KR102013400B1 - Indenophenanthrene derivatives and organic light emitting diodes comprising the derivatives - Google Patents

Abstract

The present invention relates to an organic light emitting compound and an organic light emitting device including the same, and more particularly to an indenophenanthrene derivative and an organic light emitting device having excellent luminous efficiency and brightness, and improved lifespan characteristics. .

Description

Indenophenanthrene derivatives and organic light emitting devices comprising the same {Indenophenanthrene derivatives and organic light emitting diodes comprising the derivatives}

The present invention relates to an organic light emitting compound and an organic light emitting device including the same, and more particularly to an indenophenanthrene derivative and an organic light emitting device having excellent luminous efficiency and brightness, and improved lifespan characteristics. .

An organic light emitting display device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows. Such organic light emitting diodes are known to have characteristics such as self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

The material used as the organic material layer in the organic electroluminescent device may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. . In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. A host-dopant system can be used as the luminescent material to increase the luminous efficiency through.

The principle is that when a small amount of dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high efficiency light. At this time, since the wavelength of the host shifts to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

In order for the organic electroluminescent device to fully exhibit the above-mentioned excellent features, the organic 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, etc. is supported by a stable and efficient material Although this should be preceded, the development of a stable and efficient organic material layer for an organic light emitting device has not been made yet. Therefore, the development of new materials in the art continues to be required.

Japanese Patent Application Laid-Open No. 1996-012600 discloses a device using a phenylanthracene derivative as a light emitting material. Although the anthracene derivative is used as a blue light emitting material, there is a need to improve device life and stability of a thin film. In addition, Japanese Patent Application Laid-Open No. 2002-154993 discloses a light emitting device using a compound in which an anthracene ring and a fluorene ring are directly bonded, but does not provide uniform light emission under high temperature. Accordingly, there is a demand for development of excellent materials that improve the luminous efficiency of organic light emitting diodes and have long stability and long lifespan.

Japanese Patent Publication No. 1996-012600 Japanese Patent Publication No. 2002-154993

An object of the present invention is to provide a novel indenophenanthrene compound, to implement an organic light emitting device having excellent luminous efficiency and brightness, and has a long life.

The present invention provides an indenophenanthrene derivative represented by the following [Formula 1] in order to achieve the above technical problem.

Where

이고, X₁₁은

이거나, 또는X ₃ is

, X ₁₁ is

Or

이고, X₁₁은

이며,X ₃ is

, X ₁₁ is

Is,

X ₁ , X ₂ , X ₄ X ₁₀ and X ₁₂ each independently represent a substituted or unsubstituted arylamino group having 6 to 24 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms, Substituted or unsubstituted C1-C24 alkyl group, substituted or unsubstituted C1-C24 heteroalkyl group, substituted or unsubstituted C3-C24 cycloalkyl group, substituted or unsubstituted C1-C24 alkoxy group , Cyano group, halogen group, substituted or unsubstituted aryloxy group having 6 to 24 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 24 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 24 carbon atoms, deuterium And hydrogen,

R ₁ to R ₂ , A ₁ to A ₂ are each independently a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms, a substituted or unsubstituted carbon atom 1 to An alkyl group of 24, a substituted or unsubstituted heteroalkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 24 carbon atoms, and R ₁ and R ₂ and A ₁ and A ₂ are bonded to each other; To form a saturated or unsaturated ring,

Ar ₁ to Ar ₂ is selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms,

a and b are each an integer of 0 to 2,

X ₁ , X ₂ , X ₄ When X to X ₁₀ , X ₁₂ , R ₁ to R ₂ and A ₁ to A ₂ and Ar ₁ to Ar ₂ are substituted, the substituents are each independently an aryl group having 6 to 24 carbon atoms and a heteroaryl group having 2 to 24 carbon atoms. A C1-C24 alkyl group, a C1-C24 heteroalkyl group, a C3-C24 cycloalkyl group, a C1-C24 alkoxy group, a cyano group, a halogen group, a C6-C24 aryloxy group, C1-C24 It may be selected from the group consisting of an alkylsilyl group of 24, an arylsilyl group having 6 to 24 carbon atoms, deuterium, the substituents may be bonded to each other to form a saturated or unsaturated ring, attached together or fused together in a pendant method Can be.

In addition, the present invention is an anode; Cathode; And it provides an organic electroluminescent device comprising the indenophenanthrene derivative of [Formula 1] between the anode and the cathode. In this case, the indenophenanthrene derivative is preferably included in the light emitting layer between the anode and the cathode, the device is a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection between the anode and the cathode It may further comprise one or more layers selected from the group consisting of layers.

When the indenophenanthrene derivative according to the present invention is used in the organic material layer of the organic light emitting device, the luminous efficiency and luminance are excellent, and a device having a long life can be realized.

1 is a cross-sectional view showing a layer structure of an organic light emitting display device according to an embodiment of the present invention.
2 is a graph showing the luminous efficiency of the organic light emitting display device according to Example 1-4 and Comparative Example 1 of the present invention.
3 is a graph showing luminous efficiency of the organic light emitting display device according to Example 5-8 and Comparative Example 2 of the present invention.

Hereinafter, the present invention will be described in more detail.

Indenophenanthrene derivatives according to the present invention are characterized by being represented by the following [Formula 1].

[Formula 1]

Where

이고, X₁₁은

이거나, 또는X ₃ is

, X ₁₁ is

Or

이고, X₁₁은

이며, X ₃ is

, X ₁₁ is

Is,

X ₁ , X ₂ , X ₄ X ₁₀ and X ₁₂ each independently represent a substituted or unsubstituted arylamino group having 6 to 24 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms, Substituted or unsubstituted C1-C24 alkyl group, substituted or unsubstituted C1-C24 heteroalkyl group, substituted or unsubstituted C3-C24 cycloalkyl group, substituted or unsubstituted C1-C24 alkoxy group , Cyano group, halogen group, substituted or unsubstituted aryloxy group having 6 to 24 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 24 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 24 carbon atoms, deuterium And hydrogen,

R ₁ to R ₂ , A ₁ to A ₂ are each independently a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms, a substituted or unsubstituted carbon atom 1 to An alkyl group of 24, a substituted or unsubstituted heteroalkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 24 carbon atoms, and R ₁ and R ₂ and A ₁ and A ₂ are bonded to each other; To form a saturated or unsaturated ring,

Ar ₁ to Ar ₂ is selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 24 carbon atoms,

a and b are each an integer of 0 to 2,

X ₁ , X ₂ , X ₄ When X to X ₁₀ , X ₁₂ , R ₁ to R ₂ and A ₁ to A ₂ and Ar ₁ to Ar ₂ are substituted, the substituents are each independently an aryl group having 6 to 24 carbon atoms and a heteroaryl group having 2 to 24 carbon atoms. , An alkyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, a cyano group, a halogen group, a substituted or unsubstituted aryl jade having 6 to 24 carbon atoms It may be selected from the group consisting of a period, a substituted or unsubstituted alkylsilyl group having 1 to 24 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 24 carbon atoms, deuterium, and the substituents are bonded to each other to form a saturated or unsaturated ring. It may be formed, and may be attached or fused together by a pendant method.

Specific examples of the indenophenanthrene derivatives of the above [Formula 1] include compounds represented by the following formulas (BD1) to (BD166), but are not limited thereto.

(BD1) (BD2) (BD3)

(BD4) (BD5) (BD6)

(BD7) (BD8) (BD9)

(BD10) (BD11) (BD12)

(BD13) (BD14) (BD15)

(BD16) (BD17) (BD18)

(BD19) (BD20) (BD21)

(BD22) (BD23) (BD24)

(BD25) (BD26) (BD27)

(BD28) (BD29) (BD30)

(BD31) (BD32) (BD33)

(BD34) (BD35) (BD36)

(BD37) (BD38) (BD39)

(BD40) (BD41) (BD42)

(BD43) (BD44) (BD45)

(BD46) (BD47) (BD48)

(BD49) (BD50) (BD51)

(BD52) (BD53) (BD54)

(BD55) (BD56) (BD57)

(BD58) (BD59) (BD60)

(BD61) (BD62) (BD63)

(BD64) (BD65) (BD66)

(BD67) (BD68) (BD69)

(BD70) (BD71) (BD72)

(BD73) (BD74) (BD75)

(BD76) (BD77) (BD78)

(BD79) (BD80) (BD81)

(BD82) (BD83) (BD84)

(BD85) (BD86) (BD87)

(BD88) (BD89) (BD90)

(BD91) (BD92) (BD93)

(BD94) (BD95) (BD96)

(BD97) (BD98) (BD99)

(BD100) (BD101) (BD102)

(BD103) (BD104) (BD105)

(BD106) (BD107) (BD108)

(BD109) (BD110) (BD111)

(BD112) (BD113) (BD114)

(BD115) (BD116) (BD117)

(BD118) (BD119) (BD120)

(BD121) (BD122) (BD123)

(BD124) (BD125) (BD126)

(BD127) (BD128) (BD129)

(BD130) (BD131) (BD132)

(BD133) (BD134) (BD135)

(BD136) (BD137) (BD138)

(BD139) (BD140) (BD141)

(BD142) (BD143) (BD144)

(BD145) (BD146) (BD147)

(BD148) (BD149) (BD150)

(BD151) (BD152) (BD153)

(BD154) (BD155) (BD156)

(BD157) (BD158) (BD159)

(BD160) (BD161) (BD162)

(BD163) (BD164) (BD165)

(BD166)

The present invention also provides an organic electroluminescent device comprising an anode, a cathode and an indenophenanthrene derivative represented by the above [Formula 1] between the anode and the cathode. In this case, the layer containing the indenophenanthrene derivative is preferably a light emitting layer between the anode and the cathode, the hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, the electron transport layer and the electron injection between the anode and the cathode It may further comprise one or more layers selected from the group consisting of layers.

As a specific example, a hole transport layer (HTL) may be further stacked, and an electron transport layer (ETL) may be additionally stacked between the cathode and the organic light emitting layer. The silver is stacked to facilitate the injection of holes from the anode, and the electron transport molecule having a small ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative mainly based on triphenylamine is used. It is used a lot.

The present invention is not particularly limited as long as it is commonly used in the art as a material of the hole transport layer. For example, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1 , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenylbenzidine (α-NPD) and the like can be used.

In addition, a hole injection layer (HIL) may be further stacked on the lower portion of the hole transport layer, and the hole injection layer material may be used without particular limitation as long as it is commonly used in the art. For example, CuPc (copperphthalocyanine) or starburst amines TCTA (4,4 ', 4 "-tri (N-carbazolyl) triphenyl-amine), m-MTDATA (4,4', 4" -tris- (3- methylphenylphenyl amino) triphenylamine) and the like can be used.

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention has the opportunity to recombine in the light emitting layer by smoothly transporting the electrons supplied from the cathode to the organic light emitting layer and suppressing the movement of holes not bonded in the organic light emitting layer. Serves to increase.

The electron transport layer material may be used without particular limitation as long as it is commonly used in the art, and for example, oxadiazole derivatives such as PBD, BMD, BND or Alq ₃ may be used.

Meanwhile, an electron injection layer (EIL) may be further stacked on the electron transport layer to facilitate electron injection from the cathode and ultimately improve power efficiency. Also commonly used in the art may be used without particular limitation, for example, it may be used a material such as LiF, NaCl, CsF, Li ₂ O, BaO.

The organic light emitting display device according to the present invention can be used for a display device, a display device and a monochrome or white lighting device.

1 is a cross-sectional view showing the structure of an organic light emitting display device according to the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60 and a cathode 80, and if necessary, the hole injection layer 30 and The electron injection layer 70 may be further included. In addition, an intermediate layer of one or two layers may be further formed, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to Figure 1 with respect to the organic light emitting device and a method of manufacturing the present invention are as follows. First, the anode 20 is formed by coating an anode electrode material on the substrate 10. As the substrate 10, a substrate used in a conventional organic EL device is used. An organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the anode electrode material, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), and the like, which are transparent and have excellent conductivity, are used.

The hole injection layer 30 is formed by vacuum-heat deposition or spin coating of the hole injection layer material on the anode 20 electrode. Next, the hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of the hole transport layer material on the hole injection layer 30.

Subsequently, the organic light emitting layer 50 is stacked on the hole transport layer 40, and a hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method. can do. The hole blocking layer prevents such a problem by using a material having a very low highest Occupied Molecular Orbital (HOMO) level because when the hole is introduced into the cathode through the organic light emitting layer is reduced the lifetime and efficiency of the device. . In this case, the hole blocking material to be used is not particularly limited, but should have an ionization potential higher than the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, and the like may be used.

After the electron transport layer 60 is deposited on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed and a cathode forming metal is vacuum-heated on the electron injection layer 70. The organic EL device is completed by vapor deposition to form a cathode 80 electrode. The metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lidium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag), and the like, and a transmissive cathode using ITO and IZO can be used to obtain a front light emitting device.

According to another embodiment of the present invention, at least one layer selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer is a single molecule deposition method or a solution process The organic light emitting display device according to the present invention may be used in display devices, display devices, and monochrome or white lighting devices.

< Example  >

Synthesis Example  1. Compound BD2 Synthesis of

Synthesis Example 1- (1): Synthesis of Intermediate 1-a

                                               Intermediate 1-a

50 g (194 mmol) of 9-bromo phenanthrene was added to a round bottomed flask containing 500 ml of tetrahydrofuran and the temperature was lowered to -78 degrees under nitrogen. After 30 minutes, 146 ml (233 mmol) of normal butyllithium is slowly added dropwise. After 1 hour, 28.3 g (274 mmol) of trimethyl borate was slowly added dropwise and the temperature was raised to room temperature. After stirring for about 12 hours at room temperature, 2N (normal) hydrochloric acid aqueous solution is added dropwise to the reaction solution until acid. Extract the organic layer by distillation under reduced pressure. Recrystallization with normal nucleic acid, followed by filtration and drying yielded a white solid having a yield of 35.2 g of intermediate 1-a 81%.

Synthesis Example 1- (2): Synthesis of Intermediate 1-b

                                                           Intermediate 1-b

45 g (132 mmol) methyl 5-bromo 2-iodobenzoate, 35.2 g (158 mmol) intermediate 1-a, tetrakistriphenylphosphinepalladium {Pd (PPh ₃ ) ₄ } 3.1 g (3 mmol) in a round bottom flask ), 36.5 g (264 mmol) of potassium carbonate, 90 mL of water, 225 ml of toluene and 225 mL of tetrahydrofuran were added and refluxed for 12 hours. After completion of the reaction, the reactants were separated by layer, the organic layer was concentrated under reduced pressure, dried over a column, and dried to obtain a white solid having a yield of 37 g of 72%.

Synthesis Example 1- (3): Synthesis of Intermediate 1-c

                                                            Intermediate 1-c

Add 47.5 g (303 mmol) of bromobenzene to a round-bottomed flask containing 300 ml of tetrahydrofuran and lower the temperature to -78 degrees under nitrogen. After 30 minutes, 177 ml (284 mmol) of 1.6 M normal butyllithium is slowly added dropwise. After 1 hour, slowly dropwise add 37.0g (95mmol) of intermediate 1-b and raise the temperature to room temperature. After stirring for about 2 hours at room temperature, add water. Extract the organic layer by distillation under reduced pressure. After recrystallization with normal nucleic acid, and filtered and dried to obtain a white solid of intermediate 1-c 38g yield 78%.

Synthesis Example 1- (4): Synthesis of Intermediate 1-d

                                                  Intermediate 1-d

Add 38 g (74 mmol) of Intermediate 1-c into a round bottom flask containing 304 ml of acetic acid. After raising the temperature to 80 degrees, add 1 ~ 2 rooms of aqueous hydrochloric acid solution to the reaction solution. The reaction solution is refluxed for about 2 hours. After the temperature was lowered to room temperature, the resultant solid was filtered and dried to obtain a white solid having a yield of intermediate 1-d 34g 93%.

Synthesis Example 1- (5): Synthesis of Intermediate 1-e

                                                 Intermediate 1-e

Put intermediate 1-d 34g (68 mmol) in a round bottom flask containing 272 ml of tetrahydrofuran and lower the temperature to -78 degrees under nitrogen. After 30 minutes, 47 ml (75 mmol) of 1.6 M normal butyllithium is slowly added dropwise. After 1 hour, add 20.8 g (82 mmol) of iodine and raise the temperature to room temperature. After stirring for about 2 hours at room temperature, add water. Extract the organic layer by distillation under reduced pressure. After recrystallization with normal nucleic acid, and filtered and dried to give a white solid of 80% yield of intermediate 1-e 29.8g.

Synthesis Example 1- (6): Intermediate 1-f Synthesis

                                                 Intermediate 1-f

29.8 g (55 mmol) of intermediate 1-e was added to a round bottom flask containing 238 ml of chloroform and stirred. After diluting 8.3 g (52 mmol) of bromine with 60 ml of chloroform, slowly add dropwise. Stir at room temperature for 24 hours. The resulting solid was dried after filtration to give a white solid having a yield of intermediate 1-f 30g 88%.

Synthesis Example 1- (7): Synthesis of Intermediate 1-g

                                                            Intermediate 1-g

5.9 g (48 mmol) phenylboronic acid, Intermediate 1-g 30.0 g (48 mmol) in a round bottom flask, tetrakistriphenylphosphinepalladium {Pd (PPh ₃ ) ₄ } 1.1 g (1 mmol), potassium carbonate 13.3 g (96 mmol), 60 mL of water, 150 ml of toluene and 150 mL of tetrahydrofuran were added and refluxed for 12 hours. After completion of the reaction, the reaction mixture was separated and the organic layer was concentrated under reduced pressure, recrystallized with normal nucleic acid, and then filtered and dried to obtain a white solid having a yield of 17.1 g, 62%.

Synthesis Example 1- (8): Synthesis of Compound BD2

                                                               BD2

In a round bottom flask, intermediate 1-g 10g (17 mmol), diphenylamine 3.0 g (17 mmol), palladium acetate {Pd (OAc) ₂ } 0.1 g (0.3 mmol), sodium tertiary butoxide 5.0 g (52.3 mmol) 0.1 g (0.3 mmol) of tritertiary butylphosphine and 100 ml of toluene were added thereto, and reacted under a reaction temperature of 100 ° C. for 2 hours. After the reaction is completed, the filtrate is concentrated after the filter and separated by column chromatography. Recrystallize from toluene and methanol. The resulting solid was filtered and dried to yield 4.0 g (45% yield) of a pale yellow solid.

MS: m / z 661 [M] ⁺

Synthesis Example  2. Compound BD5 Synthesis of

Synthesis was carried out in the same manner as in Synthesis Example 1- (8), except that 2-naphthylboronic acid was used instead of phenylboronic acid to obtain a pale yellow solid having a yield of 5.5 g and 40%.

MS: m / z 711 [M] ⁺

Synthesis Example  3. Compound BD20 Synthesis of

Synthesis Example 3- (1): Intermediate 3-a Synthesis

                                                           Intermediate 3-a

Intermediate 1-g 20.0g (35mmol), 4-bromophenylboronic acid 8.4g (42mmol), tetrakistriphenylphosphinepalladium {Pd (PPh ₃ ) ₄ } 0.8 g (1 mmol) in a round bottom flask , 9.6 g (70 mmol) of potassium carbonate, 40 mL of water, 100 ml of toluene, and 100 mL of tetrahydrofuran were added thereto, and the mixture was refluxed for 12 hours. After completion of the reaction, the reaction mixture was separated and the organic layer was concentrated under reduced pressure, recrystallized with normal nucleic acid, and then filtered and dried to obtain a white solid having a yield of 12.5 g of 55%.

Synthesis Example 3- (2): Synthesis of Compound BD20

                                                                 BD20

12.5 g (19.2 mmol) of intermediate 3-a, 3.3 g (19.2 mmol) of diphenylamine, 0.1 g (0.4 mmol) of palladium acetate {Pd (OAc) ₂ }, 5.5 g (57.7) of sodium tertiary butoxide in a round bottom flask mmol), tritary butylphosphine 0.1 g (0.4 mmol) and 125 ml of toluene were added and reacted under a reaction temperature of 100 ° C. for 2 hours. After the reaction is completed, the filtrate is concentrated after the filter and separated by column chromatography. Recrystallize from tetrahydrofuran and methanol. The resulting solid was filtered and dried to yield 5.2 g (37% yield) of a pale yellow solid.

MS: m / z 737 [M] ⁺

Synthesis Example  4. Compound BD32 Synthesis of

Synthesis Example 4- (1): Synthesis of Intermediate 4-a

                                                            Intermediate 4-a

42.9 g (245 mmol) of 1-bromo-3-fluorobenzene was added to a round-bottomed flask containing 240 ml of tetrahydrofuran and the temperature was lowered to -78 degrees under nitrogen. After 30 minutes, 143.8 ml (230 mmol) of 1.6 M normal butyllithium is slowly added dropwise. After 1 hour, slowly dropwise add 30.0g (77mmol) of intermediate 1-b and raise the temperature to room temperature. After stirring for about 2 hours at room temperature, add water. Extract the organic layer by distillation under reduced pressure. Recrystallization with normal nucleic acid, followed by filtration and drying yielded a white solid with 76% yield of Intermediate 4-a 32.1 g.

Synthesis Example 4- (2): Synthesis of Intermediate 4-b

                                                  Intermediate 4-b

Add 32.1 g (58 mmol) of Intermediate 4-a to a round bottom flask containing 257 ml of acetic acid. After raising the temperature to 80 degrees, add 1 ~ 2 rooms of aqueous hydrochloric acid solution to the reaction solution. The reaction solution is refluxed for about 2 hours. After the temperature was lowered to room temperature, the produced solid was filtered, recrystallized with normal nucleic acid, and then filtered and dried to obtain a white solid having an intermediate 4-b of 28.5 g yield 92%.

Synthesis Example 4- (3): Synthesis of Intermediate 4-c

                                                 Intermediate 4-c

28.5g (53mmol) of Intermediate 4-b was added to a round bottom flask containing 228ml of tetrahydrofuran and the temperature was lowered to -78 ° C under nitrogen. After 30 minutes slowly add 36.7 ml (59 mmol) of 1.6 M normal butyllithium. After 1 hour, add 16.3g (64mmol) of iodine and raise the temperature to room temperature. After stirring for about 2 hours at room temperature, add water. Extract the organic layer by distillation under reduced pressure. Recrystallization with normal nucleic acid, followed by filtration and drying yielded a white solid with an intermediate 4-c of 24.2 g yield 78%.

Synthesis Example 4- (4): Intermediate 4-d Synthesis

                                                 Intermediate 4-d

Put 24.2 g (42 mmol) of Intermediate 4-c into a round bottom flask containing 194 ml of chloroform and stir. Dilute 6.3 g (52 mmol) of bromine with 48 ml of chloroform and slowly add dropwise. Stir at room temperature for 24 hours. The resulting solid was filtered and recrystallized with normal nucleic acid, and then filtered and dried to obtain a white solid having an intermediate 4-d 22.6 g yield 82%.

Synthesis Example 4- (5): Synthesis of Intermediate 4-e

                                                        Intermediate 4-e

In a round bottom flask, 4.2 g (34 mmol) of phenylboronic acid, 22.6 g (34 mmol) of intermediate 4-d, tetrakistriphenylphosphinepalladium {Pd (PPh ₃ ) ₄ } 0.8 g (1 mmol), potassium carbonate g (69 mmol), 45 mL of water, 113 ml of toluene and 113 mL of tetrahydrofuran were added and refluxed for 12 hours. After completion of the reaction, the reaction mixture was separated and the organic layer was concentrated under reduced pressure, recrystallized with normal nucleic acid, and filtered and dried to obtain a light brown solid having a yield of 58% of 12.1 g.

Synthesis Example 4- (6): Synthesis of Compound BD32

                                                               BD32

In a round bottom flask, 12.1 g (19.9 mmol) of intermediate 4-e, 3.4 g (19.9 mmol) of diphenylamine, 0.1 g (0.5 mmol) of palladium acetate {Pd (OAc) ₂ }, 5.7 g (59.6) of sodium tert-butoxide mmol), tritary butylphosphine 0.1 g (0.4 mmol) and 121 ml of toluene were added and reacted under a reaction temperature of 100 ° C. for 2 hours. After the reaction is completed, the filtrate is concentrated after the filter and separated by column chromatography. Recrystallize from toluene and methanol. The resulting solid was filtered and dried to yield 4.7 g (34% yield) of a pale yellow solid.

MS: m / z 697 [M] ⁺

Synthesis Example  5. Compound BD73 Synthesis of

Synthesis Example 5- (1): Intermediate 5-a Synthesis

                                                 Intermediate 5-a

In a round-bottomed flask containing 160 ml of tetrahydrofuran, 20 g (32 mmol) of Intermediate 1-f is added and the temperature is reduced to -78 degrees under nitrogen. After 30 minutes, 24.1 ml (39 mmol) of 1.6 M normal butyllithium was slowly added dropwise. After 1 hour, slowly dropwise add water and raise the temperature to room temperature. After completion of the reaction, the reaction mixture was separated and the organic layer was concentrated under reduced pressure, recrystallized with normal nucleic acid, and then filtered and dried to obtain a white solid having a yield of 12.0 g, 75%.

Synthesis Example 5- (2): Synthesis of Compound BD73

                                                                 BD73

12 g (24.1 mmol) of intermediate 5-a, 4.8 g (24.1 mmol) of 4,4'-ditoluylamine, 0.1 g (0.5 mmol) of palladium acetate {Pd (OAc) ₂ }, sodium tert-butoxide in a round bottom flask 7.0 g (72.4 mmol), triglyceride butylphosphine 0.1 g (0.5 mmol) and 120 ml of toluene were added and reacted under a reaction temperature of 100 ° C. for 2 hours. After the reaction is completed, the filtrate is concentrated after the filter and separated by column chromatography. Recrystallize from toluene and methanol. The resulting solid was filtered and dried to yield 6.4 g (yield 43%) of a pale yellow solid.

MS: m / z 613 [M] ⁺

Synthesis Example  6. Compound BD103 Synthesis of

Synthesis Example 1- (8), except that (4-tert-butyl-phenyl)-(4-trimethylsilanyl-phenyl) -amine was used instead of diphenylamine, and synthesized in the same manner to obtain 5.5 g yield 40 A light yellow solid was obtained.

MS: m / z 789 [M] ⁺

Synthesis Example  7. Compound BD105 Synthesis of

Synthesis was conducted in the same manner as in Synthesis Example 1- (8), except that 3,5-bis (trimethylsilyl) -diphenylamine was used instead of diphenylamine to obtain a pale yellow solid having a 5.3g yield of 38%.

MS: m / z 805 [M] ⁺

Synthesis Example  8. Compound BD10 Synthesis of

                                                                 BD10

In a round bottom flask, Intermediate 1-d 10 g (20 mmol), diphenylamine 3.4 g (20 mmol), palladium acetate {Pd (OAc) ₂ } 0.1 g (0.4 mmol), sodium tert-butoxide 5.8 g (60.3 mmol) ), Tri tertiary butylphosphine 0.1 g (0.4 mmol) and toluene 100ml were added and reacted for 2 hours under a reaction temperature of 100 ℃. After the reaction is completed, the filtrate is concentrated after the filter and separated by column chromatography. Recrystallize from toluene and methanol. The resulting solid was filtered and dried to give 5.0 g (yield 43%) of a pale yellow solid.

MS: m / z 585 [M] ⁺

Example  1 to 8: Of organic light emitting device  Produce

The light emitting area of the ITO glass was patterned to have a size of 2 mm x 2 mm and then washed. After mounting the ITO glass in a vacuum chamber, the base pressure was 1 × 10 ⁻⁷ torr, and formed on Cu in the order of CuPc (800 kPa) and α-NPD (300 kPa) on the ITO. The film was formed by mixing the compound with 3% of the formula (BD1) prepared in the synthesis example (250 Å) and then 3,3- (3,8-di (biphenyl-4-yl) pyrene-1,6-diyl) di An organic light emitting display device was manufactured by forming a film of pyridine (350 kV), LiF (5 kV), and Al (500 kV) in this order. The emission characteristics of the organic light emitting device were measured at 0.4 mA.

In the experiment, the organic light emitting diode was manufactured in the same manner as in the following Table 1 instead of BD1, and the emission characteristics of the organic light emitting diode were measured at 0.4 mA.

(BH1)

Comparative example  1 to 2

Used in Example 1 above An organic light emitting diode was manufactured in the same manner as that of the compound, except that BD167 and BD168 were used instead of BD1, and the emission characteristics of the organic light emitting diode were measured at 0.4 mA. The structures of the BD167 and the BD168 are as follows.

(BD167) (BD168)

For the organic light emitting diodes manufactured according to Examples 1 to 8 and Comparative Examples 1 and 2, voltage, current, luminance, color coordinates, and lifetime were measured, and the results are shown in the following [Table 1]. T80 means the time taken for the luminance to decrease to 80% of the initial luminance.

Voltage Current density
(mA / cm ² ) External quantum
efficiency Whee
(cd / m ² ) CIEx CIEy T80 Example 1
(BD2) 4.0 10 6.8 569 0.138 0.093 135 Example 2
(BD5) 4.1 10 6.6 619 0.132 0.114 140 Example 3
(BD20) 4.2 10 6.8 694 0.129 0.131 100 Example 4
(BD32) 3.8 10 5.7 435 0.141 0.083 130 Example 5
(BD73) 4.1 10 6.7 670 0.129 0.126 160 Example 6
(BD103) 4.0 10 7.5 746 0.130 0.126 190 Example 7
(BD105) 3.9 10 6.6 593 0.137 0.107 150 Example 8
(BD10) 3.9 10 6.1 539 0.137 0.105 95 Comparative Example 1
(BD167) 4.3 10 5.1 534 0.133 0.137 45 Comparative Example 2
(BD168) 4.3 10 4.6 504 0.134 0.144 35

As shown in the evaluation results of [Table 1], the brightness and luminous efficiency of the organic light emitting device using the indenophenanthrene derivative according to the embodiment of the present invention is better than the comparative example, and the life is much longer. You can check it.

Claims (5)

Indenophenanthrene derivatives, characterized in that any one selected from compounds represented by the formula:
(BD1) (BD2) (BD3)

(BD4) (BD5) (BD6)

(BD7) (BD8) (BD9)

(BD10) (BD11) (BD12)

(BD13) (BD14) (BD15)

(BD16) (BD17) (BD18)

(BD19) (BD20) (BD21)

(BD22) (BD23) (BD24)

(BD25) (BD26) (BD27)

(BD28) (BD29) (BD30)

(BD32) (BD33)

(BD34) (BD35) (BD36)

(BD37) (BD38) (BD39)

(BD41) (BD42)

(BD43) (BD44) (BD45)

(BD46) (BD47) (BD48)

(BD49) (BD50)

(BD58) (BD59)

(BD67) (BD68) (BD69)

(BD70) (BD71) (BD72)

(BD73) (BD74) (BD75)

(BD76) (BD77) (BD78)

(BD79) (BD80) (BD81)

(BD82) (BD83) (BD84)

(BD85) (BD86) (BD87)

(BD88) (BD89) (BD90)

(BD91) (BD92) (BD93)

(BD94) (BD95) (BD96)

(BD97) (BD98) (BD99)

(BD100) (BD101) (BD102)

(BD103) (BD104) (BD105)

(BD106) (BD107) (BD108)

(BD109) (BD110) (BD111)

(BD112) (BD113) (BD114)

(BD115) (BD116) (BD117)

(BD118) (BD119) (BD120)

(BD121) (BD122) (BD123)

(BD124) (BD125) (BD126)

(BD127) (BD128) (BD129)

(BD130) (BD131) (BD132)

(BD133) (BD134) (BD135)

(BD136) (BD137) (BD138)

(BD139)

(BD142)

(BD145) (BD146) (BD147)

(BD148) (BD149) (BD150)

(BD165)

(BD166)

delete Anode; Cathode; And an indenophenanthrene derivative according to claim 1 between the anode and the cathode. The method of claim 3,
The indenophenanthrene derivative is an organic light emitting device, characterized in that contained in the light emitting layer between the anode and the cathode. The method of claim 4, wherein
An organic electroluminescent device further comprising at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer between the anode and the cathode.

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