation Example 38 Synthesis of Intermediate (10)

Dissolve 2 g of 4,4-dimethyl-8,8-diphenyl-4,8-dihydrocyclopenta [def] fluorene in a DMF solvent, add 1.8 g of N-bromosuccinimide, and stir at room temperature. Extract with dichloromethane and dry the solvent. This solid was filtered and purified to synthesize compound intermediate (10).

Preparation Example 39 Synthesis of Compound 275

1 g of compound intermediate (10), 0.65 g of diphenylamine, and 0.02 g of palladium acetate (2) are added and dissolved in 30 mL of toluene. When the reagents were dissolved, 0.3 g of 1 mol solution sodium-tert-butoxide and 0.31 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtrated to obtain Compound 275 as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 7.33-7.11 (m, 18H), 6.81 (t, 4H), 6.63-6.56 (m, 10H), 6.33 (s, 2H), 1.72 (s, 6H )

MS (FAB) m / z 693 [(M + H) ⁺ ].

Preparation Example 40 Synthesis of Intermediate

2 g of 2,2`-dibromobiphenyl was dissolved in 15 mL of tetrahydrofuran and the temperature was made to -78 ° C. Then 5.6 mL of butyllithium was slowly added dropwise. The mixture was stirred for 2 hours as it was, and 1.2 g propane-2-one dissolved in 35 mL tetrahydrofuran was slowly added dropwise. Slowly raised to room temperature. 50 mL of a 2% sodium bicarbonate aqueous solution was added to the solution and stirred. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of sulfuric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain compound intermediate 4,4,8,8, -tetramethyl-4,8-dihydrocyclopenta [def] fluorene.

Manufacturing example  41. Synthesis of Intermediate (11)

Dissolve 2 g of 4,4,8,8, -tetramethyl-4,8-dihydrocyclopenta [def] fluorene in a DMF solvent, add 1.8 g of N-bromosuccinimide, and stir at room temperature. Extract with dichloromethane and dry the solvent. This solid was filtered and synthesized to synthesize compound intermediate (11).

Manufacturing example  42. Synthesis of Compound 276

Add 1 g of compound intermediate (11), 0.65 g of diphenylamine, and 0.02 g of palladium acetate (2), and dissolve in 30 mL of toluene. When the reagents were dissolved, 0.3 g of 1 mol solution sodium-tert-butoxide and 0.31 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. This solid was filtered to give Compound 276 as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 7.20 (t, 8H), 6.81 (t, 4H), 6.63 (d, 8H), 6.51 (s, 4H), 1.72 (s, 12H).

MS (FAB) m / z 569 [(M + H) ⁺ ].

Manufacturing example  43. Synthesis of Intermediates

3 g of 2,2′-dibromobiphenyl was dissolved in 15 mL of tetrahydrofuran, and the temperature was set to −78 ° C. 4.61 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 1 g of propan-2-one in 25 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 40 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered to obtain the intermediate 4-bromo-9,9-dimethyl-9H-fluorene.

Manufacturing example  44.Synthesis of Intermediate 12

5.7 g of 4-bromo-9,9dimethyl-9H-fluorene was dissolved in 76 mL of tetrahydrofuran, and the temperature was -78 ° C. 4.9 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 5 g of 4,4-dibromobenzophenone in 123 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 mL of acetic acid is added to this solid and the temperature is dissolved. 10 mL of hydrochloric acid was added and the temperature was kept at 120 ° C. to reflux. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered and the intermediate 12 was obtained.

Manufacturing example  45. Synthesis of Compound 277

1 g of compound intermediate (12), 0.65 g of diphenylamine, and 0.02 g of palladium acetate (2) are added and dissolved in 30 mL of toluene. When the reagents were dissolved, 0.3 g of 1 mol solution sodium-tert-butoxide and 0.31 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtrated to obtain Compound 277 as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 7.37 (d, 2H), 7.25-7.20 (m, 12H), 6.81-6.76 (m, 8H), 6.63 (d, 8H), 6.51 (d, 4H ).

MS (FAB) m / z 693 [(M + H) ⁺ ].

Manufacturing example  46. Synthesis of Intermediates

After dissolving 3 g of 2,2′-dibromo-4,4′-dimethylbiphenyl in 15 mL of tetrahydrofuran, the temperature was set to -78 ° C. 4.61 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 1 g of propan-2-one in 25 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 40 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered to obtain the intermediate 4-bromo-2,7,9,9-tetramethyl-9H-fluorene.

Manufacturing example  47. Synthesis of Intermediate (13)

5.7 g of 4-bromo-2,7,9,9-tetramethyl-9H-fluorene was dissolved in 76 mL of tetrahydrofuran and the temperature was set to -78 ° C. 7.4 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 6.3 g of 4,4′-dibromobenzophenone in 123 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 mL of acetic acid is added to this solid and the temperature is dissolved. 10 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered and obtained to obtain the compound intermediate (13).

Manufacturing example  48. Synthesis of Compound 278

1 g of compound intermediate (13), 0.65 g of diphenylamine, and 0.02 g of palladium acetate (2) are added and dissolved in 30 mL of toluene. When the reagents were dissolved, 0.3 g of 1 mol solution sodium-tert-butoxide and 0.31 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. This solid was filtered to give Compound 278 as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 7.20 (t, 10H), 7.05 (s, 2H), 6.81-6.76 (m, 8H), 6.63 (d, 8H), 6.51 (d, 4H). 2.34 (s, 6 H), 1.72 (s, 6 H).

MS (FAB) m / z 721 [(M + H) ⁺ ].

Preparation Example 49 Synthesis of Intermediate

After dissolving 3 g of 2``, 3`-dibromo-para-quaterphenyl in 15 mL of tetrahydrofuran, the temperature was set to -78 ° C. 3.1 mL of butyllithium was slowly added dropwise and stirred for 2 hours. 1.39 g of propane-2-one was dissolved in 25 mL of tetrahydrofuran, and slowly added dropwise to raise the temperature to room temperature. After the reaction, 40 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered to obtain the intermediate 4-bromo-9,9-dimethyl-2,7-diphenyl-9H-fluorene.

Preparation 50. Synthesis of Intermediate (14)

5.7 g of 4-bromo-9,9-dimethyl-2,7-diphenyl-9H-fluorene was dissolved in 76 mL of tetrahydrofuran and the temperature was set to -78 ° C. 4.99 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 4.22 g of 4,4′-dibromobenzophenone in 123 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 mL of acetic acid is added to this solid and the temperature is dissolved. 10 mL of hydrochloric acid was added and the temperature was kept at 120 ° C. to reflux. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate compound (14).

Preparation Example 51 Synthesis of Compound 279

1 g of compound intermediate (14), 0.65 g of diphenylamine, and 0.02 g of palladium acetate (2) are added and dissolved in 30 mL of toluene. When the reagents were dissolved, 0.3 g of 1 mol solution sodium-tert-butoxide and 0.31 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. The solid was filtrated to obtain Compound 279 as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 7.51-7.41 (m, 12H), 7.20 (t, 8H), 6.81-6.76 (m, 8H), 6.63 (d, 8H), 6.51 (d, 4H ).

MS (FAB) m / z 845 [(M + H) ⁺ ].

Preparation Example 52 Synthesis of Intermediate

3 g of 2,2′-dibromobiphenyl was dissolved in 15 mL of tetrahydrofuran, and the temperature was set to −78 ° C. 4.61 mL of butyllithium was slowly added dropwise and stirred for 2 hours. 2 g of 4,4`-dimethylbenzophenone was dissolved in 25 ml of tetrahydrofuran, and slowly added dropwise thereto, and the temperature was raised to room temperature. After the reaction, 40 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. This solid was filtered and purified to obtain intermediate 4-bromo-9,9-di-p-tolyl-9H-fluorene.

Manufacturing example  53. Synthesis of Intermediates

5.7 g of 4-bromo-9,9-di-p-tolyl-9H-fluorene was dissolved in 76 mL of tetrahydrofuran, and the temperature was -78 ° C. 7.4 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 2.1 g of propane-2-one in 123 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 200 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 mL of acetic acid is added to this solid and the temperature is dissolved. 10 mL of hydrochloric acid was added and the temperature was kept at 120 ° C. to reflux. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate compound 4,4-dimethyl-8,8-di-p-tolyl-4,8-dihydrocyclopenta [def] fluorene.

Preparation Example 54 Synthesis of Intermediate (15)

Dissolve 2g of 4,4-dimethyl-8,8-di-p-tolyl-4,8-dihydrocyclopenta [def] fluorene in DMF solvent and add 1.8 g of N-bromosuccinimide and stir at room temperature. Extract with dichloromethane and dry the solvent. This solid was filtered and synthesized to synthesize compound intermediate (15).

Preparation 55. Synthesis of Compound 280

Add 1 g of compound intermediate (15), 0.65 g of diphenylamine, and 0.02 g of palladium acetate (2), and dissolve in 30 mL of toluene. When the reagents were dissolved, 0.3 g of 1 mol solution sodium-tert-butoxide and 0.31 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. This solid was filtered to give Compound 280 as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ7.20-7.11 (m. 16H), 6.81 (t, 4H), 6.63-6.57 (m, 10H), 6.45 (s, 2H), 2.34 (s, 6H ), 1.72 (s, 6 H).

MS (FAB) m / z 721 [(M + H) ⁺ ].

Manufacturing example  56. Synthesis of Intermediates

3 g of 2,2′-dibromobiphenyl was dissolved in 15 mL of tetrahydrofuran, and the temperature was set to −78 ° C. 4.61 mL of butyllithium was slowly added dropwise and stirred for 2 hours. After dissolving 2 g of 4,4`-diphenylbenzophenone in 25 mL of tetrahydrofuran, the mixture was slowly added dropwise and the temperature was raised to room temperature. After the reaction, 40 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 50 mL of acetic acid is added to this solid and the temperature is dissolved. 5 mL of hydrochloric acid was added and refluxed at 120 ° C. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain intermediate 9,9-di ([1,1′-biphenyl] -3-yl) -4-bromo-9H-fluorene.

Manufacturing example  57. Synthesis of Intermediates

5.7 g of 9,9-di ([1,1′-biphenyl] -3-yl) -4-bromo-9H-fluorene was dissolved in 76 mL of tetrahydrofuran and the temperature was set to -78 ° C. 4.9 mL of butyllithium was slowly added dropwise and stirred for 2 hours. 1.2 g of propane-2-one was dissolved in 123 mL of tetrahydrofuran, and slowly added dropwise to raise the temperature to room temperature. After the reaction, 200 mL of 2% aqueous sodium hydrogen carbonate solution was added and stirred. After extraction with dichloromethane the solvent was dried. Extract with dichloromethane and dry the solvent. 100 mL of acetic acid is added to this solid and the temperature is dissolved. 10 mL of hydrochloric acid was added and the temperature was kept at 120 ° C. to reflux. After the reaction, the solvent was dried after extraction using dichloromethane and distilled water. The solid was filtered to obtain the intermediate compound 4,4-di ([1,1'-biphenyl] -4-yl) -8,8-dimethyl-4,8-dihydrocyclopenta [def] fluorene.

Manufacturing example  58. Synthesis of Intermediate (16)

Dissolve 2 g of 4,4-di ([1,1'-biphenyl] -4-yl) -8,8-dimethyl-4,8-dihydrocyclopenta [def] fluorene in DMF solvent and add 1.8 g of N-bromosuccinimide at room temperature. Stir it. Extract with dichloromethane and dry the solvent. This solid was filtered and purified to synthesize compound intermediate (16).

Manufacturing example  59. Synthesis of Compound 281

1 g of compound intermediate (16), 0.65 g of diphenylamine, and 0.02 g of palladium acetate (2) are added and dissolved in 30 mL of toluene. When the reagents were dissolved, 0.3 g of 1 mol solution sodium-tert-butoxide and 0.31 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. This solid was filtered to give Compound 281 as a pale yellow powder.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry are as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 7.51-7.20 (m, 26H), 6.81 (t, 4H), 6.63-6.57 (m, 10H), 6.45 (s, 2H), 1.72 (s, 6H )

MS (FAB) m / z 845 [(M + H) ⁺ ].

Manufacturing example  60. Synthesis of Compound 625

Add 1 g of compound intermediate (9), 0.33 g of diphenylamine, and 0.01 g of palladium acetate (2), and dissolve in 30 mL of toluene. When the reagents were dissolved, 0.15 g of 1 mol solution sodium-tert-butoxide and 0.15 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. THF is dissolved in 0.38 g of dibenzo [ b, d ] thiophen-2-ylboronic acid and 0.10 g of palladium (0). Make 2 M aqueous solution of potassium carbonate and add it to the reaction. The temperature is raised to reflux and stirred. After the reaction was extracted with dichloromethane and distilled water and the solvent was dried. This solid was filtered to synthesize compound 625.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry were as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 8.45 (d, 1H), 8.00-7.98 (m, 3H), 7.86 (d, 1H), 7.52-7.49 (m, 4H), 7.33-7.11 (m, 24H), 6.81 (t, 2H), 6.63 (d, 4H), 6.47 (s, 2H).

MS (FAB) m / z 832 [(M + H) ⁺ ].

Manufacturing example  61. Synthesis of Compound 633

Add 1 g of compound intermediate (11), 0.40 g of diphenylamine, and 0.01 g of palladium acetate (2), and dissolve in 30 mL of toluene. When the reagents were dissolved, 0.15 g of 1 mol solution sodium-tert-butoxide and 0.15 g of tert-phosphine were added dropwise. Reflux while maintaining the temperature at 120 ° C. After the reaction, the mixture is extracted with dichloromethane and distilled water to dry the solvent. THF is dissolved in 0.57 g of dibenzo [ b, d ] thiophen-2-ylboronic acid and 0.15 g of palladium (0). Make 2 M aqueous solution of potassium carbonate and add it to the reaction. The temperature is raised to reflux and stirred. After the reaction was extracted with dichloromethane and distilled water and the solvent was dried. This solid was filtered to synthesize Compound 633.

The analysis data obtained by nuclear magnetic resonance and mass spectrometry were as follows.

NMR-1H (200 MHz, CDCl ₃ ): δ 8.45-8.41 (m, 2H), 8.20 (d, 1H), 7.98 (d, 1H), 7.58-7.50 (m, 5H), 7.20 (t, 4H) , 6.81 (t, 2H), 6.63 (d, 4H), 6.51 (s, 2H), 1.72 (s, 12H).

MS (FAB) m / z 584 [(M + H) ⁺ ].

Example 1

Compound 1 synthesized in the present invention was applied as a hole transport layer material of the green phosphor to prepare a green phosphor.

The structure of the device is ITO / DNTPD (N, N'-diphenyl-N, N'-bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl-4,4'-diamine, 60nm) / Compound 1 (30nm) / bis-9,9'-spirobi [fluoren-2-yl] -methanone (BSFM): tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) (30nm, 10%) / tris ( 8-hydroxyquinoline) aluminum (Alq ₃ , 20 nm) / LiF / Al.

Fabrication of the device was performed in the following manner. The ITO substrate was washed with pure water and isopropyl alcohol for 30 minutes in ultrasonic waves, and the surface of the ITO substrate was treated with short wavelength ultraviolet rays, and the organic material was vacuum deposited under a pressure of ¹ × 10 ⁻⁶ torr. DNTPD, Compound 1, and Alq3 were deposited at a rate of 0.1 nm / s to form films corresponding to each thickness. BSFM was vacuum deposited with Ir (ppy) ₃ dopant, and the deposition rate was BS nm at 0.1 nm / s, Ir. (ppy) ₃ was 0.01 nm / s. LiF was formed at a thickness of 1 nm at a rate of 0.01 nm / s, and Al was formed at a thickness of 100 nm at a deposition rate of 0.5 nm / sec. After the device was formed, the device was sealed using a CaO absorbent and a glass cover glass.

Comparative Example 1

Instead of compound 1, a device was fabricated using N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (NPB), which is generally applied as a hole transport layer material. The fabrication process of the device was performed in the same manner as in Example 1.

Example  2

Compound 3 synthesized in the present invention was applied as the electron transport layer material of the green phosphorescent device.

The structure of the device was ITO / DNTPD / NPB / TCTA / TCTA: Ir (ppy) 3 / Compound 3 / LiF / Al. Fabrication process of the device was the same as in Example 1.

Comparative Example 2

Instead of compound 3, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), which is generally used as an electron transport layer, was applied as an electron transport layer material of a green phosphorescent device.

The structure of the device was ITO / DNTPD / NPB / TCTA / TCTA: Ir (ppy) 3 / BCP / LiF / Al. The fabrication process of the device was the same as that of Example 2 except that BCP was applied as the electron transport layer material.

Example 3

Compound 14 synthesized in the present invention was applied as a host material of the green phosphor. The structure of the device was ITO / DNTPD / NPB / TCTA / Compound 14: Ir (ppy) 3 / BCP / LiF / Al. Fabrication process of the device was the same as in Example 1.

Comparative Example 3

Instead of compound 14, a commonly used host (4,4'-N, N'-dicarbazole) biphenyl (CBP) was applied as a host. The fabrication process of the device was the same as in Example 3 except that CBP was used instead of Compound 2.

The quantum efficiencies of Examples 1 to 3 and Comparative Examples 1 to 3 are described in G. Gu and SR Forrest, IEEE Journal of Selected Topics in Quantum Electronics, Vol. 4, No. 1, January / February 1998, p. 83 Measured as described in Table 99) and shown in Table 9. The organic light emitting device using the cyclopentafluorene-based compound of the present invention showed excellent quantum efficiency compared to the organic light emitting device of the prior art.

Quantum Efficiency (%) Color coordinates Example 1 17.8 (0.29, 0.63) Example 2 12.1 (0.32, 0.62) Example 3 18.1 (0.30, 0.63) Comparative Example 1 1.3 (0.30, 0.62) Comparative Example 2 9.0 (0.31, 0.63) Comparative Example 3 12.5 (0.29, 0.63)

Claims (13)

Cyclopentafluorene-based compound for organic electroluminescent device represented by the formula (1).
[Formula 1]

In Chemical Formula 1,
X ¹ to X ⁴ may be the same as or different from each other, and each independently a valence bond, C _6-30 Arylene group or C _5-30 Hetero arylene group,
R ¹ to R ⁴ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

, Or a heteroaryl group of the alkyl group of C _{1 -9,} C _{6 -30} aryl group or a C _{5 -30,} of a C _6-30 together in combination with the carbon atom of the adjacent benzene ring bonded aromatic ring or a _5- C ₃₀ may form a conjugated heteroaromatic ring, Y ¹ is an oxygen atom or a sulfur atom,
R ⁵ and R ⁶ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

, Or a heteroaryl group of the alkyl group of C _{1 -9,} C _{6 -30} aryl group or a C _{5 -30,} of a C _6-30 together in combination with the carbon atom of the adjacent benzene ring bonded aromatic ring or a _5- C ₃₀ may form a conjugated heteroaromatic ring, Y ² is an oxygen atom or a sulfur atom,
Ar ¹ to Ar ⁸ may be the same as or different from each other, each independently represent a hydrogen atom, an aryl group of C _6-30 or a heteroaryl group of C _5-30 ,
R ⁷ to R ¹⁶ may be the same as or different from each other, and each independently a hydrogen atom or an alkyl group of C _1-9 . The compound of claim 1, wherein X ¹ to X ⁴ may be the same as or different from each other, and each independently a valence bond, C _6-14 . Arylene groups or C _5-14 Hetero arylene group,
R ¹ to R ⁴ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

, An alkyl group of C _{1 -6,} and Y ¹ is an oxygen atom or a sulfur atom,
R ⁵ and R ⁶ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

And, an alkyl group or a C _{1 -6,} Y ² is an oxygen atom or a sulfur atom,
Ar ¹ to Ar ⁸ may be the same as or different from each other, each independently represent a hydrogen atom, an aryl group of C _6-14 or a heteroaryl group of C _5-14 ,
The R ⁷ to R ¹⁶ may be the same as or different from each other, and each independently a hydrogen atom or a C _1-6 alkyl group, characterized in that the cyclopentafluorene-based compound. The compound of claim 2, wherein X ¹ to X ⁴ may be the same as or different from each other, and each independently a valence bond, C _6-10 Arylene group or C _5-10 Hetero arylene group,
R ¹ to R ⁴ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

Or C _{1 -3} alkyl group, Y ¹ is an oxygen atom or a sulfur atom,
R ⁵ and R ⁶ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

A, or an alkyl group of C _{1 -3,} Y ² is an oxygen atom or a sulfur atom,
Ar ¹ to Ar ⁸ may be the same as or different from each other, each independently represent a hydrogen atom, an aryl group of C _6-10 or a heteroaryl group of C _5-10 ,
The R ⁷ to R ¹⁶ may be the same as or different from each other, and each independently a hydrogen atom or a C _1-3 alkyl group, characterized in that the cyclopentafluorene-based compound. The compound of claim 3, wherein X ¹ to X ⁴ may be the same as or different from each other, and each independently of the valence bond or C _6-10 . Arylene group,
R ¹ to R ⁴ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

, And an alkyl group of C _{¹ -3,} Y ₁ is a sulfur atom,
R ⁵ and R ⁶ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

A, or an alkyl group of C _{1 -3,} Y ² is a sulfur atom,
Ar ¹ to Ar ⁸ may be the same as or different from each other, each independently represent a hydrogen atom or an aryl group of C _6-10 ,
The R ⁷ to R ¹⁶ may be the same as or different from each other, and each independently a hydrogen atom or a C _1-2 alkyl group, a cyclopentafluorene-based compound. The method according to claim 4, X ¹ to X ⁴ may be the same or different from each other, each independently represent a valence bond or a phenylene group,
R ¹ to R ⁴ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

Or C _{1 -3} alkyl group, Y ¹ is a sulfur atom,
R ⁵ and R ⁶ may be the same as or different from each other, and each independently a hydrogen atom,

,

,

,

,

A, or an alkyl group of C _{1 -3,} Y ² is a sulfur atom,
Ar ¹ to Ar ⁸ may be the same as or different from each other, each independently represent a hydrogen atom or a phenyl group,
R ⁷ to R ¹⁶ is a cyclopentafluorene compound, characterized in that a hydrogen atom. A first electrode; A second electrode formed to face the first electrode; And an organic material layer formed between the first electrode and the second electrode.
The organic material layer of the organic light emitting device comprising the cyclopentafluorene compound according to claim 1. In an organic light emitting device comprising a first electrode, a second electrode, a light emitting layer, a hole transport layer and an electron transport layer, the light emitting layer comprises a host and a dopant,
The hole transport layer is an organic light emitting device comprising the cyclopentafluorene compound according to claim 1. The organic light emitting device of claim 7, wherein the electron transport layer comprises a cyclopentafluorene-based compound according to claim 1. The organic light emitting device of claim 7, wherein the host comprises a cyclopentafluorene-based compound according to claim 1. In an organic light emitting device comprising a first electrode, a second electrode, a light emitting layer, a hole transport layer and an electron transport layer, the light emitting layer comprises a host and a dopant,
The electron transport layer is an organic light emitting device comprising the cyclopentafluorene-based compound according to claim 1. In an organic light emitting device comprising a first electrode, a second electrode, a light emitting layer, a hole transport layer and an electron transport layer, the light emitting layer comprises a host and a dopant,
The host is an organic light emitting device comprising the cyclopentafluorene compound according to claim 1. The organic light emitting device of any one of claims 6, 7, 10, and 11, wherein the organic light emitting device further comprises a hole injection layer. The organic light emitting device of any one of claims 6, 7, 10, and 11, wherein the organic light emitting device further comprises an electron injection layer.

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