KR20230148750A - Novel organic compounds and an organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention provides an organic compound represented by the following formula (1) and an organic electroluminescent device containing the same:
[Formula 1]

Description

Novel organic compounds and an organic electroluminescent device comprising the same}

The present invention relates to the field of displays, and more specifically, to organic compounds that can be used in the manufacture of organic electroluminescent devices, which are a type of display, and organic electroluminescent devices containing the same.

Liquid crystal displays account for most of the flat displays to date, but efforts are being made around the world to develop new flat displays that are more economical, have better performance, and are differentiated from liquid crystal displays. Organic electroluminescent devices, which have recently been in the spotlight as next-generation flat displays, have advantages such as low driving voltage, fast response speed, and wide viewing angle compared to liquid crystal displays.

The structure of an organic electroluminescent device consists of 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 entering the hole transport layer from the light-emitting layer, and holes and electrons combine to produce light. It consists of a light emitting layer that emits light, a hole blocking layer that blocks the entry 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, an electron injection layer that accepts electrons from the cathode, and a cathode. In some cases, a light-emitting layer may be formed by doping a small amount of fluorescent or phosphorescent dye into the electron transport layer or hole transport layer without a separate light-emitting layer. When polymers are used, one polymer generally serves as the hole transport layer, light-emitting layer, and electron transport layer. can be performed simultaneously. The organic thin film layers between the two electrodes are formed by methods such as vacuum deposition, spin coating, inkjet printing, or laser thermal transfer. The reason why organic electroluminescent devices are manufactured with a multi-layer thin film structure is to stabilize the interface between the electrode and the organic material. Also, in the case of organic materials, the difference in movement speed between holes and electrons is large, so an appropriate hole transport layer and electron transport layer are used to This is because luminous efficiency can be increased by effectively transferring excess electrons to the light emitting layer and balancing the densities of holes and electrons.

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. Meanwhile, 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 area to generate excitons. This exciton changes from the excited state to the ground state, and as a result, the fluorescent molecules in the light-emitting layer emit light, forming an image. At this time, light emission as the excited state falls to the ground state through a singlet excitation state is called “fluorescence,” and light emission as the excited state falls to the ground state through a triplet excitation state is called “phosphorescence.” In the case of fluorescence, the probability of a singlet excited state is 25% (75% of a triplet state), and there is a limit to the luminous efficiency, whereas when using phosphorescence, up to 75% of the triplet state and 25% of the singlet excited state can be used for luminescence. Therefore, theoretically, internal quantum efficiency of up to 100% is possible.

The biggest problems with these organic electroluminescent devices are lifespan and efficiency, but as displays become larger in area, these efficiency and lifespan issues must be resolved.

Republic of Korea Patent No. 1022021710000 Republic of Korea Patent No. 1018256120000 Republic of Korea Patent No. 1012267000000

The present invention was devised to solve the above problems of the prior art,

The purpose is to provide a novel organic compound that is used as a material for organic electroluminescent devices and improves the luminous efficiency and luminous lifetime of organic electroluminescent devices.

In addition, the present invention aims to provide an organic electroluminescent device with improved driving voltage, luminous efficiency, and luminous lifetime by including the organic electroluminescent device material as described above.

In addition, the present invention aims to provide an organic electroluminescent device whose driving voltage, efficiency, and lifespan are further improved by including a combination of the material of the organic electroluminescent device and a specific hole transport layer material.

The present invention provides an organic compound represented by the following formula (1):

[Formula 1]

In the above equation

R1 is deuterium, halogen, CN, CF ₃ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl, biphenyl, Phenyl, naphthanyl, biphenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, substituted or unsubstituted with one or more selected from the group consisting of naphthyl and anthracenyl groups. Substituted with one or more selected from the group consisting of dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group. or an unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms,

Deuterium, halogen, CN, CF ₃ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl. , anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobifluorenyl, carbazolyl, dibenzofuran, substituted or unsubstituted with one or more selected from the group consisting of anthracenyl groups. Substituted or unsubstituted with one or more selected from the group consisting of yl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group. and is a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more elements selected from the group consisting of S, O, N, B, and Si,

Z1, Z4, Z5 are each independently a single bond or C1~C10 linear or branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, CN, CF ₃ , phenyl, naphthanyl, biphenylamine , phenyl amine substituted or unsubstituted with one or more selected from the group consisting of phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, and Si (CH ₃ ) ₃ group,

Z2 and Z3 are each independently a single bond or one or more selected from the group consisting of halogen, CN, CF ₃ , phenyl, naphthanyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, and Si(CH ₃ ) ₃ group. It is substituted or unsubstituted phenyl,

a, b, c, d, and e are each independently 0 or 1;

Z6, Z7, and Z8 are each independently a single bond, C1~C2 alkylenyl, phenyl, or biphenyl group,

f, g, and h are each independently 0 or 1;

M is boron or carbon or nitrogen;

G1, G2, G3 are each independently carbon or nitrogen or oxygen or sulfur

G4, G5, and G6 are each independently carbon or nitrogen;

R2, R3, R4, R5, R6, R7, R8 and R9 are each independently hydrogen, deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , and have 1 to 40 carbon atoms. straight-chain or branched-chain alkyl, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, or cycloalkyl group with 3 to 40 carbon atoms,

Deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms , cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethyl, substituted or unsubstituted with one or more selected from the group consisting of phenyl groups. 6 to 60 carbon atoms substituted or unsubstituted with one or more selected from the group consisting of fluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group is an aromatic hydrocarbon group, or

Deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms , cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethyl, substituted or unsubstituted with one or more selected from the group consisting of phenyl groups. Substituted with one or more selected from the group consisting of fluorenyl, spirobifluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group, or It is an unsubstituted heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more elements selected from the group consisting of S, O, N, B, and Si, or

Deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms , and phenyl, biphenyl, naphthyl, anthracenyl substituted or unsubstituted with one or more types selected from the group consisting of cycloalkyl groups having 3 to 40 carbon atoms, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9 , 9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl group. It is an amino group substituted with one or more types selected from the group consisting of .

The present invention provides a novel organic compound that is used as a material for organic electroluminescent devices and improves the luminous efficiency and luminous lifetime of organic electroluminescent devices.

In addition, the present invention provides an organic electroluminescent device with improved driving voltage, luminous efficiency, and luminous lifetime by including the organic electroluminescent device material as described above.

In addition, the present invention provides an organic electroluminescent device with further improved driving voltage, device efficiency, and lifespan by including a combination of the organic electroluminescent device material and a specific hole transport layer material.

The present invention relates to a novel organic compound represented by the following formula (1):

[Formula 1]

In the above equation

R1 is deuterium, halogen, CN, CF ₃ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl, biphenyl, Phenyl, naphthanyl, biphenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, substituted or unsubstituted with one or more selected from the group consisting of naphthyl and anthracenyl groups. Substituted with one or more selected from the group consisting of dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group. or an unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms,

Deuterium, halogen, CN, CF ₃ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl. , anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobifluorenyl, carbazolyl, dibenzofuran, substituted or unsubstituted with one or more selected from the group consisting of anthracenyl groups. Substituted or unsubstituted with one or more selected from the group consisting of yl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group. and is a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more elements selected from the group consisting of S, O, N, B, and Si,

Z1, Z4, Z5 are each independently a single bond or C1~C10 linear or branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, CN, CF ₃ , phenyl, naphthanyl, biphenylamine , phenyl amine substituted or unsubstituted with one or more selected from the group consisting of phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, and Si (CH ₃ ) ₃ group,

Z2 and Z3 are each independently a single bond or one or more selected from the group consisting of halogen, CN, CF ₃ , phenyl, naphthanyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, and Si(CH ₃ ) ₃ group. It is substituted or unsubstituted phenyl,

a, b, c, d, and e are each independently 0 or 1;

Z6, Z7, and Z8 are each independently a single bond, C1~C2 alkylenyl, phenyl, or biphenyl group,

f, g, and h are each independently 0 or 1;

M is boron or carbon or nitrogen;

G1, G2, G3 are each independently carbon or nitrogen or oxygen or sulfur

G4, G5, and G6 are each independently carbon or nitrogen;

R2, R3, R4, R5, R6, R7, R8 and R9 are each independently hydrogen, deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , and have 1 to 40 carbon atoms. straight-chain or branched-chain alkyl, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, or cycloalkyl group with 3 to 40 carbon atoms,

Deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms , cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethyl, substituted or unsubstituted with one or more selected from the group consisting of phenyl groups. 6 to 60 carbon atoms substituted or unsubstituted with one or more selected from the group consisting of fluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group is an aromatic hydrocarbon group, or

Deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms , cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethyl, substituted or unsubstituted with one or more selected from the group consisting of phenyl groups. Substituted with one or more selected from the group consisting of fluorenyl, spirobifluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group, or It is an unsubstituted heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more elements selected from the group consisting of S, O, N, B, and Si, or

Deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms , and phenyl, biphenyl, naphthyl, anthracenyl substituted or unsubstituted with one or more types selected from the group consisting of cycloalkyl groups having 3 to 40 carbon atoms, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9 , 9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl group. It is an amino group substituted with one or more types selected from the group consisting of .

Specific examples of the organic compounds include any one of the following compounds 1 to 352.

Below, the organic electroluminescent device of the present invention will be described as an example. However, the contents illustrated below do not limit the organic electroluminescent device of the present invention.

In the method of manufacturing an organic electroluminescent device according to the present invention, an anode is first formed by coating the surface of a substrate with an anode material in a conventional manner. At this time, the substrate used is preferably a glass substrate or a transparent plastic substrate with excellent transparency, surface smoothness, ease of handling, and waterproofness. In addition, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, can be used as materials for the anode.

Next, a hole injection layer (HIL) material is vacuum thermally deposited or spin coated on the surface of the anode using a conventional method to form a hole injection layer. Such hole injection layer materials include copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris(3-methylphenyl) Amino)phenoxybenzene (m-MTDAPB), starburst type amines 4,4',4"-tri(N-carbazolyl)triphenylamine (TCTA), 4,4',4"-tris Examples include (N-(2-naphthyl)-N-phenylamino)-triphenylamine (2-TNATA) or IDE406 available from Idemitsu.

A hole transport layer (HTL) material is vacuum thermally deposited or spin coated on the surface of the hole injection layer using a conventional method to form a hole transport layer. At this time, the hole transport layer materials include bis(N-(1-naphthyl-n-phenyl))benzidine (α-NPD), N,N'-di(naphthalen-1-yl)-N,N'-biphenyl -Benzidine (NPB) or N,N'-biphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), More preferably, the compound of formula 2 of the present invention can be used.

An emitting layer (EML) material is formed on the surface of the hole transport layer by vacuum thermal evaporation or spin coating using a conventional method. At this time, examples of the light-emitting materials used include phosphorescent fluorescent materials, fluorescent whitening agents, laser dyes, organic scintillators, and reagents for fluorescence analysis. Specifically, carbazole-based compounds, phosphine oxide-based compounds, carbazole-based phosphine oxide compounds, bis ((3,5-difluoro-4-cyanophenyl) pyridine) iridium picolinate (FCNIrpic), tris ( 8-hydroxyquinoline) aluminum (Alq3), polyaromatic compounds such as anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene and quinacridone, oligophenylene compounds such as quiterphenyl, 1, 4-bis (2-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, 1,4-bis (4-methyl-5-phenyl-2-oxazolyl) benzene, 1,4 -bis(5-phenyl-2-oxazolyl)benzene, 2,5-bis(5-t-butyl-2-benzoxazolyl)thiophene, 1,4-diphenyl-1,3-butadiene, 1, Scintillator for liquid scintillation such as 6-diphenyl-1,3,5-hexatriene, 1,1,4,4-tetraphenyl-1,3-butadiene, metal complex of auxin derivative, coumarin pigment, dicyano Methylenepyran dye, dicyanomethylenethiopyran dye, polymethine dye, oxobenzanthracene dye, xanthene dye, carbostyryl dye, perylene dye, oxazine compound, stilbene derivative, spiro compound, oxadiazole compound, etc. can be mentioned. In particular, in the case of a blue organic electroluminescent device, it may be desirable to use the organic compound of Formula 1 of the present invention as a dopant.

Optionally, an electron blocking layer (EBL) may be additionally formed between the hole transport layer and the light emitting layer.

An electron transport layer (ETL) material is vacuum thermally deposited or spin coated on the surface of the light emitting layer using a conventional method to form an electron transport layer. At this time, the electron transport layer material used is not particularly limited, and tris(8-hydroxyquinolinolato)aluminum (Alq ₃ ) can be preferably used.

Optionally, by additionally forming a hole blocking layer (HBL) between the light emitting layer and the electron transport layer and using a phosphorescent dopant in the light emitting layer, diffusion of triplet excitons or holes into the electron transport layer can be prevented.

The formation of the hole blocking layer can be performed by vacuum thermal evaporation and spin coating of the hole blocking material by conventional methods. The hole blocking material is not particularly limited, but is preferably (8-hydroxyquinolinola). To) Lithium (Liq), bis(8-hydroxy-2-methylquinolinolnato)-aluminum biphenoxide (BAlq), bathocuproine (BCP), and LiF can be used.

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

A cathode material is vacuum thermally deposited on the surface of the electron injection layer using a conventional method to form a cathode.

At this time, the cathode materials used are lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), and magnesium-silver. (Mg-Ag) etc. may be used. Additionally, in the case of a top-emitting organic electroluminescent device, indium tin oxide (ITO) or indium zinc oxide (IZO) can be used to form a transparent cathode through which light can transmit.

A capping layer (CPL) may be formed on the surface of the cathode using the composition for forming a capping layer of the present invention.

The organic electroluminescent device according to the present invention may be manufactured in the order described above, that is, anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode, and vice versa, cathode/electron injection layer/cathode. It may be manufactured in the following order: electron transport layer/light emitting layer/hole transport layer/hole injection layer/anode.

Next, the method for synthesizing the compound of Formula 1 will be described using representative examples. However, the method of synthesizing the compounds of the present invention is not limited to the methods exemplified below, and the compounds of the present invention can be prepared by the methods exemplified below and methods known in the field.

<Synthesis of compound of formula 1>

<Synthesis of Intermediate 1-3>

Add 100g (591mmol) of 1-1, 185.8g (591mmol) of 1-2, 11.3g (177mmol) of copper, 245.0g (1.77mol) of potassium carbonate, and 1L of nitrobenzene into a 2L 3-neck round bottom flask and heat and reflux for 12 hours. do. After completion of the reaction, it was washed with EA, filtered with celite, and concentrated. After concentrating the organic solvent, 126.5 g of 1-3 was obtained with a yield of 66%.

Intermediate 1-3 MS (FAB): 324 (M ⁺ )

<Synthesis of Intermediate 1-4>

126.5g (390mmol) of 1-3 and 72.6g (780mmol) of aniline were added to a 3L 3-neck round bottom flask and dissolved in 1.5L of toluene. 112.4 g (1.17 mol) of sodium tert-butoxide, 1.75 g (8 mmol) of palladium acetate, and 6.31 g (16 mmol) of tri-tert-butyl phosphine (50% in toluene) were added and heated to reflux. After confirming completion of the reaction, it was cooled to room temperature, and 1L of EA and 1L of water were added to extract the organic layer. The organic layer was concentrated and then recrystallized through a column to obtain 114.2 g of 1-4 with a yield of 87%.

Intermediate 1-4 MS(FAB): 336(M ⁺ )

<Synthesis of Intermediate 1-6>

Add 1-4 114.2g (339mmol), 1-5 128.0g (407mmol), copper 6.47g (102mmol), potassium carbonate 140.7g (1.02mol), and nitrobenzene 1L into a 2L 3-neck round bottom flask and heat for 12 hours. It flows back. After completion of the reaction, it was washed with EA, filtered with celite, and concentrated. After concentrating the organic solvent, 123.4 g of 1-6 was obtained with a yield of 74%.

Intermediate 1-6 MS(FAB): 491(M ⁺ )

<Synthesis of Intermediate 1-8>

123.4g (251mmol) of 1-6 and 85.0g (502mmol) of 1-7 were added to a 3L 3-necked round bottom flask and dissolved in 1.2L of THF. 72.4 g (753 mmol) of sodium tert-butoxide, 1.13 g (5 mmol) of palladium acetate, and 4.06 g (10 mmol) of tri-tert-butyl phosphine (50% in toluene) were added and heated to reflux. After confirming completion of the reaction, it was cooled to room temperature, and 1L of EA and 1L of water were added to extract the organic layer. The organic layer was concentrated and then recrystallized through a column to obtain 116.5 g of 1-8 with a yield of 80%.

Intermediate 1-8 MS(FAB): 579(M ⁺ )

<Synthesis of Intermediate 1-10>

100 g (591 mmol) of 1-9 was added to a 2L 3-neck round bottom flask, dissolved in 1L of DMF, and maintained at 0 degrees by installing an icebath. 133.0 g (591 mmol) of N-iodosuccinimide was slowly added while maintaining 0 degrees. After completion of the reaction, DMF was concentrated and the organic layer was extracted by adding 1L of EA and 1L of water. The organic layer was concentrated and then column and recrystallized to obtain 157.0g of 1-10 with a yield of 90%.

Intermediate 1-10 MS (FAB): 295 (M ⁺ )

<Synthesis of Intermediate 1-11>

Add 157.0g (532mmol) of 1-10 to a 3L three-neck round bottom flask and dissolve it in 1.5L of acetonitrile. After adding 142.5g (638mmol) of copper(II) bromide, slowly add 91.4g (798mmol) of t-Butyl nitrite while heating to 60 degrees. After heating and refluxing for 1 hour, when the reaction was completed, it was cooled to room temperature, and 1L of EA and 1L of water were added to extract the organic layer. The organic layer was concentrated and then columnarized to obtain 116.5 g of 1-11 with a yield of 61%.

Intermediate 1-11 MS(FAB): 359(M ⁺ )

<Synthesis of Intermediate 1-12>

116.5g (201mmol) of 1-8 and 86.5g (241mmol) of 1-11 were added to a 3L 3-neck round bottom flask and dissolved in 1.2L of toluene. 57.9 g (603 mmol) of sodium tert-butoxide, 900 mg (4 mmol) of palladium acetate, and 3.25 g (8 mmol) of tri-tert-butyl phosphine (50% in toluene) were added and heated to reflux. After confirming completion of the reaction, it was cooled to room temperature, and 1L of EA and 1L of water were added to extract the organic layer. The organic layer was concentrated and then recrystallized through a column to obtain 105.9 g of 1-12 with a yield of 65%.

Intermediate 1-12 MS (FAB): 810 (M ⁺ )

<Synthesis of Compound-1>

105.9 g (131 mmol) of 1-12 and 500 ml of THF were added to a 3L 3-neck round bottom flask, filled with nitrogen, and maintained at -78 degrees using a dryice bath. After adding 261ml (418mmol) of 1.6M n-Butyllithium dropwise, the dryice bath was removed and stirred at room temperature. After 1 hour, a dryice bath was installed and the temperature was maintained at -78 degrees, and then 32.7 g (131 mmol) of boron tribromide was slowly added. After removing the bath, the temperature was slowly raised to room temperature, and 1L of xylene was added and heated. THF was distilled and removed so that the internal thermometer reached 140 degrees, and when only xylene remained, a condenser was installed and heated and refluxed for 3 days. After completion of the reaction, it was cooled to room temperature and concentrated. After column recrystallization, 27.1 g of Compound-1 was obtained with a yield of 28%.

NMR (DMSO, 300Hz): δ(ppm)= 8.86~8.95(t, 1H), 7.81~8.28(m, 3H), 7.56~7.73(m, 2H), 7.37~7.48(m, 7H), 7.17~ 7.34(m, 11H), 7.01~7.11(m, 7H), 6.74~6.96(m, 5H), 5.69~5.91(d, 2H)

MS(FAB): 739(M ⁺ )

<Synthesis of intermediate 45-3>

In a 3L three-neck round bottom flask, 100 g (670 mmol) of 45-1 and 212.6 g (670 mmol) of 45-2 were dissolved in 1.5 L of toluene, and then 322 g (3.35 mol) of sodium tert-butoxide was added. Palladium acetate 3.01g (13.4mmol) and Tri-tert-butylphosphonium tetrafluoroborate 7.78g (26.8mmol) were added and heated to reflux for 5 hours. After confirming the completion of the reaction, it was cooled to room temperature, 1.5 L of water was added, and the organic layer was extracted. The water layer was further washed with 1 L of EA. After concentrating the organic layer and recrystallizing it through a column, 145.2 g of 45-3 was obtained with a yield of 64%.

Intermediate 45-3 MS(FAB): 338(M ⁺ )

<Synthesis of intermediate 45-4>

In a 3L three-neck round bottom flask, 145g (429mmol) of 45-3 was dissolved in 1.5L of dimethylacetamide, and then 419g (1.286mol) of cesium carbonate was added. After adding 1.93 g (9 mmol) of palladium acetate and 4.98 g (17 mmol) of tri-tert-butylphosphonium tetrafluoroborate, it was heated and refluxed for 5 hours. After confirming the completion of the reaction, it was cooled to room temperature and the organic layer was extracted by adding 2L of EA and 2L of water. The organic layer was concentrated and recrystallized after column to obtain 72.6 g of 45-4 with a yield of 56%.

Intermediate 45-4 MS(FAB): 302(M ⁺ )

<Synthesis of intermediate 45-5>

72.6 g (240 mmol) of 45-4 was added to a 2L 3-necked round bottom flask and then dissolved by adding 700 ml of DMF. 28.8 g (720 mmol) of NaOH was dissolved in 100 ml of water, then added and stirred for 30 minutes. 49.3g (288mmol) of benzyl bromide was slowly added using a dropping funnel. After 1 hour, the reaction was completed, 1L of EA and 1L of water were added, and the organic layer was extracted. The organic layer was concentrated and then columnarized to obtain 66.8g of 45-5 with a yield of 92%.

Intermediate 45-5 MS(FAB): 392(M ⁺ )

<Synthesis of intermediate 45-7>

66.8g (170mmol) of 45-5 and 58.5g (187mmol) of 45-6 were added to a 2L 3-neck round bottom flask and dissolved in 1L of toluene. 49.1 g (511 mmol) of sodium tert-butoxide, 760 mg (3 mmol) of palladium acetate, and 2.75 g (7 mmol) of tri-tert-butyl phosphine (50% in toluene) were added and heated to reflux. After confirming completion of the reaction, it was cooled to room temperature, and 1L of EA and 1L of water were added to extract the organic layer. The organic layer was concentrated and then recrystallized through a column to obtain 73.7 g of 45-7 with a yield of 73%.

Intermediate 45-7 MS(FAB): 592(M ⁺ )

<Synthesis of intermediate 45-8>

73.7 g (124 mmol) of 45-7 was added to a 2L 3-neck round bottom flask and dissolved in 700 ml of THF. 6.6 g (6 mmol) of Palladium on activated carbon (10%) was added and stirred while bubbling hydrogen. After confirming the completion of the reaction, it was bubbling with nitrogen for 1 hour and filtered through celite. THF was concentrated and recrystallized to obtain 59.3 g of 45-8 with a yield of 95%.

Intermediate 45-8 MS(FAB): 502(M ⁺ )

<Synthesis of intermediate 45-10>

A mechanical stirrer was installed in a 2L 3-neck round bottom flask, and 100g (438mmol) of 45-9 was added, followed by 200ml of water and 200ml of conc.HCl. The temperature was maintained at -5 degrees using an ice-salt bath, and 60.5 g (877 mmol) of sodium nitrite dissolved in 100 ml of water was slowly added. After 30 minutes, 145.5 g (877 mmol) of potassium iodide dissolved in 100 ml of water was slowly added. The bath was removed, the temperature was slowly raised to room temperature, and the mixture was stirred for 2 hours. After confirming completion of the reaction, 500 ml of water was added, stirred, and then filtered. After column recrystallization, 62.4 g of 45-10 was obtained with a yield of 41%.

Intermediate 45-10 MS(FAB): 339(M ⁺ )

<Synthesis of intermediate 45-11>

59.3 g (118 mmol) of 45-8 and 48.0 g (142 mmol) of 45-10 were added to a 1L 3-neck round bottom flask, and then 600 ml of xylene was added. 4.5 g (24 mmol) of copper(I) iodide, 2.84 g (24 mmol) of ethylene diamine, and 32.6 g (236 mmol) of potassium carbonate were added and heated to reflux. After completion of the reaction, it was washed with EA, filtered with celite, and concentrated. After recrystallization after the column, 64.9 g of 45-11 was obtained with a yield of 77%.

Intermediate 45-11 MS(FAB): 713(M ⁺ )

<Synthesis of Compound-45>

64.9 g (91 mmol) of 45-11 and 300 ml of THF were added to a 1L 3-neck round bottom flask, filled with nitrogen, and maintained at -78 degrees using a dryice bath. After adding 187ml (300mmol) of 1.6M n-Butyllithium dropwise, the dryice bath was removed and stirred at room temperature. After 1 hour, a dryice bath was installed and the temperature was maintained at -78 degrees, and then 22.8 g (91 mmol) of boron tribromide was slowly added. After removing the bath, the temperature was slowly raised to room temperature, and 500ml of xylene was added and heated. THF was distilled and removed so that the internal thermometer reached 140 degrees, and when only xylene remained, a condenser was installed and heated and refluxed for 3 days. After completion of the reaction, it was cooled to room temperature and concentrated. After column recrystallization, 22.8 g of Compound-45 was obtained with a yield of 39%.

NMR (DMSO, 300Hz): δ(ppm)= 8.91~8.98(s, 1H), 8.21~8.29(d, 1H), 7.82~7.89(m, 1H), 7.62~7.68(m, 1H), 7.41~ 7.53(m, 4H), 7.25~7.35(m, 2H), 7.01~7.15(m, 7H), 5.62~5.78(s, 2H), 1.43~1.52(s, 18H), 1.28~1.39(s, 18H) )

MS(FAB): 642(M ⁺ )

<Synthesis of Intermediate 107-2>

100 g (405 mmol) of 107-1, 200 ml of ammonia (25-30%), and 400 ml of PEG300 were added to a 1L high-pressure reactor, and then 7.7 g (40 mmol) of copper(I) iodide was added and stirred at 180 degrees overnight. After cooling to room temperature, 1L of EA and 1L of water were added to the reaction solution to extract the organic layer. The organic layer was concentrated and then recrystallized to obtain 71.9 g of 107-2 with a yield of 97%.

Intermediate 107-2 MS(FAB): 183(M ⁺ )

<Synthesis of Intermediate 107-3>

71.92g (393mmol) of 107-2 was added to a 2L 3-necked round bottom flask, dissolved in 700ml of DMF, and maintained at 0 degrees by installing an icebath. 88.3 g (393 mmol) of N-iodosuccinimide was slowly added while maintaining 0 degrees. After completion of the reaction, DMF was concentrated, and 500 ml of EA and 500 ml of water were added to extract the organic layer. The organic layer was concentrated and then recrystallized with a column to obtain 51.0 g of 107-3 with a yield of 42%.

Intermediate 107-3 MS(FAB): 309(M ⁺ )

<Synthesis of Intermediate 107-4>

Add 51.0g (165mmol) of 107-3 to a 1L 3-neck round bottom flask and dissolve it in 500ml of acetonitrile. After adding 44.2g (198mmol) of copper(II) bromide, slowly add 28.3g (247mmol) of t-Butyl nitrite while heating to 60 degrees. After heating and refluxing for 1 hour, when the reaction was completed, it was cooled to room temperature, and 1L of EA and 1L of water were added to extract the organic layer. The organic layer was concentrated and then column-processed to obtain 44.9 g of 107-4 with a yield of 73%.

Intermediate 107-4 MS(FAB): 372(M ⁺ )

<Synthesis of Intermediate 107-6>

50g (178mmol) of 107-5 was added to a 1L 3-neck round bottom flask and dissolved in 500ml of DMF. The temperature was maintained at 0 degrees using an icebath, and 31.6 g (178 mmol) of N-Bromosuccinimide was slowly added. After completion of the reaction, DMF was distilled, concentrated, and columnarized to obtain 58.3 g of 107-6 with a yield of 91%.

Intermediate 107-6 MS (FAB): 360 (M ⁺ )

<Synthesis of Intermediate 107-7>

Add 44.9g (120mmol) of 107-4, 43.4g (120mmol) of 107-6, 2.3g (36mmol) of copper, 49.9g (361mmol) of potassium carbonate, and 500ml of nitrobenzene into a 1L 3-neck round bottom flask and heat and reflux for 12 hours. do. After completion of the reaction, it was washed with EA, filtered with celite, and concentrated. After concentrating the organic solvent, 40.8 g of 107-7 was obtained with a yield of 56%.

Intermediate 107-7 MS(FAB): 605(M ⁺ )

<Synthesis of Compound-107>

40.8g (67mmol) of 107-7 was added to a 1L 3-necked round bottom flask and dissolved in 400ml of THF. A dryice bath was installed to maintain -78 degrees Celsius, and 177ml (283mmol) of 1.6M n-Butyllithium was added dropwise. The bath was removed, the temperature was slowly raised to room temperature, and the mixture was stirred for 1 hour. A dryice bath was installed to maintain -78 degrees Celsius, and 16.9 g (67 mmol) of boron tribromide was slowly added. After 1 hour, 23ml (67mmol) of phenylmagnesium (3M) was added, the bath was removed, the temperature was slowly raised to room temperature, and 500ml of xylene was added and heated. THF was distilled and removed so that the internal thermometer reached 140 degrees, and when only xylene remained, a condenser was installed and heated and refluxed for 3 days. After completion of the reaction, it was cooled to room temperature and concentrated. After column recrystallization, 12.5 g of Compound-107 was obtained with a yield of 35%.

NMR (DMSO, 300Hz): δ(ppm)= 7.81~8.28(m, 2H), 7.52~7.73(m, 5H), 7.31-7.46(m, 6H), 7.13~7.25(m, 4H), 6.94- 7.09(d, 1H), 1.43~1.53(s, 9H), 1.28~1.39(s, 9H),

MS(FAB): 533(M ⁺ )

<Synthesis of intermediate 165-3>

71.92g (393mmol) of 107-2 was added to a 2L 3-necked round bottom flask, dissolved in 700ml of DMF, and maintained at 0 degrees by installing an icebath. 88.3 g (393 mmol) of N-iodosuccinimide was slowly added while maintaining 0 degrees. After completion of the reaction, DMF was concentrated, and 500 ml of EA and 500 ml of water were added to extract the organic layer. The organic layer was concentrated and recrystallized with a column to obtain 43.7 g of 165-3 with a yield of 36%.

Intermediate 165-3 MS(FAB): 309(M ⁺ )

<Synthesis of intermediate 165-4>

Add 43.7g (141mmol) of 165-3 to a 1L 3-neck round bottom flask and dissolve it in 500ml of acetonitrile. After adding 37.9g (170mmol) of copper(II) bromide, slowly add 24.3g (212mmol) of t-Butyl nitrite while heating to 60 degrees. After heating and refluxing for 1 hour, when the reaction was completed, it was cooled to room temperature, and 1L of EA and 1L of water were added to extract the organic layer. The organic layer was concentrated and then column-processed to obtain 39.5 g of 165-4 with a yield of 75%.

Intermediate 165-4 MS(FAB): 372(M ⁺ )

<Synthesis of intermediate 165-7>

Add 39.5g (106mmol) of 165-4, 39.2g (106mmol) of 107-6, 2.0g (32mmol) of copper, 44.0g (318mmol) of potassium carbonate, and 500ml of nitrobenzene into a 1L 3-neck round bottom flask and heat and reflux for 12 hours. do. After completion of the reaction, it was washed with EA, filtered with celite, and concentrated. After concentrating the organic solvent, 39.1 g of 165-7 was obtained with a yield of 61%.

Intermediate 165-7 MS(FAB): 605(M ⁺ )

<Synthesis of Compound-165>

39.1g (65mmol) of 165-7 was added to a 1L 3-necked round bottom flask and dissolved in 400ml of THF. A dryice bath was installed to maintain -78 degrees Celsius, and 170ml (272mmol) of 1.6M n-Butyllithium was added dropwise. The bath was removed, the temperature was slowly raised to room temperature, and the mixture was stirred for 1 hour. A dryice bath was installed to maintain -78 degrees Celsius, and 16.2 g (65 mmol) of boron tribromide was slowly added. After 1 hour, 22ml (65mmol) of phenylmagnesium (3M) was added, the bath was removed, the temperature was slowly raised to room temperature, and 500ml of xylene was added and heated. THF was distilled and removed so that the internal thermometer reached 140 degrees, and when only xylene remained, a condenser was installed and heated and refluxed for 3 days. After completion of the reaction, it was cooled to room temperature and concentrated. After column recrystallization, 13.2 g of Compound-165 was obtained with a yield of 38%.

NMR (DMSO, 300Hz): δ(ppm)= 7.73~8.28(m, 3H), 7.57~7.69(m, 2H), 7.31-7.48(m, 8H), 7.14~7.25(m, 4H), 6.94- 7.09(d, 1H), 1.43~1.52(s, 9H), 1.29~1.39(s, 9H),

MS(FAB): 533(M ⁺ )

<Synthesis of Intermediate 201-2>

100 g (546 mmol) of 201-1 was added to a 2L 3-neck round bottom flask, dissolved in 1L of DMF, and maintained at 0 degrees by installing an icebath. 122.8 g (546 mmol) of N-iodosuccinimide was slowly added while maintaining 0 degrees. After completion of the reaction, DMF was concentrated and the organic layer was extracted by adding 1L of EA and 1L of water. The organic layer was concentrated and then recrystallized with a column to obtain 121.5 g of 201-2 with a yield of 72%.

Intermediate 201-2 MS(FAB): 309(M ⁺ )

<Synthesis of Intermediate 201-3>

121.5 g (393 mmol) of 201-2 was added to a 2L 3-neck round bottom flask, dissolved in 1L of DMF, and maintained at 0 degrees by installing an icebath. While maintaining 0 degrees, 69.9 g (393 mmol) of N-Bromosuccinimide was slowly added. After completion of the reaction, DMF was concentrated and the organic layer was extracted by adding 1L of EA and 1L of water. The organic layer was concentrated and then recrystallized with a column to obtain 134.2 g of 201-3 with a yield of 88%.

Intermediate 201-3 MS(FAB): 388(M ⁺ )

<Synthesis of Intermediate 201-4>

134.2 g (346 mmol) of 201-3 and 1.3 L of ethanol were added to a 3 L three-neck round bottom flask, and 270 ml of sulfuric acid was slowly added. While heating and refluxing, 123.1 g (692 mmol) of sodium nitrite was slowly added in portions. After the addition was completed, it was heated and refluxed for 3 hours, and when the reaction was completed, it was cooled to room temperature. 1.5L of water was added, and the resulting solid was filtered and columned to obtain 80.0g of 201-4 with a yield of 62%.

Intermediate 201-4 MS(FAB): 372(M ⁺ )

<Synthesis of Intermediate 201-6>

Add 80.0g (214mmol) of 201-4, 67.1g (214mmol) of D-5, 4.1g (64mmol) of copper, 88.9g (643mmol) of potassium carbonate, and 800ml of nitrobenzene into a 2L 3-neck round bottom flask and heat and reflux for 12 hours. do. After completion of the reaction, it was washed with EA, filtered with celite, and concentrated. After concentrating the organic solvent, 72.3 g of 201-6 was obtained with a yield of 64%.

Intermediate 201-6 MS(FAB): 526(M ⁺ )

<Synthesis of Intermediate 201-7>

72.3 g (137 mmol) of 201-6, 350 ml of DMF, and 58.1 g (274 mmol) of Copper(I) iodide were added to a 2L 3-neck round bottom flask. 321 g (1.78 mol) of sodium methoxide (30% in MeOH) was slowly added and heated to reflux. After confirming the completion of the reaction, it was cooled to room temperature and the organic layer was extracted by adding 1L of EA and 1L of water. The organic layer was concentrated and then column-processed to obtain 61.0 g of 201-7 with a yield of 93%.

Intermediate 201-7 MS(FAB): 477(M ⁺ )

<Synthesis of Intermediate 201-8>

61 g (128 mmol) of 201-7 was added to a 2L 3-neck round bottom flask and dissolved in 600 ml of THF. A dryice bath was installed to maintain -78 degrees Celsius, and 88ml (140mmol) of n-Butyllithium (1.6M) was added dropwise. The bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 30 minutes. A dryice bath was installed to maintain -78 degrees Celsius, and 21.0 g (153 mmol) of isobutyl bromide was added dropwise. The bath was removed and the temperature was gradually raised to room temperature. After completion of the reaction, it was concentrated, and 500 ml of EA and 500 ml of water were added to extract the organic layer. After concentration and columnarization, 57.2 g of 201-8 was obtained with a yield of 84%.

Intermediate 201-8 MS(FAB): 533(M ⁺ )

<Synthesis of Intermediate 201-9>

In a 1L 3-neck round bottom flask, 57.2g (107mmol) of 201-8 was dissolved in 600ml of MC and maintained at 0 degrees by installing an icebath. Boron tribromide 29.5g (118mmol) was slowly added dropwise, and after confirmation of completion of the reaction, 500ml of water was added. The organic layer was extracted, concentrated, and recrystallized to obtain 50.1 g of 201-9 with a yield of 90%.

Intermediate 201-9 MS(FAB): 519(M ⁺ )

<Synthesis of intermediate 201-10>

50.1 g (96 mmol) of 201-9, 32.7 g (96 mmol) of 45-10, and 41.0 g (193 mmol) of potassium phosphate tribasic were added to a 1L 3-neck round bottom flask, and then 500 ml of DMSO was added. 3.7g (19mmol) of copper(I) iodide and 6.8g (19mmol) of iron(III) acetyl acetonate were added and heated to 110 degrees. After completion of the reaction, it was cooled to room temperature, and 1L of EA and 1L of water were added to extract and concentrate the organic layer. After column, 50.8g of 201-10 was obtained with a yield of 72%.

Intermediate 201-10 MS(FAB): 730(M ⁺ )

<Synthesis of Compound-201>

50.8g (69mmol) of 201-10 was added to a 1L 3-neck round bottom flask and dissolved in 400ml of THF. A dryice bath was installed to maintain -78 degrees Celsius, and 139ml (222mmol) of 1.6M n-Butyllithium was added dropwise. The bath was removed, the temperature was slowly raised to room temperature, and the mixture was stirred for 1 hour. A dryice bath was installed to maintain -78 degrees Celsius, and 17.4 g (69 mmol) of boron tribromide was slowly added. The bath was removed, the temperature was slowly raised to room temperature, and 500ml of xylene was added and heated. THF was distilled and removed so that the internal thermometer reached 140 degrees, and when only xylene remained, a condenser was installed and heated and refluxed for 3 days. After completion of the reaction, it was cooled to room temperature and concentrated. After column recrystallization, 14.6 g of Compound-201 was obtained with a yield of 32%.

NMR (DMSO, 300Hz): δ(ppm)= 7.92~8.05(d, 1H), 7.56~7.69(m, 2H), 7.29-7.48(m, 4H), 7.02~7.21(m, 6H), 6.84- 6.98(d, 1H), 2.47~2.54(d, 2H), 1.91~1.99(m, 1H), 1.42~1.53(s, 18H), 1.28~1.39(s, 9H), 0.91~0.99(d, 6H) )

MS(FAB): 659(M ⁺ )

<Synthesis of intermediate 249-3>

100 g (598 mmol) of 249-1, 92.8 g (658 mmol) of 249-2, 584.5 g (1.79 mol) of Cesium carbonate, and 1 L of DMF were added to a 2L 3-neck round bottom flask and heated to reflux. After the reaction was completed, it was cooled to room temperature and concentrated. The organic layer was extracted by adding 1L of EA and 1L of water, and then concentrated through a silicagel filter. After recrystallization, 117.3 g of 249-3 was obtained with a yield of 68%.

Intermediate 249-3 MS(FAB): 288(M ⁺ )

<Synthesis of intermediate 249-4>

117.3 g (407 mmol) of 249-3 and 183.5 g (813 mmol) of Tin(II) chloride dehydrate were added to a 2L three-neck round bottom flask, and then 1 L of Ethanol was added and heated to reflux. After confirming completion of the reaction, it was cooled to room temperature and concentrated. The organic layer was extracted by adding 1L of EA and 1L of water and then concentrated. After recrystallization after the column, 88.2 g of 249-4 was obtained with a yield of 84%.

Intermediate 249-4 MS(FAB): 258(M ⁺ )

<Synthesis of intermediate 249-5>

88.2 g (342 mmol) of 249-4, 880 ml of acetic acid, and 88 g of sulfuric acid were added to a 3L 3-neck round bottom flask. Sodium nitrite 47.1g (683mmol) was dissolved in 88ml of water, then added dropwise and heated to reflux. After confirming completion of the reaction, it was cooled to room temperature and acetic acid was distilled. After extraction by adding 1L of EA and 1L of water, the organic layer was concentrated. After column recrystallization, 46.2 g of 249-5 was obtained with a yield of 56%.

Intermediate 249-5 MS(FAB): 241(M ⁺ )

<Synthesis of intermediate 249-6>

46.2g (191mmol) of 249-5 was added to a 1L 3-neck round bottom flask and dissolved in 500ml of MC. After installing the ice bath and maintaining the temperature at 0 degrees, 34.1 g (191 mmol) of N-Bromosuccinimide was slowly added. After confirming the completion of the reaction, 500 ml of water was added, and the organic layer was extracted and concentrated. After recrystallization after the column, 44.1 g of 249-6 was obtained with a yield of 72%.

Intermediate 249-6 MS(FAB): 320(M ⁺ )

<Synthesis of intermediate 249-8>

100 g (379 mmol) of 249-7 and 1 L of Ethanol were added to a 2L 3-neck round bottom flask, and while stirring, 35.3 g (379 mmol) of aniline was added. It was heated to reflux, and after confirmation of completion of the reaction, it was cooled to room temperature and filtered. 125.9 g of 249-8 was obtained with a yield of 98%.

Intermediate 249-8 MS(FAB): 339(M ⁺ )

<Synthesis of intermediate 249-10>

125.9 g (477 mmol) of 249-8 and 74.7 g (477 mmol) of 249-9 were added to a 2L three-neck round bottom flask, then 1 L of EtOH was added and stirred. 57.2 g (1.43 mol) of sodium hydroxide was slowly added and heated to reflux. After confirming the completion of the reaction, it was cooled to room temperature, filtered, and recrystallized. 198.3g of 249-10 was obtained with a yield of 89%.

Intermediate 249-10 MS(FAB): 467(M ⁺ )

<Synthesis of intermediate 249-11>

198.3 g (425 mmol) of 249-10 was added to a 3 L three-neck round bottom flask and dissolved in 2 L of THF. A dryice bath was installed to maintain -78 degrees Celsius, and 271ml (433mmol) of n-Butyllithium (1.6M) was added dropwise. After 30 minutes, 48.5 g (467 mmol) of trimethylborate was added. After confirming the completion of the reaction, it was concentrated, 1L of 2N HCl and 1L of EA were added, and then extracted. After concentrating the organic layer, it was recrystallized to obtain 122.9 g of 249-11 with a yield of 67%.

Intermediate 249-11 MS(FAB): 432(M ⁺ )

<Synthesis of intermediate 249-13>

50g (347mmol) of 249-12 was added to a 1L 3-neck round bottom flask and dissolved in 500ml of THF. A dryice bath was installed to maintain -78 degrees Celsius, and 221ml (354mmol) of n-Butyllithium (1.6M) was added dropwise. After 30 minutes, 96.8 g (381 mmol) of iodine was added and the temperature was raised to room temperature. After confirming the completion of the reaction, it was concentrated, 500 ml of EA and 500 ml of water were added, and the organic layer was extracted. By recrystallization, 127.4 g of 249-13 was obtained with a yield of 85%.

Intermediate 249-13 MS(FAB): 270(M ⁺ )

<Synthesis of intermediate 249-14>

Add 100g (231mmol) of 249-11, 75.0g (278mmol) of 249-13, 13.4g (12mmol) of Pd(PPh3)4, 347ml (694mmol) of 2M K2CO3, and 1L of THF to a 3L 3-neck round bottom flask and heat to reflux. did. After confirming completion of the reaction, it was cooled to room temperature and concentrated. After adding 500ml of MC and 500ml of water, the organic layer was extracted and concentrated. After column recrystallization, 67.5 g of 249-14 was obtained with a yield of 55%.

Intermediate 249-14 MS(FAB): 530(M ⁺ )

<Synthesis of intermediate 249-15>

67.5 g (127 mmol) of 249-14 was added to a 2L 3-neck round bottom flask and dissolved in 700 ml of THF. A dryice bath was installed to maintain -78 degrees Celsius, and 81ml (130mmol) of n-Butyllithium (1.6M) was added dropwise. After 30 minutes, 14.6g (140mmol) of trimethylborate was added. After confirming the completion of the reaction, it was concentrated, 500 ml of 2N HCl and 500 ml of EA were added, and then extracted. After concentrating the organic layer, it was recrystallized to obtain 37.2 g of 249-15 with a yield of 59%.

Intermediate 249-15 MS(FAB): 495(M ⁺ )

<Synthesis of Compound-249>

Add 37.2g (75mmol) of 249-15, 24.1g (75mmol) of 249-6, 4.3g (4mmol) of Pd(PPh3)4, 113ml (225mmol) of 2M K2CO3, and 400ml of THF into a 1L 3-neck round bottom flask and heat. It refluxed. After confirming completion of the reaction, it was cooled to room temperature and concentrated. After adding 500ml of MC and 500ml of water, the organic layer was extracted and concentrated. After recrystallization after the column, 34.7 g of Compound-249 was obtained with a yield of 67%.

NMR (DMSO, 300Hz): δ(ppm)= 8.31~8.45(m, 4H), 8.15~8.26(d, 2H), 7.95~8.11(m, 3H), 7.64~7.83(m, 2H), 7.46- 7.61(m, 14H), 7.32~7.41(m, 2H), 7.11~7.20(m, 3H)

MS(FAB): 690(M ⁺ )

Hereinafter, the present invention will be described in more detail through examples and experimental examples of organic electroluminescent devices. Since these examples and experimental examples are only for illustrating the present invention, the scope of the present invention is not limited to these examples and experimental examples.

<Manufacture of organic electroluminescent devices>

Example 1

An anode was formed with ITO on the substrate with a reflective layer, and the surface was treated with N ₂ plasma or UV-Ozone. On top of this, HAT-CN was deposited to a thickness of 10 nm as a hole injection layer (HIL). Next, NPD was deposited to a thickness of 120 nm as a hole transport layer (HTL). On the hole transport layer, 9,10-bis(2-naphthyl)anthracene (ADN), which can form blue EML, was deposited to a thickness of 25 nm as a light emitting layer (EML), and Compound 1 as a compound of formula 1 of the present invention was used as a dopant for about 5 nm. It was doped by about %. On top of this, ET-254 and LiQ were mixed 1:1 to deposit an electron transport layer (ETL) to a thickness of 30 nm, and LiQ was deposited to a thickness of 10 nm as an electron injection layer (EIL) on top of this. Afterwards, a 9:1 mixture of magnesium and silver (Ag) was deposited to a thickness of 15 nm as a cathode, and N4,N4'-bis[4-[bis(3-methylphenyl) was deposited on the cathode as a capping layer. Amino]phenyl]-N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (DNTPD) was deposited to a thickness of 65 nm. An organic electroluminescent device was manufactured by attaching a seal cap containing a moisture absorbent to the top using a UV curing adhesive to protect the organic electroluminescent device from O ₂ or moisture in the atmosphere.

Examples 2 to 51

In Example 1, instead of compound 1 of formula 1 as the dopant of blue EML, compounds 3, 19, 24, 27, 35, 37, 45, 55, 56, 64, 72, 88, 93, 102 of formula 1 were used, respectively. 107, 123, 140, 145, 151, 158, 161, 165, 178, 184, 201, 215, 221, 224, 226, 230, 236, 242, 249, 263, 264, 265, 268, 275, 2 90, Organic electroluminescent devices of Examples 2 to 51 were manufactured in the same manner as Example 1, except that 293, 301, 320, 337, 339, 344, 346, 348, 349, 350, and 352 were used.

Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that 2,5,8,11-Tetra-butyl-Perylene (t-Bu-Perylene) was used as a dopant of blue EML as an emitting layer (EML). Manufactured.

The compounds used in Examples 1 to 51 and Comparative Example 1 are shown below.

Test example: Evaluation of characteristics of organic electroluminescent devices

The characteristics of the organic electroluminescent devices manufactured in Examples 1 to 51 and Comparative Example 1 were measured at a current density of 10 mA/cm ² , and the results are shown in Table 1 below.

Voltage
(V) EQE
(%) T ₉₅ (hr) Wavelength Example 1 3.6 9.2 384 462 Example 2 3.2 8.3 362 461 Example 3 3.5 9.1 381 462 Example 4 3.6 9.7 396 461 Example 5 3.4 9.4 392 460 Example 6 3.4 9.1 386 462 Example 7 3.7 8.9 398 462 Example 8 3.6 10.3 367 461 Example 9 3.3 10.7 406 460 Example 10 3.2 10.1 392 461 Example 11 3.5 10.4 398 463 Example 12 3.7 9.8 402 458 Example 13 3.2 10.7 394 457 Example 14 3.4 10.9 381 460 Example 15 3.3 10.8 386 459 Example 16 3.8 8.7 355 464 Example 17 3.5 10.9 398 460 Example 18 3.7 10.5 376 459 Example 19 3.4 10.1 392 460 Example 20 3.5 10.3 395 460 Example 21 3.6 10.4 377 461 Example 22 3.5 10.1 391 460 Example 23 3.7 9.2 374 464 Example 24 3.4 10.3 396 460 Example 25 3.9 7.1 314 464 Example 26 3.3 10.1 408 459 Example 27 3.4 9.9 398 461 Example 28 3.3 9.6 405 462 Example 29 3.4 10.5 392 461 Example 30 3.3 10.3 396 461 Example 31 3.3 9.8 391 460 Example 32 3.5 10.1 395 462 Example 33 3.4 9.9 408 460 Example 34 3.4 8.2 375 464 Example 35 3.1 7.9 361 463 Example 36 3.3 7.8 384 464 Example 37 3.3 10.1 381 461 Example 38 3.2 10.9 417 462 Example 39 3.5 10.6 394 460 Example 40 3.3 9.3 390 463 Example 41 3.4 9.1 387 463 Example 42 3.5 10.2 399 464 Example 43 3.1 10.6 402 459 Example 44 3.4 11 396 460 Example 45 3.1 10.1 405 462 Example 46 3.3 10.4 401 461 Example 47 3.3 11.1 392 459 Example 48 3.4 10.5 407 462 Example 49 3.2 10.3 429 457 Example 50 3.5 11.3 391 459 Example 51 3.4 10.6 387 460 Comparative Example 1 4.7 6.2 96 466

As a result of the above experiment, the organic electroluminescent devices of Examples 1 to 51, which included the organic compound of Formula 1 of the present invention as a dopant in the light emitting layer, showed improved efficiency and voltage characteristics compared to the conventional organic electroluminescent device of Comparative Example 1. showed.

In addition, as a result of measuring the afterimage lifespan ( _T95 ), it was confirmed that the organic electroluminescent device of Comparative Example 1 had a lifespan of less than 100 hours, while Examples 1 to 51 had a long lifespan of more than 300 hours. In particular, the organic electroluminescent devices of Examples 9, 12, 26, 28, 33, 38, 43, 45, 46, 48, and 49 were confirmed to have a long lifespan of more than 400 hours, overcoming the lifespan limitations of existing blue materials. The range of uses for organic electroluminescent devices will be able to be further expanded.

In addition, the organic electroluminescent devices of Examples 1 to 51, in which the compound of Formula 1 of the present invention was used as a dopant in the light-emitting layer, showed significantly improved efficiency and voltage characteristics compared to the conventional organic electroluminescent device of Comparative Example 1.

Accordingly, it can be seen that the organic electroluminescent device containing the organic compound of Formula 1 of the present invention as a dopant in the light-emitting layer has excellent efficiency, voltage, and lifespan characteristics.

Claims (4)

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

In the above equation
R1 is deuterium, halogen, CN, CF ₃ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl, biphenyl, Phenyl, naphthanyl, biphenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, carbazolyl, substituted or unsubstituted with one or more selected from the group consisting of naphthyl and anthracenyl groups. Substituted with one or more selected from the group consisting of dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group. or an unsubstituted aromatic hydrocarbon group having 6 to 60 carbon atoms,
Deuterium, halogen, CN, CF ₃ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, cycloalkyl with 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl. , anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethylfluorenyl, spirobifluorenyl, carbazolyl, dibenzofuran, substituted or unsubstituted with one or more selected from the group consisting of anthracenyl groups. Substituted or unsubstituted with one or more selected from the group consisting of yl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl, quinolinyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, or phenyl triazinyl group. and is a heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more elements selected from the group consisting of S, O, N, B, and Si,
Z1, Z4, Z5 are each independently a single bond or C1~C10 linear or branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, CN, CF ₃ , phenyl, naphthanyl, biphenylamine , phenyl amine substituted or unsubstituted with one or more selected from the group consisting of phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, and Si (CH ₃ ) ₃ group,
Z2 and Z3 are each independently a single bond or one or more selected from the group consisting of halogen, CN, CF ₃ , phenyl, naphthanyl, phenyl pyridinyl, phenyl pyrimidinyl, phenyl imidazole, and Si(CH ₃ ) ₃ group. It is substituted or unsubstituted phenyl,
a, b, c, d, and e are each independently 0 or 1;
Z6, Z7, and Z8 are each independently a single bond, C1~C2 alkylenyl, phenyl, or biphenyl group,
f, g, and h are each independently 0 or 1;
M is boron or carbon or nitrogen;
G1, G2, G3 are each independently carbon or nitrogen or oxygen or sulfur
G4, G5, and G6 are each independently carbon or nitrogen;
R2, R3, R4, R5, R6, R7, R8 and R9 are each independently hydrogen, deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , and have 1 to 40 carbon atoms. straight-chain or branched-chain alkyl, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms, or cycloalkyl group with 3 to 40 carbon atoms,
Deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms , cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethyl, substituted or unsubstituted with one or more selected from the group consisting of phenyl groups. 6 to 60 carbon atoms substituted or unsubstituted with one or more selected from the group consisting of fluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group is an aromatic hydrocarbon group, or
Deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms , cycloalkyl having 3 to 40 carbon atoms, phenyl, biphenyl, naphthyl, anthracenyl, anthracenyl, phenanthrenyl, pyrenyl, 9,9-dimethyl, substituted or unsubstituted with one or more selected from the group consisting of phenyl groups. Substituted with one or more selected from the group consisting of fluorenyl, spirobifluorenyl, carbazolyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, pyrimidinyl group, and quinolinyl group, or It is an unsubstituted heteroaromatic hydrocarbon group having 5 to 70 carbon atoms containing one or more elements selected from the group consisting of S, O, N, B, and Si, or
Deuterium, F, Cl, Br, I, CN, Si(CH ₃ ) ₃ , B(OH) ₂ , straight or branched chain alkyl with 1 to 40 carbon atoms, alkoxy with 1 to 40 carbon atoms, thioalkyl with 1 to 40 carbon atoms , and phenyl, biphenyl, naphthyl, anthracenyl substituted or unsubstituted with one or more types selected from the group consisting of cycloalkyl groups having 3 to 40 carbon atoms, anthracenyl substituted with a phenyl group, phenanthrenyl, pyrenyl, 9 , 9-dimethylfluorenyl, carbazolyl, quinolinyl, dibenzofuranyl, pyrrole, triazole, pyridinyl, pyrazinyl, and pyrimidinyl group. It is an amino group substituted with one or more types selected from the group consisting of . In claim 1,
The organic compound is any one of the following compounds 1 to 352.



























































































In an organic electroluminescent device in which an organic thin film layer consisting of one or multiple layers including at least a light-emitting layer is laminated between the cathode and the anode,
An organic electroluminescent device characterized in that the light-emitting layer contains the organic compound of claim 1 alone or in a combination of two or more types. In an organic electroluminescent device in which an organic thin film layer consisting of one or multiple layers including at least a light-emitting layer is laminated between the cathode and the anode,
An organic electroluminescent device, characterized in that the organic thin film layer excluding the light-emitting layer contains the organic compound of claim 1 alone or in a combination of two or more types.