WO2018147638A1 - Organic compound and organic electroluminescent element using same - Google Patents

Abstract

The present invention relates to a novel organic compound and an organic electroluminescent element using the same and, more specifically, to a novel organic compound having excellent electron transfer ability and to an organic electroluminescent element having improved characteristics, such as light emission efficiency, a driving voltage, and a lifespan, by containing the compound as a material of an organic material layer.

Description

Organic Compounds and Organic Electroluminescent Devices Using the Same

The present invention relates to a novel organic compound and an organic electroluminescent device using the same, and more particularly, to include a novel organic compound having excellent electron transporting ability and the like as a material of the organic material layer, such as luminous efficiency, driving voltage, lifetime The present invention relates to an organic electroluminescent device having improved characteristics.

In 1965, research on organic electroluminescent (EL) devices (hereinafter simply referred to as 'organic EL devices') led to blue electroluminescence using anthracene single crystals was followed, and in 1987, a hole layer was formed by Tang. An organic EL device having a two-layer laminated structure composed of (NPB) and a light emitting layer (Alq ₃ ) has been proposed. Afterwards, in order to realize high efficiency and long life characteristics of the organic EL device, the electroluminescence is caused by the combination of the organic layer responsible for hole injection and transport, the organic layer responsible for electron injection and transport, and holes and electrons. Forms of multi-layered laminate structures have been proposed that impart respective distinctive and granular functions, such as inducing organic layers. The introduction of a multilayered laminate structure improves the performance of organic EL devices to commercialization characteristics, and is expanding the application range from portable radio display products in 1997 to portable information display devices and TV display devices.

The demand for larger displays and higher resolutions has led to problems of high efficiency and long life of organic EL devices. In particular, in the case of high resolution that is realized by forming more pixels in the same area, the result is a reduction in the emission area of the organic EL pixel, which inevitably reduces the lifetime, and the most important technical problem to be overcome by the organic EL device is It became.

In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination. However, holes move faster than electrons, and excitons generated in the emission layer are transferred to the electron transport layer, resulting in charge unbalance in the emission layer, thereby emitting light at the electron transport layer interface. When emitting light at the electron transport layer interface, there is a problem that the color purity and efficiency of the organic EL device is deteriorated, and in particular, when the organic EL device is manufactured, high temperature stability is lowered, thereby shortening the life of the organic EL device. Therefore, it is time to develop an electron transport material having high temperature stability, high T1 value, and fast and efficient hole blocking ability.

That is, in order to fully exhibit the excellent characteristics of the organic electroluminescent device, a material forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a light emitting auxiliary layer material, etc. Supported by an efficient material should be preceded, but development of a stable and efficient organic material layer for an organic electroluminescent device has not been made yet. Therefore, the development of new materials continues to be required, and in particular, the development of material combinations such as a hole transport layer and an electron transport layer is urgently required.

[Preceding technical literature]

[Patent Documents]

Korean Patent Publication No. 2015-0106067

An object of the present invention is to provide a novel organic compound which is excellent in electron transport ability, electron injection ability, and the like, which can be used as an organic material layer material.

Another object of the present invention is to provide an organic electroluminescent device including the novel organic compound having a low driving voltage, high luminous efficiency, and an improved lifetime.

In order to achieve the above object, an example of the present invention provides a compound represented by the following formula (1).

In Chemical Formula 1,

A and B are different from each other, and can be independently represented by the formula (2) to (5)

In Chemical Formulas 2 to 5,

* Means a part in which the bond with Formula 1 is formed,

X ₁ to X ₄ are different from each other, and contain an atom of any one of S, O, N (Ar ₁ ), C (Ar ₂ ) (Ar ₃ ),

n is an integer of 0 to 4,

C is a substituent represented by the following formula (6),

In Chemical Formula 6,

* Means a part in which the bond with Formula 1 is formed,

Z ₁ to Z ₅ are the same as or different from each other, represented by N or C (Ar ₄ ),

R ₁ and Ar ₁ to Ar ₄ are hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C ₆ -C ₆₀ aryl group, C _5-60 heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C _6- C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphazene group, selected from the group consisting of an arylamine C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ C ₆₀ of, or by combining the adjacent tile to form a condensed ring;

The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron of R ₁ and Ar ₁ to Ar ₄ Group, aryl boron group, arylphosphanyl group, mono or diaryl phosphinyl group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenes group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, an aryloxy group of nuclear atoms of 5 to 60 heteroaryl group, C ₆ ~ C _60, alkyloxy group of C ₁ ~ C ₄₀ of the , C ₆ ~ C ₆₀ arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group , the group consisting of C ₆ ~ C ₆₀ aryl group of boron, C ₆ ~ C ₆₀ aryl phosphazene group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ C ₆₀ aryl group in the silyl When substituted with at least one selected more substituents or being unsubstituted, substituted by a plurality of substituents, they are same as or different from each other.

In addition, another example of the present invention is an organic electroluminescent device comprising an anode, a cathode and one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is represented by Formula 1 above. It provides an organic electroluminescent device comprising the compound represented.

Since the compound represented by Chemical Formula 1 according to an example of the present invention has excellent heat resistance, electron injection ability, electron transport ability, etc., it may be used as an organic material layer material, preferably an electron injection layer material, or an electron transport layer material of an organic EL device. Can be.

In addition, the organic electroluminescent device including the compound according to an example of the present invention in the electron injection layer or the electron transport layer can be greatly improved in terms of driving voltage, efficiency, lifespan, and the like. It can be effectively applied to the back.

Hereinafter, the present invention will be described in detail.

1. Organic Compound

The organic compound of the present invention is a compound having a structure in which one or more substituents are linked directly or through a linker group as a basic skeleton to a moiety bonded to a substituent including two or more 5-membered aromatic rings or 5-membered aromatic hetero rings. It is represented by Formula (1).

At this time, the substituent containing a 5-membered aromatic ring or 5-membered aromatic hetero ring is a benzoheteropentagon compound, such as benzotriazole, indazole, indole, indene, benzofuran ( benzofuran) and the like.

More specifically, the compound represented by the formula (1) of the present invention is a direct linker group (EWG) or a linker group to the moiety bonded to a substituent containing a five-membered aromatic hetero ring, such as two or more benzotriazole, indazole, etc. EWG is attached to a moiety in which a substituent includes a 5-membered aromatic heterocyclic ring such as benzotriazole, indazole, etc., or a substituent including 5-membered aromatic ring such as indene, benzofuran, etc. It has a structure connected directly or through a linker group.

The T1 value (2.0 eV) of Alq used as the electron transport layer is significantly lower than the T1 value (2.4 eV) of Ir (ppy) used as the dopant in the light emitting layer, whereas the T1 value of the compound of the present invention is generally higher than Ir (ppy). (2.4 eV or more), not only to improve hole blocking ability, but also to relatively increase the probability that excitons stay well in the light emitting layer.

In addition, since the 5-membered aromatic ring or 5-membered aromatic hetero ring has a lower molecular weight than the conventional compound, it is possible to deposit at a relatively lower temperature than the materials during deposition, thereby improving processability and thermal stability.

Therefore, the compound represented by Formula 1 of the present invention can be used as an organic material layer material of the organic electroluminescent device, preferably an electron transporting layer / injection layer material material.

In addition, the organic electroluminescent device including the compound of Formula 1 may significantly improve performance and lifespan characteristics, and the full-color organic light emitting panel to which the organic electroluminescent device is applied may also maximize its performance.

An organic compound according to one embodiment of the present invention is represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

A and B are different from each other, and can be independently represented by the formula (2) to (5)

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Chemical Formulas 2 to 5,

* Means a part in which the bond with Formula 1 is formed,

X ₁ to X ₄ are different from each other, and contain an atom of any one of S, O, N (Ar ₁ ), C (Ar ₂ ) (Ar ₃ ),

n is an integer of 0 to 4,

C is a substituent represented by the following formula (6),

[Formula 6]

In Chemical Formula 6,

* Means a part in which the bond with Formula 1 is formed,

Z ₁ to Z ₅ are the same as or different from each other, represented by N or C (Ar ₄ ),

R ₁ and Ar ₁ to Ar ₄ are hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C ₆ -C ₆₀ aryl group, C _5-60 heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C _6- C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphazene group, selected from the group consisting of an arylamine C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ C ₆₀ of, or by combining the adjacent tile to form a condensed ring;

The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron of R ₁ and Ar ₁ to Ar ₄ Group, aryl boron group, arylphosphanyl group, mono or diaryl phosphinyl group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenes group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, an aryloxy group of nuclear atoms of 5 to 60 heteroaryl group, C ₆ ~ C _60, alkyloxy group of C ₁ ~ C ₄₀ of the , C ₆ ~ C ₆₀ arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group , the group consisting of C ₆ ~ C ₆₀ aryl group of boron, C ₆ ~ C ₆₀ aryl phosphazene group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ C ₆₀ aryl group in the silyl When substituted with at least one selected more substituents or being unsubstituted, substituted by a plurality of substituents, they are same as or different from each other.

According to an example of the present invention, the compound represented by Chemical Formula 1 may be represented by the following Chemical Formulas 7 to 10.

In Chemical Formulas 7 to 10,

X ₁ to X ₄ , n, R ₁ and Z are each as defined in Formula 1 to Formula 6.

According to a preferred embodiment of the present invention, A in Formula 1 may be selected from the following structures, but is not limited thereto.

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According to a preferred embodiment of the present invention, B of Formula 1 may be selected from the following structures, but is not limited thereto.

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According to a preferred embodiment of the present invention, C may be pyrimidine or triazine. In addition, Ar ₄ is the same as or different from each other, but may be selected from the following structure, but is not limited thereto.

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According to a preferred embodiment of the present invention, C of Formula 1 may be selected from the following structures, but is not limited thereto.

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Examples of the compound represented by Formula 1 according to an example of the present invention include compounds R1 to R140, but are not limited thereto.

"Alkyl" in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms, non-limiting examples thereof are methyl, ethyl, propyl, isobutyl, sec-butyl , Pentyl, iso-amyl, hexyl and the like.

In the present invention, "cycloalkyl" means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 carbon atoms. Non-limiting examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine and the like.

In the present invention, "heterocycloalkyl" means a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 nuclear atoms, and preferably at least one carbon in the ring, preferably 1 Carbon of 3 to 3 is substituted with a hetero atom such as N, O or S. Non-limiting examples thereof include morpholine, piperazine and the like.

In the present invention, "aryl" means a monovalent functional group obtained by removing a hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms, which is a single ring or two or more rings combined. In this case, the two or more rings may be attached in a simple or condensed form with each other. Non-limiting examples thereof include phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl and the like.

In the present invention, "heteroaryl" is a monovalent functional group obtained by removing a hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 Is substituted with a heteroatom such as nitrogen (N), oxygen (O), sulfur (S) or selenium (Se). In this case, the heteroaryl may be attached in a form in which two or more rings are simply attached or condensed with each other, and may also include a condensed form with an aryl group. Non-limiting examples of such heteroaryls include six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indole Polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, and 2-furanyl, N-imidazolyl, 2- Isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like.

In the present invention, "alkyloxy" means a monovalent functional group represented by RO-, wherein R is an alkyl having 1 to 40 carbon atoms, and may include a linear, branched or cyclic structure. Can be. Non-limiting examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

In the present invention, "aryloxy" means a monovalent functional group represented by R'O-, wherein R 'is aryl having 6 to 60 carbon atoms. Non-limiting examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.

In the present invention, "alkylsilyl" refers to silyl substituted with alkyl having 1 to 40 carbon atoms, "arylsilyl" refers to silyl substituted with aryl having 6 to 60 carbon atoms, and "alkylboron group" is used for 1 to 40 carbon atoms. It means a boron group substituted with 40 alkyl, "aryl boron group" means a boron group substituted with aryl having 6 to 60 carbon atoms, "arylphosphine group" means a phosphine group substituted with an aryl having 1 to 60 carbon atoms. "Arylamine" refers to an amine substituted with aryl having 6 to 60 carbon atoms.

As used herein, "condensed ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

2. Organic electroluminescent device

On the other hand, the present invention provides an organic electroluminescent device comprising a compound represented by the formula (1).

Specifically, an example of the present invention includes an anode, a cathode, and one or more organic material layers interposed between the anode and the cathode, and at least one of the one or more organic material layers is a compound represented by Formula 1 above. It provides an organic electroluminescent device comprising a. In this case, the compound represented by Formula 1 may be used alone, or two or more may be mixed and used.

According to one embodiment of the present invention, the one or more organic material layers include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, wherein at least one organic material layer may include a compound represented by the formula (1). have. Preferably, the organic material layer including the compound of Formula 1 may be an electron transport layer. An organic electroluminescent device according to an example of the present invention is a sugar except that at least one or more of the organic material layer (eg, at least one of the light emitting layer, the electron transporting layer, and the light emitting auxiliary layer) is formed to include the compound represented by Chemical Formula 1, It can be prepared by forming other organic material layers and electrodes using materials and methods known in the art.

The organic material layer may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

The substrate usable in the present invention is not particularly limited, and silicon wafers, quartz, glass plates, metal plates, plastic films, sheets, and the like may be used.

Examples of the anode material include i) metals such as vanadium, chromium, copper, zinc and gold or alloys thereof, ii) metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO), iii) combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb, iv) polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thi Conductive polymers such as OPEN] (PEDT), polypyrrole or polyaniline tube, and v) carbon black and the like can be used, but is not limited thereto.

In addition, the negative electrode material may be magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or metals such as M or alloys thereof, and multilayer structures such as LiF / Al or LiO ₂ / Al. Materials and the like may be used, but are not limited thereto.

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following Examples are merely to illustrate the present invention, the present invention is not limited by the following Examples.

Preparation Example 1 Synthesis of A1

9.2 g (16.9 mmol) of 4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2-phenylpyrimidine, 2.4 g (20.2 mmol) of 1H-indazole, 0.8 g (5 mol%) under nitrogen stream Pd ₂ (dba) ₃ , tri- tert -butylphosphine, 0.2 g (0.8 mmol) and sodium tert-butoxide, 5.0 g (50.6 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound A1 6.4 g (11.0 mmol, 65% yield).

GC-Mass (Theoretical value: 579.49 g / mol, Measured value: 579 g / mol)

1 H-NMR: δ 7.41-7.55 (m, 11H), 7.65-7.88 (m, 4H), 8.01-8.28 (m, 8H)

Preparation Example 2 Synthesis of A2

9.2 g (16.9 mmol) of 4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2-phenylpyrimidine under nitrogen stream, 3.4 g (20.2 mmol) of 3H-benzo [e] indazole, 0.8 g ( 5 mol%) of Pd ₂ (dba) ₃ , 0.2 g (0.8 mmol) of tri- tert- butylphosphine, 5.0 g (50.6 mmol) of sodium tert-butoxide, and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purification by column chromatography gave 6.9 g (11.0 mmol, yield 65%) of the target compound A2.

GC-Mass (Theoretical value: 629.55 g / mol, Measured value: 629 g / mol)

1 H-NMR: δ 7.41-7.55 (m, 11H), 7.65-7.88 (m, 4H), 8.01-8.31 (m, 10H)

Preparation Example 3 Synthesis of A3

9.2 g (16.9 mmol), 3- (pyridin-4-yl)-4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2- (pyridin-4-yl) pyrimidine under nitrogen stream 100 ml with 4.0 g (20.2 mmol) of 1H-indazole, 0.8 g (5 mol%) of Pd ₂ (dba) ₃ , 0.2 g (0.8 mmol) of tri- tert- butylphosphine and 5.0 g (50.6 mmol) of sodium tert-butoxide Toluene was added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain 7.2 g (11.0 mmol, yield 65%) of the target compound A3.

GC-Mass (Theoretical value: 657.56 g / mol, Measured value: 657 g / mol)

1 H-NMR: δ 7.42 to 7.53 (m, 8H), 7.69 to 7.94 (m, 6H), 8.01 to 8.25 (m, 6H), 8.45 to 8.75 (m, 5H).

Preparation Example 4 Synthesis of A4

7.9 g (16.9 mmol) of 4- (2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine, 2.4 g (20.2 mmol) of 1H-indazole, 0.8 g (5) mol%) of Pd ₂ (dba) ₃ , 0.2 g (0.8 mmol) of tri- tert- butylphosphine, 5.0 g (50.6 mmol) of Sodium tert-butoxide and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain 5.5 g (11.0 mmol, yield 65%) of the title compound A4.

GC-Mass (Theoretical value: 504.38 g / mol, Measured value: 504 g / mol)

1H-NMR: δ 7.41-7.56 (m, 8H), 7.65-7.75 (m, 2H), 8.01-8.31 (m, 8H)

Preparation Example 5 Synthesis of A5

10.9 g (16.9 mmol), 1H-indazole 2.4 in 2,4-bis (dibenzo [b, d] furan-2-yl) -6- (3,5-dibromophenyl) -1,3,5-triazine under nitrogen stream g (20.2 mmol), 0.8 g (5 mol%) of Pd ₂ (dba) ₃ , 0.2 g (0.8 mmol) of tri- tert- butylphosphine, 5.0 g (50.6 mmol) of sodium tert-butoxide and 100 ml of Toluene Stir at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain 7.5 g (11.0 mmol, yield 65%) of the target compound A5.

GC-Mass (Theoretical value: 684.54 g / mol, Measured value: 684 g / mol)

1 H-NMR: δ 7.32-7.43 (m, 7H), 7.51-7.74 (m, 8H), 7.80-7.73 (m, 4H), 8.01-8.25 (m, 3H)

Preparation Example 6 Synthesis of A6

9.2 g (16.9 mmol) of 4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2-phenylpyrimidine under nitrogen stream, 4.8 g (20.2 mmol) of 1-phenyl-1H-indazol-5-ylboronic acid ), 1.0 g (5 mol%) of Pd (PPh ₃ ) ₄ , 7.0 g (50.6 mmol) of potassium carbonate and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added at 110 for 3 hours. Stirred.

After completion of the reaction, the organic layer was separated using methylene chloride and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give the title compound A6 (7.2 g, 11.0 mmol, 65% yield).

GC-Mass (Theoretical value: 655.58 g / mol, Measured value: 655 g / mol)

1 H-NMR: δ 7.42 to 7.54 (m, 13H), 7.61 to 7.84 (m, 6H), 8.09 to 8.28 (m, 8H)

Preparation Example 7 Synthesis of A7

9.2 g (16.9 mmol) of 4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2-phenylpyrimidine, 2.4 g of 1H-benzo [d] [1,2,3] triazole under nitrogen stream 20.2 mmol), 0.8 g (5 mol%) of Pd ₂ (dba) ₃ , 0.2 g (0.8 mmol) of tri- tert- butylphosphine, 5.0 g (50.6 mmol) of sodium tert-butoxide and 100 ml of Toluene were added at 110 Stir for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound A7 6.6 g (11.3 mmol, yield 67%).

GC-Mass (Theoretical value: 580.48 g / mol, Measured value: 580 g / mol)

1 H-NMR: δ 7.41-7.54 (m, 11H), 7.63-7.88 (m, 4H), 8.01-8.27 (m, 7H)

Preparation Example 8 Synthesis of A8

9.2 g (16.9 mmol), 3H-naphtho [2,1-d] [1,2,3], 4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2-phenylpyrimidine under nitrogen stream 3.4 g (20.2 mmol) triazole, 0.8 g (5 mol%) Pd ₂ (dba) ₃ , 0.2 g (0.8 mmol) tri- tert- butylphosphine and 5.0 g (50.6 mmol) Sodium tert-butoxide with 100 ml of Toluene Was added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain 7.1 g (11.3 mmol, yield 67%) of the target compound A8.

GC-Mass (Theoretical value: 630.53 g / mol, Measured value: 630 g / mol)

1 H-NMR: δ 7.42-7.55 (m, 11H), 7.65-7.88 (m, 4H), 8.01-8.31 (m, 9H)

Preparation Example 9 Synthesis of A9

9.2 g (16.9 mmol), 1H-benzo [d] [1,2,4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2- (pyridin-4-yl) pyrimidine under nitrogen stream 4.0 g (20.2 mmol) of triazole, 0.8 g (5 mol%) of Pd ₂ (dba) ₃ , 0.2 g (0.8 mmol) of tri- tert- butylphosphine and 5.0 g (50.6 mmol) of sodium tert-butoxide and 100 Add ml of Toluene and stir at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain 6.6 g (11.3 mmol, yield 67%) of the target compound A9.

GC-Mass (Theoretical value: 581.46 g / mol, Measured value: 581 g / mol)

1 H-NMR: δ 7.41-7.52 (m, 8H), 7.69-7.74 (m, 6H), 8.01-8.25 (m, 6H), 8.43-8.73 (m, 4H),

Preparation Example 10 Synthesis of A10

7.9 g (16.9 mmol) of 4- (2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine, 1H-benzo [d] [1,2,3] triazole under nitrogen stream a 2.4 g (20.2 mmol), 0.8 g (5 mol%) of _{Pd 2 (dba) 3, tri-} tert -butylphosphine 0.2 g (0.8 mmol) and Sodium tert-butoxide 5.0 g (50.6 mmol) and 100 ml of Toluene Put and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound A10 5.7 g (11.3 mmol, yield 67%).

GC-Mass (Theoretical value: 505.37 g / mol, Measured value: 505 g / mol)

1 H-NMR: δ 7.41-7.56 (m, 8H), 7.65-7.75 (m, 2H), 8.01-8.31 (m, 7H)

Preparation Example 11 Synthesis of A11

10.9 g (16.9 mmol), 1H-benzo [2,4-bis (dibenzo [b, d] furan-2-yl) -6- (3,5-dibromophenyl) -1,3,5-triazine, under nitrogen stream d] [1,2,3] triazole 2.4 g (20.2 mmol), 0.8 g (5 mol%) of Pd ₂ (dba) ₃ , 0.2 g (0.8 mmol) tri- tert- butylphosphine and 5.0 g Sodium tert-butoxide (50.6 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound A11 7.7 g (11.3 mmol, yield 67%).

GC-Mass (Theoretical value: 685.53 g / mol, Measured value: 685 g / mol)

1 H-NMR: δ 7.32-7.43 (m, 7H), 7.51-7.73 (m, 8H), 7.80-7.92 (m, 4H), 8.00-8.23 (m, 2H)

Preparation Example 12 Synthesis of A12

9.2 g (16.9 mmol), 1-phenyl-1H-benzo [d] [1,2,3], 4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2-phenylpyrimidine under nitrogen stream 4.8 g (20.2 mmol) of triazol-5-ylboronic acid, 1.0 g (5 mol%) of Pd (PPh ₃ ) ₄ , and 7.0 g (50.6 mmol) of potassium carbonate and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol was added and stirred at 110 for 3 hours.

After completion of the reaction, the organic layer was separated using methylene chloride and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give the title compound A12 (7.4 g, 11.3 mmol, yield 67%).

GC-Mass (Theoretical value: 656.57 g / mol, Measured value: 656 g / mol)

1H-NMR: δ 7.41-7.54 (m, 13H), 7.61-7.84 (m, 6H), 8.09-8.25 (m, 7H)

Preparation Example 13 Synthesis of A13

9.2 g (16.9 mmol) of 4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2-phenylpyrimidine, 3.8 g of 1,1-dimethyl-1H-inden-5-ylboronic acid under nitrogen stream 20.2 mmol), 1.0 g (5 mol%) of Pd (PPh ₃ ) ₄ , 7.0 g (50.6 mmol) of potassium carbonate and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added at 110 to 3 Stir for hours.

After completion of the reaction, the organic layer was separated using methylene chloride and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give the title compound A13 (6.8 g, 11.3 mmol, 67% yield).

GC-Mass (Theoretical value: 605.56 g / mol, Measured value: 605 g / mol)

1H-NMR: δ 1.65 (s, 6H), 6.41 ~ 55 (m, 2H), 7.22 ~ 35 (m, 2H), 7.41 ~ 7.54 (m, 11H), 7.61 ~ 7.84 (m, 4H), 8.01 ~ 8.25 (m, 4H)

Preparation 14 Synthesis of A14

7.9 g (16.9 mmol) of 4- (2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine, 1,1-dimethyl-1H-inden-5-ylboronic acid under nitrogen stream 3.8 g (20.2 mmol), 1.0 g (5 mol%) of Pd (PPh ₃ ) ₄ , 7.0 g (50.6 mmol) of potassium carbonate and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol Stir at 110 for 3 hours.

After completion of the reaction, the organic layer was separated using methylene chloride and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give the title compound A14 (6.0 g, 11.3 mmol, 67% yield).

GC-Mass (Theoretical value: 530.46 g / mol, Measured value: 530 g / mol)

1 H-NMR: δ 1.65 (s, 6H), 6.41 to 55 (m, 2H), 7.22 to 33 (m, 2H), 7.41 to 7.51 (m, 8H), 7.60 to 7.84 (m, 2H), 8.01 to 8.25 (m, 4H)

Preparation 15 Synthesis of A15

9.2 g (16.9 mmol) of 4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2-phenylpyrimidine, 6.3 g of 1,1-diphenyl-1H-inden-5-ylboronic acid under nitrogen stream 20.2 mmol), 1.0 g (5 mol%) of Pd (PPh ₃ ) ₄ , and potassium carbonate, 7.0 g (50.6 mmol) and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added at 110 Stir for 3 hours.

After completion of the reaction, the organic layer was separated using methylene chloride and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give the title compound A15 (8.3 g, 11.3 mmol, yield 67%).

GC-Mass (Theoretical value: 729.70 g / mol, Measured value: 729 g / mol)

1 H-NMR: δ 6.41 to 55 (m, 2H), 7.22 to 37 (m, 12H), 7.45 to 7.51 (m, 10H), 7.60 to 7.89 (m, 4H), 8.01 to 8.25 (m, 5H)

Preparation 16 Synthesis of A16

9.2 g (16.9 mmol) of 4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2-phenylpyrimidine, 2.4 g (20.2 mmol) of 1H-indole, 0.8 g (5 mol%) under nitrogen stream of _{Pd 2 (dba) 3, tri-} tert -butylphosphine 0.2 g (0.8 mmol) and Sodium tert-butoxide 5.0 g (50.6 mmol) and placed in 100 ml of Toluene was stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound A16 6.3 g (11.0 mmol, 65% yield).

GC-Mass (Theoretical value: 578.50 g / mol, Measured value: 578 g / mol)

1 H-NMR: δ 7.41-7.57 (m, 12H), 7.65-7.88 (m, 4H), 8.01-8.28 (m, 8H)

Preparation 17 Synthesis of A17

9.2 g (16.9 mmol) of 4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2-phenylpyrimidine under nitrogen stream, 3.4 g (20.2 mmol) of 3H-benzo [e] indole, 0.8 g ( 5 mol%) of Pd ₂ (dba) ₃ , 0.2 g (0.8 mmol) of tri- tert- butylphosphine, 5.0 g (50.6 mmol) of sodium tert-butoxide, and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound A17 6.9 g (11.0 mmol, 65% yield).

GC-Mass (Theoretical value: 628.56 g / mol, Measured value: 628 g / mol)

1 H-NMR: δ 7.41-7.58 (m, 12H), 7.65-7.88 (m, 4H), 8.01-8.30 (m, 10H)

Preparation 18 Synthesis of A18

7.9 g (16.9 mmol) of 4- (2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine, 2.4 g (20.2 mmol) of 1H-indole, 0.8 g (5) mol%) of Pd ₂ (dba) ₃ , 0.2 g (0.8 mmol) of tri- tert- butylphosphine, 5.0 g (50.6 mmol) of Sodium tert-butoxide and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give 5.5 g (11.0 mmol, yield 65%) of the target compound A18.

GC-Mass (Theoretical value: 503.39 g / mol, Measured value: 503 g / mol)

1 H-NMR: δ 7.41-7.58 (m, 9H), 7.65-7.73 (m, 2H), 8.01-8.31 (m, 8H)

Preparation 19 Synthesis of A19

9.2 g (16.9 mmol) of 4- (biphenyl-4-yl) -6- (3,5-dibromophenyl) -2-phenylpyrimidine under nitrogen stream, 3.3 g (20.2 mmol) of benzofuran-5-ylboronic acid, 1.0 g (5 mol%) of Pd (PPh ₃ ) ₄ , 7.0 g (50.6 mmol) of potassium carbonate and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added and stirred at 110 for 3 hours.

After completion of the reaction, the organic layer was separated using methylene chloride and water was removed using MgSO ₄ . After removing the solvent of the organic layer was purified by column chromatography to give the title compound A19 (6.4 g, 11.0 mmol, 65% yield).

GC-Mass (Theoretical value: 579.48 g / mol, Measured value: 579 g / mol)

1H-NMR: δ 6.65-6.66 (m, 1H), 7.40-7.51 (m, 11H), 7.61-7.81 (m, 6H), 8.08-8.25 (m, 5H)

[ Synthesis Example  1] Synthesis of R1

6.4 g (11.0 mmol) of A1, 2.2 g (13.2 mmol) of 9H-carbazole, 0.5 g (5 mol%) of Pd ₂ (dba) ₃ , 0.1 g (0.6 mmol) of tri- tert- butylphosphine and Sodium tert -butoxide 3.2 g (32.9 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R1 5.5 g (8.2 mmol, 75% yield).

GC-Mass (Theoretical value: 665.78 g / mol, Measured value: 665 g / mol)

[ Synthesis Example  2] Synthesis of R3

6.9 g (11.0 mmol) of A2, 2.2 g (13.2 mmol) of 9H-carbazole, 0.5 g (5 mol%) of Pd ₂ (dba) ₃ , 0.1 g (0.6 mmol) of tri- tert -butylphosphine and Sodium tert -butoxide 3.2 g (32.9 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound R3 5.9 g (8.2 mmol, 75% yield).

GC-Mass (Theoretical value: 715.84 g / mol, Measured value: 715 g / mol)

[ Synthesis Example  3] Synthesis of R4

7.2 g (11.0 mmol) of A3, 2.2 g (13.2 mmol) of 9H-carbazole, 0.5 g (5 mol%) of Pd ₂ (dba) ₃ , 0.1 g (0.6 mmol) of tri- tert- butylphosphine and Sodium tert under nitrogen stream -butoxide 3.2 g (32.9 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound R4 6.1g (8.2 mmol, 75% yield).

GC-Mass (Theoretical value: 743.85 g / mol, Measured value: 743 g / mol)

[ Synthesis Example  4] Synthesis of R5

Under nitrogen stream, 5.5 g (11.0 mmol) of A4, 2.2 g (13.2 mmol) of 9H-carbazole, 0.5 g (5 mol%) of Pd ₂ (dba) ₃ , 0.1 g (0.6 mmol) of tri- tert -butylphosphine and Sodium tert -butoxide 3.2 g (32.9 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R5 4.9 g (8.2 mmol, 75% yield).

GC-Mass (Theoretical value: 590.67 g / mol, Measured value: 590 g / mol)

[ Synthesis Example  5] Synthesis of R6

In a nitrogen atmosphere A5 7.5 g (11.0 mmol), 9H-carbazole 2.2 g (13.2 mmol), 0.5 g (5 mol%) of _{Pd 2 (dba) 3, tri-} tert -butylphosphine 0.1 g (0.6 mmol) and Sodium tert -butoxide 3.2 g (32.9 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound R6 6.3 g (8.2 mmol, 75% yield).

GC-Mass (Theoretical value: 770.83 g / mol, Measured value: 770 g / mol)

[ Synthesis Example 6 Synthesis of R7

7.2 g (11.0 mmol) of A6, 2.2 g (13.2 mmol) of 9H-carbazole, 0.5 g (5 mol%) of Pd ₂ (dba) ₃ , 0.1 g (0.6 mmol) of tri- tert -butylphosphine and Sodium tert -butoxide 3.2 g (32.9 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound R7 6.1g (8.2 mmol, 75% yield).

GC-Mass (Theoretical value: 741.88 g / mol, Measured value: 741 g / mol)

[ Synthesis Example 7 Synthesis of R11

In a nitrogen stream A1 6.4 g (11.0 mmol), 9,9-dimethyl-9H-fluoren-3-ylboronic acid 3.1 g (13.2 mmol), 0.5 g (5 mol%) of _{Pd 2 (dba) 3, tri-} tert 0.1 g (0.6 mmol) of -butylphosphine and 3.2 g (32.9 mmol) of sodium tert-butoxide and 100 ml of Toluene were added thereto and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R11 5.7 g (8.2 mmol, 75% yield).

GC-Mass (Theoretical value: 692.85 g / mol, Measured value: 692 g / mol)

[ Synthesis Example 8 Synthesis of R14

In a nitrogen stream A1 6.4 g (11.0 mmol), dibenzo [b, d] furan-2-ylboronic acid 2.8 g (13.2 mmol), 0.5 g Pd 2 (dba) of _{(5 mol%) 3, tri-} tert -butylphosphine 0.1 g (0.6 mmol) and 3.2 g (32.9 mmol) of sodium tert-butoxide and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give 5.5 g (8.2 mmol, yield 75%) of the target compound.

GC-Mass (Theoretical value: 666.77 g / mol, Measured value: 666 g / mol)

[ Synthesis Example 9 Synthesis of R18

6.4 g (11.0 mmol) of A1, 4.7 g (13.2 mmol) of 9,9'-spirobi [fluorene] -3-ylboronic acid, 0.5 g (5 mol%) of Pd ₂ (dba) ₃ , tri- tert 0.1 g (0.6 mmol) of -butylphosphine and 3.2 g (32.9 mmol) of sodium tert-butoxide and 100 ml of Toluene were added thereto and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound R14 6.7 g (8.2 mmol, 75% yield).

GC-Mass (Theoretical value: 814.97 g / mol, Measured value: 814 g / mol)

[ Synthesis Example  10] Synthesis of R21

6.6 g (11.3 mmol) A9, 9H-carbazole, 2.3 g (13.6 mmol), 0.5 g (5 mol%) of Pd ₂ (dba) ₃ , 0.1 g (0.6 mmol) tri- tert- butylphosphine under nitrogen stream 3.3 g (33.9 mmol) of tert-butoxide and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R21 5.7 g (8.5 mmol, 75% yield).

GC-Mass (Theoretical value: 666.77 g / mol, Measured value: 666 g / mol)

[ Synthesis Example  11] Synthesis of R23

7.1 g (11.3 mmol) of A8, 2.3 g (13.6 mmol) of 9H-carbazole, 0.5 g (5 mol%) of Pd ₂ (dba) ₃ , 0.1 g (0.6 mmol) of tri- tert -butylphosphine and sodium tert under nitrogen stream -butoxide 3.3 g (33.9 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound R23 6.1 g (8.5 mmol, 75% yield).

GC-Mass (Theoretical value: 716.83 g / mol, Measured value: 716 g / mol)

[ Synthesis Example  12] Synthesis of R25

5.7 g (11.3 mmol) of A10, 2.3 g (13.6 mmol) of 9H-carbazole, 0.5 g (5 mol%) of Pd ₂ (dba) ₃ , 0.1 g (0.6 mmol) of tri- tert -butylphosphine and sodium tert under nitrogen stream -butoxide 3.3 g (33.9 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain 5.0 g (8.5 mmol, yield 75%) of the title compound R25.

GC-Mass (Theoretical value: 519.66 g / mol, Measured value: 519 g / mol)

[ Synthesis Example  13] Synthesis of R26

A11 7.8 g (11.3 mmol), 9H-carbazole 2.3 g (13.6 mmol), 0.5 g (5 mol%) of _{Pd 2 (dba) 3, tri-} tert -butylphosphine 0.1 g (0.6 mmol) and Sodium tert conducted in a nitrogen atmosphere -butoxide 3.3 g (33.9 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound R26 6.5 g (8.5 mmol, yield 75%).

GC-Mass (Theoretical value: 771.82 g / mol, Measured value: 771 g / mol)

[ Synthesis Example  14] Synthesis of R27

In a nitrogen atmosphere A7 6.6 g (11.3 mmol), 9-phenyl-9H-carbazol-3-ylboronic acid 3.9 g (13.6 mmol), Pd 2 (dba) of _{0.5g (5 mol%) 3,} tri- tert -butylphosphine 0.1 g (0.6 mmol) and 3.3 g (33.9 mmol) of sodium tert-butoxide and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound R27 6.3 g (8.5 mmol, yield 75%).

GC-Mass (Theoretical value: 742.87 g / mol, Measured value: 742 g / mol)

[ Synthesis Example  15] Synthesis of R31

In a nitrogen atmosphere A7 6.6 g (11.3 mmol), 9,9-dimethyl-9H-fluoren-3-ylboronic acid 3.9 g (13.6 mmol), 0.5 g (5 mol%) of _{Pd 2 (dba) 3, tri-} tert 0.1 g (0.6 mmol) of -butylphosphine and 3.3 g (33.9 mmol) of sodium tert-butoxide and 100 ml of toluene were added thereto, and the mixture was stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R31 5.9 g (8.5 mmol, yield 75%).

GC-Mass (Theoretical value: 693.84 g / mol, Measured value: 693 g / mol)

[ Synthesis Example  16] Synthesis of R41

6.8 g (11.3 mmol) of A13, 2.3 g (13.6 mmol) of 9H-carbazole, 0.6 g (5 mol%) of Pd (PPh ₃ ) ₄ , and 4.7 g (33.9 mmol) of potassium carbonate and 80 ml / 40 Toluene / H ₂ O / Ethanol ml / 40 ml was added and stirred at 110 for 3 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R41 5.7 g (8.3 mmol, 73% yield).

GC-Mass (Theoretical value: 691.86 g / mol, Measured value: 691 g / mol)

[ Synthesis Example  17] Synthesis of R45

6.0 g (11.3 mmol) of A14, 2.3 g (13.6 mmol) of 9H-carbazole, 0.6 g (5 mol%) of Pd (PPh ₃ ) ₄ , and 4.7 g (33.9 mmol) of potassium carbonate and 80 ml / 40 Toluene / H ₂ O / Ethanol ml / 40 ml was added and stirred at 110 for 3 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound R45 5.1 g (8.3 mmol, 73% yield).

GC-Mass (Theoretical value: 616.75 g / mol, Measured value: 616 g / mol)

[ Synthesis Example  18] Synthesis of R47

6.8 g (11.3 mmol) of A13, 3.9 g (13.6 mmol) of 9-phenyl-9H-carbazol-3-ylboronic acid, 0.6 g (5 mol%) of Pd (PPh ₃ ) ₄ , and 4.7 g of potassium carbonate (33.9 mmol) and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added and stirred at 110 for 3 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R47 6.3 g (8.3 mmol, 73% yield).

GC-Mass (Theoretical value: 767.95 g / mol, Measured value: 767 g / mol)

[ Synthesis Example  19] Synthesis of R51

6.8 g (11.3 mmol) of A13, 3.2 g (13.6 mmol) of 9,9-dimethyl-9H-fluoren-3-ylboronic acid, 0.6 g (5 mol%) of Pd (PPh ₃ ) ₄ , and potassium carbonate 4.7 g (33.9 mmol) and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added and stirred at 110 for 3 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound R51 5.9 g (8.3 mmol, 73% yield).

GC-Mass (Theoretical value: 718.92 g / mol, Measured value: 718 g / mol)

[ Synthesis Example  20] Synthesis of R61

Under nitrogen stream, 8.3 g (11.3 mmol) of A15, 2.3 g (13.6 mmol) of 9H-carbazole, 0.6 g (5 mol%) of Pd (PPh ₃ ) ₄ , and 4.7 g (33.9 mmol) of potassium carbonate and 80 ml / 40 Toluene / H ₂ O / Ethanol ml / 40 ml was added and stirred at 110 for 3 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give 6.2 g (7.6 mmol, yield 67%) of the title compound R61.

GC-Mass (Theoretical value: 816.00 g / mol, Measured value: 816 g / mol)

[ Synthesis Example  21] Synthesis of R67

8.3 g (11.3 mmol) of A15, 3.9 g (13.6 mmol) of 9-phenyl-9H-carbazol-3-ylboronic acid, 0.6 g (5 mol%) of Pd (PPh ₃ ) ₄ , and potassium carbonate 4.7 g (33.9 mmol) and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added thereto and stirred at 110 for 3 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R67 7.4 g (8.3 mmol, 73% yield).

GC-Mass (Theoretical value: 892.09 g / mol, Measured value: 892 g / mol)

[ Synthesis Example  22] Synthesis of R71

8.3 g (11.3 mmol) of A15, 3.9 g (13.6 mmol) of 9,9-dimethyl-9H-fluoren-3-ylboronic acid, 0.6 g (5 mol%) of Pd (PPh ₃ ) ₄ , and potassium carbonate 4.7 g (33.9 mmol) and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added and stirred at 110 for 3 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R71 7.0 g (8.3 mmol, 73% yield).

GC-Mass (Theoretical value: 843.06 g / mol, Measured value: 843 g / mol)

[ Synthesis Example  23] Synthesis of R81

6.3 g (11.0 mmol) of A16, 2.2 g (13.2 mmol) of 9H-carbazole, 0.5 g (5 mol%) of Pd ₂ (dba) ₃ , 0.1 g (0.6 mmol) of tri- tert- butylphosphine and Sodium tert -butoxide 3.2 g (32.9 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give 5.3 g (8.0 mmol, 73% yield) of the title compound R81.

GC-Mass (Theoretical value: 664.79 g / mol, Measured value: 664 g / mol)

[ Synthesis Example  24] Synthesis of R83

6.9 g (11.0 mmol) of A17, 2.2 g (13.2 mmol) of 9H-carbazole, 0.5 g (5 mol%) of Pd ₂ (dba) ₃ , 0.1 g (0.6 mmol) of tri- tert- butylphosphine and Sodium tert under nitrogen stream -butoxide 3.2 g (32.9 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to obtain the title compound R83 5.7 g (8.0 mmol, 73% yield).

GC-Mass (Theoretical value: 714.85 g / mol, Measured value: 714 g / mol)

[ Synthesis Example  25] Synthesis of R85

5.5 g (11.0 mmol) of A18, 2.2 g (13.2 mmol) of 9H-carbazole, 0.5 g (5 mol%) of Pd ₂ (dba) ₃ , 0.1 g (0.6 mmol) of tri- tert- butylphosphine and Sodium tert under nitrogen stream -butoxide 3.2 g (32.9 mmol) and 100 ml of Toluene were added and stirred at 110 for 4 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give 4.7 g (8.0 mmol, 73% yield) of the title compound R85.

GC-Mass (Theoretical value: 589.69 g / mol, Measured value: 589 g / mol)

[ Synthesis Example 26 Synthesis of R88

6.3 g (11.0 mmol) of A16, 3.8 g (13.2 mmol) of 9-phenyl-9H-carbazol-3-ylboronic acid, 0.6 g (5 mol%) of Pd (PPh ₃ ) ₄ , and 4.7 g of potassium carbonate (33.9 mmol) and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added and stirred at 110 for 3 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound R88 5.9 g (8.0 mmol, 73% yield).

GC-Mass (Theoretical value: 740.89 g / mol, Measured value: 740 g / mol)

[ Synthesis Example 27 Synthesis of R91

6.3 g (11.0 mmol) of A16, 3.1 g (13.2 mmol) of 9,9-dimethyl-9H-fluoren-3-ylboronic acid, 0.6 g (5 mol%) of Pd (PPh ₃ ) ₄ , and potassium carbonate 4.7 g (33.9 mmol) and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added and stirred at 110 for 3 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give the title compound R91 5.5g (8.0 mmol, 73% yield).

GC-Mass (Theoretical value: 691.86 g / mol, Measured value: 691 g / mol)

[ Synthesis Example 28 Synthesis of R107

6.4 g (11.0 mmol) of A19, 3.8 g (13.2 mmol) of 9-phenyl-9H-carbazol-3-ylboronic acid, 0.6 g (5 mol%) of Pd (PPh ₃ ) ₄ , and 4.7 g of potassium carbonate (33.9 mmol) and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added and stirred at 110 for 3 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purified by column chromatography to give 5.3 g (7.1 mmol, yield 65%) of the title compound R107.

GC-Mass (Theoretical value: 741.88 g / mol, Measured value: 741 g / mol)

[ Synthesis Example 29 Synthesis of R111

6.4 g (11.0 mmol) of A19, 3.1 g (13.2 mmol) of 9,9-dimethyl-9H-fluoren-3-ylboronic acid, 0.6 g (5 mol%) of Pd (PPh ₃ ) ₄ , and potassium carbonate 4.7 g (33.9 mmol) and 80 ml / 40 ml / 40 ml of Toluene / H ₂ O / Ethanol were added and stirred at 110 for 3 hours.

After the reaction was terminated, the organic layer was separated with methylene chloride, and then water was removed using MgSO ₄ . Purification by column chromatography gave 4.9 g (8.0 mmol, yield 73%) of the title compound R111.

GC-Mass (Theoretical value: 692.84 g / mol, Measured value: 692 g / mol)

Examples 1 to 29 Fabrication of Green Organic EL Devices

Compounds synthesized in Synthesis Example After a high purity sublimation tablet using a commonly known method, a green organic EL device was manufactured according to the following procedure.

First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 mm 3 was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech) and then the substrate is cleaned for 5 minutes by UV and vacuum evaporator The substrate was transferred to.

M-MTDATA (60 nm) / TCTA (80 nm) / CBP + 10% Ir (ppy) ₃ (300 nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1) The organic EL device was fabricated by laminating in order of nm) / Al (200 nm).

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ , CBP, Alq3 and BCP are as follows.

Comparative Example 1 Fabrication of Green Organic EL Device

A green organic EL device was manufactured in the same manner as in Example 1, except that Alq ₃ , which is an electron transport layer material, was deposited at 30 nm.

[Evaluation Example 1]

For each of the green organic EL devices produced in Examples 1 to 28 and Comparative Example 1, the driving voltage, current efficiency, and emission peak at current density (10) mA / cm 2 were measured, and the results are shown in Table 1 below. It was.

Sample Electron transport layer Driving voltage (V) Light emitting peak (nm) Current efficiency (cd / A) Example 1 R1 4.0 515 18.1 Example 2 R3 4.0 515 17.2 Example 3 R4 4.2 515 17.9 Example 4 R5 3.9 515 17.1 Example 5 R6 4.0 515 18.5 Example 6 R7 4.3 515 17.9 Example 7 R11 4.2 515 18.2 Example 8 R14 4.2 515 17.6 Example 9 R18 4.1 515 17.1 Example 10 R21 3.6 515 18.0 Example 11 R23 4.4 515 17.3 Example 12 R25 4.0 515 18.3 Example 13 R26 4.3 515 17.9 Example 14 R27 4.2 515 17.9 Example 15 R31 4.2 515 17.5 Example 16 R41 4.0 515 18.2 Example 17 R45 4.3 515 17.7 Example 18 R47 4.2 515 17.7 Example 19 R51 4.1 515 17.1 Example 20 R61 4.1 515 18.3 Example 21 R67 3.5 515 17.3 Example 22 R71 4.0 515 18.3 Example 23 R81 4.3 515 17.9 Example 24 R83 3.9 515 17.9 Example 25 R85 4.1 515 18.3 Example 26 R88 4.0 515 17.9 Example 27 R91 4.0 515 17.8 Example 28 R107 3.8 515 18.5 Example 29 R111 4.2 515 18.1 Comparative Example 1 Alq ₃ 4.8 515 16.0

As shown in Table 1 above, when the compound according to the present invention (Examples 1-29) was used as the light emitting layer of the green organic EL device, it was compared with the green organic EL device (Comparative Example 1) using Alq3 as the electron transporting layer. It can be seen that the better performance in terms of efficiency and driving voltage.

Claims (9)

Compound represented by the following formula (1): [Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Chemical Formulas 2 to 5, * Means a part in which the bond with Formula 1 is formed, X ₁ to X ₄ are different from each other, and contain an atom of any one of S, O, N (Ar ₁ ), C (Ar ₂ ) (Ar ₃ ), n is an integer of 0 to 4, C is a substituent represented by the following formula (6), [Formula 6]

In Chemical Formula 6, * Means a part in which the bond with Formula 1 is formed, Z ₁ to Z ₅ are the same as or different from each other, represented by N or C (Ar ₄ ), R ₁ and Ar ₁ to Ar ₄ are hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C ₆ -C ₆₀ aryl group, C _5-60 heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C _6- C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphazene group, selected from the group consisting of an arylamine C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ C ₆₀ of, or by combining the adjacent tile to form a condensed ring; The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron of R ₁ and Ar ₁ to Ar ₄ Group, aryl boron group, arylphosphanyl group, mono or diaryl phosphinyl group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenes group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, an aryloxy group of nuclear atoms of 5 to 60 heteroaryl group, C ₆ ~ C _60, alkyloxy group of C ₁ ~ C ₄₀ of the , C ₆ ~ C ₆₀ arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group , the group consisting of C ₆ ~ C ₆₀ aryl group of boron, C ₆ ~ C ₆₀ aryl phosphazene group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ C ₆₀ aryl group in the silyl When substituted with at least one selected more substituents or being unsubstituted, substituted by a plurality of substituents, they are same as or different from each other. The method of claim 1, The compound of Formula 1 is a compound represented by the following formula 7 to formula 10: [Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In Chemical Formulas 7 to 10, X ₁ to X ₄ , n, R ₁ and Z ₁ to Z ₅ are each as defined in claim 1 above. The method of claim 1, A is selected from the following structures:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

The method of claim 1, Wherein B is selected from the following structures:

,

,

,

,

,

,

,

,

,

,

,

,

,

. The method of claim 1, C is pyrimidine or triazine. The method of claim 1, Ar ₄ is the same as or different from each other, and a compound selected from the following structures:

,

,

,

. The method of claim 1, Wherein C is selected from the following structures:

,

,

,

. An organic electroluminescent device comprising an anode, a cathode and at least one organic material layer interposed between the anode and the cathode, At least one of the one or more organic material layers is an organic electroluminescent device comprising the compound according to any one of claims 1 to 7. The method of claim 8, The one or more organic material layers include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, One or more organic material layers containing the compound is an electron transport layer or an electron injection layer.