KR102095632B1 - Blue luminescent compounds and organic electroluminescence element comprising the same and application thereof - Google Patents

Abstract

그 중에서 R1, R4는 각각 독립적으로 치환 또는 비치환된 페닐, 피리딘, 나프탈렌, 페난트렌, 안트라센, 페난트리딘, 바이페닐, 피리디닐, 피리미디닐, 또는 트리아지닐기이며; R2, R3, R5는 각각 독립적으로 수소, C1~C20의 직쇄 또는 분지쇄 알킬이거나 치환 또는 비치환된 페닐, 피리딘, 나프탈렌, 페난트렌, 안트라센, 페난트리딘, 바이페닐, 피리디닐, 피리미디닐, 또는 트리아지닐기이다.
본 발명의 화합물을 청색 호스트 물질로 사용하는 유기전계발광소자는 고효율 및 긴수명 등의 우수한 성능을 가지고 있다.The present invention provides a blue light emitting compound represented by the following formula and an organic electroluminescent device comprising the same. The formula is as follows.

R1 and R4 are each independently substituted or unsubstituted phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl group; R2, R3, and R5 are each independently hydrogen, C1 to C20 linear or branched alkyl, or substituted or unsubstituted phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl Or a triazinyl group.
The organic electroluminescent device using the compound of the present invention as a blue host material has excellent performance such as high efficiency and long life.

Description

Blue light emitting compounds and organic electroluminescent devices and applications including the same {BLUE LUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENCE ELEMENT COMPRISING THE SAME AND APPLICATION THEREOF}

The present invention relates to the field of light emitting material technology, and more particularly, to a blue light emitting compound used as a blue host and an organic light emitting device including the same.

Until now, liquid crystal displays (LCDs) occupy most of flat panel displays, but efforts to develop a new flat panel display that is differentiated from liquid crystal displays have been actively conducted around the world as they are more economical and performant. The organic light emitting device, which has recently been spotlighted as a next-generation flat panel display, has advantages such as a low driving voltage, a fast response speed, and a wide viewing angle compared to a liquid crystal display. Since the 1980s, organic electroluminescent devices have started to be applied to industries. Examples include cameras, computers, cell phones, and television displays. Since then, organic electroluminescence technology has been steadily improving through efforts in each field. However, the short lifespan and low efficiency of the organic light emitting device still remain technical difficulties, and these problems limit the development of the organic light emitting device.

The structure of the organic light emitting device includes a substrate, an anode, a hole injection layer that accepts holes from the anode, a hole transport layer that transports holes, an electron blocking layer that blocks electrons from the light emitting layer to the hole transport layer, and holes and electrons combined to light It is composed of a light emitting layer emitting a, a hole blocking layer that blocks the entrance of holes from the light emitting layer to the electron transport layer, an electron transport layer that accepts electrons from the cathode and transports them to the light emitting layer, and an electron injection layer and cathode that accepts electrons from the cathode.

The driving principle of the organic electroluminescent device is as follows. When a voltage is applied between the anode and the cathode, holes injected from the anode are moved to the light emitting layer via the hole injection layer and the hole transport layer. On the other hand, electrons are injected into the light emitting layer from the cathode via the electron injection layer and the electron transport layer, and carriers recombine in the light emitting layer region to generate an exiton. The exciton is changed from an excited state to a ground state, whereby the fluorescent molecules in the light-emitting layer emit light to form an image. At this time, the light emitted while the excitation state falls to the ground state through the singlet excitation state is called “fluorescence”, and the light emitted while falling to the ground state through the triplet excitation state is called “phosphorescence”. In the case of fluorescence, the probability of singlet excitation state is 25% (triple state 75%), and there is a limitation in luminous efficiency, whereas phosphorescence is used for luminescence up to 75% triplet state and 25% singlet excitation state. In theory, the internal quantum efficiency can be up to 100%. The phosphorescent layer is composed of a host and a dopant material. The dopant material emits light by receiving energy from the host material. Compounds such as iridium metal compounds can be used as the dopant material. In particular, an iridium compound based on (4,6-F2ppy) 2Irpic (79 APPL.PHYS.LETT., 3082-3084 (2001)) and a fluorinated ppy ligand structure (CHEM.COMMUN., 1494-1495 ( 2001)) is used as a blue light emitting compound. And 4,4'-N, N'-dicarbazolyl-biphenyl (CBP) materials are already widely used as host materials. CBP's triple energy gap can produce blue and red light, but it is too small to produce blue light when dissipating. Since the CBP host cannot generate blue light by dissipating heat, there is a high possibility of efficiency and lifetime problems.

In order to overcome the above defect, an mCP (1,3-biscarbazolyl-9-benzene) compound having a larger triple energy gap than a CBP compound is used, but there are still problems in that the molecular weight is low and the stability is poor. Therefore, the focus is on developing blue light-emitting compounds having a low driving voltage, high efficiency, good stability, and long life.

In view of this, the present invention has been proposed.

The first object of the present invention is to provide a kind of blue light emitting compound. When used as a blue host material, the compound can lower the driving voltage of the organic light emitting device and improve light emission efficiency, brightness, thermal stability, color, and device life.

The second object of the present invention is that a kind of blue light emitting compound provides an application for manufacturing an organic electroluminescent device. When the above-described blue light emitting compound is applied to an organic light emitting device, efficiency and service life of the light emitting device can be improved.

The third object of the present invention is to provide a kind of organic electroluminescent device. This organic light emitting device has excellent performance of high efficiency and long life using the above-described blue light emitting compound as a host material.

The following technical measures are used to achieve the above objectives.

First, the present invention provides a blue light emitting compound. Its chemical formula is as follows.

R1 and R4 are each independently substituted or unsubstituted phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl group;

R2, R3, and R5 are each independently hydrogen, C1 to C20 linear or branched alkyl, or substituted or unsubstituted phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl Or a triazinyl group.

As a preferential technique, hydrogen is independently C1 ~ C20 straight chain among R1 phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl groups. Or substituted with one or more selected from the group consisting of branched alkyl, C3 to C24 cycloalkyl, C1 to C20 alkoxy, halogen, CN, CF ₃ and Si (CH ₃ ) ₃ group, C6 to C50 aryl group Will;

As a preferential technique, hydrogen is independently C1 ~ C20 straight chain among phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl groups of R2. Or branched chain alkyl, C3 ~ C24 cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ or Si (CH ₃ ) ₃ group, naphthyl, anthracenyl, phenanthrenyl, dibenzofuran group, fluorene A group, a carbazole group, a spiro fluorene group, and one or more selected from the group consisting of a heteroaryl group having 5 to 20 nuclear atoms;

As a preferential technique, hydrogen is independently C1 ~ C20 straight chain among R3 phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl groups. Or branched chain alkyl, C3 ~ C24 cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ or Si (CH ₃ ) ₃ group, naphthyl, anthracenyl, phenanthrenyl, dibenzofuran group, fluorene A group, a carbazole group, a spiro fluorene group, and one or more selected from the group consisting of a heteroaryl group having 5 to 20 nuclear atoms;

As a preferential technique, hydrogen is independently C1 ~ C20 straight chain among R4 phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl groups. Or substituted with one or more selected from the group consisting of branched alkyl, C3 to C24 cycloalkyl, C1 to C20 alkoxy, halogen, CN, CF ₃ and Si (CH ₃ ) ₃ group, C6 to C50 aryl group Will;

As a preferential technique, hydrogen is independently C1 to C20 straight chains among R5 phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl groups. Or branched chain alkyl, C3 ~ C24 cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ or Si (CH ₃ ) ₃ group, naphthyl, anthracenyl, phenanthrenyl, dibenzofuran group, fluorene It may be substituted with one or more selected from the group consisting of a group, a carbazole group, a spiro fluorene group and a heteroaryl group having 5 to 20 nuclear atoms.

Specific examples of the blue light emitting compound include any one of the following compounds 1 to 120:

Second, the present invention provides an organic electroluminescent device comprising the compounds.

Third, the organic light emitting device provided by the present invention comprises an anode, a light emitting layer, and a cathode in order, and the light emitting layer includes the above-described blue light emitting compound.

In a preferred technology scheme, the present invention provides an organic electroluminescent device comprising a hole injection layer and a hole transport layer between an anode and a light emitting layer, and an electron transport layer and an electron injection layer between a light emitting layer and a cathode. do.

The beneficial effects of the present invention over the prior art are as follows.

The blue light-emitting compound provided by the present invention can be used as a blue fluorescent host material to lower the driving voltage of the organic light emitting device and improve light emission efficiency, brightness, thermal stability, color, and device life.

The blue light emitting compound provided by the present invention provides an application of manufacturing a light emitting device. When the above-described blue light-emitting compound is applied to a light-emitting device, efficiency and service life of the light-emitting device can be improved.

The organic light emitting device using the blue light emitting compound provided by the present invention as a host material has excellent performance of high efficiency and long life.

Hereinafter, a method for synthesizing the compound will be described below as a representative example. However, it will be understood by those skilled in the art that the method for synthesizing the compounds of the present invention is not limited to the methods exemplified below. In the absence of specific description, the compounds of the present invention can be prepared by standard conditions and methods provided by the manufacturer.

In the phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl group of R1, hydrogen is independently C1 to C20 straight or branched chain alkyl, C3 to C24 Cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ And Si (CH ₃ ) ₃ groups, C6 ~ C50 is substituted with one or more selected from the group consisting of aryl groups,

Of the phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl groups of R4, hydrogen is independently C1 to C20 straight or branched chain alkyl, C3 to C24 It is substituted with one or more selected from the group consisting of cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ and Si (CH ₃ ) ₃ group, C6 ~ C50 aryl group.

C3-C24 cycloalkyl in this embodiment is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;

The alkoxy structures of C1 to C20 are as follows. R in the atomic group represented by -OR is alkyl and alkyl is methyl, ethyl, propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-myristyl, n-pentadecyl, n-cetyl, n-heptadecyl, n-octadecyl , n-nonadecyl, n-acyl;

C6-C50 aryl is phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4- Phenanthryl, 9-phenanthryl, 1-naphthacene, 2-naphthacene, 9-naphthacene, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-biphenyl, 3-biphenyl, 4- Biphenyl, p-terphenyl-4, p-terphenyl-3, p-terphenyl-2, m-terphenyl-4, m-terphenyl-3, m-terphenyl-2, o-methylphenyl, m -Methylphenyl, p-methylphenyl, pt-butylphenyl, p- (2-phenylpropyl) phenyl, 3-methyl-2-naphthyl, 4-methyl-1-naphthyl, 4-methyl-1-anthryl, 4 '-Methylbiphenyl, 4 "-tert-butyl-p-terphenyl-4.

In a more preferred embodiment, among the phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl groups of R2, hydrogen is independently C1 to C20 straight-chain or branched Chain alkyl, C3 ~ C24 cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ or Si (CH ₃ ) ₃ group, naphthyl, anthracenyl, phenanthrenyl, dibenzofuran group, fluorene group, It is substituted with one or more selected from the group consisting of a carbazole group, a spiro fluorene group and a heteroaryl group having 5 to 20 nuclear atoms,

Preferred among R3 phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl groups, hydrogen is independently C1 to C20 straight or branched chain alkyl, C3 ~ C24 cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ or Si (CH ₃ ) ₃ group, naphthyl, anthracenyl, phenanthrenyl, dibenzofuran group, fluorene group, carbazole group, spiro It is substituted with one or more selected from the group consisting of a fluorene group and a heteroaryl group having 5 to 20 nuclear atoms,

Preferred among R5 phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl groups, hydrogen is independently C1 to C20 straight or branched chain alkyl, C3 ~ C24 cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ or Si (CH ₃ ) ₃ group, naphthyl, anthracenyl, phenanthrenyl, dibenzofuran group, fluorene group, carbazole group, spiro It is substituted with one or more selected from the group consisting of a fluorene group and a heteroaryl group having 5 to 20 nuclear atoms.

C3-C24 cycloalkyl in this embodiment is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;

The alkoxy structures of C1 to C20 are as follows. R in the atomic group represented by -OR is alkyl and alkyl is methyl, ethyl, propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl;

The number of nuclear atoms 5 to 20 heteroaryl group is 1-pyryl, 2-pyryl, 3-pyryl, pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 1-indolyl, 2-indolyl, 3-indoleyl, 4-indoleyl, 5-indoleyl, 6-indoleyl, 7-indoleyl, 1-isoindoleyl, 2-isoindoleyl, 3-isoindoleyl, 4-isoindoleyl, 5 -Isoindolyl, 6-isoindolyl, 7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuran, 3-benzofuran, 4-benzofuran, 5-benzofuran, 6-benzofuran, 7-benzofuran, 1-isobenzofuran, 3-isobenzofuran, 4-isobenzofuran, 5-isobenzofuran, 6-isobenzofuran, 7-isobenzofuran, 2-quinolinyl, 3-qui Nolinyl, 4-quinolinyl, 5-quinolinyl, 6-quinolinyl, 7-quinolinyl, 8-quinolinyl, 1-isoquinolinyl, 3-isoquinolinyl, 4-iso Quinolinyl, 5-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolinyl, 8-isoquinolinyl, 2-quinoxalyl, 5-quinoxalyl, 6-quinoxalyl, 1-phenane Tridinyl, 2-phenanthridinyl, 3-phenanthridinyl, 4 -Phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl, 1,7-phenanthrolin-2-yl, 1,7 -Phenanthroline-3-yl, 1,7-phenanthrolin-4-yl, 1,7-phenanthrolin-5-yl, 1,7-phenanthroline-6-yl, 1,7-phenan Troline-8-day, 1,7-phenanthroline-9-day, 1,7-phenanthroline-10-day, 1,8-phenanthroline-2-yl, 1,8-phenanthroline -3-day, 1,8-phenanthroline-4-yl, 1,8-phenanthroline-5-yl, 1,8-phenanthroline-6-day, 1,8-phenanthroline-7 -Day, 1,8-phenanthroline-9-day, 1,8-phenanthroline-10-day, 1,9-phenanthroline-2-yl, 1,9-phenanthroline-3-yl , 1,9-phenanthroline-4-yl, 1,9-phenanthrolin-5-yl, 1,9-phenanthroline-6-yl, 1,9-phenanthroline-7-yl, 1 , 9-phenanthroline-8-day, 1,9-phenanthroline-10-day, 1,10-phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1,10 -Phenanthroline-4-yl, 1,10-phenanthrolin-5-yl, 2,9-phenanthrolin-1-yl, 2,9-phenanthrolin-3-yl, 2,9-phenan Trolin-4-yl, 2,9-phenanthroline-5 -Day, 2,9-phenanthroline-6-day, 2,9-phenanthroline-7-day, 2,9-phenanthroline-8-day, 2,9-phenanthroline-10-day , 2,8-phenanthrolin-1-yl, 2,8-phenanthrolin-3-yl, 2,8-phenanthrolin-4-yl, 2,8-phenanthrolin-5-yl, 2 , 8-phenanthroline-6-day, 2,8-phenanthroline-7-day, 2,8-phenanthroline-9-day, 2,8-phenanthroline-10-day, 2,7 -Phenanthroline-1-yl, 2,7-phenanthrolin-3-yl, 2,7-phenanthrolin-4-yl, 2,7-phenanthrolin-5-yl, 2,7-phenan Troline-6-day, 2,7-phenanthroline-8-day, 2,7-phenanthroline-9-day, 2,7-phenanthroline-10-day, 2-oxazolyl, 4- Oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-oxadiazolyl, 3-furazanyl, 2-thienyl, 3-thienyl, 2-methylpyridin-1-yl, 2-methylpyrrole- 3-yl, 2-methylpyrrole-4-yl, 2-methylpyrrole-5-yl, 3-methylpyrrole-1-yl, 3-methylpyrrole-2-yl, 3-methylpyrrole-4-yl, or 3-methylpyrrole-5-yl.

Among the preferred methods of implementation, C1 to C20 linear or branched alkyl of R1, R2, R3, R4 and R5 is methyl, ethyl, propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, tertiary butyl , n-pentyl, n-hexyl, n-heptyl, n-octyl.

The blue light-emitting compounds provided by the present invention will be described in more detail with reference to Examples 1 to 6 below.

Example 1

A kind of blue light emitting compound

Compound 32 was prepared by the following method

Synthesis of intermediate (1)

[Scheme 1]

Dissolve 33.6g (100mmol) of 1,8-bibromphenanthrene in glacial acetic acid 600ml in 1L 3-neck round-bottom flask and dropwise Br ₂ 63.9g (400mml) at room temperature. It was allowed to reflux for 18 hours. After the reaction was completed, saturated Na ₂ SO ₃ aqueous solution was added and stirred for 1 hour to form a solid. After filtering under reduced pressure, the filter cake was washed with water, washed again with ethanol, dried, and recrystallized from toluene and ethanol to obtain 33.6 g of intermediate (1). The yield was 81%.

Synthesis of intermediate (2)

[Scheme 2]

33.6 g (81 mmol) of the intermediate (1) and 24.1 g (89.1 mmol) of 8-iodine-2-hydroxy-naphthalene obtained in [Reaction Scheme 1] were dissolved in 700 ml of DMF and stirred in a dried 2 L 3-neck round bottom flask. While passing through a nitrogen stream for 15 minutes, 0.55 g (3% mol) of Pd (OAc) ₂ and 1.3 g (6% mol) of PPh ₃ were added. Then, 79.2 g (243 mmol) of Cs ₂ CO ₃ was slowly added thereto, and the temperature was raised to 160 ° C. to reflux for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, the toluene layer was extracted, and then activated carbon was added to the column, followed by recrystallization from toluene and ethanol to obtain 32.6 g of intermediate (2). The yield was 77%.

Synthesis of Compound 32

[Scheme 3]

Dissolve 32.6g (62.4mmol) of intermediate (2) and 16.7g (137.3mmol) of phenyl boronic acid in 600ml of toluene and 150ml of ethanol in a 2L 3-neck round bottom flask and pass through a nitrogen stream for 15 minutes. In addition, 94 ml of K ₂ CO ₃ (187.2mmol, 2M) and 1.4 g (2 mol%) of Pd (PPh ₃ ) ₄ were added. The reaction was terminated after 12 hours by raising the temperature to 110 ° C, and the toluene layer was extracted, adsorbed with activated carbon, filtered under reduced pressure, and dried. Recrystallization from toluene and ethanol yielded 23.2 g of compound 32. The yield was 79%.

¹ H NMR (DMSO, 300Hz): δ (ppm) = 9.26-9.01 (m, 2H), 8.57-8.38 (d, 1H), 8.35-8.13 (m, 4H), 8.11-8.02 (d, 1H), 8.00-7.86 (s, 1H), 7.83-7.65 (m, 6H), 7.55-7.07 (m, 7H)

MS (FAB): 470 (M ⁺ )

Example 2

A kind of blue light emitting compound

Compound 51 was prepared by the following method.

Synthesis of intermediate (1)

[Reaction Scheme 4]

33.6 g (100 mmol) of 1,8-bibromphenanthrene was dissolved in 600 ml of glacial acetic acid in a 1 L 3-neck round bottom flask, and 63.9 g (400 mml) of Br ₂ was added dropwise at room temperature. It was allowed to reflux for 18 hours. After the reaction was completed, saturated Na ₂ SO ₃ aqueous solution was added and stirred for 1 hour to form a solid. After filtering under reduced pressure, the filter cake was washed with water, then washed again with ethanol, dried, and recrystallized from toluene and ethanol to obtain 35.7 g of intermediate (1). The yield was 86%.

Synthesis of intermediate (2)

[Scheme 5]

35.7 g (86 mmol) of intermediate (1) and 25.5 g (94.6 mmol) of 8-iodine-2-hydroxy-naphthalene obtained in [Reaction Scheme 4] were dissolved in 700 ml of DMF and stirred in a dried 2 L 3-neck round bottom flask. While passing through a nitrogen stream for 15 minutes, 0.58 g (3% mol) of Pd (OAc) ₂ and 1.4 g (6% mol) of PPh ₃ were added. Thereafter, 84.1 g (258 mmol) of Cs ₂ CO ₃ was slowly added thereto, and the temperature was raised to 160 ° C. to reflux for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, activated carbon was added, and the remaining solution was extracted with toluene and water, and then the organic phase was washed 4 times and recrystallized from toluene and ethanol to obtain 34.2 g of intermediate (2). The yield was 76%.

Synthesis of intermediate (3)

[Scheme 6]

To a 2 L 3-neck round bottom flask, 34.2 g (65.4 mmol) of the intermediate (2) obtained from [Scheme 5] was dissolved in 650 ml of TFA, and 4.9 g (78.4 mmol) of concentrated nitric acid was added dropwise. Raised until reflux for 12 hours. After the reaction was completed, it was cooled to room temperature and 1 L of water was added to form a solid. After lowering the temperature, the mixture was filtered under reduced pressure, the filter cake was washed several times with water, recrystallized from toluene and ethanol, and dried to obtain 32.7 g of an intermediate (3). The yield was 88%.

Synthesis of intermediate (4)

[Scheme 7]

Dissolve 35.3 g (57.6 mmol) of the intermediate (3) and 15.4 g (126.6 mmol) of phenyl boronic acid in 700 ml of toluene and 150 ml of ethanol in a 2 L 3-neck round bottom flask and pass through a nitrogen stream for 15 minutes. In addition, 173 ml (345.6 mmol, 2M) of K ₂ CO ₃ and 2.7 g (4 mol%) of Pd (PPh ₃ ) ₄ were added. The reaction was terminated after 12 hours by raising the temperature to 110 ° C, and the toluene layer was extracted, adsorbed with activated carbon, filtered under reduced pressure, and dried. Recrystallization from toluene and ethanol gave 23.8 g of intermediate (4). The yield was 80%.

Synthesis of intermediate (5)

[Scheme 8]

23.8 g (46.2 mmol) of the intermediate (4) obtained in [Scheme 7] was added to a 2 L 3-neck round bottom flask, and nitrogen was discharged three times through a T-shape, dissolved in ethanol / THF = 450 ml / 90 ml solvent, and then nitrogen again. Was discharged three times and hydrogen was passed through. 1.2 g of 5% palladium on carbon was taken and reacted for 5 hours at room temperature. After the reaction is completed, it is filtered under reduced pressure with silica gel. The filtrate was rotary evaporated and dried, and then recrystallized from THF and ethanol to obtain 19.5 g of intermediate (5). The yield was 87%.

Synthesis of intermediate (6)

[Scheme 9]

19.5 g (40.2 mmol) of the intermediate (5) and 14.7 g (40.2 mmol) of CuI ₂ were dissolved in 400 ml of dried acetonitrile in a dried 1 L 3-neck round bottom flask, and the temperature was cooled to 0 ° C. After lowering and dividing several times, trimethyl acetonitrile (140.7 mmol) was added. A suspension was formed and stirred under this temperature condition for 1 hour to add 1 L of ice water, stirred for 0.5 hour, and then filtered under reduced pressure. Dissolved with dichloromethane, washed 3 times with water, dried and the solvent was evaporated, and recrystallized from toluene / petroleum ether to obtain 18.2 g of intermediate (6). The yield was 76%.

Synthesis of Compound 51

[Scheme 10]

Dissolve 18.2 g (30.6 mmol) of intermediate (6) and 5.8 g (33.6 mmol) of 1-naphthaleneboric acid in 400 ml of toluene and 100 ml of ethanol in a 1 L 3-neck round bottom flask and dissolve nitrogen stream for 15 minutes. After passing, 46 ml of K ₂ CO ₃ (91.8 mmol, 2M) and 0.71 g (2 mol%) of Pd (PPh ₃ ) ₄ were added. The reaction was terminated after 12 hours by raising the temperature to 110 ° C. After extracting the toluene layer, it was adsorbed with activated carbon, filtered under reduced pressure and dried. Recrystallization from toluene and ethanol gave 16.3 g of compound 51. The yield was 89%.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 9.45-9.28 (s, 1H), 9.26-8.85 (m, 2H), 8.62-8.40 (m, 3H), 8.35-8.17 (m, 3H), 8.14-7.98 (m, 2H), 7.96-7.78 (s, 1H), 7.74-7.58 (m, 7H), 7.55-7.21 (m, 9H)

MS (FAB): 596 (M ⁺ )

Example 3

A kind of blue light emitting compound

Compound 54 was prepared by the following method.

Synthesis of intermediate (7)

[Scheme 11]

25.7 g (100 mmol) of 1-bromphenanthrene was dissolved in 500 ml of TFA in a 2 L 3-neck round bottom flask, and 7.6 g (78.4 mmol) of concentrated nitric acid was added dropwise. After completion of the dropwise addition, the temperature was raised to 90 ° C and refluxed for 12 hours. Was made. After the reaction was completed, it was cooled to room temperature and 1 L of water was added to form a solid. After the temperature was lowered, it was filtered under reduced pressure, and the filter cake was washed several times with water, then recrystallized from ethanol and dried to obtain 26.9 g of an intermediate (7). The yield was 89%.

Synthesis of intermediate (8)

[Scheme 12]

26.9 g (89 mmol) of the intermediate (7) obtained in [Scheme 11] was added to a 2 L 3-neck round bottom flask, and nitrogen was discharged through the T-shape three times, followed by dissolving in ethanol / THF = 500 ml / 100 ml solvent and nitrogen again. Hydrogen was passed through three discharges. 1.3 g of 5% palladium on carbon was taken and reacted for 5 hours at room temperature. After the reaction is completed, it is filtered under reduced pressure with silica gel. The filtrate was rotary evaporated and dried, and then recrystallized from ethanol to obtain 22.3 g of an intermediate (8). The yield was 92%.

Synthesis of intermediate (9)

[Scheme 13]

Dissolve 22.3 g (81.9 mmol) of the intermediate (8) obtained in [Scheme 12] in 200 ml HBr in a 2 L 3-neck round bottom flask and cool to 0 ° C to -10 ° C (ice-salt baths), Slowly, an aqueous solution of sodium nitrite 24.6 ml 4M (6.78 g, 98.3 mmol) was added dropwise over 2 hours. A solid precipitated and reacted for 2 hours while heating and dissolving 23.5 g (163.8 mmol) of CuBr in 250 mL of HBr in another three-necked flask. This solution was added dropwise to the diazo salt and allowed to reflux for 12 hours at 80 ° C. After the reaction was completed, the mixture was cooled to room temperature, and then the solution was neutralized with aqueous ammonia. Extracted with ethyl acetate, washed with water, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and the solution was subjected to rotary evaporation, and recrystallized from toluene and ethanol to obtain 30.2 g of intermediate (9). The yield was 89%.

Synthesis of intermediate (10)

[Scheme 14]

30.2 g (72.9 mmol) of intermediate (9) and 21.7 g (80.2 mmol) of 4-iodine-2-naphthol were dissolved in 600 ml of DMF in a dried 2 L 3-neck round-bottom flask and stirred while stirring. Pd (OAc) ₂ 0.5g (3% mol) and PPh ₃ 1.1g (6% mol) were added while passing a nitrogen stream for a minute. After that, 71.3 g (218.7 mmol) of Cs ₂ CO ₃ was slowly added, and the temperature was raised to 160 ° C. to reflux for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, activated carbon was added, and the column was extracted with silicon, and then the solution was extracted with toluene and water, and then the organic phase was washed 4 times, and recrystallized from toluene and ethanol to obtain 29 g of intermediate (10). The yield was 76%.

Synthesis of intermediate (11)

[Scheme 15]

In a 2L three-necked round bottom flask, 2-bromine-9,9'-spiralbifluorenyl 39.5g (100mmol) and 1,3-diphenylboric acid 18.2g (110mmol) 800ml toluene and 200ml ethanol And dissolved in a nitrogen stream for 15 minutes, and 150 ml (300 mmol, 2M) of K ₂ CO ₃ and 2.3 g (2 mol%) of Pd (PPh ₃ ) ₄ were added. The reaction was terminated after 12 hours by raising the temperature to 110 ° C. After extracting the toluene layer, it was adsorbed with activated carbon, filtered under reduced pressure and dried. Recrystallization from toluene and ethanol yielded 32.7 g of intermediate (11). The yield was 75%.

Synthesis of intermediate (12)

[Reaction Scheme 16]

In a 2 L 3-neck round bottom flask, 29 g (55.4 mmol) of the intermediate (10) obtained from [Scheme 14] and 26.6 g (61 mmol) of the intermediate (11) obtained from [Scheme 15] were dissolved in 1000 ml of toluene and 250 ml of ethanol for 15 minutes. While passing through a nitrogen stream, 83 ml (166.2 mmol, 2M) of K ₂ CO ₃ and 1.3 g (2 mol%) of Pd (PPh ₃ ) ₄ were added. The reaction was terminated after 12 hours by raising the temperature to 110 ° C. After extracting the toluene layer, it was adsorbed with activated carbon, filtered under reduced pressure and dried. Recrystallization from toluene and ethanol yielded 38.8 g of intermediate (12). The yield was 89%.

Synthesis of intermediate (13)

[Scheme 17]

After dissolving 28.6 g (100 mmol) of 2,6-bibromnaphthalene in 600 mL of dried THF in a dried 2 L 3-neck round bottom flask, the temperature was lowered to -78 ° C and 88 mL 2.5M n-BuLi (220 mmol, 2.2) eq.） was added dropwise. After the dropwise addition, the mixture was stirred for 1 hour under this temperature, and 10.3 g of TMB (260 mmol, 2.6 eq.) Was added dropwise and stirred at room temperature for 12 hours. After the reaction was completed, 4M HCL solution was added, extracted with dichloromethane, and the organic phase was washed with saturated aqueous sodium chloride solution until neutral, dried, the solvent was removed, and the obtained crude product was ethyl. After purification with acetate, the filter cake was dried and obtained as a boric acid intermediate (13). The total was 15.5g and the yield was 72%.

Synthesis of intermediate (14)

[Reaction Scheme 18]

15.5 g (72 mmol) and 16.2 bromine bibenzofuryl 16.2 g (65.5 mmol) obtained from [Scheme 17] were dissolved in 1 mL 3-neck round bottom flask in 300 mL of toluene and 75 mL of ethanol for 15 minutes. After passing through a nitrogen stream, 98.3 mL of a K ₂ CO ₃ (196.5 mmol, 2M) aqueous solution and 1.5 g of Pd (PPh ₃ ) ₄ (2 mol%) were added, and then the temperature was raised to 110 ° C. and the reaction was terminated after 12 hours. After extracting the toluene layer, it was purified with activated carbon, filtered under reduced pressure to remove the solvent, and then dried. Recrystallization from toluene and ethanol gave 19 g of intermediate (14) and yield was 86%.

Synthesis of Compound 54

[Scheme 19]

To a 2 L 3-neck round bottom flask, 38.8 g (49.3 mmol) of the intermediate (12) obtained from [Scheme 16] and 18.3 g (54.2 mmol) of the intermediate (14) obtained from [Scheme 18] were dissolved in 1000 mL of toluene and 250 mL of ethanol. After dissolving and passing through a nitrogen stream for 15 minutes, 74 mL of an aqueous solution of K ₂ CO ₃ (147.9mmol, 2M) and 1.1 g of Pd (PPh ₃ ) ₄ (2 mol%) were added and then heated to 110 ° C. Ended. After extracting the toluene layer, it was purified with activated carbon, filtered under reduced pressure to remove the solvent, and then dried. Recrystallization from toluene and ethanol gave 40.5 g of compound 54 and the yield was 82%.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 9.16-8.86 (m, 2H), 8.54-8.35 (m, 2H), 8.32-8.19 (d, 1H), 8.17-8.02 (d, 1H), 7.99-7.81 (m, 7H), 7.79-7.21 (m, 31H)

MS (FAB): 1001 (M ⁺ )

Example 4

A kind of blue light emitting compound

Compound 64 was prepared by the following method.

Synthesis of intermediate (15)

[Scheme 20]

In a 1L 3-neck round bottom flask, 25.7 g (100 mmol) of 1-bromphenanthrene was dissolved in 500 ml of glacial acetic acid, and Br ₂ 63.9 g (400 mml) was added dropwise at room temperature. When the dropwise addition was completed, the temperature was raised to 120 ° C. for 18 hours. To reflux. After the reaction was completed, a saturated Na ₂ SO ₃ aqueous solution was added and stirred for 1 hour to form a solid. After filtering under reduced pressure, the filter cake was washed with water, washed again with ethanol, dried, and recrystallized from toluene and ethanol to obtain 29.9 g of an intermediate (15). The yield was 89%.

Synthesis of intermediate (16)

[Scheme 21]

29.9 g (89 mmol) of the intermediate (15) and 26.4 g (97.9 mmol) of 8-iodine-2-hydroxy-naphthalene obtained in [Reaction Scheme 20] in a dried 2 L 3-neck round bottom flask were dissolved in 600 ml of DMF and stirred. While passing through a nitrogen stream for 15 minutes, 0.6 g (3% mol) of Pd (OAc) ₂ and 1.4 g (6% mol) of PPh ₃ were added. Thereafter, 87 g (267 mmol) of Cs ₂ CO ₃ was slowly added thereto, and the temperature was raised to 160 ° C. to reflux for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, activated carbon was added, and after columning with silicon, the solution was extracted with toluene and water, and then the organic phase was washed 4 times and recrystallized from toluene and ethanol to obtain 31.6 g of intermediate (16). The yield was 80%.

Synthesis of intermediate (17)

[Scheme 22]

31.6 g (71.2 mmol) of the intermediate (16) obtained in [Scheme 21] was dissolved in 600 ml of TFA in a 2 L 3-neck round bottom flask, and 5.4 g (78.4 mmol) of concentrated nitric acid was added dropwise. Raise until until reflux for 12 hours. After the reaction was completed, it was cooled to room temperature and 1 L of water was added to form a solid. After the temperature was lowered, it was filtered under reduced pressure and the filter cake was washed several times with water, then recrystallized from ethanol to dry and 29.6 g of an intermediate (17) was obtained. The yield was 85%.

Synthesis of intermediate (18)

[Scheme 23]

Dissolve 29.6 g (60.5 mmol) of the intermediate (17) and 8.1 g (66.6 mmol) of phenyl boronic acid in 600 ml of toluene and 150 ml of ethanol in a 2 L 3-neck round bottom flask and pass through a nitrogen stream for 15 minutes. In addition, 92 ml (181.5 mmol, 2M) of K ₂ CO ₃ and 1.4 g (2 mol%) of Pd (PPh ₃ ) ₄ were added. The reaction was terminated after 12 hours by raising the temperature to 110 ° C. After extracting the toluene layer, it was adsorbed with activated carbon, filtered under reduced pressure and dried. Recrystallization from toluene and ethanol yielded 24.2 g of intermediate (18). The yield was 91%.

Synthesis of intermediate (19)

[Reaction Scheme 24]

24.2 g (55.1 mmol) of the intermediate (18) obtained in [Scheme 23] was added to a 2 L 3-neck round bottom flask, and nitrogen was discharged three times through a T-tube, followed by dissolving in ethanol / THF = 500 ml / 100 ml solvent and again nitrogen Was discharged three times and hydrogen was passed through. 1.2 g of 5% palladium on carbon was taken and reacted for 5 hours at room temperature. After the reaction is completed, it is filtered under reduced pressure with silica gel. The filtrate was evaporated to dryness, and then recrystallized from ethanol to obtain 20.3 g of an intermediate (19). The yield was 90%.

Synthesis of intermediate (20)

[Reaction Scheme 25]

20.3 g (49.6 mmol) of the intermediate (19) and 18.9 g (59.5 mmol) of CuI ₂ were dissolved in 400 ml of dried acetonitrile in a dried 1 L 3-neck round bottom flask, and the temperature was cooled to 0 ° C. After lowering and dividing several times, 18.6 g (223.2 mmol) of trimethylacetonitrile was added. When a suspension was formed, the mixture was stirred for 1 hour under this temperature condition, 1 L of ice water was added and stirred for 0.5 hour, and then filtered under reduced pressure. Dissolved with dichloromethane, washed with water three times, dried, and then the solvent was evaporated, and recrystallized from toluene / petroleum ether to obtain 20.1 g of intermediate (20). The yield was 78%.

Synthesis of Compound 64

[Scheme 26]

800 ml of 20.1 g (38.7 mmol) of the intermediate (20) and 10.1 g (42.6 mmol) of 9,9'-dimethyl-9H-fluorenyl-4-boric acid obtained in [Scheme 25] in a 2 L 3-neck round bottom flask And dissolved in 200 ml of ethanol, nitrogen gas was passed through for 15 minutes, and 58 ml (116.1 mmol, 2M) of K ₂ CO ₃ and 0.89 g (2 mol%) of Pd (PPh ₃ ) ₄ were added. The temperature was raised to 110 ° C, and the reaction was terminated overnight. After extracting the toluene layer, it was adsorbed with activated carbon, filtered under reduced pressure and dried. Recrystallization from toluene and ethanol yielded 18.6 g of compound 64. The yield was 82%.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 9.56-9.36 (s, 1H), 8.97-8.73 (d, 1H), 8.58-8.40 (m, 2H), 8.28-8.01 (d, 1H), 7.99-7.84 (m, 4H), 7.82-7.35 (m, 14H), 7.32-7.21 (t, 1H), 1.46-1.25 (s, 6H)

MS (FAB): 586 (M ⁺ )

Example 5

A kind of blue light emitting compound

Compound 84 was prepared by the following method.

Synthesis of intermediate (21)

[Scheme 27]

In a 1L 3-neck round bottom flask, 25.7 g (100 mmol) of 1-bromphenanthrene was dissolved in 500 ml of glacial acetic acid and Br ₂ 63.9 g (400 mml) was added dropwise at room temperature. When the dropwise addition was completed, the temperature was raised to 120 ° C. and 18 hours. During reflux. After the reaction was completed, saturated Na ₂ SO ₃ aqueous solution was added and stirred for 1 hour to form a solid. After filtering under reduced pressure, the filter cake was washed with water, washed again with ethanol, dried, and recrystallized from toluene and ethanol to obtain 30.6 g of an intermediate (21). The yield was 91%.

Synthesis of intermediate (22)

[Scheme 28]

30.6 g (91 mmol) of the intermediate (21) and 26.9 g (100.1 mmol) of 1-iodine-2-hydroxy-naphthalene obtained in [Reaction Scheme 26] were dissolved in 600 ml of DMF and stirred in a dried 2 L 3-neck round bottom flask. While passing through a nitrogen stream for 15 minutes, 0.6 g (3% mol) of Pd (OAc) ₂ and 1.4 g (6% mol) of PPh ₃ were added. Thereafter, 88.9 g (273 mmol) of Cs ₂ CO ₃ was slowly added to raise the temperature to 160 ° C. and reflux for 24 hours. Upon completion of the reaction, the mixture was cooled to room temperature, activated carbon was added, and after columning with silicon, the solution was extracted with toluene and water, and then the organic phase was washed 4 times and recrystallized from toluene and ethanol to obtain 31.5 g of intermediate (22). The yield was 78%.

Synthesis of intermediate (23)

[Scheme 29]

31.5 g (71 mmol) of the intermediate (22) obtained in [Scheme 28] was dissolved in 600 ml of trichloromethane and 30 g (212.9 mmol) of liquid bromine was added dropwise to the dried 2 L 3-neck round bottom flask. The temperature was raised to 70 ° C and allowed to reflux for 16 hours. When the reaction was completed, ₂ L of saturated Na ₂ SO ₃ aqueous solution was stirred and stirred for 1 hour while forming a large amount of solid, filtered under reduced pressure, washed with water and dissolved in trichloromethane. Then, washed three times with water, dried and the solvent was evaporated, and recrystallized from toluene and petroleum ether to obtain 30.8 g of an intermediate (23). The yield was 72%.

Synthesis of intermediate (24)

[Scheme 30]

Dissolve 30.8 g (51.1 mmol) of intermediate (23) and 12.5 g (56.2 mmol) of phenyl boronic acid in 600 ml of toluene and 150 ml of ethanol in a 2 L 3-neck round bottom flask and pass through a nitrogen stream for 15 minutes. The solution was added with 76.7 ml of K ₂ CO ₃ (153.3 mmol, 2M) and 1.2 g (2 mol%) of Pd (PPh ₃ ) ₄ . The temperature was raised to 110 ° C, and the reaction was terminated after 12 hours. After extracting the toluene layer, it was adsorbed with activated carbon, filtered under reduced pressure and dried. Recrystallization from toluene and ethanol yielded 23.7 g of intermediate (24). The yield was 71%.

Synthesis of intermediate (25)

[Scheme 31]

23.7 g (36.3 mmol) of the intermediate (24) and 4.9 g (40 mmol) of phenyl boronic acid were dissolved in 400 ml of toluene and 100 ml of ethanol in a 1 L 3-neck round bottom flask, and passed through a nitrogen stream for 15 minutes. In addition, 54 ml (108.9 mmol, 2M) of K ₂ CO ₃ and 0.8 g (2 mol%) of Pd (PPh ₃ ) ₄ were added. The reaction was terminated after 12 hours by raising the temperature to 110 ° C. After extracting the toluene layer, it was adsorbed with activated carbon, filtered under reduced pressure and dried. Recrystallization from toluene and ethanol yielded 17.7 g of intermediate (25). The yield was 75%.

Synthesis of Compound 84

[Scheme 32]

Dissolve 17.7 g (27.2 mmol) of the intermediate (25) and 5.9 g (30 mmol) of phenyl boronic acid in 400 ml of toluene and 100 ml of ethanol in a 1 L 3-neck round bottom flask and pass nitrogen stream for 15 minutes. An aqueous solution of K ₂ CO ₃ 40.8 ml (81.6 mmol, 2M) and Pd (PPh ₃ ) ₄ 0.6 g (2 mol%) were added. The temperature was raised to 110 ° C., and the reaction was terminated after 12 hours. After extracting the toluene layer, it was adsorbed with activated carbon, filtered under reduced pressure and dried. Recrystallization from toluene and ethanol yielded 16.9 g of compound 84. The yield was 86%.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 9.34-9.17 (d, 1H), 9.15-9.02 (d, 1H), 8.99-8.79 (d, 1H), 8.62-8.41 (m, 4H), 8.36-8.14 (m, 3H), 8.11-7.96 (m, 2H), 7.91-7.66 (m, 5H), 7.61-7.32 (m, 13H), 7.28-7.07 (m, 4H)

MS (FAB): 722 (M ⁺ )

Example 6

A kind of blue light emitting compound

Compound 117 was prepared by the following method.

Synthesis of intermediate (26)

[Reaction Scheme 33]

In a 2L 3-neck round bottom flask, 25.7 g (100 mmol) of 4-bromophenanthrene and 18.2 g (110 mmol) of 1,3-benzene hypoboric acid were dissolved in 600 ml of toluene and 150 ml of ethanol and passed through a nitrogen stream for 15 minutes. ₂ CO ₃ 150 ml (300 mmol, 2M) of an aqueous solution and Pd (PPh ₃ ) ₄ 2.3g (2 mol%) were added. The reaction was terminated after 12 hours by raising the temperature to 110 ° C. After extracting the toluene layer, it was adsorbed with activated carbon, filtered under reduced pressure and dried. Recrystallization from toluene and ethanol yielded 23.3 g of intermediate (26). The yield was 78%.

Synthesis of intermediate (27)

[Scheme 34]

23.3 g (78 mmol) of the intermediate (26) and 19.4 g (70.9 mmol) of 4-bromine-9,9'-dimethyl fluorenyl obtained from [Equation 33] in a 2 L 3-neck round bottom flask 500 ml of toluene and 125 ml of ethanol Dissolved in nitrogen and passed through a nitrogen stream for 15 minutes, and 106.4 ml (212.7 mmol, 2M) of K ₂ CO ₃ and 1.6 g (2 mol%) of Pd (PPh ₃ ) ₄ were added. The reaction was terminated after 12 hours by raising the temperature to 110 ° C. After extracting the toluene layer, it was adsorbed with activated carbon, filtered under reduced pressure and dried. Recrystallization from toluene and ethanol gave 28.2 g of an intermediate (27). The yield was 89%.

Synthesis of intermediate (28)

[Scheme 35]

After dissolving 28.2 g (63.1 mmol) of the intermediate (27) obtained in [Reaction Scheme 34] into 600 mL of dried THF in a dried 2 L three-neck round bottom flask, cooled to -78 ° C, and LDA 33.1 mL 2M (66.3 mmol) THF solution was added dropwise. The mixture was stirred for 1 hour under this temperature, and liquid bromine (Br ₂ ) 11.1 g (69.4 mmol) was added and stirred at room temperature for 12 hours. When the reaction was completed, 4M hydrochloric acid solution was added and extracted with dichloromethane. The organic phase was washed with saturated brine until neutral, dried, and the solution was evaporated, and recrystallized from toluene and ethanol to obtain 23.9 g of an intermediate (28). The yield was 72%.

Synthesis of intermediate (29)

[Scheme 36]

Dissolve 23.9 g (45.4 mmol) of the intermediate (28) obtained from [Scheme 35] in 500 ml of glacial acetic acid in a 1 L 3-neck round bottom flask and dropwise add Br ₂ 63.9 g (181.7 mmol) at room temperature. It was raised to 120 ° C and allowed to reflux for 18 hours. After the reaction was completed, saturated Na ₂ SO ₃ aqueous solution was added and stirred for 1 hour, and a solid was formed. After filtering under reduced pressure, the filter cake was washed with water, washed again with ethanol, dried, and recrystallized from toluene and ethanol to obtain 22 g of an intermediate (29). The yield was 80%.

Synthesis of intermediate 30

[Reaction Scheme 37]

After dissolving 22.3 g (100 mmol) of 1-bromine-3-naphthol in 400 ml of dried THF in a dried 2-liter 3-neck round-bottom flask, the mixture was cooled to -78 ° C and LDA 105 ml 2M (210 mmol) THF solution was added dropwise. . The mixture was stirred for 1 hour under this temperature, 27.9 g (110 mmol) of iodine was added, and the mixture was stirred overnight at room temperature. When the reaction was completed, 4M hydrochloric acid solution was added and extracted with dichloromethane. The organic phase was washed with saturated brine until neutral, dried and the solution was evaporated, and recrystallized from toluene and ethanol to obtain 26.2 g of an intermediate (30). The yield was 75%.

Synthesis of intermediate (31)

[Scheme 38]

26.2 g (75 mmol) of intermediate (30) and 18.3 g (82.5 mmol) of 2-phenanthreneboric acid obtained in [Scheme 37] were dissolved in 600 ml of toluene and 150 ml of ethanol in a 2 L 3-neck round bottom flask, and a nitrogen stream was added for 15 minutes. The solution was passed through 112 ml (225 mmol, 2M) of K ₂ CO ₃ and 1.7 g (2 mol%) of Pd (PPh ₃ ) ₄ . The temperature was raised to 110 ° C and left overnight, and the reaction was terminated. After extracting the toluene layer, it was adsorbed with activated carbon, filtered under reduced pressure and dried. Recrystallization from toluene and ethanol yielded 22.8 g of intermediate (31). The yield was 76%.

Synthesis of intermediate (32)

[Scheme 39]

22.8g (57mmol) and 9- (4'-bromo-3-biphenyl) -9H-carbazole 22.8g (62.7mmol) obtained from [Scheme 38] in a 1L 3-neck round bottom flask Dissolved in 400 ml of toluene and 100 ml of ethanol, passed through a nitrogen stream for 15 minutes, and 85.5 ml (171 mmol, 2M) of K ₂ CO ₃ and 1.3 g (2 mol%) of Pd (PPh ₃ ) ₄ were added. The temperature was raised to 110 ° C, and the reaction was terminated after 12 hours. After extracting the toluene layer, it was adsorbed with activated carbon, filtered under reduced pressure and dried. Recrystallization from toluene and ethanol yielded 29.8 g of intermediate (32). The yield was 82%.

Synthesis of Compound 117

[Reaction Scheme 40]

In a dried 2 L 3-neck round bottom flask, 22 g (36.4 mmol) of the intermediate (29) obtained from [Scheme 36] and 25.5 g (40 mmol) of the intermediate (32) obtained from [Scheme 39] were dissolved in 600 ml of DMF and stirred 15 Pd (OAc) ₂ 0.25 g (3% mol) and PPh ₃ 0.57 g (6% mol) were added while passing through a nitrogen stream for a minute. After that, 35.6 g (109.2 mmol) of Cs ₂ CO ₃ was slowly added to raise the temperature to 160 ° C. and reflux for 24 hours. Upon completion of the reaction, the mixture was cooled to room temperature, activated carbon was added, and after columning with silicon, the solution was extracted with toluene and water, and then the organic phase was washed 4 times and recrystallized from toluene and ethanol to obtain 29.9 g of Compound 117. The yield was 71%.

¹ H NMR (DMSO, 300 Hz): δ (ppm) = 9.37-8.93 (m, 4H), 8.91-8.76 (m, 2H), 8.71-8.48 (m, 2H), 8.45-8.12 (m, 7H), 8.10-8.01 (s, 1H), 7.97-7.76 (m, 4H), 7.74-7.09 (m, 35H)

MS (FAB): 1158 (M ⁺ )

Compounds 1 to 120 shown in the present invention can be made according to the above reaction schemes 1 to 40.

The structure of the organic electroluminescent device of the present invention is as follows, but is not limited thereto.

(1) anode / light emitting layer / cathode;

(2) anode / hole injection layer / light emitting layer / cathode;

(3) anode / hole injection layer / hole transport layer / light emitting layer / cathode;

(4) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / cathode;

(5) anode / light emitting layer / electron injection layer / cathode;

(6) anode / light emitting layer / electron transport layer / electron injection layer / cathode;

(7) anode / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode;

(8) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode;

(9) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode / capping layer;

A method of manufacturing an organic electroluminescent device such as structure (8) includes the following steps.

Step 1, a positive electrode is formed on the surface of the substrate by coating a material for an anode. At this time, it is preferable that the substrate used is a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, handling ease, and waterproofness. In addition, as the material for the anode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and excellent in conductivity, may be used.

Step 2, a hole injection layer (HIL) material is vacuum-deposited or spin coated on the anode surface by a conventional method to form a hole injection layer. Examples of the hole injection layer material include CuPc, m-MTDATA, m-MTDAPB, and starburst amines TCTA, 2-TNATA, or IDE406 available from Idemitsu.

Step 3, a hole transport layer (HTL) material is vacuum-deposited or spin coated on the surface of the hole injection layer in a conventional manner to form a hole transport layer. At this time, examples of the hole transport layer material include α-NPD, NPB, or TPD.

Step 4, a light emitting layer (EML) material is vacuum-deposited or spin coated on the surface of the hole transport layer in a conventional manner to form a light emitting layer. It may be desirable to use the organic compound of the present invention as a dopant to be doped with a host material.

Step 5, an electron transport layer (ETL) material is vacuum-deposited or spin coated on the surface of the light emitting layer in a conventional manner to form an electron transport layer. In this case, the electron transport layer material used is not particularly limited, and Alq ₃ may be preferably used.

Step 6, an electron injection layer (EIL) material is vacuum-deposited or spin coated on the surface of the electron transport layer in a conventional manner to form an electron injection layer. At this time, as the electron injection layer material used, materials such as LiF, Liq, Li ₂ O, BaO, NaCl, and CsF may be used.

Step 7, a negative electrode is formed on the surface of the electron injection layer by vacuum thermal vapor deposition or spin coating in a conventional manner. At this time, the negative electrode material used is lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and the like can be used. In addition, in the case of a front emission organic electroluminescent device, a transparent cathode through which light can pass may be formed using indium tin oxide (ITO) or indium zinc oxide (IZO).

Optionally, by forming a hole blocking layer (HBL) between the light emitting layer and the electron transport layer and using a phosphorescent dopant together in the light emitting layer, it is possible to prevent the phenomenon of triplet excitons or holes from diffusing into the electron transport layer. The hole blocking layer may be formed by vacuum thermal evaporation and spin coating of a hole blocking layer material (HBL) in a conventional manner, and the hole blocking layer material is not particularly limited, but preferably Liq, bis (8) -Hydroxy-2-methylquinolinolnato) -aluminum biphenoxide (BAlq), BCP and LiF, and the like can be used.

Optionally, the light-emitting layer is prepared by using the blue light-emitting compound of the present invention as a host material and a dopant material, and doping a known light-emitting material other than the present invention in a range that does not impair the object of the present invention.

Hereinafter, the organic electroluminescent device according to the present invention will be described in more detail with reference to Examples 7 to 17 and Comparative Example 1.

Example 7

A type of organic electroluminescent device comprising an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode and a capping layer arranged in order, wherein the above-described light emitting layer includes a host material and a dopant material, Among them, the compound 32 provided in Example 1 can be used as the host material.

An anode was formed of ITO on the substrate on which the reflective layer was formed, and the surface was treated with N ₂ plasma or UV-ozone. HAT-CN was deposited on the hole injection layer (HIL) to a thickness of 10 nm. Subsequently, NPD was deposited to a thickness of 120 nm with a hole transport layer (HTL). The compound 32 of the present invention capable of forming blue EML as an emission layer (EML) on the hole transport layer was doped with t-Bu-perylene about 5% while depositing 25 nm. Anthracene derivative and Liq were mixed 1: 1 to deposit an electron transport layer (ETL) with a thickness of 35 nm, and Liq was deposited with an electron injection layer (EIL) to a thickness of 2 nm. Then, a mixture of magnesium and silver (Ag) 9: 1 as a cathode was deposited to a thickness of 15 nm, and N, N′-bis [4- [bis (3) as a capping layer (CPL) on the cathode. -Methylphenyl) amino] phenyl] -N, N'-diphenyl- [1,1'-biphenyl] -4,4'-diamine (DNTPD) was deposited to a thickness of 65 nm. On top of that, an organic electroluminescent device was manufactured by bonding a seal cap containing a moisture absorbent with a UV curable adhesive to protect the organic electroluminescent device from O ₂ or moisture in the air.

The compounds from the examples have the following structure.

Examples 8-17

The organic compounds of Examples 8 to 17 were performed in the same manner as in Example 7, except that Compound 2, 23, 42, 51, 54, 64, 70, 84, 92, and 117 were used as a host for the light emitting layer (blue EML). An electroluminescent device was manufactured.

Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example 7, except that 9,10-bis (2-naphthyl) anthracene (ADN) was used as a host for the light emitting layer.

The properties of the organic electroluminescent devices manufactured in Examples 7 to 17 and Comparative Examples 1 were measured at a current density of 10 mA / cm ² , and the results are shown in the following table.

As a result of the experiment, the organic electroluminescent devices of Examples 7 to 17 including the organic compound of the present invention as a host, compared to the conventional organic electroluminescent devices of Comparative Example 1, improved efficiency up to 58.5% and lowered the driving voltage. The results showed. In addition, it was confirmed that CIE-Y values of Examples 7 to 17 were lower than those of the organic electroluminescent devices of Comparative Example 1 according to the results of the color coordinates (CIE X, Y), thereby having deep blue characteristics. Therefore, it was found that the organic light emitting device including the blue light emitting compound of the present invention as the host of the organic compound in the light emitting layer has excellent characteristics of efficiency, voltage and life.

Although the invention has been illustrated and described with reference to specific embodiments, it should be understood that many other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, all such changes and modifications within the scope of the present invention are intended to be included in the appended claims.

Claims (10)

A blue light-emitting compound, characterized by having the following structure:

In the above formula
R1 and R4 are each independently substituted or unsubstituted phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl group;
R2, R3, and R5 are each independently hydrogen, C1 to C20 straight chain alkyl, or C3 to C20 branched chain alkyl, or substituted or unsubstituted phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridine It is a diynyl, pyrimidinyl, or triazinyl group. The method according to claim 1, R1 of the phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl group, hydrogen is independently C1 ~ C20 straight-chain alkyl, C3 ~ C20 branched chain alkyl, C3 ~ C24 cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ and Si (CH ₃ ) ₃ group, C6 ~ C50 aryl group Substituted, a blue light-emitting compound. The method according to claim 1, R2 of the phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl group, hydrogen is independently C1 ~ C20 straight-chain alkyl, C3 ~ C20 branched chain alkyl, C3 ~ C24 cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ or Si (CH ₃ ) ₃ group, naphthyl, anthracenyl, phenanthrenyl, dibenzofuran group, A blue light-emitting compound, which is substituted with one or more selected from the group consisting of a fluorene group, a carbazole group, a spiro fluorene group, and a heteroaryl group having 5 to 20 nuclear atoms. The method according to claim 1, R3 of the phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl group, hydrogen is independently C1 ~ C20 straight-chain alkyl, C3 ~ C20 branched chain alkyl, C3 ~ C24 cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ or Si (CH ₃ ) ₃ group, naphthyl, anthracenyl, phenanthrenyl, dibenzofuran group, A blue light-emitting compound, which is substituted with one or more selected from the group consisting of a fluorene group, a carbazole group, a spiro fluorene group, and a heteroaryl group having 5 to 20 nuclear atoms. The method according to claim 1, R4 of phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl group, hydrogen is independently C1 ~ C20 straight-chain alkyl, C3 ~ C20 branched chain alkyl, C3 ~ C24 cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ and Si (CH ₃ ) ₃ group, C6 ~ C50 aryl group Substituted, a blue light-emitting compound. The method according to claim 1, R5 of phenyl, pyridine, naphthalene, phenanthrene, anthracene, phenanthridine, biphenyl, pyridinyl, pyrimidinyl, or triazinyl group, hydrogen is independently C1 ~ C20 straight-chain alkyl, C3 ~ C20 branched chain alkyl, C3 ~ C24 cycloalkyl, C1 ~ C20 alkoxy, halogen, CN, CF ₃ or Si (CH ₃ ) ₃ group, naphthyl, anthracenyl, phenanthrenyl, dibenzofuran group, A blue light-emitting compound, which is substituted with one or more selected from the group consisting of a fluorene group, a carbazole group, a spiro fluorene group, and a heteroaryl group having 5 to 20 nuclear atoms. The method according to claim 1, characterized in that any one of the following compounds 1 to 120, blue light-emitting compound:

An organic electroluminescent device comprising the blue light-emitting compound according to any one of claims 1 to 7. An organic electroluminescent device comprising an anode, a light emitting layer comprising the blue light emitting compound according to any one of claims 1 to 7, and a cathode. The organic electroluminescent device according to claim 9, comprising a hole injection layer and a hole transport layer between the anode and the light emitting layer, and an electron transport layer and an electron injection layer between the light emitting layer and the cathode.