KR102279196B1 - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound employed in an organic light emitting device, characterized in that it is represented by the following [Formula I], and by employing it in an electron blocking layer, light emitting properties such as luminous efficiency and quantum efficiency are significantly improved compared to conventional devices It relates to an organic light emitting compound capable of implementing an excellent organic light emitting device.
[Formula Ⅰ]

Description

An electroluminescent compound and an electroluminescent device comprising the same

The present invention relates to a novel organic light emitting compound and an organic light emitting device capable of implementing a device having remarkably excellent light emitting characteristics such as light emitting efficiency and quantum efficiency by employing the same in an organic material layer of the device.

The organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often composed of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer. It can be made in various ways, such as layers. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up. Such an organic light emitting device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

The material used as the organic material layer in the organic light emitting device may be classified into a light emitting material, a charge transport material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, a hole blocking material and an electron blocking material according to their function. . In addition, the light emitting material may be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary to realize a better natural color according to the emission color.

In order for an organic light emitting device to sufficiently exhibit the above-described excellent characteristics, it is necessary that the various materials constituting the organic material layer in the device be supported by stable and efficient materials, but the development of stable and efficient organic material layer materials for organic light emitting devices is still insufficient. has not been done Therefore, the development of new materials is continuously required, and the necessity of such material development is the same in other organic electronic devices.

An object of the present invention is to provide a novel organic light emitting compound capable of implementing excellent light emitting properties such as luminous efficiency and quantum efficiency by being employed in an organic layer of an organic light emitting device and an organic light emitting device including the same.

The present invention provides an organic light emitting device represented by the following [Formula I] in order to solve the above problems.

[Formula Ⅰ]

The specific structure and substituents of the [Formula I] will be described later.

In addition, the present invention is an organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one layer of the organic material layer comprises the organic light emitting compound It provides an organic light emitting device comprising.

The device employing the organic light emitting compound according to the present invention as an electron blocking layer has superior light emitting characteristics such as luminous efficiency and quantum efficiency compared to conventional devices, and thus can be usefully applied to various display devices.

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

One aspect of the present invention relates to an organic light emitting compound that is employed in an organic material layer, preferably an electron blocking layer, of an organic light emitting device to realize excellent light emitting characteristics such as luminous efficiency and quantum efficiency, and is represented by the following [Formula I] characterized in that

[Formula Ⅰ]

In the [Formula I],

X is CR ₁ R ₂ , O or S, wherein R ₁ to R ₂ are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted C 1 to C 7 alkyl group, and a substituted or unsubstituted C 6 to C 6 It is selected from the aryl group of 30, wherein R _{1 To} R ₂ may be connected to each other or adjacent substituents to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle.

L _{1 To} L _{2 Are} the same as or different from each other, and each independently is a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted a carbazolylene group, or a substituted or unsubstituted heteroarylene group containing at least one of N, O and S atoms.

Ar _{1 To} Ar ₃ are the same or different from each other, and each independently represents hydrogen, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 3 to C 30 heteroaryl group, or a substituted or unsubstituted C 6 C heteroaryl group. A substituted or unsubstituted aryl group having 6 to 30 carbon atoms in which one or more 3 to 20 cycloalkyl is fused, a substituted or unsubstituted C 3 to 30 aryl group having 3 to 20 carbon atoms fused to one or more substituted or unsubstituted cycloalkyl groups of a heteroaryl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted carbazole group.

Meanwhile, the substituted or unsubstituted means 1 or 2 selected from the group consisting of hydrogen, deuterium, a halogen group, a cyano group, a nitro group, a hydroxy group, a silyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group, and a heterocyclic group It means that it is substituted with one or more substituents, is substituted with a substituent to which two or more of the substituents are connected, or does not have any substituents.

For specific examples, the substituted arylene group includes a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, and a tetracenyl group. It means that the anthracenyl group is substituted with another substituent.

The substituted heteroarylene group includes a pyridyl group, a thiophenyl group, a triazine group, a quinoline group, a phenanthroline group, an imidazole group, a thiazole group, an oxazole group, a carbazole group and a condensed heterocyclic group thereof, such as a benzquinoline group, It means that a benzimidazole group, a benzoxazole group, a benzthiazole group, a benzcarbazole group, a dibenzothiophenyl group, a dibenzofuran group, etc. are substituted with other substituents.

In the present invention, examples of the substituents will be described in detail below, but the present invention is not limited thereto.

In the present invention, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, and specific examples include a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, a n-butyl group, and an iso Butyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group , n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1 -Methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2 ,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but these not limited

In the present invention, the alkoxy group may be straight-chain or branched. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably within a range that does not interfere with stericity, and specifically, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, i-propyloxy group, n-butoxy group , isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyl It may be an oxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, benzyloxy group, p-methylbenzyloxy group, and the like, but is not limited thereto.

In the present invention, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, and specific examples include a vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3- Butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1-butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenyl Vinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl) ) vinyl-1-yl group, stilbenyl group, styrenyl group, and the like, but is not limited thereto.

In the present invention, the aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 30. Examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and a stilbene group, and examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, and a tetracenyl group. , chrysenyl group, fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthrene group, etc., but the scope of the present invention is not limited to these examples.

In the present invention, the heterocyclic group is a heterocyclic group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but it is preferably from 3 to 30 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , indole group, carbazole group, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, and the like, but is not limited thereto.

In the present invention, the cycloalkyl group is not particularly limited, but preferably has 3 to 20 carbon atoms, and specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohex Sil group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclo There is an octyl group, and the like, but is not limited thereto.

In the present invention, examples of the halogen group include fluorine, chlorine, bromine or iodine.

,

등이 있다.In the present invention, the fluorenyl group is a structure in which two ring organic compounds are connected through one atom, for example,

,

etc.

,

등이 있다.In the present invention, the fluorenyl group includes a structure of an open fluorenyl group, wherein the open fluorenyl group is a structure in which one ring compound is disconnected in a structure in which two ring organic compounds are connected through one atom. , for example

,

etc.

In the present invention, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.

The organic light emitting compound according to the present invention represented by the above [Formula I] may be used as an organic material layer of an organic light emitting device due to its structural specificity, and more specifically, it may be used as an electron blocking layer material of the organic material layer.

Preferred examples of the compound represented by [Formula I] according to the present invention include the following compounds, but are not limited thereto.

By introducing various substituents into the core structure of the above structure, it is possible to synthesize an organic light emitting compound having the intrinsic properties of the introduced substituent, and through this, a material satisfying the conditions required by various organic material layers of the organic light emitting device can be manufactured. have. The compound of the present invention can be applied to a device according to a conventional method for manufacturing an organic light emitting device.

The organic light emitting device according to an embodiment of the present invention may have a structure including a first electrode and a second electrode and an organic material layer disposed therebetween, and the organic light emitting compound according to the present invention is used for the organic material layer of the device. Except for that, it may be manufactured using a conventional device manufacturing method and material.

The organic material layer of the organic light emitting device according to the present invention may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, as well as layers having various functions. However, the present invention is not limited thereto and may include a smaller number of organic material layers.

Accordingly, in the organic light emitting device according to the present invention, one or more of the layers may include the compound represented by the [Formula I].

In addition, the organic light emitting device according to the present invention uses a PVD (physical vapor deposition) method, such as sputtering or e-beam evaporation, to form a metal or a conductive metal oxide or an alloy thereof on a substrate. It can be prepared by depositing an anode to form an anode, forming an organic material layer including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.

In addition to this method, an organic light emitting diode may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic layer is formed using a variety of polymer materials by a solvent process rather than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or a thermal transfer method. It can be made in layers.

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc. Metal oxides, combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT) , a conductive polymer such as polypyrrole and polyaniline, but is not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof, and multilayers such as _{LiF/Al or LiO 2 /Al} Structural materials and the like, but are not limited thereto.

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but is not limited thereto.

As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is suitable, and a material having high hole mobility is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole and Benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, rubrene, and the like, but are not limited thereto.

As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline _{, a complex including Alq 3} , an organic radical compound, and a hydroxyflavone-metal complex.

The organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.

In addition, the organic light emitting compound according to the present invention can act on a principle similar to that applied to the organic light emitting device in organic electronic devices including organic solar cells, organic photoreceptors, organic transistors, and the like.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereby.

Synthesis example 1: Synthesis of compound 29

(1) Synthesis of Intermediate 29-1

4-bromo-1-fluoro-2-nitrobenzene (20 g, 0.091 mol, sigma aldrich), phenylboronic acid (13.30 g, 0.109 mol, sigma aldrich), potassium carbonate (25.13 g, 0.182 mol, sigma aldrich), Pd ( PPh ₃ ) ₄ (3.15 g, 0.0027 mol, sigma aldrich), 220 mL of Toluene, and 40 mL of Ethanol were added, and the reaction was stirred under reflux for 5 hours. After completion of the reaction, 17.6 g (yield 89%) of <Intermediate 29-1> was obtained through column purification (N-HEXANE: MC) after layer separation using _{H 2 O: MC.}

(2) Synthesis of Intermediate 29-2

Add 200 mL of dimethylformamide to Intermediate 29-1 (15 g, 0.069 mol, sigma aldrich), 2-bromophenol (11.95 g, 0.069 mol, sigma aldrich), potassium carbonate (19.09 g, 0.138 mol, sigma aldrich) at 90 ° C. After stirring for an hour, the catalyst Pd(OAc) ₂ (0.78 g, 0.0035 mol, sigma aldrich), triphenylphosphin e (1.81 g, 0.007 mol, sigma Aldrich) was further added, and the reaction was stirred at 90 ° C. for 2.5 hours. After completion of the reaction, 15.8 g (yield 79%) of <Intermediate 29-2> was obtained by column purification (N-HEXANE: EA) after layer separation in _{H 2 O:EA.}

(3) Synthesis of Intermediate 29-3

Intermediate 29-2 (15 g, 0.052 mol) was added to Ethanol: H ₂ O (4:1), then iron powder (14.48 g, 0.26 mol, sigma Aldrich) and hydrochloric acid were added, followed by reaction under reflux stirring for 2 hours. . After completion of the reaction, 10 g (yield 74%) of <Intermediate 29-3> was obtained by performing column purification (N-HEXANE:EA) after layer separation in _{H 2 O:EA.}

(4) Synthesis of intermediate 29-4

2-bromo-4-iodophenol (20 g, 0.067 mol, yurui), phenylboronic acid (9.79 g, 0.080 mol, sigma aldrich), potassium carbonate (18.50 g, 0.134 mol, sigma aldrich), Pd(PPh ₃ ) ₄ ( 3.87 g, 0.0033 mol, sigma aldrich), 220 mL of Toluene, and 40 mL of Ethanol were added, and the reaction was stirred under reflux for 4 hours. After completion of the reaction, 14.1 g (yield 84.6%) of <Intermediate 29-4> was obtained by performing column purification (N-HEXANE: MC) after layer separation using _{H 2 O:MC.}

(5) Synthesis of intermediate 29-5

Intermediate 29-4 (14 g, 0.056 mol), 2-fluorophenylboronic acid (9.44 g, 0.067 mol, sigma aldrich), potassium carbonate (15.54 g, 0.112 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (3.25 g, 0.0028 mol, sigma aldrich), 200 mL of toluene, and 40 mL of ethanol were added, and the reaction was stirred under reflux for 4 hours. After completion of the reaction, 13.2 g of <Intermediate 29-5> was obtained (yield 88.9%) by column purification (N-HEXANE: MC) after layer separation using _{H 2 O: MC.}

(6) Synthesis of intermediate 29-6

Intermediate 29-5 (13 g, 0.050 mol), N-Bromosuccinimide (8.76 g, 0.050 mol, sigma aldrich), and 150 mL of dimethylformamide were added and reacted by stirring at 60 °C for 12 hours. After completion of the reaction, 1M aqueous NaOH solution was added, stirred, filtered, and dried to obtain 10.2 g (yield: 60%) of <Intermediate 29-6>.

(7) Synthesis of intermediate 29-7

Intermediate 29-6 (10 g, 0.030 mol), NaH (1.4 g, 0.058 mol, sigma aldrich), 100 mL of dimethyl sulfoxide were added, and the reaction was stirred at 140 °C for 5 hours. After completion of the reaction _{, layer separation was performed on H 2} O:MC, and column purification (N-HEXANE:MC) was performed to obtain 3 g (yield 31.9%) of <Intermediate 29-7>.

(8) Synthesis of intermediate 29-8

Intermediate 29-3 (10 g, 0.039 mol), 4-bromobiphenyl (9.89 g, 0.042 mol, sigma aldrich), Sodium tert-butoxide (7.41 g, 0.077 mol, sigma aldrich), catalyst Pd(dba) ₂ (1.11 g) , 0.0019 mol, sigma aldrich), tri-tert-Bu-phosphine (0.78 g, 0.004 mol, sigma aldrich) was added with 150 mL of toluene and stirred at 100 °C for 4 hours to react. After completion of the reaction, 12.4 g (yield 78%) of <Intermediate 29-8> was obtained by performing column purification (N-HEXANE: EA) after layer separation in _{H 2 O:EA.}

(9) Synthesis of compound 29

Intermediate 29-8 (10 g, 0.024 mol), Intermediate 29-7 (9.42 g, 0.029 mol), Sodium tert-butoxide (4.67 g, 0.049 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.70 g, 0.0012) mol, sigma aldrich), tri-tert-Bu-phosphine (0.49 g, 0.0024 mol, sigma aldrich) was added with 150 mL of toluene and stirred at 100 °C for 4 hours to react. After completion of the reaction, 11.7 g (yield 73.6%) of compound 29 was obtained by performing column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

H-NMR (200 MHz, CDCl3): δ ppm, 2H (7.89/d, 7.66/d, 7.57/s, 7.54/d, 7.38/m, 7.32/m, 7.07/s, 6.69/d) 3H (7.41/ m) 6H (7.52/d, 7.51/m)

LC/MS: m/z=653 [(M+1) ⁺ ]

Synthesis example 2: Synthesis of compound 38

(1) Synthesis of Intermediate 38-1

4,6-dibromodibenzofuran (20 g, 0.061 mol, Yurui), phenylboronic acid (8.98 g, 0.074 mol, sigma aldrich), potassium carbonate (16.96 g, 0.123 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (3.54 g) , 0.0031 mol, sigma aldrich), THF 250 mL, H ₂ O 50 mL, and reacted by stirring under reflux for 4 hours. After completion of the reaction, 14.3 g (yield 72%) of <Intermediate 38-1> was obtained by performing layer separation using _{H 2 O: MC and column purification (N-HEXANE: MC).}

(2) Synthesis of Intermediate 38-2

Intermediate 38-1 (14 g, 0.043 mol), Bis(pinacolato)dibron (14.3 g, 0.056 mol, sigma aldrich), potassium acetate (8.50 g, 0.087 mol, sigma aldrich), PdCl ₂ (dppf) (0.95 g, 0.0013 mol, sigma aldrich) and 1,4-Dioxane (200 mL) were added, and the reaction was stirred at 95 °C for 12 hours. After completion of the reaction, H ₂ O was added, the layers were separated, and column purification (N-HEXANE: MC) was performed to obtain 11.3 g (yield 70.5%) of <Intermediate 38-2>.

(3) Synthesis of Intermediate 38-3

1-bromo-4-iodobenzene (10 g, 0.035 mol, sigma aldrich), intermediate 38-2 (15.71 g, 0.042 mol, sigma aldrich), potassium carbonate (9.77 g, 0.071 mol, sigma aldrich), Pd (PPh ₃₎ ) ₄ (2.04 g, 0.0018 mol, sigma aldrich), 250 mL of THF, _{and 50 mL of H 2} O were added, and the reaction was stirred under reflux for 12 hours. After completion of the reaction, 11.6 g (yield 82%) of <Intermediate 38-3> was obtained by performing layer separation using _{H 2 O: MC and column purification (N-HEXANE: MC).}

(4) Synthesis of compound 38

Intermediate 29-8 (10 g, 0.024 mol), Intermediate 38-3 (11.64 g, 0.03 mol, sigma Aldrich), Sodium tert-butoxide (4.67 g, 0.049 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.70) g, 0.0012 mol, sigma aldrich), tri-tert-Bu-phosphine (0.49 g, 0.0024 mol, sigma aldrich) was added with 150 mL of toluene, followed by stirring at 100 °C for 8 hours. After the reaction was completed, 13.2 g of compound 38 (yield 74.4%) was obtained by performing column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

H-NMR (200 MHz, CDCl3): δ ppm, 1H (7.89/d, 7.66/d, 7.57/s, 7.32/m, 7.07/s) 2H (7.85/d, 7.81/d) 3H (7.41/m, 7.38/m) 4H (7.54/d, 6.69/d) 6H (7.52/d, 7.51/m)

LC/MS: m/z=729 [(M+1) ⁺ ]

Synthesis example 3: Synthesis of compound 48

(1) Synthesis of Intermediate 48-1

Add 200 mL of dimethylformamide to 2-bromo-4-chlorobenzoic acid (20 g, 0.085 mol, sigma aldrich), iodomethane (18.08 g, 0.127 mol, sigma aldrich), sodium bicarbonate (14.27 g, 0.17 mol, sigma aldrich) 60 The reaction was stirred at ℃ for 24 hours. After completion of the reaction, 12.4 g (yield 79%) of <Intermediate 48-1> was obtained by performing column purification (N-HEXANE: EA) after layer separation in _{H 2 O:EA.}

(2) Synthesis of Intermediate 48-2

150 mL of THF was added to Intermediate 48-1 (12 g, 0.048 mol), and phenyl magnesium bromide (13.08 g, 0.072 mol, sigma aldrich) was slowly added thereto while stirring at 0 °C, followed by stirring at room temperature for 12 hours to react. After completion of the reaction, 11.2 g (yield 78.8%) of <Intermediate 48-2> was obtained by column purification (N-HEXANE: EA) after layer separation in _{H 2 O:EA.}

(3) Synthesis of Intermediate 48-3

Intermediate 48-2 (20 g, 0.068 mol), silver oxide (23.52 g, 0.102 mol, sigma aldrich), potassium carbonate (23.38 g, 0.169 mol, sigma aldrich), catalyst Pd(OAc) ₂ (0.61 g, 0.0011 mol) , sigma aldrich) was added with trifluoroacetic acid (TFA), and the reaction was stirred at 140 °C for 24 hours. After completion of the reaction, 12.6 g (yield 77%) of <Intermediate 48-3> was obtained by performing column purification (N-HEXANE: EA) after layer separation in _{H 2 O:EA.}

(4) Synthesis of Intermediate 48-4

Intermediate 48-3 (20 g, 0.068 mol), sodium borohydride (149.07 g, 0.341 mol, sigma aldrich), anhydrous aluminum chloride (3.87 g, 0.102 mol, sigma aldrich), 300 mL of tetrahydrofuran were added and stirred under reflux for 2 hours. reacted. After completion of the reaction _{, layer separation was performed on H 2} O:EA, followed by column purification (N-HEXANE:EA) to obtain 13 g (yield 68%) of <Intermediate 48-3>.

(5) Synthesis of intermediate 48-5

Intermediate 48-4 (15 g, 0.054 mol), potassium tertbutoxide (18.06 g, 0.161 mol, sigma aldrich) was added to 200 mL of tetrahydrofuran and stirred at 0 °C for 10 minutes, followed by iodomethane (22.85 g, 0.161 mol, sigma aldrich). and stirred at room temperature for 12 hours to react. After completion of the reaction, hexane was added, stirred, filtered, and column purified (N-HEXANE: EA) to obtain 11 g (yield 66.7%) of <Intermediate 48-5>.

(6) Synthesis of intermediate 48-6

Intermediate 48-5 (15 g, 0.049 mol), 4-aminobiphenyl (9.90 g, 0.059 mol, sigma Aldrich), Sodium tert-butoxide (9.37 g, 0.098 mol, sigma aldrich), catalyst Pd(dba) ₂ (1.40 g) , 0.0024 mol, sigma aldrich), tri-tert-Bu-phosphine (0.99 g, 0.0049 mol, sigma aldrich) was added with 150 mL of toluene, followed by stirring at 100 °C for 6 hours. After completion of the reaction, 15.8 g (yield 82%) of <Intermediate 48-6> was obtained by column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

(7) Synthesis of intermediate 48-7

Intermediate 48-6 (15 g, 0.038 mol), phenylboronic acid (5.54 g, 0.046 mol, sigma aldrich), potassium carbonate (10.47 g, 0.076 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (2.19 g, 0.0019 mol) , sigma aldrich), toluene 200 mL, and ethanol 40 mL, and reacted by stirring under reflux for 4 hours. After completion of the reaction, 13.3 g (yield 80%) of <Intermediate 48-7> was obtained by performing layer separation using _{H 2 O: MC and column purification (N-HEXANE: MC).}

(8) Synthesis of compound 48

Intermediate 48-5 (10 g, 0.023 mol), Intermediate 38-3 (10.95 g, 0.027 mol), Sodium tert-butoxide (4.39 g, 0.046 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.66 g, 0.0011) mol, sigma aldrich), tri-tert-Bu-phosphine (0.46 g, 0.0023 mol, sigma aldrich) was added with 150 mL of toluene and stirred at 100 °C for 6 hours to react. After completion of the reaction, 13.2 g (yield 76%) of compound 48 was obtained by performing column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

H-NMR (200 MHz, CDCl3): δ ppm, 1H (7.87/d, 7.55/d, 7.42/s, 7.28/m, 6.70/s) 2H (7.85/d, 7.81/d) 3H (7.41/m, 7.38/m) 4H (7.54/d, 6.69/d) 6H (7.52/d, 7.51/m, 1.72/s)

LC/MS: m/z=755[(M+1) ⁺ ]

Synthesis example 4: Synthesis of compound 58

(1) Synthesis of Intermediate 58-1

2-bromo-4-iodobenzenethiol (15 g, 0.048 mol, yurui), phenylboronic acid (6.99 g, 0.057 mol, sigma aldrich), potassium carbonate (13.21 g, 0.096 mol, sigma aldrich), Pd(PPh ₃ ) ₄ ( 2.76 g, 0.0024 mol, sigma aldrich), 200 mL of toluene, and 40 mL of ethanol were added, and the reaction was stirred under reflux for 4 hours. After completion of the reaction, _{the layers were separated using H 2} O: MC, and then column purification (N-HEXANE: MC) was performed to obtain 10 g (yield 79%) of <Intermediate 58-1>.

(2) Synthesis of Intermediate 58-2

Intermediate 58-1 (15 g, 0.057 mol), 2-fluorophenylboronic acid (9.50 g, 0.068 mol, sigma aldrich), potassium carbonate (15.64 g, 0.113 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (3.27 g, 0.0028 mol, sigma aldrich), 200 mL of toluene, and 40 mL of ethanol were added, and the reaction was stirred under reflux for 4 hours. After completion of the reaction, 12.7 g (yield 80%) of <Intermediate 58-2> was obtained by performing layer separation using _{H 2 O: MC and column purification (N-HEXANE: MC).}

(3) Synthesis of Intermediate 58-3

Intermediate 58-2 (10 g, 0.0360 mol), N-Bromosuccinimide (6.35 g, 0.036 mol, sigma aldrich), and 150 mL of Dimethylformamide were added and reacted by stirring at 60 °C for 12 hours. After completion of the reaction, 1M aqueous NaOH solution was added, stirred, filtered, and dried to obtain 9.7 g (yield 75.7%) of <Intermediate 58-3>.

(4) Synthesis of intermediate 58-4

Intermediate 29-6 (10 g, 0.028 mol), NaH (1.0 g, 0.042 mol, sigma aldrich), and 100 mL of dimethyl sulfoxide were added, and the reaction was stirred at 140 °C for 5 hours. After completion of the reaction _{, layer separation was performed on H 2} O: MC, and column purification (N-HEXANE: MC) was performed to obtain 3.3 g (yield 35%) of <Intermediate 58-4>.

(5) Synthesis of intermediate 58-5

Intermediate 58-4 (10 g, 0.029 mol), 4-aminobiphenyl (5.97 g, 0.035 mol, sigma aldrich), Sodium tert-butoxide (5.65 g, 0.059 mol, sigma aldrich), catalyst Pd(dba) ₂ (0.85 g , 0.0015 mol, sigma aldrich), tri-tert-Bu-phosphine (0.60 g, 0.0029 mol, sigma aldrich) was added with 150 mL of toluene, followed by stirring at 100 °C for 6 hours. After completion of the reaction, 10 g (yield 79.5%) of <Intermediate 58-5> was obtained by column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

(6) Synthesis of compound 58

Intermediate 58-5 (10 g, 0.023 mol), Intermediate 38-3 (11.21 g, 0.028 mol), Sodium tert-butoxide (4.5 g, 0.047 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.67 g, 0.0012) mol, sigma aldrich), tri-tert-Bu-phosphine (0.47 g, 0.0023 mol, sigma aldrich) was added with 150 mL of toluene and stirred at 100 °C for 6 hours to react. After the reaction was completed, 13.9 g of compound 58 (yield 79.7%) was obtained by performing column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

H-NMR (200 MHz, CDCl3): δ ppm, 1H (8.45/d, 7.98/d, 7.50/m, 7.36/s, 7.15/s) 2H (7.85/d, 7.81/d, 7.38/m) 3H ( 7.41/m) 4H (7.54/d, 6.69/d) 6H (7.51/m) 7H (7.52/m)

LC/MS: m/z=745[(M+1) ⁺ ]

Synthesis example 5: Synthesis of compound 69

(1) Synthesis of Intermediate 69-1

2-bromodibenzofuran (15 g, 0.061 mol, sigma aldrich), Bis(pinacolato)dibron (13.58 g, 0.079 mol, sigma aldrich), potassium acetate (11.92 g, 0.121 mol, sigma aldrich), PdCl ₂ (dppf) (1.33) g, 0.0018 mol, sigma aldrich), and 1,4-Dioxane (200 mL) were added, and the reaction was stirred at 95 °C for 12 hours. After completion of the reaction _{, 12.5 g (yield 70%) of <Intermediate 69-1> was obtained by adding H 2} O, performing layer separation, and performing column purification (N-HEXANE: MC).

(2) Synthesis of Intermediate 69-2

1-bromo-4-iodobenzene (10 g, 0.035 mol, sigma aldrich), Intermediate 69-1 (13.52 g, 0.046 mol), potassium carbonate (9.77 g, 0.071 mol, sigma aldrich), Pd(PPh ₃ ) ₄ ( 2.04 g, 0.0018 mol, sigma aldrich), 250 mL of THF, _{and 50 mL of H 2} O were added, and the reaction was stirred under reflux for 12 hours. After completion of the reaction, _{layer separation was performed using H 2} O: MC, and column purification (N-HEXANE: MC) was performed to obtain 9.6 g (yield 84%) of <Intermediate 69-2>.

(3) Synthesis of Intermediate 69-3

Intermediate 29-3 (10 g, 0.039 mol), Intermediate 29-7 (14.96 g, 0.046 mol), Sodium tert-butoxide (7.41 g, 0.077 mol, sigma aldrich), Catalyst Pd(dba) ₂ (1.11 g, 0.0019) mol, sigma aldrich), tri-tert-Bu-phosphine (0.78 g, 0.0039 mol, sigma aldrich) was added with 150 mL of toluene and stirred at 100 °C for 6 hours to react. After completion of the reaction, 15.3 g (yield 79%) of <Intermediate 69-3> was obtained by performing column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

(4) Synthesis of compound 69

Intermediate 69-3 (10 g, 0.020 mol), Intermediate 69-2 (7.73 g, 0.024 mol), Sodium tert-butoxide (3.83 g, 0.040 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.57 g, 0.0010) mol, sigma aldrich), tri-tert-Bu-phosphine (0.40 g, 0.0020 mol, sigma aldrich) was added with 150 mL of toluene and stirred at 100 °C for 12 hours to react. After the reaction was completed, 11.7 g of compound 69 was obtained (yield 78.9%) by column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

H-NMR (200 MHz, CDCl3): δ ppm, 1H (7.85/d, 7.81/d) 2H (7.57/s, 7.54/d, 7.41/m, 7.07/s, 6.69/d) 3H (7.89/d, 7.66/d, 7.32/m) 4H (7.52/d, 7.51/m, 7.38/m)

LC/MS: m/z=743[(M+1) ⁺ ]

Synthesis example 6: Synthesis of compound 75

(1) Synthesis of Intermediate 75-1

Intermediate 29-7 (15 g, 0.046 mol), Bis(pinacolato)dibron (10.38 g, 0.060 mol, sigma aldrich), potassium acetate (9.11 g, 0.093 mol, sigma aldrich), PdCl ₂ (dppf) (1.02 g, 0.0014 mol, sigma aldrich) and 1,4-Dioxane (200 mL) were added, and the reaction was stirred at 95 °C for 12 hours. After completion of the reaction, H ₂ O was added, and the layers were separated and then purified by column (N-HEXANE: MC) to obtain 12.6 g (yield 73%) of <Intermediate 75-1>.

(2) Synthesis of Intermediate 75-2

1-bromo-4-iodobenzene (10 g, 0.035 mol, sigma aldrich), intermediate 75-1 (15.71 g, 0.042 mol), potassium carbonate (9.77 g, 0.071 mol, sigma aldrich), Pd(PPh ₃ ) ₄ ( 2.04 g, 0.0018 mol, sigma aldrich), 150 mL of THF, _{and 30 mL of H 2} O were added, and the reaction was stirred under reflux for 6 hours. After completion of the reaction, 11.7 g (yield 83%) of <Intermediate 75-2> was obtained by performing layer separation using _{H 2 O: MC and column purification (N-HEXANE: MC).}

(3) Synthesis of intermediate 75-3

9,9-dimethyl-9H-fluoren-2-amine (20 g, 0.096 mol, Yurui), 4-bromobiphenyl (22.28 g, 0.096 mol, sigma aldrich), Sodium tert-butoxide (27.55 g, 0.28 mol, sigma aldrich) ), catalyst Pd(dba) ₂ (2.75 g, 0.005 mol, sigma aldrich), tri-tert-Bu-phosphine (1.93 g, 0.01 mol, sigma aldrich) into 200 mL of Toluene and stirred at 100 °C for 3 hours. reacted. After completion of the reaction _{, the layer was separated on H 2} O: MC and then column purified (N-HEXANE:MC) to obtain 28 g (yield 81%) of <Intermediate 75-3>.

(4) Synthesis of compound 75

Intermediate 75-2 (10 g, 0.025 mol), Intermediate 75-3 (10.86 g, 0.030 mol), Sodium tert-butoxide (4.81 g, 0.050 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.72 g, 0.0013) mol, sigma aldrich), tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, sigma aldrich) was added with 150 mL of toluene and stirred at 100 °C for 8 hours to react. After the reaction was completed, 13.7 g of compound 75 was obtained (yield 75%) by column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

H-NMR (200 MHz, CDCl3): δ ppm, 1H (7.89/d, 7.87/d, 7.67/s, 7.66/d, 7.63/s, 7.62/d, 7.55/d, 7.32/m, 7.28/m, 6.75/s, 6.58/d) 2H (7.41/m, 7.38/m) 4H (7.54/d, 7.52/d, 7.51/m, 6.69/d) 6H (1.72/s)

LC/MS: m/z=679[(M+1) ⁺ ]

Synthesis example 7: Synthesis of compound 86

(1) Synthesis of Intermediate 86-1

Intermediate 75-2 (10 g, 0.025 mol), 4-aminobiphenyl (5.09 g, 0.030 mol, sigma aldrich), Sodium tert-butoxide (4.81 g, 0.050 mol, sigma aldrich), catalyst Pd(dba) ₂ (0.72 g) , 0.0013 mol, sigma aldrich), tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, sigma aldrich) was added with 150 mL of toluene, followed by stirring at 100 °C for 6 hours. After completion of the reaction _{, layer separation was performed on H 2} O:MC, followed by column purification (N-HEXANE:MC) to obtain 9.6 g of <Intermediate 86-1> (yield 78.6%).

(2) Synthesis of compound 86

Intermediate 38-3 (10 g, 0.025 mol), Intermediate 86-1 (14.65 g, 0.030 mol), Sodium tert-butoxide (4.81 g, 0.051 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.72 g, 0.0013) mol, sigma aldrich), tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, sigma aldrich) was added with 150 mL of toluene and stirred at 100 °C for 8 hours to react. After the reaction was completed, 16.5 g of compound 86 was obtained (yield: 81.7%) by column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

H-NMR (200 MHz, CDCl3): δ ppm, 1H (7.89/d, 7.67/s, 7.66/d, 7.63/s, 7.32/m) 2H (7.85/d, 7.81/d) 3H (7.41/m, 7.38/m) 6H (7.54/d, 7.52/d, 7.51/m, 6.69/d)

LC/MS: m/z=805[(M+1) ⁺ ]

Synthesis example 8: Synthesis of compound 96

2-amino-9,9-dimethylfluorene (10 g, 0.025 mol, TCI), intermediate 75-3 (14.80 g, 0.030 mol), sodium tert-butoxide (4.86 g, 0.051 mol, sigma aldrich), catalyst Pd (dba ) ₂ (0.73 g, 0.0013 mol, sigma aldrich), tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, sigma aldrich) was added with 150 mL of toluene and reacted by stirring at 100 °C for 8 hours. After completion of the reaction, 16.4 g (yield 81%) of compound 96 was obtained by performing column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

H-NMR (200 MHz, CDCl3): δ ppm, 1H (7.89/d, 7.87/d, 7.67/s, 7.66/d, 7.63/s, 7.62/d, 7.55/d, 7.32/m, 7.28/m, 6.75/s, 6.58/d) 2H (7.75/d, 7.41/m, 7.38/m, 7.35/d, 7.19/m, 7.16/m) 4H (7.54/d, 7.52/d, 7.51/m, 6.69/ d)

LC/MS: m/z=801[(M+1) ⁺ ]

Synthesis example 9: Synthesis of compound 111

(1) Synthesis of intermediate 111-1

Intermediate 75-2 (10 g, 0.025 mol), 2-amino-9,9-dimethylfluorene (6.29 g, 0.030 mol, TCI), Sodium tert-butoxide (4.81 g, 0.050 mol, sigma aldrich), Catalyst Pd (dba ) ₂ (0.72 g, 0.0013 mol, sigma aldrich), tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, sigma aldrich) was added with 150 mL of toluene, followed by stirring at 100 °C for 4 hours. After completion of the reaction, 10.6 g (yield 80%) of <Intermediate 111-1> was obtained by performing column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

(2) Synthesis of compound 111

Intermediate 111-1 (10 g, 0.019 mol), 2-bromo-9,9-dimethylfluorene (6.21 g, 0.023 mol, sigma aldrich), Sodium tert-butoxide (3.64 g, 0.038 mol, sigma aldrich), catalyst Pd ( 150 mL of Toluene was added to dba) ₂ (0.54 g, 0.0009 mol, sigma aldrich), tri-tert-Bu-phosphine (0.38 g, 0.0019 mol, sigma aldrich), and the reaction was stirred at 100 °C for 8 hours. After completion of the reaction, 10.8 g (yield 79%) of compound 111 was obtained by performing column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

H-NMR (200 MHz, CDCl3): δ ppm, 1H (7.89/d, 7.67/s, 7.66/d, 7.63/s, 7.41/m, 7.32/m) 2H (7.87/d, 7.62/d, 7.55/ d, 7.54/d, 7.52/d, 7.51/m, 7.28/m, 6.75/s, 6.69/d, 6.58/d) 3H (7.38/m) 12H (1.72/s)

LC/MS: m/z=719[(M+1) ⁺ ]

Synthesis example 10: Synthesis of compound 126

(1) Synthesis of Intermediate 126-1

2-bromo-9,9-dimethylfluorene (15 g, 0.055 mol, sigma aldrich), Bis(pinacolato)dibron (18.13 g, 0.071 mol, sigma aldrich), potassium acetate (10.78 g, 0.110 mol, sigma aldrich), PdCl ₂ (dppf) (1.21 g, 0.0016 mol, sigma aldrich), 200 mL of 1,4-Dioxane was added, and the reaction was stirred at 95 °C for 12 hours. After completion of the reaction, H ₂ O was added, the layers were separated, and column purification was performed (N-HEXANE: MC) to obtain 12.3 g (yield 70%) of <Intermediate 126-1>.

(2) Synthesis of Intermediate 126-2

2-bromo-4-iodophenol (10 g, 0.034 mol, yurui), intermediate 126-1 (12.86 g, 0.040 mol), potassium carbonate (9.25 g, 0.067 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (1.93) g, 0.0017 mol, sigma aldrich), THF 150 mL, H ₂ O 30 mL, and reacted by stirring under reflux for 5 hours. After completion of the reaction, _{layer separation was performed using H 2} O: MC, and column purification (N-HEXANE: MC) was performed to obtain 10 g (yield 82%) of <Intermediate 126-2>.

(3) Synthesis of Intermediate 126-3

Intermediate 126-2 (15 g, 0.041 mol), 2-fluorophenylboronic acid (6.90 g, 0.049 mol, sigma aldrich), potassium carbonate (11.35 g, 0.082 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (2.37 g, 0.0021 mol, sigma aldrich), 200 mL of toluene, and 40 mL of ethanol were added, and the reaction was stirred under reflux for 4 hours. After completion of the reaction, 12.2 g (yield 78%) of <Intermediate 126-3> was obtained through column purification (N-HEXANE: MC) after layer separation using _{H 2 O: MC.}

(4) Synthesis of Intermediate 126-4

Intermediate 126-4 (15 g, 0.050 mol), N-Bromosuccinimide (7.72 g, 0.043 mol, sigma aldrich), and 200 mL of dimethylformamide were added and reacted by stirring at 60 °C for 12 hours. After completion of the reaction, 1M aqueous NaOH solution was added, stirred, filtered, and dried to obtain 13 g (yield 71.8%) of <Intermediate 126-4>.

(5) Synthesis of Intermediate 126-5

Intermediate 126-4 (15 g, 0.033 mol), NaH (1.18 g, 0.049 mol, sigma aldrich), 200 mL of dimethyl sulfoxide was added, and the reaction was stirred at 140 °C for 5 hours. After completion of the reaction _{, layer separation was performed on H 2} O: MC, followed by column purification (N-HEXANE: MC) to obtain 5.6 g (yield 39%) of <Intermediate 126-5>.

(6) Synthesis of Intermediate 126-6

Intermediate 126-5 (15 g, 0.034 mol), 4-aminobiphenyl (6.93 g, 0.041 mol, sigma Aldrich), Sodium tert-butoxide (6.56 g, 0.068 mol, sigma aldrich), catalyst Pd(dba) ₂ (0.98 g) , 0.0017 mol, sigma aldrich), tri-tert-Bu-phosphine (0.68 g, 0.0034 mol, sigma aldrich) was added with 200 mL of toluene and stirred at 100 °C for 6 hours to react. After completion of the reaction, 14.5 g (yield 80.5%) of <Intermediate 126-6> was obtained by column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

(7) Synthesis of Intermediate 126-7

3-bromo-9H-carbazole (20 g, 0.081 mol, sigma aldrich), iodobenzene (41.4 g, 0.203 mol, sigma aldrich), potassium carbonate (33.69 g, 0.244 mol, sigma aldrich), Cu (10.33 g, 0.162 mol) , sigma aldrich), dibenzo-18-crown-6 (2.93 g, 0.008 mol, sigma Aldrich), and 150 mL of dimethylformamide were added and reacted by stirring at 150 °C for 12 hours. After the reaction was completed _{, the layers were separated in H 2} O:MC and then column purified (N-HEXANE) to obtain 24 g (yield 93%) of <Intermediate 126-7>.

(8) Synthesis of Intermediate 126-8

Intermediate 126-7 (36.86 g, 0.114 mol), Bis(pinacolato)dibron (34.86 g, 0.137 mol, sigma aldrich), potassium acetate (33.68 g, 0.343 mol, sigma aldrich), PdCl ₂ (dppf) (2.488 g, 0.0034 mol, sigma aldrich) and 1,4-Dioxane (400 mL) were added, and the reaction was stirred at 95 °C for 12 hours. After the reaction was completed _{, the layers were separated in H 2} O: Toluene, and then column purification (N-HEXANE: MC) was performed to obtain 19 g (yield 40%) of <Intermediate 126-8>.

(9) Synthesis of Intermediate 126-9

Intermediate 126-8 (17 g, 0.046 mol), 1-boromo-4-iodobenzene (15.68 g, 0.055 mol, sigma aldrich), sodium hydroxide (5.54 g, 0.138 mol, sigma aldrich), Pd(PPh ₃ ) ₄ ( 3.26 g, 0.0028 mol, sigma aldrich), 200 mL of THF, and 60 mL of water were added, and the reaction was stirred at 60 °C for 12 hours. After completion of the reaction, 16.9 g (yield 92%) of <Intermediate 126-9> was obtained by performing layer separation using _{H 2 O: MC and column purification (N-HEXANE: MC).}

(10) Synthesis of compound 126

Intermediate 126-9 (10 g, 0.025 mol), Intermediate 126-6 (15.9 g, 0.030 mol), Sodium tert-butoxide (4.83 g, 0.050 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.72 g, 0.0013) mol, sigma aldrich), tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, sigma aldrich) was added with 150 mL of toluene, followed by stirring at 100 °C for 6 hours. After completion of the reaction _{, layer separation was performed on H 2} O: MC, followed by column purification (N-HEXANE: MC) to obtain 17 g of compound 126 (yield 80%).

H-NMR (200 MHz, CDCl3): δ ppm, 1H (8.55/d, 7.94/d, 7.93/d, 7.89/d, 7.69/d, 7.66/d, 7.63/d, 7.57/s, 7.55/d, 7.45/m, 7.41/m, 7.33/m, 7.32/m, 7.28/m, 7.25/m, 7.07/s) 2H (7.87/d, 7.77/d, 7.58/m, 7.52/d, 7.51/m, 7.50/d, 7.38/m) 4H (7.54/d, 6.69/d) 6H (1.72/s)

LC/MS: m/z=844 [(M+1) ⁺ ]

Synthesis example 11: Synthesis of compound 133

Intermediate 126-6 (10 g, 0.019 mol), 2-amino-9,9-dimethylfluorene (8.99 g, 0.023 mol, TCI), Sodium tert-butoxide (3.65 g, 0.038 mol, sigma aldrich), Catalyst Pd (dba ) ₂ (0.54 g, 0.0009 mol, sigma aldrich), tri-tert-Bu-phosphine (0.38 g, 0.0019 mol, sigma aldrich) was added with 150 mL of Toluene, followed by stirring at 100 °C for 8 hours. After completion of the reaction _{, layer separation was performed on H 2} O: MC, followed by column purification (N-HEXANE: MC) to obtain 13 g of compound 133 (yield 81%).

H-NMR (200 MHz, CDCl3): δ ppm, 1H (7.93/d, 7.89/d, 7.77/s, 7.66/d, 7.63/d, 7.62/d, 7.57/s, 7.41/m, 7.32/m, 7.07/s, 6.75/s, 6.58/d) 2H (7.87/d, 7.55/d, 7.54/d, 7.52/d, 7.51/m, 7.28/m, 7.26/m, 6.69/d) 3H (7.38/d) m) 4H (7.33/m, 7.11/d) 6H (1.72/s)

LC/MS: m/z=844 [(M+1) ⁺ ]

Synthesis example 12: Synthesis of compound 134

Intermediate 126-6 (10 g, 0.019 mol), 2-amino-9,9-dimethylfluorene (6.21 g, 0.023 mol, TCI), Sodium tert-butoxide (3.64 g, 0.038 mol, sigma aldrich), Catalyst Pd (dba ) ₂ (0.54 g, 0.0009 mol, sigma aldrich), tri-tert-Bu-phosphine (0.38 g, 0.0019 mol, sigma aldrich) was added with 150 mL of Toluene, followed by stirring at 100 °C for 8 hours. After completion of the reaction, 11.3 g (yield 82.8%) of compound 134 was obtained by performing column purification (N-HEXANE: MC) after layer separation in _{H 2 O:MC.}

H-NMR (200 MHz, CDCl3): δ ppm, 1H (7.93/d, 7.89/d, 7.77/s, 7.66/d, 7.63/d, 7.62/d, 7.57/s, 7.41/m, 7.32/m, 7.07/s, 6.75/s, 6.58/d) 2H (7.87/d, 7.55/d, 7.54/d, 7.52/d, 7.51/m, 7.28/m, 6.69/d) 3H (7.38/m) 12H ( 1.72/s)

LC/MS: m/z=719[(M+1) ⁺ ]

Synthesis example 13: Synthesis of compound 146

(1) Synthesis of Intermediate 146-1

2-bromo-4-iodophenol (20 g, 0.067 mol, yurui), 4-biphenylboronic acid (15.90 g, 0.080 mol, sigma aldrich), potassium carbonate (18.50 g, 0.134 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (3.87 g, 0.0033 mol, sigma aldrich), 250 mL of toluene, and 50 mL of ethanol were added, and the reaction was stirred under reflux for 4 hours. After completion of the reaction, 17.4 g (yield 80%) of <Intermediate 146-1> was obtained by performing column purification (N-HEXANE: MC) after layer separation using _{H 2 O: MC.}

(2) Synthesis of Intermediate 146-2

Intermediate 146-1 (20 g, 0.062 mol), 2-fluorophenylboronic acid (10.33 g, 0.074 mol, sigma aldrich), potassium carbonate (17.00 g, 0.123 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (3.55 g, 0.0031 mol, sigma aldrich), 250 mL of toluene, and 40 mL of ethanol were added, and the reaction was stirred under reflux for 4 hours. After completion of the reaction, _{layer separation was performed using H 2} O: MC, followed by column purification (N-HEXANE: MC) to obtain 17 g (yield 81%) of <Intermediate 146-2>.

(3) Synthesis of intermediate 146-3

Intermediate 146-2 (15 g, 0.044 mol), N-Bromosuccinimide (8.63 g, 0.049 mol, sigma aldrich), and 200 mL of Dimethylformamide were added and reacted by stirring at 60 °C for 12 hours. After completion of the reaction, 1M aqueous NaOH solution was added, stirred, filtered, and dried to obtain 13.5 g (yield 73%) of <Intermediate 146-3>.

(4) Synthesis of Intermediate 146-4

Intermediate 146-4 (15 g, 0.036 mol), NaH (1.03 g, 0.043 mol, sigma aldrich), 200 mL of dimethyl sulfoxide was added, and the reaction was stirred at 140 °C for 5 hours. After completion of the reaction _{, layer separation was performed on H 2} O:MC, and column purification (N-HEXANE:MC) was performed to obtain 5.7 g (yield 40%) of <Intermediate 146-4>.

(5) Synthesis of compound 146

Intermediate 146-4 (10 g, 0.025 mol), Intermediate 75-3 (10.86 g, 0.042 mol), Sodium tert-butoxide (4.81 g, 0.050 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.72 g, 0.0013) mol, sigma aldrich), tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, sigma aldrich) was added with 150 mL of toluene and stirred at 100 °C for 4 hours to react. After the reaction was completed, 13.9 g of compound 146 was obtained (yield: 81.6%) by column purification (N-HEXANE: EA) after layer separation in _{H 2 O:EA.}

H-NMR (200 MHz, CDCl3): δ ppm, 1H (7.89/d, 7.87/d, 7.66/d, 7.62/d, 7.57/s, 7.55/d, 7.32/m, 7.28/m, 7.07/s, 6.75/s, 6.58/d) 2H (7.54/d, 7.41/m, 7.38/m, 6.69/d) 4H (7.52/d, 7.51/m, 7.25/d) 6H (1.72/s)

LC/MS: m/z=679[(M+1) ⁺ ]

device embodiment

In an embodiment according to the present invention, the ITO transparent electrode is patterned so that the light emitting area is 2 mm × 2 mm on a glass substrate of 25 mm × 25 mm × 0.7 mm, using an ITO glass substrate to which an ITO transparent electrode is attached. After that, it was washed. After the substrate was mounted in a vacuum chamber, the base pressure was set to 1 × 10 ^-6 torr, and the organic material and the metal were deposited on the ITO in the following structure.

Device Examples 1 to 15

By using the compound implemented by [Formula I] according to the present invention as the compound of the electron blocking layer, a blue light emitting organic electroluminescent device having the following device structure was manufactured, and luminescent properties including luminous efficiency were measured.

ITO / hole injection layer (HAT_CN 5 nm) / hole transport layer (a-NPB 100 nm) / electron blocking layer (10 nm) / light emitting layer (20 nm) / electron transport layer (201:Liq 30 nm) / LiF (1 nm) / Al (100 nm)

To form a hole injection layer on the ITO transparent electrode, [HAT_CN] was used to form a hole injection layer with a thickness of 5 nm by vacuum thermal evaporation, and then a hole transport layer was formed using α-NPB. The electron blocking layer was formed to a thickness of 10 nm using Chemical Formulas 29, 38, 48, 58, 69, 75, 86, 96, 111, 126, 133, 134, 146, 155, and 176 implemented in the present invention. In addition, the light emitting layer was formed to have a thickness of about 20 nm using [BH1] as a host compound and [BD1] as a dopant compound, and additionally an electron transport layer (doped with 50% of the compound Liq below [201]) 30 nm and 1 nm of LiF and 100 nm of aluminum were deposited by vapor deposition to prepare an organic electroluminescent device.

Device Comparative Example 1

The organic electroluminescent device for Device Comparative Example 1 was manufactured in the same manner except that the electron blocking layer was not used in the device structure of Example 1.

Experimental Example 1: Light emitting properties of Device Examples 1 to 15

The organic electroluminescent device manufactured according to the above example was measured for voltage, current and luminous efficiency using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and a current density of 10 mA/cm 2 The resulting voltage was defined as "driving voltage" and compared. The results are shown in [Table 1] below.

Example electronic barrier layer V cd/A QE (%) CIEx CIEy One Formula 29 4.18 8.13 7.62 0.145 0.154 2 Formula 38 4.20 8.07 7.60 0.145 0.155 3 Formula 48 4.22 8.19 7.70 0.144 0.154 4 Formula 58 4.20 8.18 7.65 0.144 0.155 5 Formula 69 4.16 8.12 7.64 0.145 0.155 6 Formula 75 4.08 8.20 7.72 0.145 0.155 7 Formula 86 4.13 8.15 7.65 0.146 0.154 8 Formula 96 4.10 8.16 7.60 0.144 0.155 9 Formula 111 4.15 8.04 7.68 0.146 0.156 10 Formula 126 4.23 8.03 7.64 0.145 0.154 11 Formula 133 4.21 8.14 7.68 0.145 0.155 12 Formula 134 4.17 8.20 7.71 0.144 0.154 13 Formula 146 4.07 8.12 7.67 0.145 0.154 14 Formula 155 4.14 8.10 7.65 0.145 0.155 15 Formula 176 4.16 8.13 7.62 0.144 0.155 comparative example not used 4.14 5.4 4.6 0.147 0.156

Looking at the results shown in [Table 1], first, in the case of a device employing the compound implemented by [Formula I] according to the present invention as an electron blocking layer compound, the luminous efficiency and quantum efficiency compared to the conventional device (Comparative Example) It can be seen that the light emission characteristics are remarkably excellent.

[HAT_CN] [α-NPB] [BH1] [BD1] [201]

Claims (8)

An organic light emitting compound represented by the following [Formula I]:
[Formula Ⅰ]

In the [Formula I],
X is CR ₁ R ₂ , O or S;
Wherein R _{1 To} R ₂ are the same or different from each other, and each independently is any one selected from hydrogen, a substituted or unsubstituted C 1 to C 7 alkyl group, and a substituted or unsubstituted C 6 to C 30 aryl group,
The R _{1 To} R ₂ may be connected to each other or an adjacent substituent to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle,
L ₁ to L ₂ are the same as or different from each other, and each independently is a single bond, an arylene group, a fluorenylene group, a carbazolylene group, or a heteroarylene group including at least one of N, O and S atoms,
Ar _{1 is any one selected} from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms (except for a naphthyl group, an anthracenyl group, and a phenanthrenyl group) and a substituted or unsubstituted fluorenyl group,
Ar ₂ and Ar ₃ are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or a substituted or unsubstituted fluorenyl group and a substituted or unsubstituted carbazole group, wherein _{at least one of Ar 2} and Ar ₃ is a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazole group, or a substituted or unsubstituted dibenzofuran. Any one selected from a diyl group and a substituted or unsubstituted dibenzothiophenyl group,
However, when X is O and _{any one of Ar 2} and Ar ₃ is a substituted or unsubstituted dibenzofuranyl group, (i) the _{other one of Ar 2} and Ar ₃ is substituted or unsubstituted having 6 to 30 carbon atoms Any selected from an aryl group, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted fluorenyl group (provided that the spiro structure fluorenyl group is excluded) and a substituted or unsubstituted carbazole group any one of the following; (ii) _{at least one of L 1} to L ₂ is not a single bond,
The substituted or unsubstituted means deuterium, a halogen group, a cyano group, a nitro group, a silyl group, an alkyl group, a cycloalkyl group, an aryl group and a heteroaryl group substituted with one or two or more substituents selected from the group consisting of, or two or more substituents among the substituents It means that is substituted with a linked substituent, or does not have any substituents. According to claim 1,
The compound represented by the [Formula I] is an organic light emitting compound, characterized in that any one selected from the group consisting of the following compounds:

An organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic light emitting device comprising the organic light emitting compound represented by the [Formula I] of claim 1. 4. The method of claim 3,
The organic material layer includes at least one layer from among a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, and an electron injection layer,
At least one of the layers comprises an organic light emitting compound represented by the [Formula I]. 5. The method of claim 4,
The organic light emitting device, characterized in that the electron blocking layer comprises an organic light emitting compound represented by the [Formula I]. 4. The method of claim 3,
An organic light emitting device, characterized in that the organic material layer further comprises at least one organic light emitting layer emitting red, green or blue light to emit white light. An organic light-emitting compound, characterized in that any one selected from the group consisting of the following compounds:

An organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode,
The organic material layer includes at least one layer from among a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, and an electron injection layer,
The organic light emitting device, characterized in that the electron blocking layer comprises an organic light emitting compound represented by the [Formula I].