KR102423699B1 - Novel compound and organic electroluminescent device comprising same - Google Patents

Abstract

The present invention relates to a novel compound, particularly when applied to an organic light emitting device, has excellent hole and electron transport properties, can realize high triplet energy and high Tg at the same time, and has low driving voltage, low power consumption, high efficiency and long life. It relates to a novel compound capable of having, and an organic light emitting device comprising the same.

Description

Novel compound and organic light emitting device comprising the same {NOVEL COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING SAME}

The present invention relates to a novel compound and an organic light emitting device comprising the same, and particularly, when applied to an organic light emitting device, it has excellent hole and electron transport properties, and can realize high triplet energy and high Tg at the same time, low driving voltage, It relates to a novel compound capable of having low power consumption, high efficiency and long life.

Recently, the organic light emitting device capable of low voltage driving as a self-emitting type has excellent viewing angle, contrast ratio, etc., compared to liquid crystal display (LCD), which is the mainstream of flat panel display devices, and is lightweight and thin because it does not require a backlight. It is advantageous in terms of power consumption and has a wide color reproduction range, attracting attention as a next-generation display device.

Materials used as organic layers in organic light emitting devices may be classified into light emitting materials, hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, according to their functions. The light emitting material can be classified into high molecular weight and low molecular weight according to molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to a light emitting mechanism. can be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary to realize better natural colors according to the emission color. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a small amount of a dopant having a smaller energy band gap and excellent luminous efficiency than the host constituting the light emitting layer is mixed in the light emitting layer in a small amount, excitons generated from the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of dopant and host used.

To date, various compounds are known as materials used in such organic light emitting devices, but in the case of organic light emitting devices using known materials, there were many difficulties in practical application due to high driving voltage, low efficiency and short lifespan. Accordingly, efforts have been made to develop an organic light emitting diode having low voltage driving, high luminance, and long lifespan using a material having excellent properties.

In order to solve the above problems, the present invention has excellent hole and electron transport characteristics when applied to an organic light emitting device, and can realize high triplet energy and high Tg at the same time, low driving voltage, low power consumption, high efficiency and long life. An object of the present invention is to provide a novel compound that can have

The present invention also includes the novel compound, which has excellent hole and electron transport properties, can realize high triplet energy and high Tg at the same time, and can have low driving voltage, low power consumption, high efficiency and long life. It aims to provide a device.

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

[Formula 1]

In the above formula,

* combines with 1 and 2 respectively,

X is O, S, Se, Te or NAr, wherein Ar is a C _6-50 aryl group substituted or unsubstituted with deuterium, halogen, amino, nitrile, or nitro; Or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group,

A is each independently N or CR, wherein each R is independently hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group, and A between the dotted lines may be connected to each other, and when A is CR, adjacent R may form a ring with each other. can,

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; or a C _2-50 heteroaryl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group, and R ₁ and R ₂ of the dotted line may be connected to each other.

In addition, the present invention provides an organic light emitting device comprising the compound represented by the formula (1).

When the compound of the present invention is applied to an organic light emitting device, it has excellent hole and electron transport characteristics, can realize high triplet energy and high Tg at the same time, and can have low driving voltage, low power consumption, high efficiency and long life.

1 schematically shows a cross-section of an OLED according to an embodiment of the present invention.
drawing sign
10: substrate
11: positive electrode
12: hole injection layer
13: hole transport layer
14: light emitting layer
15: electron transport layer
16: cathode

The compound of the present invention is characterized in that it is represented by the following formula (1).

[Formula 1]

In the above formula,

* combines with 1 and 2 respectively,

X is O, S, Se, Te or NAr, wherein Ar is a C _6-50 aryl group substituted or unsubstituted with deuterium, halogen, amino, nitrile, or nitro; Or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group,

A is each independently N or CR, wherein each R is independently hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group, and A between the dotted lines may be connected to each other, and when A is CR, adjacent R may form a ring with each other. can,

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; or a C _2-50 heteroaryl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group, and R ₁ and R ₂ of the dotted line may be connected to each other.

In the present invention, the compound represented by Formula 1 may be one of those represented by Formulas 2 to 5 below.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5, X, A, R ₁ and R ₂ are as defined in Formula 1.

In the present invention, preferred examples of the compound represented by Formula 1 are as follows:

The compound of Formula 1 according to the present invention has excellent hole and electron transport properties, can realize high triplet energy and high Tg at the same time, and has low driving voltage, low power consumption, high efficiency and long lifespan, when applied to an organic light emitting device Excellent device characteristics can be exhibited.

In addition, the compound of the present invention can be prepared through the reaction schemes represented by the following Schemes 1 to 4:

[Scheme 1]

[Scheme 2]

[Scheme 3]

[Scheme 4]

In the above schemes, X and A are as defined in Formula 1, and R is the same as R ₁ and R ₂ of Formula 1;

In addition, the present invention provides an organic light emitting device comprising the compound represented by Formula 1 in an organic material layer. Preferably, the compound represented by Formula 1 is included in the organic light emitting device as a light emitting material or a hole transport material.

In addition, since the organic light emitting device of the present invention includes one or more organic material layers including the compound represented by Formula 1, a method of manufacturing the organic light emitting device will be described as follows.

The organic light emitting device includes an organic material layer such as a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL) between an anode and a cathode. It may contain more than one.

First, an anode is formed by depositing a material for an anode electrode having a high work function on a substrate. In this case, as the substrate, a substrate used in a conventional organic light emitting device may be used, and in particular, it is preferable to use a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance. In addition, as the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, may be used. The material for the anode electrode may be deposited by a conventional anode forming method, and specifically, may be deposited by a deposition method or a sputtering method.

Then, the hole injection layer material on the anode electrode can be formed by a method such as vacuum deposition, spin coating, casting, LB (Langmuir-Blodgett) method, etc., but it is easy to obtain a uniform film quality, and also It is preferable to form by the vacuum evaporation method from the point of being difficult to generate|occur|produce. In the case of forming the hole injection layer by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal characteristics of the desired hole injection layer, etc., but in general, a deposition temperature of 50-500 ℃, It is preferable to appropriately select a vacuum degree of 10 ^-8 to 10 ^-3 torr, a deposition rate of 0.01 to 100 Å/sec, and a layer thickness of 10 Å to 5 μm.

The material for the hole injection layer is not particularly limited, and TCTA (4,4',4"-tri(N-carbazolyl)tri, which is a phthalocyanine compound such as copper phthalocyanine or starburst-type amine derivatives disclosed in US Patent No. 4,356,429. phenylamine), m-MTDATA (4,4',4"-tris(3-methylphenylamino)triphenylamine), m-MTDAPB(4,4',4"-tris(3-methylphenylamino)phenoxybenzene ), HI-406(N ¹ ,N ¹ '-(biphenyl-4,4'-diyl)bis(N ¹ -(naphthalen-1-yl)-N ⁴ ,N ⁴ -diphenylbenzene-1,4 -diamine) and the like may be used as the hole injection layer material.

Next, the hole transport layer material on the hole injection layer can be formed by a method such as vacuum deposition, spin coating, casting, LB method, etc., but it is easy to obtain a uniform film quality, It is preferable to form by vapor deposition. In the case of forming the hole transport layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same range of conditions as those for forming the hole injection layer.

In addition, it is preferable to use the compound represented by Formula 1 of the present invention as the hole transport layer material, and may be arbitrarily selected from commonly known materials used for the hole transport layer, and the compound represented by Formula 1 of the present invention and A known hole transport layer material may be mixed and used. Specifically, the known hole transport layer material is a carbazole derivative such as N-phenylcarbazole and polyvinylcarbazole, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1 -Biphenyl]-4,4'-diamine (TPD), N.N'-di(naphthalen-1-yl)-N,N'-diphenyl benzidine (α-NPD), etc. having an aromatic condensed ring of amine derivatives and the like may be used.

Thereafter, the light emitting layer material on the hole transport layer can be formed by methods such as vacuum deposition, spin coating, casting, LB, etc., but it is easy to obtain a uniform film quality and it is difficult to generate pin holes. It is preferable to form by In the case of forming the light emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select the light emitting layer within the same range of conditions as those for forming the hole injection layer. In addition, as the light emitting layer material, the compound represented by Formula 1 of the present invention may be used as a host or a dopant.

When the compound represented by Formula 1 is used as a light emitting host, a phosphorescent or fluorescent dopant may be used together to form the light emitting layer. In this case, as a fluorescent dopant, IDE102 or IDE105, or BD142 (N ⁶ ,N ¹² -bis(3,4-dimethylphenyl)-N ⁶ ,N ¹² -dimethylchrysene-, available from Idemitsu) 6,12-diamine) can be used, and the phosphorescent dopant is a green phosphorescent dopant Ir(ppy) ₃ (tris(2-phenylpyridine) iridium), and a blue phosphorescent dopant F2Irpic (iridium(III) bis[4,6- Difluorophenyl)-pyridinato-N,C2'] picolinic acid salt), UDC's red phosphorescent dopant RD61, etc. may be co-evacuated (doped). The doping concentration of the dopant is not particularly limited, but it is preferable that the dopant be doped in an amount of 0.01 to 15 parts by weight relative to 100 parts by weight of the host. If the dopant content is less than 0.01 parts by weight, there is a problem that the color development is not performed properly because the dopant amount is insufficient.

In addition, when used with a phosphorescent dopant in the light emitting layer, in order to prevent a phenomenon in which triplet excitons or holes are diffused into the electron transport layer, it is preferable to further laminate a hole blocking material (HBL) by vacuum deposition or spin coating. In this case, the hole-blocking material that can be used is not particularly limited, and any one can be used by selecting from known materials used as the hole-blocking material. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or a hole-inhibiting material described in Japanese Patent Application Laid-Open No. Hei 11-329734 (A1), etc. are mentioned. Representatively, Balq (bis(8-hyde) hydroxy-2-methylquinolinol nato)-aluminum biphenoxide), phenanthrolines-based compounds (eg, UDC's BCP (vasocuproin)), etc. may be used.

An electron transport layer is formed on the light emitting layer formed as described above. In this case, the electron transport layer is formed by a vacuum deposition method, a spin coating method, a casting method, etc., and is particularly preferably formed by a vacuum deposition method.

The electron transport layer material functions to stably transport electrons injected from the electron injection electrode, and the type thereof is not particularly limited. For example, a quinoline derivative, particularly tris(8-quinolinolato)aluminum (Alq ₃ ) ), or ET4 (6,6'-(3,4-dimethyl-1,1-dimethyl-1H-silol-2,5-diyl)di-2,2'-bipyridine) can be used. In addition, an electron injection layer (EIL), which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer, and as the electron injection layer material, LiF, NaCl, CsF, Li ₂ O, BaO, etc. material can be used.

In addition, although the deposition conditions of the electron transport layer vary depending on the compound used, in general, it is preferable to select the electron transport layer within the same range of conditions as those for the formation of the hole injection layer.

Thereafter, an electron injection layer material may be formed on the electron transport layer, and in this case, the electron transport layer is formed by vacuum deposition, spin coating, cast method, etc. of a conventional electron injection layer material, particularly in the vacuum deposition method. It is preferable to form by

Finally, a metal for forming a cathode on the electron injection layer is formed by a method such as a vacuum deposition method or a sputtering method and used as a cathode. Here, as the metal for forming the cathode, a metal having a low work function, an alloy, an electrically conductive compound, and a mixture thereof may be used. Specific examples include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), etc. There is this. In addition, in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

The organic light emitting device of the present invention may have an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and an organic light emitting device having a cathode structure, as well as a structure of an organic light emitting device having a variety of structures. It is also possible to further form a layer or an intermediate layer of two layers.

As described above, the thickness of each organic material layer formed according to the present invention can be adjusted according to the required degree, preferably 10 to 1,000 nm, more preferably 20 to 150 nm.

In the present invention, the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent shape stability because the thickness of the organic material layer can be adjusted in molecular units.

The organic light emitting device of the present invention has excellent hole and electron transport characteristics, including the compound represented by Formula 1, can realize high triplet energy and high Tg, and has low driving voltage, low power consumption, high efficiency and long life. have

Hereinafter, the structure of the compound according to the present invention, a synthesis example thereof, and an organic electroluminescent device using the same will be described.

Synthesis of Intermediate A and A2

[Synthesis of A-1]

50.0 g of 2-bromobenzofuran, 42.2 g of methyl 2-aminobenzoate, 36.6 g of t-BuONa, 9.3 g of Pd ₂ (dba) ₃ , and 11.3 ml of (t-Bu) ₃ P were dissolved in 750 ml of toluene and stirred under reflux. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 50.2 g of Intermediate A-1 (yield 74%).

[Synthesis of A-2]

After dissolving 50.0 g of the intermediate A-1 in 1200 ml of THF, the temperature was lowered to 0 °C. 187.1 ml of CH ₃ MgBr was slowly added, and the mixture was slowly raised to room temperature, stirred for 2 hours, and stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 33.5 g of Intermediate A-2 (yield 67%).

[Synthesis of A]

After adding 335 ml of acetic acid and 1.4 ml of hydrochloric acid to 33.5 g of A-2, the mixture was stirred under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column to obtain 20.3 g of Intermediate A (yield 65%).

m/z: 249.12 (100.0%), 250.12 (18.6%), 251.12 (1.9%)

[Synthesis of A1]

A 7.0 g, bromobenzene 5.73 g, t-BuONa 4.0 g, Pd ₂ (dba) ₃ 1.0 g, (t-Bu) ₃ P 1.5 ml was dissolved in 100 ml toluene and stirred under reflux. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 7.04 g of Intermediate A1 (yield 77%).

[Synthesis of A2]

After dissolving 7 g of A1 in 70 ml of MC, 4.0 g of NBS was added dropwise, followed by stirring for 6 hours. The organic layer was extracted using distilled water and MC, filtered under reduced pressure, and column purified to obtain 6.18 g of Intermediate A2 (yield 71%).

m/z: 405.06 (100.0%), 403.06 (99.5%), 404.06 (25.0%), 406.06 (24.4%), 407.06 (3.2%)

Synthesis of intermediates B and B2

Intermediate B and Intermediate B2 were synthesized in the same manner as Intermediate A-1, Intermediate A-2, Intermediate A, Intermediate A1, and Intermediate A2 except that 2-bromobenzo[b]thiophene was used instead of 2-bromobenzofuran.

m/z: 265.09 (100.0%), 266.10 (18.6%), 267.09 (4.6%), 267.10 (1.8%), 266.09 (1.2%)

Synthesis of Intermediate C

Intermediate C was synthesized in the same manner as Intermediate A-1, Intermediate A-2, Intermediate A, Intermediate A1, and Intermediate A2 except that 2-bromo-1-phenyl-1H-indole was used instead of 2-bromobenzofuran.

Synthesis of Intermediate D

[Synthesis of D-1]

In a round-bottom flask, 4.41 g of NaH and 30 g of 2-bromo-1H-indole were dissolved in 300 ml of THF, followed by stirring. Triisopropylsilyl chloride 32.45 g was added to the solution, stirred for 2 hours, and the solvent was filtered under reduced pressure to obtain 50.15 g of an intermediate D-1 (yield 93%).

[Synthesis of D-2]

50.0 g of the intermediate D-1, 23.6 g of methyl 2-aminobenzoate, 20.5 g of t-BuONa, 5.2 g of Pd ₂ (dba) ₃ , and 6.5 ml of (t-Bu) ₃ P were dissolved in 750 ml of toluene and stirred under reflux. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 40.8 g of intermediate D-2 (yield 68%).

[Synthesis of D-3]

After dissolving 40.8 g of the intermediate D-2 in 1000 ml of THF, the temperature was lowered to 0 °C. CH ₃ MgBr 96.5 ml was slowly added, and the mixture was slowly raised to room temperature, stirred for 2 hours, and then stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 27.7 g of intermediate D-3 (yield 68%).

[Synthesis of D-4]

After adding 277 ml of acetic acid and 1.1 ml of hydrochloric acid to 27.7 g of D-3, the mixture was stirred under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column to obtain 17.8 g of Intermediate D-4 (yield 67%).

[Synthesis of D-5]

17.8 g of Intermediate D-4, 8.3 g of bromobenzene, 6.4 g of t-BuONa, 1.6 g of Pd ₂ (dba) ₃ , and 2.2 ml of (t-Bu) ₃ P were dissolved in 270 ml of toluene and stirred under reflux. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 12.7 g (yield: 60%) of Intermediate D-5.

[Synthesis of D]

After dissolving 12.7 g of Intermediate D-5 and 1.05 g of Tetra-n-butylammonium fluoride in 250 ml of THF, stirring for 1 hour, the organic layer was extracted with distilled water and MC, filtered under reduced pressure, and purified by column to obtain 7.63 g of Intermediate D (yield 89). %) was obtained.

m/z: 324.16 (100.0%), 325.17 (25.1%), 326.17 (3.0%)

Synthesis of Intermediate E and E2

[Synthesis of E-1]

50.0 g of methyl 3-aminobenzofuran-2-carboxylate, 38.4 g of bromobenzene, 36.6 g of t-BuONa, 9.30 g of Pd ₂ (dba) ₃ , and 10.3 ml of (t-Bu) ₃ P were dissolved in 750 ml of toluene and stirred under reflux. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 47.5 g of Intermediate E-1 (yield 70%).

[Synthesis of E-2]

After dissolving 47.4 g of Intermediate E-1 in 1100 ml of THF, the temperature was lowered to 0 °C. 177.4 ml of CH ₃ MgBr was slowly added, and the mixture was slowly raised to room temperature, stirred for 2 hours, and stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 33.2 g of Intermediate E-2 (yield 70%).

[Synthesis of E]

After adding 330 ml of acetic acid and 1.4 ml of hydrochloric acid to 33.2 g of E-2, the mixture was stirred under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column to obtain 19.5 g of Intermediate E (yield 63%).

m/z: 249.12 (100.0%), 250.12 (18.6%), 251.12 (1.9%)

[Synthesis of E1]

E 7.0 g, bromobenzene 5.73 g, t-BuONa 4.0 g, Pd ₂ (dba) ₃ 1.0 g, (t-Bu) ₃ P 1.5 ml was dissolved in 100 ml toluene and stirred under reflux. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 6.85 g of Intermediate E1 (yield 75%).

[Synthesis of E2]

After dissolving 6.85 g of E1 in 70 ml of MC, 3.9 g of NBS was added dropwise, followed by stirring for 6 hours. The organic layer was extracted using distilled water and MC, filtered under reduced pressure, and column purified to obtain 5.9 g of Intermediate E2 (yield 70%).

m/z: 405.06 (100.0%), 403.06 (99.5%), 404.06 (25.0%), 406.06 (24.4%), 407.06 (3.2%)

Synthesis of intermediates F and F2

Except for the reaction with methyl 3-aminobenzo[b]thiophene-2-carboxylate instead of methyl 3-aminobenzofuran-2-carboxylate, follow the same procedure as Intermediate E-1, Intermediate E-2, Intermediate E, Intermediate E1, Intermediate E2. Intermediate F and Intermediate F2 were synthesized.

Synthesis of Intermediate G

Except for the reaction with methyl 3-amino-1-phenyl-1H-indole-2-carboxylate instead of methyl 3-aminobenzofuran-2-carboxylate, follow the same procedure as Intermediate C-1, Intermediate C-2, and Intermediate C to Intermediate G was synthesized.

Synthesis of Intermediate H

[Synthesis of H-1]

In a round-bottom flask, 3.4 g of NaH and 30 g of methyl 3-bromo-1H-indole-2-carboxylate were dissolved in 300 ml of THF and stirred. Triisopropylsilyl chloride 25.04 g was added to the solution, stirred for 2 hours, and the solvent was filtered under reduced pressure to obtain 42.64 g of an intermediate H-1 (yield 88%).

[Synthesis of H-2]

42.6 g of the intermediate H-1, 19.3 g of diphenylamine, 14.9 g of t-BuONa, 3.8 g of Pd ₂ (dba) ₃ , and 4.6 ml of (t-Bu) ₃ P were dissolved in 650 ml of toluene and stirred under reflux. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 37.8 g (yield 73%) of Intermediate H-2.

[Synthesis of H-3]

After dissolving 37.8 g of the intermediate H-2 in 900 ml of THF, the temperature was lowered to 0 °C. 75.8 ml of CH ₃ MgBr was slowly added, and the mixture was slowly raised to room temperature, stirred for 2 hours, and stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 26.8 g of intermediate H-3 (yield 71%).

[Synthesis of H-4]

After adding 270 ml of acetic acid and 1.1 ml of hydrochloric acid to 26.8 g of H-3, the mixture was stirred under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column to obtain 18.1 g of Intermediate H-4 (yield 70%).

[Synthesis of H]

After dissolving 18.1 g of Intermediate H-4 and 1.5 g of Tetra-n-butylammonium fluoride in 360 ml of THF, stirring for 1 hour, the organic layer was extracted with distilled water and MC, filtered under reduced pressure, and column purified by column purification of Intermediate H 10.53 g (yield 86) %) was obtained.

m/z: 324.16 (100.0%), 325.17 (25.1%), 326.17 (3.0%)

Synthesis of compound 1

2.5 g of Intermediate A, 3.73 g of 4-bromo-2,6-diphenylpyridine, 1.45 g of t-BuONa, 0.37 g of Pd ₂ (dba) ₃ , 0.5 ml of (t-Bu) ₃ P were dissolved in 40 ml of toluene and refluxed stirred. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 2.93 g of Compound 1 (yield 61%).

m/z: 478.20 (100.0%), 479.21 (37.1%), 480.21 (6.9%)

Synthesis of compound 2

Compound 2 was synthesized in the same manner as in Compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 2-bromo-4,6-diphenylpyridine.

m/z: 478.20 (100.0%), 479.21 (37.1%), 480.21 (6.9%)

Synthesis of compound 3

Compound 3 was synthesized in the same manner as in Compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 4-bromo-2,6-diphenylpyrimidine.

m/z: 479.20 (100.0%), 480.20 (36.8%), 481.21 (6.3%)

Synthesis of compound 4

Compound 4 was synthesized in the same manner as in Compound 1, except that 4-bromo-2,6-diphenylpyridine was reacted with 2-bromo-4,6-diphenylpyrimidine.

m/z: 479.20 (100.0%), 480.20 (36.8%), 481.21 (6.3%)

Synthesis of compound 5

2.5 g of Intermediate A and 0.30 g of NaH were added to 25 ml of DMF and stirred. Here, 3.22 g of 2-chloro-4,6-diphenyl-1,3,5-triazine was dissolved in 30 ml of DMF, and then slowly added dropwise. After stirring at room temperature, the completion of the reaction was confirmed by TLC and recrystallized after silica filter to obtain 2.56 g of compound 5 (yield 53%).

m/z: 480.20 (100.0%), 481.20 (34.9%), 482.20 (6.6%), 481.19 (1.5%)

Synthesis of compound 6

Compound 6 was synthesized in the same manner as in Compound 5, except that Intermediate A was reacted with Intermediate B.

m/z: 496.17 (100.0%), 497.18 (34.9%), 498.18 (5.9%), 498.17 (5.3%), 497.17 (2.3%), 499.17 (1.6%)

Synthesis of compound 7

Compound 7 was synthesized in the same manner as in Compound 5, except that Intermediate A was reacted with Intermediate C.

m/z: 555.24 (100.0%), 556.25 (41.4%), 557.25 (8.4%), 556.24 (1.8%), 558.25 (1.2%)

Synthesis of compound 8

Compound 8 was synthesized in the same manner as in Compound 5, except that Intermediate A was reacted with Intermediate E.

m/z: 480.20 (100.0%), 481.20 (34.9%), 482.20 (6.6%), 481.19 (1.5%)

Synthesis of compound 9

Compound 9 was synthesized in the same manner as in Compound 5, except that Intermediate A was reacted with Intermediate F.

m/z: 496.17 (100.0%), 497.18 (34.9%), 498.18 (5.9%), 498.17 (5.3%), 497.17 (2.3%), 499.17 (1.6%)

Synthesis of compound 10

Compound 10 was synthesized in the same manner as in Compound 5, except that Intermediate A was reacted with Intermediate G.

m/z: 555.24 (100.0%), 556.25 (41.4%), 557.25 (8.4%), 556.24 (1.8%), 558.25 (1.2%)

Synthesis of compound 11

In a round-bottom flask, 3.0 g of intermediate A2, N-phenyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'- 3.98 g of biphenyl]-4-amine was dissolved in 30 ml of toluene, 12 ml of K ₂ CO ₃ (2M) and 0.26 g of Pd(PPh ₃ ) ₄ were added, followed by stirring under reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and purified by column to obtain 2.17 g of compound 11 (yield 57%).

m/z: 644.28 (100.0%), 645.29 (51.3%), 646.29 (13.1%), 647.29 (2.3%)

Synthesis of compound 12

N-phenyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'-biphenyl]-4-amine instead of N- ([1,1'-biphenyl]-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)naphthalen-1-amine Compound 12 was synthesized in the same manner as in Compound 11, except that it was reacted with

m/z: 694.30 (100.0%), 695.30 (56.4%), 696.31 (15.2%), 697.31 (2.8%)

Synthesis of compound 13

Compound 13 was synthesized in the same manner as in Compound 11, except that intermediate B2 was used instead of intermediate A2.

m/z: 736.29 (100.0%), 737.29 (58.9%), 738.30 (16.4%), 738.29 (5.4%), 739.30 (3.2%), 739.29 (2.7%)

Synthesis of compound 14

N-phenyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'-biphenyl]- as intermediate B2 instead of intermediate A2 N-([1,1'-biphenyl]-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl instead of 4-amine ) Compound 14 was synthesized in the same manner as compound 11 except for reaction with naphthalen-1-amine.

m/z: 776.32 (100.0%), 777.33 (61.1%), 778.33 (18.8%), 778.32 (5.0%), 779.33 (3.8%), 779.32 (2.8%), 777.32 (1.5%)

Synthesis of compound 15

Compound 15 was synthesized in the same manner as in Compound 11, except that Intermediate E2 was used instead of Intermediate A2.

m/z: 720.31 (100.0%), 721.32 (57.8%), 722.32 (16.6%), 723.32 (3.2%)

Synthesis of compound 16

N-phenyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'-biphenyl]- as intermediate E2 instead of intermediate A2 N-([1,1'-biphenyl]-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl instead of 4-amine ) Compound 16 was synthesized in the same manner as compound 11 except for reaction with naphthalen-1-amine.

m/z: 760.35 (100.0%), 761.35 (61.1%), 762.35 (19.0%), 763.36 (3.6%)

Synthesis of compound 17

Compound 17 was synthesized in the same manner as in Compound 11, except that the reaction was performed with Intermediate F2 instead of Intermediate A2.

m/z: 736.29 (100.0%), 737.29 (58.9%), 738.30 (16.4%), 738.29 (5.4%), 739.30 (3.2%), 739.29 (2.7%)

Synthesis of compound 18

N-phenyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'-biphenyl]- as intermediate F2 instead of intermediate A2 N-([1,1'-biphenyl]-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl instead of 4-amine ) Compound 18 was synthesized in the same manner as compound 11 except for reaction with naphthalen-1-amine.

m/z: 776.32 (100.0%), 777.33 (61.1%), 778.33 (18.8%), 778.32 (5.0%), 779.33 (3.8%), 779.32 (2.8%), 777.32 (1.5%)

Synthesis of compound 19

2.5 g of intermediate A, N,N-di([1,1'-biphenyl]-4-yl)-4'-bromo-[1,1'-biphenyl]-4-amine 6.65 g, t-BuONa 1.45 g, Pd ₂ (dba) ₃ 0.37 g, (t-Bu) ₃ P 0.5 ml was dissolved in 100 ml of toluene and stirred under reflux. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 3.98 g of compound 19 (yield 55%).

m/z: 720.31 (100.0%), 721.32 (57.8%), 722.32 (16.6%), 723.32 (3.2%)

Synthesis of compound 20

Compound 20 was synthesized in the same manner as in Compound 19, except that intermediate B was used instead of intermediate A.

m/z: 736.29 (100.0%), 737.29 (58.9%), 738.30 (16.4%), 738.29 (5.4%), 739.30 (3.2%), 739.29 (2.7%)

Synthesis of compound 21

Compound 21 was synthesized in the same manner as in Compound 19, except that Intermediate E was used instead of Intermediate A.

m/z: 720.31 (100.0%), 721.32 (57.8%), 722.32 (16.6%), 723.32 (3.2%)

Synthesis of compound 22

Compound 22 was synthesized in the same manner as in Compound 19, except that Intermediate F was used instead of Intermediate A.

m/z: 736.29 (100.0%), 737.29 (58.9%), 738.30 (16.4%), 738.29 (5.4%), 739.30 (3.2%), 739.29 (2.7%)

Manufacture of organic light emitting device

An organic light emitting diode was manufactured according to the structure shown in FIG. 1 . The organic light emitting device is stacked in the order of the hole injection electrode 11 / hole injection layer 12 / hole transport layer 13 / light emitting layer 14 / electron transport layer 15 / electron injection electrode 16 from the bottom.

The following materials were used for the hole injection layer 12, the hole transport layer 13, the light emitting layer 14, and the electron transport layer 15 of Examples and Comparative Examples.

Example 1

A glass substrate coated with indium tin oxide (ITO) having a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After cleaning with distilled water, ultrasonic cleaning is performed with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, and transferred to a plasma cleaner. After cleaning the substrate using oxygen plasma for 5 minutes, a thermal vacuum evaporator (thermal) An evaporator) was used to form a hole injection layer HT01 600 Å and NPB 250 Å as a hole transport layer. Next, the light emitting layer was doped with Compound 1: Ir(ppy) ₃ 10% to form a film of 250 Å. Next, ET01:Liq (1:1) 300 Å was formed as an electron transport layer, LiF 10 Å, and aluminum (Al) 1000 Å were formed into a film, and a green organic light emitting device was manufactured by encapsulating the device in a glove box. .

Examples 2 to 10

In the same manner as in Example 1, green organic light emitting diodes were fabricated using compounds 2 to 10 as light emitting layer hosts, respectively.

Example 11

A glass substrate coated with indium tin oxide (ITO) having a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After cleaning with distilled water, ultrasonic cleaning is performed with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, and transferred to a plasma cleaner. After cleaning the substrate using oxygen plasma for 5 minutes, a thermal vacuum evaporator (thermal) An evaporator) was used to form a hole injection layer HT01 600 Å and compound 11 250 Å as a hole transport layer. Next, the light emitting layer was doped with 5% BH01:BD01 to form a film of 300 Å. Next, Alq ₃ :Liq (1:1) 300 Å was formed as an electron transport layer, Liq 10 Å, and aluminum (Al) 1000 Å were formed into a film, and an organic light emitting device was manufactured by encapsulating the device in a glove box. .

Examples 12 to 22

In the same manner as in Example 1, an organic light emitting device formed into a film using compounds 12 to 22, respectively, as a hole transport layer was manufactured.

Comparative Example 1

A green organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound 1 was used as CBP as the light emitting layer host.

Comparative Example 2

A green organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound 1 was used as Ref.1 as the light emitting layer host.

Comparative Example 3

A green organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound 1 was used as Ref.2 as the host of the light emitting layer.

Comparative Example 4

An organic light emitting diode was manufactured in the same manner as in Example 20, except that Compound 20 was used as the NPB as the hole transport layer.

Performance evaluation of organic light emitting devices

Electrons and holes are injected by applying voltage with a Kiethley 2400 source measurement unit, and the luminance when light is emitted is measured using a Konica Minolta spectroradiometer (CS-2000). By doing so, the performance of the organic light emitting devices of Examples and Comparative Examples was evaluated by measuring current density and luminance with respect to applied voltage under atmospheric pressure conditions, and the results are shown in Tables 1 and 2.

Op. V QE (%) Cd/A lm/w CIEx CIEy life span@
5000nit Example 1 5.98 17.33 45.98 19.81 0.301 0.621 81 Example 2 5.98 17.10 47.13 21.03 0.299 0.619 85 Example 3 6.02 16.98 50.20 20.04 0.298 0.620 90 Example 4 5.94 17.54 47.22 19.98 0.300 0.623 83 Example 5 6.08 16.85 48.39 21.23 0.298 0.614 79 Example 6 6.12 17.26 46.83 18.72 0.298 0.609 101 Example 7 6.34 17.01 49.17 22.46 0.297 0.618 95 Example 8 5.92 17.07 45.55 21.98 0.302 0.609 90 Example 9 6.01 16.93 43.62 20.76 0.300 0.620 75 Example 10 6.19 17.36 47.45 18.99 0.299 0.622 90 Comparative Example 1 7.02 12.43 22.12 10.72 0.301 0.623 25 Comparative Example 2 6.52 14.56 35.98 15.60 0.300 0.613 42 Comparative Example 3 7.74 6.12 8.31 7.76 0.667 0.333 -

Op. V mA/cm2 Cd/A lm/w CIEx CIEy LT95
(hr) Example 11 4.05 10 6.49 5.02 0.141 0.112 44 Example 12 4.03 10 6.45 5.00 0.141 0.112 45 Example 13 3.91 10 6.65 5.25 0.142 0.111 50 Example 14 3.85 10 6.82 5.30 0.139 0.111 55 Example 15 3.92 10 6.63 5.95 0.138 0.110 48 Example 16 3.92 10 6.60 5.40 0.140 0.111 50 Example 17 3.90 10 6.70 5.90 0.140 0.110 52 Example 18 3.90 10 6.70 5.27 0.140 0.110 47 Example 19 3.93 10 6.73 5.40 0.138 0.112 45 Example 20 3.87 10 6.89 5.29 0.141 0.111 53 Example 21 3.93 10 6.75 5.35 0.142 0.111 46 Example 22 3.87 10 6.90 5.35 0.141 0.111 58 Comparative Example 4 5.43 10 5.35 4.24 0.143 0.120 22

As shown in Table 1, it can be confirmed that the examples of the present invention have superior physical properties when used as a host for the light emitting layer of the green organic light emitting device compared to Comparative Examples 1 to 3. In addition, as shown in Table 2, it can be seen that the efficiency and lifespan are remarkably excellent even when used as a hole transport layer.

Claims (6)

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

In the above formula,
* combines with 1 and 2 respectively,
X is O, S or NAr, wherein Ar is a C _6-50 aryl group substituted or unsubstituted with deuterium, halogen, amino, nitrile, or nitro; Or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group,
A is each independently N or CR, wherein each R is independently hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-50 aryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group, and A between the dotted lines may be connected to each other, and when A is CR, adjacent R may form a ring with each other. can,
R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro; C _2-30 alkenyl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _1-30 alkoxy group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, or nitro group; C _6-50 aryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; or a C _2-50 heteroaryl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group, and R ₁ and R ₂ of the dotted line may be connected to each other. According to claim 1,
A compound characterized in that it is represented by one of the following formulas 2 to 5:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5, X, A, R ₁ and R ₂ are as defined in Formula 1. According to claim 1,
A compound characterized by being represented by any one of the following formulas:

A method of preparing Formulas 2 to 5 represented by any one of the following Reaction Schemes 1 to 4:
[Scheme 1]

[Scheme 2]

[Scheme 3]

[Scheme 4]

In the above schemes, X and A are as defined in Formula 1, and R is the same as R ₁ and R ₂ of Formula 1; An organic light emitting device comprising an anode, a cathode, and at least one organic material layer containing the compound of claim 1 between the two electrodes. 6. The method of claim 5,
The organic light emitting device, characterized in that the organic layer contains the compound of claim 1 as a light emitting host or dopant.

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