WO2021132952A1 - Compound, organic electroluminescent element, and display device - Google Patents

Abstract

Provided according to the present invention are: a compound which can be applied to, for example, an electron transport layer, an electron transport auxiliary layer, and a light-emitting layer of an organic electroluminescent element; an organic electroluminescent element in which the compound is used; and an organic EL display device comprising the organic electroluminescent element.

Description

Compounds, organic electroluminescent devices and display devices

The present invention relates to a novel organic compound that can be used as a material for an organic electroluminescent device, an organic electroluminescent device including the same, and a display device.

The organic electroluminescent device typically has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electroluminescent device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

When a voltage is applied between the two electrodes in the structure of such an organic electroluminescent device, holes are injected into the emission layer through the hole injection layer and the hole transport layer in the anode, and electrons are injected into the emission layer through the electron injection layer and the electron transport layer in the cathode. The formed holes and electrons recombine to form excitons, and when these excitons fall back to the ground state, light is emitted.

_{Heteroaromatic compounds such as Alq 3} and BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) are known as electron transport materials for organic electroluminescent devices, but these conventional electron transport materials emit light. Further improvement is required in terms of efficiency and driving voltage.

In particular, in the conventional organic electroluminescent device, excitons generated in the light emitting layer diffuse into the electron transport layer and emit light at the interface with the electron transport layer, resulting in reduced luminous efficiency and reduced lifetime.

The present invention provides a compound that has high stability and high electron mobility with respect to electrons, and can suppress the diffusion of excitons into an electron transport layer, and an organic electroluminescent device having high efficiency and low driving voltage by employing such a compound, and An object of the present invention is to provide a display device using the same.

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

Here, Ar ₁ , Ar ₂ are each independently, a substituted or unsubstituted C ₆ ~ C ₆₀ aryl group; Or a substituted or unsubstituted C9~ C60 condensed polycyclic group,

L is a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted C9~ C60 condensed polycyclic group,

A1 is represented by any one of the following structures,

X1 is C or N.

In particular, when the novel compound represented by Formula 1 of the present invention is used as a material for an electron transport layer or an electron transport auxiliary layer, an organic electroluminescent device having superior light emitting performance, low driving voltage, high efficiency and long lifespan compared to conventional materials is manufactured In addition, it is possible to manufacture a full-color display panel with greatly improved performance and lifespan.

1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the components of the present invention, when it is described that a component is “connected”, “coupled” or “connected” to another component, the component is directly connected to the other component or may be connected, but another element may be "connected", "coupled" or "connected" between each element.

Terms used in this specification and appended claims have the following meanings, unless otherwise stated.

As used herein, the term "halo" or "halogen" is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), unless otherwise specified.

As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, unless otherwise specified, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo means a radical of saturated aliphatic functional groups including alkyl groups, cycloalkyl-substituted alkyl groups. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

As used herein, the term "heteroalkyl group" means that at least one of the carbon atoms constituting the alkyl group is replaced with a heteroatom.

As used herein, the term “cycloalkyl” refers to an alkyl forming a ring having 3 to 60 carbon atoms unless otherwise specified, but is not limited thereto. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or multiple ring aromatic, and includes an aromatic ring formed by a neighboring substituent joining or participating in a reaction. For example, the aryl group may include, but is not limited to, a phenyl group, a biphenyl group, and a terphenyl group as a single ring aryl group, and as a multicyclic aryl group, a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, It may include a chrysenyl group, a fluorenyl group, and a spirofluorene group, but is not limited thereto.

The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl group or arylene group having 2 to 60 carbon atoms each containing one or more heteroatoms, unless otherwise specified, No, it includes at least one of a single ring and a multiple ring, and may be formed by combining adjacent functional groups.

The term "heterocyclic group" used in the present invention, unless otherwise specified, contains one or more heteroatoms, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes a heteroaliphatic ring and a heterocyclic group. containing aromatic rings. It may be formed by combining adjacent functional groups. "Heteroatom" refers to N, O, S, P or Si unless otherwise specified. In addition, the "heterocyclic group" may include a ring including _{SO 2 instead of carbon forming the ring.}

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, phenanthroline group, thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

Unless otherwise specified, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocycle having 2 to 60 carbon atoms, or a combination thereof, saturated or unsaturated rings.

Other heterocompounds or heteroradicals other than the above-mentioned heterocompounds include one or more heteroatoms, but are not limited thereto.

In addition, unless otherwise explicitly stated, in the term "substituted or unsubstituted" used in the present invention, "substituted" means deuterium, halogen, amino group, nitrile group, nitro group, C1-C20 alkyl group, C1-C20 alkoxyl group. , C1~ C20 alkylamine group, C1~ C20 alkylthiophene group, C6~ C20 arylthiophene group, C2~ C20 alkenyl group, C2~ C20 alkynyl group, C3~ C20 cycloalkyl group, C6~ One or more substituents selected from the group consisting of a C20 aryl group, a C6~ C20 aryl group substituted with deuterium, a C5~ C20 arylalkenyl group, a silane group, a boron group, a germanium group, and a C2~ C20 heterocyclic group It means substituted with, but is not limited to these substituents.

1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

As shown in FIG. 1 , the organic electroluminescent device 1 according to the present invention includes a first electrode 10 , a second electrode 20 , and a first electrode 10 and a second electrode ( 20) and an organic material layer 30 formed therebetween, wherein the organic material layer 30 includes the compound represented by Chemical Formula 1 above. The first electrode 10 may be an anode (anode), and the second electrode 20 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

As the anode material, a material having a large work function is preferable 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; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO:Al or SNO ₂ : a combination of metal and oxide such as Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

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

The organic material layer 30 may include a hole injection layer 310, a hole transport layer 320, a light emitting layer 350, an electron transport layer 370, and an electron injection layer 380 sequentially from the first electrode 10. . In this case, at least some of the remaining layers except for the emission layer 350 may not be formed.

Among the organic material layers, the layers formed between the first electrode 10 and the emission layer 350 constitute a hole transport region, and the layers formed between the emission layer 350 and the second electrode 20 constitute an electron transport region.

The hole injection layer 310 is a layer that facilitates injection of holes from the first electrode 10, and as the hole injection material, a compound excellent in the hole injection effect from the anode and the ability to form a thin film is preferable. For this, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene. organic materials, anthraquinone, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

The hole transport layer 320 is a layer that receives holes from the hole injection layer 310 and transports holes to the light emitting layer 350 . As the hole transport material, 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 layer 350 is a layer that emits light in the visible ray region by receiving and combining holes and electrons from the hole transport layer 320 and the electron transport layer 370 , respectively. Light emission wavelengths of green, red, blue, etc. are determined according to the material used for the light emitting layer 350 .

The light emitting mechanism of the light emitting layer 350 is divided into fluorescence and phosphorescence. Fluorescence is a mechanism in which excitons in a singlet state among excitons generated by the combination of holes and electrons emit light while descending to the ground state, and phosphorescence is a mechanism in which excitons in a triplet state emit light while descending to the ground state. 25% of singlet excitons and 75% of triplet excitons are generated by the combination of holes and electrons. Unlike fluorescence, where only 25% of singlet excitons contribute to light emission, in phosphorescence, 75% of triplet excitons and Since 25% of singlet excitons that can be converted to triplet excitons through intercalation all contribute to light emission, it is theoretically possible to realize 100% internal quantum efficiency.

The emission layer 350 may include a host and a dopant to improve color purity and quantum efficiency. In the light emitting layer 350 having such a structure, excitons generated in the host are transferred to the dopant to emit light.

Examples of the host material include a condensed aromatic ring derivative or a heterocyclic compound containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The electron transport layer 370 is a layer that receives electrons from the electron injection layer 380 and transports electrons to the light emitting layer 350 . The material of the electron transport layer 370 is a compound having electron accepting properties and high mobility for electrons. This is suitable. In addition, the emission layer 350 must have a lowest unoccupied molecular orbital (LUMO) energy level suitable for injecting electrons into the emission layer 350 , and also prevent holes from passing through the emission layer 350 to the electron transport layer 370 . The difference from the HOMO (Highest Occupied Molecular Orbital) energy level should be large. Specific examples of the material of the electron transport layer 370 include an Al complex of 8-hydroxyquinoline (Alq3); heteroaromatic compounds, and the like, but are not limited thereto. The compound represented by Formula 1 of the present invention may be used as an electron transport material, which will be described later.

The electron injection layer 380 is a layer that facilitates injection of electrons from the second electrode 20, and is preferably a compound having the ability to transport electrons, and excellent in the electron injection effect and thin film formation ability from the cathode electrode. . Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto. Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, and tris. (8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]qui Nolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (o -Crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. not limited

The organic material layer 30 may further include a hole transport auxiliary layer 330 between the hole transport layer 320 and the light emitting layer 350 , and an electron transport auxiliary layer 360 between the electron transport layer 370 and the light emitting layer 350 . may further include.

The hole transport auxiliary layer 330 and the electron transport auxiliary layer 360 are layers that prevent excitons generated in the emission layer 350 from diffusing into the electron transport layer 370 or the hole transport layer 320 adjacent to the emission layer 350 . As a result, the number of excitons contributing to light emission in the light emitting layer is increased, so that the luminous efficiency of the device can be improved and the driving voltage can be lowered, and the durability and stability of the device can also be improved, thereby effectively increasing the lifetime of the device. The compound represented by Formula 1 of the present invention may be preferably used as a material for the electron transport auxiliary layer.

The organic material layer 30 may further include a light emitting auxiliary layer (not shown) between the hole transport auxiliary layer 330 and the light emitting layer 350 , and life is improved when the electron transport auxiliary layer 360 and the light emitting layer 350 are used. It may further include a layer (not shown).

The light emitting auxiliary layer may serve to transport holes to the light emitting layer 350 and to adjust the thickness of the organic layer 30 . The light emitting auxiliary layer may include a hole transport material, and may be made of the same material as the hole transport layer 320 .

The lifetime improvement layer prevents the holes transported to the light emitting layer 350 from diffusing or moving to the electron transport layer 370 , thereby limiting the holes to the light emitting layer. The electron transport layer 370 moves electrons by reduction (electron acceptor). When holes are diffused into the electron transport layer, an irreversible decomposition reaction occurs due to oxidation, thereby reducing the lifespan. Accordingly, by providing a lifespan improving layer that suppresses the diffusion of holes into the electron transport layer 370 , it is possible to contribute to the improvement of the lifespan of the organic light emitting diode.

In addition, although not shown, the organic electroluminescent device according to the present invention has a protective layer or light efficiency improvement layer formed on at least one surface of at least one surface of the first electrode 10 and the second electrode 20 opposite to the organic material layer (Capping layer) may further include.

In the present specification, the embodiment in which the compound according to the present invention is used in the electron transport region such as the electron transport layer 370 and the electron transport auxiliary layer 360 is mainly described, but the present invention is not limited thereto, and the light emitting layer 350 is It can also be used as a material for a host (especially an n-type host).

The organic electroluminescent device 1 according to an embodiment of the present invention may be manufactured using a vacuum deposition method. For example, an organic material layer including a hole injection layer 310 , a hole transport layer 320 , a light emitting layer 350 , an electron transport layer 370 , and an electron injection layer 380 on the substrate on which the anode 10 is formed is organic in a vacuum chamber. After forming through evaporation of the material, it can be manufactured by depositing a material that can be used as the cathode 20 thereon.

In addition, the organic layer is a solution process or a solvent process rather than a vacuum deposition method using various polymer materials, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, a roll-to-roll process, a doctor It can be manufactured with a smaller number of layers by a method such as a blading process, a screen printing process, or a thermal transfer method. The organic material layer according to the present invention may be formed by various methods, and the scope of the present invention is not limited by the formation method.

Another embodiment of the present invention includes a display device including a thin film transistor for selecting and driving the organic electroluminescent device and the organic electroluminescent device of the present invention described above, and an electronic device including a control unit for controlling the display device can do. In this case, the electronic device may be a current or future wired/wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote control, a navigation system, a game machine, various TVs, and various computers.

Hereinafter, the compound according to one aspect of the present invention will be described.

According to one aspect of the present invention, there is provided a compound represented by the following formula (1).

Here, Ar ₁ , Ar ₂ are each independently, a substituted or unsubstituted C ₆ ~ C ₆₀ aryl group; Or a substituted or unsubstituted C9~ C60 condensed polycyclic group,

L is a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted C9~ C60 condensed polycyclic group,

A1 is represented by any one of the following structures,

X1 is C or N.

According to a preferred embodiment of the present invention, Ar1, Ar2 are each independently a substituted or unsubstituted C ₆ ~ C ₆₀ aryl group, L is a direct bond; or a substituted or unsubstituted arylene group.

According to a preferred embodiment of the present invention, the compound of Formula 1 is any one of the following compounds.

An organic electroluminescent device according to another aspect of the present invention, a first electrode; a second electrode opposite to the first electrode; and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer includes the compound of Formula 1 above. .

According to a preferred embodiment of the present invention, in the organic electroluminescent device, the first electrode is an anode, the second electrode is a cathode, and the organic layer is i) a light emitting layer, ii) the first electrode and the light emitting layer interposed therebetween, a hole transport region including at least one of a hole injection layer, a hole transport layer, and a hole transport auxiliary layer; and iii) interposed between the light emitting layer and the second electrode, an electron transport auxiliary layer, an electron transport layer and an electron injection and an electron transport region including at least one of the layers, wherein the electron transport region includes the compound of Formula 1 above.

According to a preferred embodiment of the present invention, in the organic electroluminescent device, the electron transport layer or the electron transport auxiliary layer includes the compound of Formula 1 above.

According to another aspect of the present invention, a display including the organic electroluminescent device and a thin film transistor (TFT) connected thereto, wherein a first electrode of the organic electroluminescent device is electrically connected to a source electrode or a drain electrode of the thin film transistor A device is provided.

Hereinafter, a synthesis example of the compound represented by Formula 1 and a manufacturing example of an organic electroluminescent device according to the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

[Synthesis method of intermediate products]

(1) Intermediate 1

Bromobenzene (7.9 g, 50.3 mmol), magnesium turning (1.22 g, 50.3 mmol), and a very small amount of iodine were added to degassed THF under a nitrogen atmosphere. After stirring under reflux at 80 °C for 2 hours until the Magnesium disappeared, it was cooled to 0 °C again, BF ₃ *Et ₂ O (3.6 g, 25.2 mmol) was added, and the mixture was stirred at room temperature overnight. THF was removed through distillation and extracted with hexane and water. The extract is filtered and the supernatant is concentrated. The concentrated compound was purified by sublimation to obtain fluorodiphenylborane (3.7 g, 79 %).

(2) intermediate product 2

2-bromo-1,3-dimethylbenzene (10 g, 54.04 mmol), magnesium turning (1.31 g, 54.04 mmol), and a very small amount of iodine were added to degassed THF under a nitrogen atmosphere. After stirring under reflux at 80 °C for 2 hours until the Magnesium disappeared, it was cooled to 0 °C again, BF ₃ *Et ₂ O (3.8 g, 27.02 mmol) was added, and the mixture was stirred at room temperature overnight. THF was removed through distillation and extracted with hexane and water. The extract is filtered and the supernatant is concentrated. The concentrated compound was purified by sublimation to obtain bis(2,6-dimethylphenyl)fluoroborane (8 g, 61.7 %).

(3) intermediate product 3

1-bromo-2-methylbenzene (10 g, 58.5 mmol), magnesium turning (1.42 g, 58.5 mmol), and a very small amount of iodine were added to degassed THF under a nitrogen atmosphere. After stirring under reflux at 80 °C for 2 hours until the Magnesium disappeared, it was cooled to 0 °C again, BF ₃ *Et ₂ O (4.15 g, 29.2 mmol) was added, and the mixture was stirred at room temperature overnight. THF was removed through distillation and extracted with hexane and water. The extract is filtered and the supernatant is concentrated. The concentrated compound was purified by sublimation to obtain fluorodi-o-tolylborane (7 g, 60.5 %).

(4) intermediate 4

2-bromo-1,3,5-trimethylbenzene (10 g, 50.23 mmol), magnesium turning (1.22 g, 50.23 mmol), and a very small amount of iodine were added to degassed THF under a nitrogen atmosphere. After stirring under reflux at 80 °C for 2 hours until the Magnesium disappeared, it was cooled to 0 °C again, BF ₃ *Et ₂ O (3.6 g, 25.1 mmol) was added, and the mixture was stirred at room temperature overnight. THF was removed through distillation and extracted with hexane and water. The extract is filtered and the supernatant is concentrated. The concentrated compound was purified by sublimation to obtain fluorodimesitylborane (7 g, 60.5 %).

(5) intermediate product 5

4-bromo-1,1'-biphenyl (10g, 42.9 mmol), magnesium turning (1.04 g, 42.9 mmol), and a very small amount of iodine were added to degassed THF under a nitrogen atmosphere. After stirring under reflux at 80 °C for 2 hours until the Magnesium disappeared, it was cooled to 0 °C again, BF ₃ *Et ₂ O (3.04 g, 21.45 mmol) was added, and the mixture was stirred at room temperature overnight. THF was removed through distillation and extracted with hexane and water. The extract is filtered and the supernatant is concentrated. The concentrated compound was purified by sublimation to obtain di([1,1'-biphenyl]-4-yl) fluoroborane (9 g, 62.4 %).

(6) Intermediate product 6

4-bromo-3,5-dimethyl-1,1'-biphenyl (10 g, 38.3 mmol), magnesium turning (0.93 g, 38.3 mmol), and a very small amount of iodine were added to degassed THF under a nitrogen atmosphere. After stirring under reflux at 80 °C for 2 hours until the Magnesium disappeared, it was cooled to 0 °C again, BF ₃ *Et ₂ O (2.7 g, 19.15 mmol) was added, and the mixture was stirred at room temperature overnight. THF was removed through distillation and extracted with hexane and water. The extract is filtered and the supernatant is concentrated. The concentrated compound was purified by sublimation to obtain bis(3,5-dimethyl-[1,1'-biphenyl]-4-yl)fluoroborane (9 g, 59.9 %).

[ Synthesis example and of the final product FDMS data]

(1) compound 1-1-1

1,4-Dibromobenzene (6.1 g, 25.9 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78 °C, n -BuLi (1.3 g, 19.9 mmol) was added dropwise, and stirred for 3 hours. _{Et 2} O in which fluorodiphenylborane (3.7 g, 19.9 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (4-bromophenyl)diphenylborane (6.7 g, 80%).

(4-bromophenyl)diphenylborane (6.7 g, 20.87 mmol) was dissolved in DMF in a round bottom flask, and then 4,4,4',4',5,5,5',5'-octamethyl-2,2'- bi(1,3,2-dioxaborolane) (7.95 g, 31.31 mmol), Pd(dppf)Cl ₂ (0.46 g, 0.63 mmol) and KOAc (6.15 g, 62.61 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silica gel column and 2-(4-(diphenylboraneyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6 g , 78.1 %) was obtained.

After dissolving 2-(4-(diphenylboraneyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6 g, 16.3 mmol) in THF, 8-bromobenzo[h]isoquinoline (4.63 g, 17.93 mmol), Pd(PPh ₃ ) ₄ (0.57 g, 0.49 mmol), K ₂ CO ₃ (6.76 g, 48.9 mmol), and water were added, followed by stirring under reflux at 100° C. for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 5 g of a final product (yield: 73.2%).

(2) compound 1-2-1

2,5-dibromo-1,3-dimethylbenzene (6.8 g, 25.9 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78°C, and n- BuLi (1.3 g, 19.9 mmol) was added dropwise. Stirred for 3 hours. _{Et 2} O in which fluorodiphenylborane (3.7 g, 19.9 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (4-bromo-2,6-dimethylphenyl)diphenylborane (7 g, 77.5%).

(4-bromo-2,6-dimethylphenyl)diphenylborane (7 g, 20.05 mmol) was dissolved in DMF in a round-bottom flask, and then 4,4,4',4',5,5,5',5'-octamethyl -2,2'-bi(1,3,2-dioxaborolane) (7.64 g, 30.08 mmol), Pd(dppf)Cl ₂ (0.44 g, 0.6 mmol) and KOAc (5.9 g, 60.16 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized on a silica gel column to 2-(4-(diphenylboraneyl)-3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2 -dioxaborolane (6 g, 75.5 %) was obtained.

After dissolving 2-(4-(diphenylboraneyl)-3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6 g, 15.15 mmol) in THF, 3-bromophenanthridine ( 4.3 g, 16.7 mmol), Pd(PPh ₃ ) ₄ (0.53 g, 0.45 mmol), K ₂ CO ₃ (6.28 g, 45.4 mmol), and water were added, followed by stirring under reflux at 100° C. for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 5 g of a final product (yield: 73.8%).

(3) compound 1-3-2

3-Chlorobenzo[b]thiophene-2-carbonyl chloride (15.2g, 65.8mmol) and pyridin-4-amine (6.2g, 65.8mmol) were dissolved in benzene, and triethylamine (9.4ml,67.8mmol) was added thereto for 1 hour. Stir under reflux. After completion of the reaction, benzene was removed under reduced pressure, extracted with MC and water, dried over MgSO4, concentrated, and the resulting organic material was recrystallized from ethanol to produce 3-chloro-N-(pyridin-4-yl)benzo[b]thiophene- 15.2 g of 2-carboxamide (yield: 80%) was obtained.

3-chloro-N-(pyridin-4-yl)benzo[b]thiophene-2-carboxamide (12.9g, 44.6mmol) was dissolved in benzene, stirred, and triethylamine (4.7g, 4.64mmol) was added dropwise, followed by 450watt A high-pressure mercury lamp is irradiated for 10 hours. When the reaction is complete, benzene is removed by distillation under reduced pressure, and the solid is washed several times with water and dried to 9.4 g of Benzo[4,5]thieno[2,3-c][1,6]naphthyridin-6(5H)-one (Yield: 83%) was obtained.

Phosphorus oxychloride was added to benzo[4,5]thieno[2,3-c][1,6]naphthyridin-6(5H)-one (10.0g, 39.6mmol) and stirred under reflux for 4 hours. When the reaction is complete, distillation under reduced pressure removes Phosphorus oxychloride, and after adding ice water, the mixture is stirred. Ammonium hydroxide is added dropwise to basify to pH 9. The resulting brown solid was filtered, washed several times with water, and recrystallized from benzene to obtain 7.8 g (yield: 73%) of 6-chlorobenzo[4,5]thieno[2,3-c][1,6]naphthyridine.

After dissolving 2-(3-(diphenylboraneyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5 g, 13.58 mmol) in THF, 6-chlorobenzo[4,5]thieno Add [2,3-c][1,6]naphthyridine (4.7 g, 14.94 mmol), Pd(PPh ₃ ) ₄ (0.47 g, 0.41 mmol), K ₂ CO ₃ (5.63 g, 40.75 mmol), water After that, the mixture was stirred under reflux at 100 °C for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 4.5 g of a final product (yield: 69.5%).

(4) compound 1-4-1

4,4'-dibromo-1,1'-biphenyl (8.1 g, 25.9 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere, and after cooling to -78 ° C, n- BuLi (1.3 g, 19.9 mmol) was added. It was added dropwise and stirred for 3 hours. _{Et 2} O in which fluorodiphenylborane (3.7 g, 19.9 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (4'-bromo-[1,1'-biphenyl]-4-yl)diphenylborane (7 g, 68.1 %). .

(4'-bromo-[1,1'-biphenyl]-4-yl)diphenylborane (7 g, 17.63 mmol) was dissolved in DMF in a round bottom flask, 4,4,4',4',5,5 ,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (6.7 g, 26.44 mmol), Pd(dppf)Cl ₂ (0.39 g, 0.53 mmol) and KOAc (5.2 g, 52.88 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized using a silica gel column to 2-(4'-(diphenylboraneyl)-[1,1'-biphenyl]-4-yl)-4,4,5,5 -tetramethyl-1,3,2-dioxaborolane (6 g, 76.6 %) was obtained.

2-(4'-(diphenylboraneyl)-[1,1'-biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6 g, 13.5 mmol) in THF After dissolving in , 6-bromobenzo[h]quinoline (3.8 g, 14.86 mmol), Pd(PPh ₃ ) ₄ (0.47 g, 0.41 mmol), K ₂ CO ₃ (5.6 g, 40.72 mmol), and water were added. Stir under reflux at 100 °C for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 5 g of a final product (yield: 74.7%).

( 5) compound 1-5-3

1,3-dibromobenzene (8.1 g, 25.9 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78 °C, n- BuLi (1.3 g, 19.9 mmol) was added dropwise, and stirred for 3 hours. _{Et 2} O in which fluorodiphenylborane (3.7 g, 19.9 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (3-bromophenyl)diphenylborane (6 g, 72.2 %).

(3-bromophenyl)diphenylborane (6 g, 18.7 mmol) was dissolved in DMF in a round bottom flask, and then 4,4,4',4',5,5,5',5'-octamethyl-2,2'- bi(1,3,2-dioxaborolane) (7.12 g, 28.04 mmol), Pd(dppf)Cl ₂ (0.41 g, 0.56 mmol) and KOAc (5.5 g, 56.07 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized on a silica gel column to 2-(3-(diphenylboraneyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.5 g , 79%) was obtained.

(3-bromophenyl)diphenylborane (5.5 g, 17.13 mmol) was dissolved in DMF in a round bottom flask, 1,4-dibromobenzene (4.45 g, 18.85 mmol), Pd(dppf)Cl ₂ (0.59 g, 0.51 mmol) and KOAc (7.1 g, 51.4 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was separated and purified by a silica gel column to obtain (4'-bromo-[1,1'-biphenyl]-3-yl)diphenylborane (5 g, 73.5%).

(4'-bromo-[1,1'-biphenyl]-3-yl)diphenylborane (5 g, 12.59 mmol) was dissolved in DMF in a round bottom flask, 4,4,4',4',5,5 ,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (4.8 g, 18.9 mmol), Pd(dppf)Cl ₂ (0.21 g, 0.38 mmol) and KOAc (3.71 g, 37.77 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized using a silica gel column to 2-(3'-(diphenylboraneyl)-[1,1'-biphenyl]-4-yl)-4,4,5,5 -tetramethyl-1,3,2-dioxaborolane (4 g, 71.5 %) was obtained.

2-(3'-(diphenylboraneyl)-[1,1'-biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4 g, 9.01 mmol) in THF After dissolving in 7-chlorobenzo[4,5]thieno[2,3-b]quinoxaline (3.12 g, 9.91 mmol), Pd(PPh ₃ ) ₄ (0.31 g, 0.27 mmol), K ₂ CO ₃ (3.73 g) , 27.02 mmol) and water, and then stirred under reflux at 100 °C for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 3.5 g of a final product (yield: 70.3%).

(6) compound 1-6-2

3,3'-dibromo-1,1'-biphenyl (8.07 g, 25.9 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere, and after cooling to -78 ° C, n- BuLi (1.3 g, 19.9 mmol) was added. It was added dropwise and stirred for 3 hours. _{Et 2} O in which fluorodiphenylborane (3 g, 19.9 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (3'-bromo-[1,1'-biphenyl]-3-yl)diphenylborane (7 g, 68%). .

(3'-bromo-[1,1'-biphenyl]-3-yl)diphenylborane (7 g, 17.63 mmol) was dissolved in DMF in a round bottom flask, 4,4,4',4',5,5 ,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (6.71 g, 26.44 mmol), Pd(dppf)Cl ₂ (0.39 g, 0.53 mmol) and KOAc (5.2 g, 52.9 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was separated and purified by a silica gel column to 2-(3'-(diphenylboraneyl)-[1,1'-biphenyl]-3-yl)-4,4,5, 5-tetramethyl-1,3,2-dioxaborolane (5.5 g, 70.2 %) was obtained.

2-(3'-(diphenylboraneyl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.5 g, 12.4 mmol) in THF After dissolving in 11-chlorobenzofuro[2,3-b][1,5]naphthyridine (3.47 g, 13.62 mmol), Pd(PPh ₃ ) ₄ (0.43 g, 0.37 mmol), K ₂ CO ₃ (5.13 g, 37.15 mmol), water was added, and the mixture was stirred under reflux at 100 °C for 3 hours. After the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 4.5 g of a final product (yield: 67.7%).

(7) compound 1-9-1

1,3-dibromo-2,4-dimethylbenzene (6.8 g, 25.9 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78 °C, and n- BuLi (1.3 g, 19.9 mmol) was added dropwise. Stirred for 3 hours. _{Et 2} O in which fluorodiphenylborane (3.7 g, 19.9 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (3-bromo-2,6-dimethylphenyl)diphenylborane (7 g, 77.5%).

(3-bromo-2,6-dimethylphenyl)diphenylborane (7 g, 20.05 mmol) was dissolved in DMF in a round-bottom flask, and then 4,4,4',4',5,5,5',5'-octamethyl -2,2'-bi(1,3,2-dioxaborolane) (7.64 g, 30.08 mmol), Pd(dppf)Cl ₂ (0.44 g, 0.6 mmol) and KOAc (5.9 g, 60.16 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized on a silica gel column to 2-(3-(diphenylboraneyl)-2,4-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2 -dioxaborolane (6 g, 75.5 %) was obtained.

After dissolving 2-(3-(diphenylboraneyl)-2,4-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6 g, 15.15 mmol) in a round-bottom flask with DMF, 1,3-dibromobenzene (3.93 g, 16.66 mmol), Pd(dppf)Cl ₂ (0.53 g, 0.45 mmol) and KOAc (6.28 g, 45.44 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was separated and purified by a silica gel column (3'-bromo-2,4-dimethyl-[1,1'-biphenyl]-3-yl)diphenylborane (5 g, 77.6%) was obtained.

(3'-bromo-2,4-dimethyl-[1,1'-biphenyl]-3-yl)diphenylborane (5 g, 11.76 mmol) was dissolved in DMF in a round-bottom flask, 4,4,4', 4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (4.5 g, 17.64 mmol), Pd(dppf)Cl ₂ (0.26 g, 0.35 mmol) and KOAc (3.5 g, 35.3 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized on a silica gel column to 2-(3'-(diphenylboraneyl)-2',4'-dimethyl-[1,1'-biphenyl]-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4 g, 72.03 %) was obtained.

A mixture of thiochromeno[4,3,2-de]quinolin-2(3H)-one (7.5g, 30mmole) and PBr ₅ (13g, 30mmole) was heated at 80°C for 30 minutes and then at 130°C for an additional 1 hour. did. The mixture was then cooled, neutralized with water and NaOH, and filtered. The resulting compound was subjected to silica gel column and recrystallization to obtain 2-bromothiochromeno[4,3,2-de]quinoline (3.4 g, 34%).

2-(3'-(diphenylboraneyl)-2',4'-dimethyl-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( After dissolving 4 g, 8.47 mmol) in THF, 2-bromothiochromeno[4,3,2-de]quinoline (2.93 g, 9.32 mmol), Pd(PPh ₃ ) ₄ (0.29 g, 0.25 mmol), K ₂ CO ₃ (3.51 g, 25.41 mmol), water was added, and the mixture was stirred under reflux at 100 °C for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 3.2 g of a final product (yield: 65.2%).

( 8) compound 1-11-1

After dissolving 2-(4-(diphenylboraneyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6 g, 16.3 mmol) in THF, 6-bromobenzo[j]phenanthridine (5.53 g, 17.93 mmol), Pd(PPh ₃ ) ₄ (0.57 g, 0.49 mmol), K ₂ CO ₃ (6.76 g, 48.9 mmol), and water were added, followed by stirring under reflux at 100° C. for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 5 g of a final product (yield: 65.3%).

(9) compound 2-1-3

1,4-dibromobenzene (10.2 g, 43.3 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78 °C, n- BuLi (2.1 g, 33.31 mmol) was added dropwise, and stirred for 3 hours. _{Et 2} O in which bis(2,6-dimethylphenyl)fluoroborane (8 g, 33.31 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (4-bromophenyl)bis(2,6-dimethylphenyl)borane (12 g, 74.3%).

(4-bromophenyl)bis(2,6-dimethylphenyl)borane (12 g, 31.82 mmol) was dissolved in DMF in a round-bottom flask, and then 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (12.12 g, 47.73 mmol), Pd(dppf)Cl ₂ (0.7 g, 0.95 mmol) and KOAc (9.37 g, 95.46 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 2-(4-(bis(2,6-dimethylphenyl)boraneyl)phenyl)-4,4,5,5-tetramethyl-1, 3,2-dioxaborolane (9 g, 66.7 %) was obtained.

After dissolving 2-(4-(bis(2,6-dimethylphenyl)boraneyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9 g, 21.22 mmol) in THF, 6 -chlorobenzo[4,5]thieno[2,3-c][1,5]naphthyridine (6.32 g, 23.34 mmol), Pd(PPh ₃ ) ₄ (0.74 g, 0.64 mmol), K ₂ CO ₃ (8.8 g) , 63.65 mmol) and water, and then stirred under reflux at 100 °C for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 8 g of a final product (yield: 70.8%).

(10) compound 2-3-1

N,N- Dimethylacetamide to benzo[h]quinoline (3.6g, 20mmole), N- Bromosuccinimide (7.1g, 40mmole), [RuCl ₂ (p-cymene0) ₂ (5 mol%) was added and stirred at 80° C. for 24 hours. After the reaction was completed, the reaction product was cooled to room temperature and extracted with water and EtOAc. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by a silica gel column to obtain 7-bromobenzo[h]quinoline (4.1 g, 79%).

After dissolving 2-(3-(diphenylboraneyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5 g, 13.58 mmol) in THF, 7-bromobenzo[h]quinoline (3.9 g, 14.94 mmol), Pd(PPh ₃ ) ₄ (0.47 g, 0.41 mmol), K ₂ CO ₃ (5.63 g, 40.75 mmol), and water were added, followed by stirring under reflux at 100° C. for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 4 g of a final product (yield: 70.2%).

(11) compound 2-4-2

4,4'-dibromo-1,1'-biphenyl (13.51 g, 43.32 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere, and after cooling to -78 ° C., n- BuLi (2.13 g, 33.32 mmol) was added. It was added dropwise and stirred for 3 hours. _{Et 2} O in which bis(2,6-dimethylphenyl)fluoroborane (8 g, 33.32 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column (4'-bromo-[1,1'-biphenyl]-4-yl)bis(2,6-dimethylphenyl)borane ( 15 g, 76.4%) was obtained.

(4'-bromo-[1,1'-biphenyl]-4-yl)bis(2,6-dimethylphenyl)borane (15 g, 33.1 mmol) was dissolved in DMF in a round-bottom flask, 4,4,4 ',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (12.6g, 49.63mmol), Pd(dppf)Cl ₂ (0.99 g, 0.73 mmol) and KOAc (9.74 g, 99.3 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized using a silica gel column to 2-(4'-(bis(2,6-dimethylphenyl)boraneyl)-[1,1'-biphenyl]-4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (12 g, 72.5%) was obtained.

2-(4'-(bis(2,6-dimethylphenyl)boraneyl)-[1,1'-biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( After dissolving 12 g, 23.99 mmol) in THF, 8-chlorobenzo[4,5]thieno[3,2-c]cinnoline (7.15 g, 26.4 mmol), Pd(PPh ₃ ) ₄ (0.83 g, 0.72 mmol) , K ₂ CO ₃ (9.94 g, 71.96 mmol), and water were added, and the mixture was stirred under reflux at 100 °C for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 10 g of a final product (yield: 68.5%).

(12) compound 2-5-1

1,3-dibromobenzene (10.2 g, 43.32 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78 °C, and n- BuLi (2.1 g, 33.32 mmol) was added dropwise and stirred for 3 hours. _{Et 2} O in which bis(2,6-dimethylphenyl)fluoroborane (8 g, 33.32 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (3-bromophenyl)bis(2,6-dimethylphenyl)borane (12 g, 73.5%).

(3-bromophenyl)bis(2,6-dimethylphenyl)borane (12 g, 31.82 mmol) was dissolved in DMF in a round-bottom flask, and then 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (12.12 g, 47.73 mmol), Pd(dppf)Cl ₂ (0.7 g, 0.95 mmol) and KOAc (9.37 g, 95.5 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 2-(3-(bis(2,6-dimethylphenyl)boraneyl)phenyl)-4,4,5,5-tetramethyl-1, 3,2-dioxaborolane (10 g, 74.1 %) was obtained.

2-(3-(bis(2,6-dimethylphenyl)boraneyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10 g, 23.57 mmol) was dissolved in DMF in a round-bottom flask After dissolving, 1,4-dibromobenzene (6.12 g, 25.93 mmol), Pd(dppf)Cl ₂ (0.82 g, 0.71 mmol) and KOAc (9.77 g, 70.72 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was separated and purified by a silica gel column (4'-bromo-[1,1'-biphenyl]-3-yl)bis(2,6-dimethylphenyl)borane (9 g, 84.2%) was obtained.

(4'-bromo-[1,1'-biphenyl]-3-yl)bis(2,6-dimethylphenyl)borane (9 g, 19.86 mmol) was dissolved in DMF in a round-bottom flask, 4,4,4 ',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (7.56 g, 29.79 mmol), Pd(dppf)Cl ₂ (0.44 g, 0.6 mmol) and KOAc (5.85 g, 59.57 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized using a silica gel column to 2-(3'-(bis(2,6-dimethylphenyl)boraneyl)-[1,1'-biphenyl]-4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7 g, 70.5 %) was obtained.

2-(3'-(bis(2,6-dimethylphenyl)boraneyl)-[1,1'-biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( After dissolving 7 g, 13.99 mmol) in THF, 3-bromobenzo[kl]thioxanthene (4.82 g, 15.4 mmol), Pd(PPh ₃ ) ₄ (0.49 g, 0.42 mmol), K ₂ CO ₃ (5.8 g, 47.97) mmol) and water, and then stirred under reflux at 100 °C for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 5.5 g of a final product (yield: 64.8%).

(13) compound 2-6-3

3,3'-dibromo-1,1'-biphenyl (8 g, 33.33 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere, and after cooling to -78 ° C, n- BuLi (1.6 g, 25.64 mmol) was added. It was added dropwise and stirred for 3 hours. _{Et 2} O in which bis(2,6-dimethylphenyl)fluoroborane (8 g, 25.64 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column (3'-bromo-[1,1'-biphenyl]-3-yl)bis(2,6-dimethylphenyl)borane ( 10 g, 66.2%) was obtained.

(3'-bromo-[1,1'-biphenyl]-3-yl)bis(2,6-dimethylphenyl)borane (10 g, 22.06 mmol) was dissolved in DMF in a round-bottom flask, 4,4,4 ',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (8.4 g, 33.1 mmol), Pd(dppf)Cl ₂ (0.48 g, 0.66 mmol) and KOAc (6.5 g, 66.2 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized on a silica gel column to 2-(3'-(bis(2,6-dimethylphenyl)boraneyl)-[1,1'-biphenyl]-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7 g, 63.4 %) was obtained.

2-(3'-(bis(2,6-dimethylphenyl)boraneyl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( After dissolving 7g, 13.99mmol) in THF, 8-chlorobenzo[4,5]thieno[3,2-c]cinnoline (4.17g, 15.4mmol), Pd(PPh ₃ ) ₄ (0.49g, 0.42mmol), K ₂ CO ₃ (5.8 g, 41.97 mmol) and water were added, and the mixture was stirred under reflux at 100 °C for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 6 g of a final product (yield: 70.5%).

(14) compound 2-7-2

1,4-Dibromobenzene (61 g, 259 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78 °C, and n -BuLi (13 g, 199 mmol) was added dropwise and stirred for 3 hours. _{Et 2} O in which bis(2,6-dimethylphenyl)fluoroborane (48 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (4-bromophenyl)bis(2,6-dimethylphenyl)borane (60 g, 80%).

(4-bromophenyl)bis(2,6-dimethylphenyl)borane (60 g, 159.2 mmol) was dissolved in DMF in a round bottom flask, and then 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (60 g, 238.8 mmol), Pd(dppf)Cl ₂ (3.5 g, 4.8 mmol), KOAc (46.9 g, 477.6 mmol) were added and stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried with MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(4-(bis(2,6-dimethylphenyl)boraneyl)phenyl)-4,4,5,5-tetramethyl-1, 3,2-dioxaborolane (45.2 g, 67%) was obtained.

After dissolving 2-(4-(bis(2,6-dimethylphenyl)boraneyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (45.2 g, 106.7 mmol) in THF, 1 ,3-dibromobenzene (27.7 g, 117.4 mmol), Pd(PPh ₃ ) ₄ (3.7 g, 3.2 mmol), K ₂ CO ₃ (44.2 g, 320.1 mmol), and water were added and refluxed at 100 °C for 3 hours. agitate. When the reaction is complete, the organic layer is extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material is separated and purified by a silicagel column (3'-bromo-[1,1'-biphenyl]-4-yl)bis( 2,6-dimethyl phenyl)borane (31.4 g, 65%) was obtained.

(3'-bromo-[1,1'-biphenyl]-4-yl)bis(2,6-dimethylphenyl)borane (31.4 g, 69.4 mmol) was dissolved in DMF in a round-bottom flask, 4,4,4 ',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (26.4 g, 104.1 mmol), Pd(dppf)Cl ₂ (1.5 g, 2.1 mmol) and KOAc (20.4 g, 208.2 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(4'-(bis(2,6-dimethylphenyl)boraneyl)-[1,1'-biphenyl]-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (21.2 g, 61 %) was obtained.

2-(4'-(bis(2,6-dimethylphenyl)boraneyl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( After dissolving 21.2 g, 42.3 mmol) in THF, 8-chloropyrido[4',3':4,5]furo[3,2-c]quinoline (11.8 g, 46.5 mmol), Pd(PPh ₃ ) ₄ ( 1.5 g, 1.3 mmol), K ₂ CO ₃ (17.5 g, 126.9 mmol), and water were added, and the mixture was stirred under reflux at 100° C. for 3 hours. After completion of the reaction, extraction with EA and water was performed, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 15.5 g of a final compound (yield: 62%).

(15) compound 3-3-1

1,3-Dibromobenzene (61 g, 259 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78°C, and n -BuLi (13 g, 199 mmol) was added dropwise and stirred for 3 hours. _{Et 2} O in which fluorodi-o-tolylborane (42.2 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (3-bromophenyl)di-o-tolylborane (56.3 g, 81%).

(3-bromophenyl)di-o-tolylborane (56.3 g, 161.2 mmol) was dissolved in DMF in a round bottom flask, and then 4,4,4',4',5,5,5',5'-octamethyl-2 ,2'-bi(1,3,2-dioxaborolane) (61.4 g, 241.8 mmol), Pd(dppf)Cl ₂ (3.5 g, 4.8 mmol), and KOAc (47.5 g, 483.6 mmol) were added at 130 °C. It was stirred under reflux for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(3-(di-o-tolylboraneyl)phenyl)-4,4,5,5-tetramethyl-1,3,2- Dioxaborolane (44.1 g, 69%) was obtained.

_{Toluene and PtCl 2} (10 mol %) in which 2-(3-chlorophenyl)-3-ethynylpyridine (42.7 g, 200 mmole) was dissolved in a screw-cap vial under argon were put. After the vial was closed, the mixture was stirred at 110°C for 24 hours. When the reaction was completed, the solvent was removed under reduced pressure, and the resulting compound was purified by a silicagel column to obtain 9-chlorobenzo[h]quinoline (26.1 g, 61%).

After dissolving 2-(3-(di-o-tolylboraneyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (44.1 g, 111.2 mmol) in THF, 9-chlorobenzo[h ] After adding quinoline (26.1 g, 122.3 mmol), Pd(PPh ₃ ) ₄ (3.9 g, 3.3 mmol), K ₂ CO ₃ (46.1 g, 333.6 mmol), and water, the mixture was stirred under reflux at 100° C. for 3 hours. . When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 29.8 g (yield: 60%) of the final compound.

(16) compound 3-9-1

1,3-dibromo-2,4-dimethylbenzene (68.4 g, 259 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78 °C, and n- BuLi (13 g, 199 mmol) was added dropwise. Stirred for 3 hours. _{Et 2} O in which fluorodi-o-tolylborane (42.2 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (3-bromo-2,6-dimethylphenyl)di-o-tolylborane (59.3 g, 79%).

(3-bromo-2,6-dimethylphenyl)di-o-tolylborane (59.3 g, 157.2 mmol) was dissolved in DMF in a round-bottom flask, 4,4,4',4',5,5,5', 5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (59.9 g, 235.8 mmol), Pd(dppf)Cl ₂ (3.5 g, 4.7 mmol), KOAc (46.3 g, 471.6 mmol) was added and stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(3-(di-o-tolylboraneyl)-2,4-dimethylphenyl)-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane (44.7 g, 67 %) was obtained.

After dissolving 2-(3-(di-o-tolylboraneyl)-2,4-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (44.7 g, 105.3 mmol) in THF, 1,3-dibromobenzene (27.3 g, 115.8 mmol), Pd(PPh ₃ ) ₄ (3.7 g, 3.2 mmol), K ₂ CO ₃ (43.7 g, 315.9 mmol), and water were added and then water was added at 100° C. for 3 hours. reflux and stir. After completion of the reaction, extraction with EA and water, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was separated and purified by silicagel column (3'-bromo-2,4-dimethyl-[1,1'-biphenyl]- 3-yl)di-o-tolylborane (32.9 g, 69%) was obtained.

((3'-bromo-2,4-dimethyl-[1,1'-biphenyl]-3-yl)di-o-tolylborane (32.9 g, 72.7 mmol) was dissolved in DMF in a round-bottom flask, 4, 4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (27.7 g, 109.1 mmol), Pd(dppf)Cl ₂ ( 1.6 g, 2.2 mmol) and KOAc (21.4 g, 218.1 mmol) were added, and the mixture was stirred under reflux for 4 hours at 130° C. When the reaction was completed, DMF was removed through distillation, and the mixture was extracted with _{CH 2} Cl _{2 and water.} After drying and concentration with MgSO ₄ , the resulting compound was recrystallized by silicagel column to 2-(3'-(di-o-tolylboraneyl)-2',4'-dimethyl-[1,1'-biphenyl]-3- yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (24.7 g, 68%) was obtained.

A mixture of thiochromeno[4,3,2-de]quinolin-2(3H)-one (7.5g, 30mmole) and PBr ₅ (13g, 30mmole) was heated at 80°C for 30 minutes and then at 130°C for an additional 1 hour. did. The mixture was then cooled, neutralized with water and NaOH, and filtered. The resulting compound was subjected to silica gel column and recrystallization to obtain 2-bromothiochromeno[4,3,2-de]quinoline (3.4 g, 34%).

2-(3'-(di-o-tolylboraneyl)-2',4'-dimethyl-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3, After dissolving 2-dioxaborolane (24.7 g, 49.4 mmol) in THF, 2-bromothiochromeno[4,3,2-de]quinoline (17.1 g, 54.3 mmol), Pd(PPh ₃ ) ₄ (1.7 g, 1.5 mmol) , K ₂ CO ₃ (20.5 g, 148.2 mmol) and water were added, and the mixture was stirred under reflux at 100° C. for 3 hours. After completion of the reaction, extraction with EA and water was performed, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 18.3 g of a final compound (yield: 61%).

(17) compound 3-10-3

2,5-dibromo-1,3-dimethylbenzene (68.4 g, 259 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78°C, and n- BuLi (13 g, 199 mmol) was added dropwise. Stirred for 3 hours. _{Et 2} O in which fluorodi-o-tolylborane (42.2 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (4-bromo-2,6-dimethylphenyl)di-o-tolylborane (78.1 g, 80%).

(4-bromo-2,6-dimethylphenyl)di-o-tolylborane (78.1 g, 207.2 mmol) was dissolved in DMF in a round bottom flask, 4,4,4',4',5,5,5', 5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (78.9 g, 310.8 mmol), Pd(dppf)Cl ₂ (4.5 g, 6.2 mmol), KOAc (61.0 g, 621.6 mmol) was added and stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(4-(di-o-tolylboraneyl)-3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane (58.0 g, 66%) was obtained.

After dissolving 2-(4-(di-o-tolylboraneyl)-3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (58.0 g, 136.8 mmol) in THF, 1,3-dibromobenzene (35.5 g, 150.5 mmol), Pd(PPh ₃ ) ₄ (4.7 g, 4.1 mmol), K ₂ CO ₃ (56.7 g, 410.4 mmol), and water were added and then water was added at 100 °C for 3 hours. reflux and stir. After completion of the reaction, extraction with EA and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was separated and purified by silicagel column (3'-bromo-3,5-dimethyl-[1,1'-biphenyl]- 4-yl)di-o-tolylborane (43.4 g, 70%) was obtained.

(3'-bromo-3,5-dimethyl-[1,1'-biphenyl]-4-yl)di-o-tolylborane (43.4 g, 95.8 mmol) was dissolved in DMF in a round-bottom flask, 4,4 ,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (36.5 g, 143.7 mmol), Pd(dppf)Cl ₂ (2.1 g, 2.9 mmol) and KOAc (28.2 g, 287.4 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(4'-(di-o-tolylboraneyl)-3',5'-dimethyl-[1,1'-biphenyl]- 3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (30.2 g, 63%) was obtained.

2-(4'-(di-o-tolylboraneyl)-3',5'-dimethyl-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3, After dissolving 2-dioxaborolane (30.2 g, 60.4 mmol) in THF, 8-chloropyrido[4',3':4,5]furo[3,2-c]quinoline (16.9 g, 66.4 mmol), Pd(PPh) ₃ ) ₄ (2.1 g, 1.8 mmol), K ₂ CO ₃ (25.0 g, 181.2 mmol), and water were added, and the mixture was stirred under reflux at 100° C. for 3 hours. After completion of the reaction, extraction with EA and water was performed, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 24.3 g of a final compound (yield: 68%).

(18) compound 4-2-3

2,5-dibromo-1,3-dimethylbenzene (68.4 g, 259 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78°C, and n- BuLi (13 g, 199 mmol) was added dropwise. Stirred for 3 hours. _{Et 2} O in which fluorodimesitylborane (53.4 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (4-bromo-2,6-dimethylphenyl)dimesitylborane (93.1 g, 83%).

(4-bromo-2,6-dimethylphenyl)dimesitylborane (93.1 g, 215.0 mmol) was dissolved in DMF in a round-bottom flask, and then 4,4,4',4',5,5,5',5'-octamethyl -2,2'-bi(1,3,2-dioxaborolane) (81.9 g, 322.5 mmol), Pd(dppf)Cl ₂ (4.7 g, 6.5 mmol), KOAc (63.3 g, 645.0 mmol) were added 130 It was stirred under reflux at ℃ for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(4-(dimesitylboraneyl)-3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2 -dioxaborolane (62.0 g, 60%) was obtained.

3-Chlorobenzo[b]thiophene-2-carbonyl chloride (15.2g, 65.8mmol) and pyridin-3-amine (6.2g, 65.8mmol) were dissolved in benzene, and triethylamine (9.4ml, 67.8mmol) was added thereto for 1 hour. Stir under reflux. After completion of the reaction, benzene was removed under reduced pressure, extracted with MC and water, dried over MgSO4, concentrated, and the resulting organic material was recrystallized from ethanol to produce 3-chloro-N-(pyridin-3-yl)benzo[b]thiophene- 15.2 g of 2-carboxamide (yield: 80%) was obtained.

3-chloro-N-(pyridin-3-yl)benzo[b]thiophene-2-carboxamide (12.9g, 44.6mmol) was dissolved in benzene, stirred, and triethylamine (4.7g, 4.64mmol) was added dropwise, followed by 450watt A high-pressure mercury lamp is irradiated for 10 hours. When the reaction is complete, benzene is removed by distillation under reduced pressure, and the solid is washed several times with water and dried to 9.4 g of benzo[4,5]thieno[2,3-c][1,7]naphthyridin-6(5H)-one (Yield: 83%) was obtained.

Phosphorus oxychloride was added to benzo[4,5]thieno[2,3-c][1,7]naphthyridin-6(5H)-one (10.0g, 39.6mmol) and stirred under reflux for 4 hours. When the reaction is complete, distillation under reduced pressure removes Phosphorus oxychloride, and after adding ice water, the mixture is stirred. Ammonium hydroxide is added dropwise to basify to pH 9. The resulting brown solid was filtered, washed several times with water, and recrystallized from benzene to obtain 7.8 g (yield: 73%) of 6-chlorobenzo[4,5]thieno[2,3-c][1,7]naphthyridine.

After dissolving 2-(4-(dimesitylboraneyl)-3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (62.0 g, 129 mmol) in THF, 6-chlorobenzo[ 4,5]thieno[2,3-c][1,7]naphthyridine (38.4 g, 141.9 mmol), Pd(PPh ₃ ) ₄ (4.5 g, 3.9 mmol), K ₂ CO ₃ (53.5 g, 387.0 mmol) ), water was added, and the mixture was stirred under reflux at 100 °C for 3 hours. After completion of the reaction, extraction with EA and water was performed, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 53.9 g of a final compound (yield: 71%).

(19) compound 4-8-2

2,5-dibromo-1,3-dimethylbenzene (68.4 g, 259 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78°C, and n- BuLi (13 g, 199 mmol) was added dropwise. Stirred for 3 hours. _{Et 2} O in which fluorodimesitylborane (53.4 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (4-bromo-2,6-dimethylphenyl)dimesitylborane (69.0 g, 80%).

(4-bromo-2,6-dimethylphenyl)dimesitylborane (69.0 g, 159.2 mmol) was dissolved in DMF in a round-bottom flask, and then 4,4,4',4',5,5,5',5'-octamethyl -2,2'-bi(1,3,2-dioxaborolane) (60.6 g, 238.8 mmol), Pd(dppf)Cl ₂ (3.5 g, 4.8 mmol), KOAc (46.9 g, 477.6 mmol) were added 130 It was stirred under reflux at ℃ for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(4-(dimesitylboraneyl)-3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2 -dioxaborolane (57.3 g, 75%) was obtained.

After dissolving 2-(4-(dimesitylboraneyl)-3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (57.3 g, 119.4 mmol) in THF, 1,4- After addition of dibromobenzene (31.0 g, 131.3 mmol), Pd(PPh ₃ ) ₄ (4.1 g, 3.6 mmol), K ₂ CO ₃ (49.5 g, 358.2 mmol), and water, the mixture was stirred under reflux at 100° C. for 3 hours. When the reaction is complete, the organic layer is extracted with EA and water, dried over MgSO ₄ and concentrated, and the resulting organic material is separated and purified by silicagel column (4'-bromo-3,5-dimethyl-[1,1'-biphenyl]- 4-yl) dimesitylborane (43.8 g, 72%) was obtained.

(4'-bromo-3,5-dimethyl-[1,1'-biphenyl]-4-yl)dimesitylborane (43.8g, 86.0 mmol) was dissolved in DMF in a round-bottom flask, 4,4,4', 4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (32.8 g, 129.0 mmol), Pd(dppf)Cl ₂ (1.9 g, 2.6 mmol) ), KOAc (25.3 g, 258.0 mmol) was added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column to 2-(4'-(dimesitylboraneyl)-3',5'-dimethyl-[1,1'-biphenyl]-4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (30.1 g, 63%) was obtained.

2-(4'-(dimesitylboraneyl)-3',5'-dimethyl-[1,1'-biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane ( After dissolving 30.1 g, 54.2 mmol) in THF, 11-chlorobenzofuro[2,3-b][1,5]naphthyridine (15.2 g, 59.6 mmol), Pd(PPh ₃ ) ₄ (1.9 g, 1.6 mmol), After adding K ₂ CO ₃ (22.5 g, 162.6 mmol) and water, the mixture was stirred under reflux at 100° C. for 3 hours. After completion of the reaction, extraction with EA and water was performed, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 25.3 g of a final compound (yield: 72%).

(20) compound 4-11-1

4,4'-dibromo-1,1'-biphenyl (80.8 g, 259 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere, and after cooling to -78 ° C, n- BuLi (13 g, 199 mmol) was added. It was added dropwise and stirred for 3 hours. _{Et 2} O in which fluorodimesitylborane (53.4 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain (4'-bromo-[1,1'-biphenyl]-4-yl)dimesitylborane (92.2 g, 74%). .

(4'-bromo-[1,1'-biphenyl]-4-yl)dimesitylborane (92.2 g, 191.7 mmol) was dissolved in DMF in a round bottom flask, 4,4,4',4',5,5 ,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (73.0 g, 287.6 mmol), Pd(dppf)Cl ₂ (4.2 g, 5.8 mmol), KOAc (56.4 g , 575.1 mmol) was added and stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(4'-(dimesitylboraneyl)-[1,1'-biphenyl]-4-yl)-4,4,5,5 -tetramethyl-1,3,2-dioxaborolane (76.0 g, 75%) was obtained.

2-(4'-(dimesitylboraneyl)-[1,1'-biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (76.0 g, 143.8 mmol) in THF After dissolving in , 5-bromobenzo[i]phenanthridine (48.7 g, 158.2 mmol), Pd(PPh ₃ ) ₄ (5.0 g, 4.3 mmol), K ₂ CO ₃ (59.6 g, 431.4 mmol), and water were added. Stir under reflux at 100 °C for 3 hours. After completion of the reaction, extraction with EA and water was performed, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 69.7 g of a final compound (yield: 77%).

(21) compound 4-11-3

3-Chlorobenzo[b]thiophene-2-carbonyl chloride (15.2g, 65.8mmol) and pyridin-3-amine (6.2g, 65.8mmol) were dissolved in benzene, and triethylamine (9.4ml, 67.8mmol) was added thereto for 1 hour. Stir under reflux. After completion of the reaction, benzene was removed under reduced pressure, extracted with MC and water, dried over MgSO4, concentrated, and the resulting organic material was recrystallized from ethanol to produce 3-chloro-N-(pyridin-3-yl)benzo[b]thiophene- 15.2 g of 2-carboxamide (yield: 80%) was obtained.

3-chloro-N-(pyridin-3-yl)benzo[b]thiophene-2-carboxamide (12.9g, 44.6mmol) was dissolved in benzene, stirred, and triethylamine (4.7g, 4.64mmol) was added dropwise, followed by 450watt A high-pressure mercury lamp is irradiated for 10 hours. When the reaction is complete, benzene is removed by distillation under reduced pressure, and the solid is washed several times with water and dried to 9.4 g of benzo[4,5]thieno[2,3-c][1,7]naphthyridin-6(5H)-one (Yield: 83%) was obtained.

Phosphorus oxychloride was added to benzo[4,5]thieno[2,3-c][1,7]naphthyridin-6(5H)-one (10.0g, 39.6mmol) and stirred under reflux for 4 hours. When the reaction is complete, distillation under reduced pressure removes Phosphorus oxychloride, and after adding ice water, the mixture is stirred. Ammonium hydroxide is added dropwise to basify to pH 9. The resulting brown solid was filtered, washed several times with water, and recrystallized from benzene to obtain 7.8 g (yield: 73%) of 6-chlorobenzo[4,5]thieno[2,3-c][1,7]naphthyridine.

2-(4'-(dimesitylboraneyl)-[1,1'-biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (76.0 g, 143.8 mmol) in THF After dissolving in 6-chlorobenzo [4,5]thieno[2,3-c][1,7]naphthyridine (42.8 g, 158.2 mmol), Pd(PPh ₃ ) ₄ (5.0 g, 4.3 mmol), K ₂ After adding CO ₃ (59.6 g, 431.4 mmol) and water, the mixture was stirred under reflux at 100° C. for 3 hours. After completion of the reaction, extraction with EA and water was performed, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 62.3 g of a final compound (yield: 68%).

(22) compound 5-1-4

1,4-dibromobenzene (61.1 g, 259 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78 °C, and n- BuLi (13 g, 199 mmol) was added dropwise and stirred for 3 hours. _{Et 2} O in which di([1,1'-biphenyl]-4-yl)fluoroborane (66.9 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to obtain di([1,1'-biphenyl]-4-yl)(4-bromophenyl)borane (78.4 g, 64 %). got it

After dissolving di([1,1'-biphenyl]-4-yl)(4-bromophenyl)borane (78.4 g, 165.8 mmol) with DMF in a round-bottom flask, 4,4,4',4',5, 5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (63.2 g, 248.7 mmol), Pd(dppf)Cl ₂ (3.6 g, 5.0 mmol), KOAc (48.8) g, 497.4 mmol) was added and stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(4-(di([1,1'-biphenyl]-4-yl)boraneyl)phenyl)-4,4,5 ,5-tetramethyl-1,3,2-dioxaborolane (54.3 g, 63 %) was obtained.

Dissolve 2,3-dichloroquinoxaline (5.1g, 25.6mmol, 1.0 eq) and 6-bromonaphthalen-2-ol (5.7g, 25.6mmol, 1 eq) in 1,2-dichloroethane, add AlCl3 (1.0 eq), and 80 ^The mixture was stirred under reflux at o C for 30 minutes, cooled to room temperature, and again AlCl3 (1.0 eq) was added, followed by ^{stirring under reflux at 80 o} C for 30 minutes. After extraction with MC and water, the mixture was concentrated, and the resulting organic material was recrystallized using a silica gel column to obtain 7.2 g of 3-bromonaphtho[1',2':4,5]furo[2,3-b]quinoxaline (yield: 81%). .

2-(4-(di([1,1'-biphenyl]-4-yl)boraneyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (54.3 g, 104.5 mmol) After dissolving in THF, 3-chloronaphtho[1',2':4,5]furo[2,3-b]quinoxaline (35.0 g, 115.0 mmol), Pd(PPh ₃ ) ₄ (3.6 g, 3.1 mmol) , K ₂ CO ₃ (43.3 g, 313.5 mmol) and water were added, and the mixture was stirred under reflux at 100° C. for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 46.4 g of a final compound (yield: 67%).

(23) compound 5-2-1

2,5-dibromo-1,3-dimethylbenzene (68.4 g, 259 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78°C, and n- BuLi (13 g, 199 mmol) was added dropwise. Stirred for 3 hours. _{Et 2} O in which di([1,1'-biphenyl]-4-yl)fluoroborane (66.9 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to di([1,1'-biphenyl]-4-yl)(4-bromo-2,6-dimethylphenyl)borane (62.8). g, 63%) was obtained.

After dissolving di([1,1'-biphenyl]-4-yl)(4-bromo-2,6-dimethylphenyl)borane (62.8 g, 125.4 mmol) in a round-bottom flask with DMF, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (47.8 g, 188.1 mmol), Pd(dppf)Cl ₂ (2.8 g, 3.8 mmol) and KOAc (36.9 g, 376.2 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(4-(di([1,1'-biphenyl]-4-yl)boraneyl)-3,5-dimethylphenyl)- 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (42.6 g, 62%) was obtained.

2-(4-(di([1,1'-biphenyl]-4-yl)boraneyl)-3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (42.6 g, 77.7 mmol) in THF, 3-bromophenanthridine (22.1 g, 85.5 mmol), Pd(PPh ₃ ) ₄ (2.7 g, 2.3 mmol), K ₂ CO ₃ (32.2 g, 233.1 mmol), and water After addition, the mixture was stirred under reflux at 100 °C for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 34.9 g (yield: 75%) of the final compound.

(24) compound 5-4-3

4,4'-dibromo-1,1'-biphenyl (80.8g, 259mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78°C, and n- BuLi (13g, 199mmol) was added dropwise to 3 stirred for hours. _{Et 2} O in which di([1,1'-biphenyl]-4-yl)fluoroborane (66.9 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to di([1,1'-biphenyl]-4-yl)(4'-bromo-[1,1'-biphenyl] -4-yl)borane (89.6 g, 63 %) was obtained.

di([1,1'-biphenyl]-4-yl)(4'-bromo-[1,1'-biphenyl]-4-yl)borane (89.6 g, 163.2 mmol) was dissolved in DMF in a round bottom flask Later, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (62.2 g, 244.8 mmol), Pd (dppf )Cl ₂ (3.6 g, 4.9 mmol) and KOAc (48.0 g, 489.6 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(4'-(di([1,1'-biphenyl]-4-yl)boraneyl)-[1,1'- biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (67.2 g, 69%) was obtained.

2-(4'-(di([1,1'-biphenyl]-4-yl)boraneyl)-[1,1'-biphenyl]-4-yl)-4,4,5,5-tetramethyl-1 After dissolving ,3,2-dioxaborolane (67.2 g, 112.6 mmol) in THF, 4-chloropyrido[2',3':4,5]thieno[2,3-b]quinoxaline (33.7 g, 123.9 mmol), After adding Pd(PPh ₃ ) ₄ (3.9 g, 3.4 mmol), K ₂ CO ₃ (46.7 g, 337.8 mmol), and water, the mixture was stirred under reflux at 100° C. for 3 hours. After completion of the reaction, extraction with EA and water was performed, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 60.4 g of a final compound (yield: 76%).

(25) compound 5-8-3

2,5-dibromo-1,3-dimethylbenzene (68.4 g, 259 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78°C, and n- BuLi (13 g, 199 mmol) was added dropwise. Stirred for 3 hours. _{Et 2} O in which di([1,1'-biphenyl]-4-yl)fluoroborane (66.9 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column to di([1,1'-biphenyl]-4-yl)(4-bromo-2,6-dimethylphenyl)borane (79.8). g, 80%) was obtained.

After dissolving di([1,1'-biphenyl]-4-yl)(4-bromo-2,6-dimethylphenyl)borane (79.8 g, 159.2 mmol) in DMF in a round bottom flask, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (60.6 g, 238.8 mmol), Pd(dppf)Cl ₂ (3.5 g, 4.8 mmol) and KOAc (46.9 g, 477.6 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(4-(di([1,1'-biphenyl]-4-yl)boraneyl)-3,5-dimethylphenyl)- 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (61.1 g, 70%) was obtained.

2-(4-(di([1,1'-biphenyl]-4-yl)boraneyl)-3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (61.1 g, 111.4 mmol) in THF, 1,4-dibromobenzene (28.9 g, 122.5 mmol), Pd(PPh ₃ ) ₄ (3.9 g, 3.3 mmol), K ₂ CO ₃ (46.2 g, 334.2 mmol), After adding water, the mixture was stirred under reflux at 100 °C for 3 hours. After completion of the reaction, extraction with EA and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was separated and purified by a silicagel column to di([1,1'-biphenyl]-4-yl)(4'-bromo- 3,5-dimethyl-[1,1'-biphenyl]-4-yl)borane (43.7 g, 68 %) was obtained.

di([1,1'-biphenyl]-4-yl)(4'-bromo-3,5-dimethyl-[1,1'-biphenyl]-4-yl)borane (43.7 g, 75.8 mmol) After dissolving in DMF in a bottom flask, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (28.9 g, 113.7 mmol), Pd(dppf)Cl ₂ (1.7 g, 2.3 mmol), and KOAc (22.3 g, 227.4 mmol) were added and the mixture was stirred under reflux at 130° C. for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column to 2-(4'-(di([1,1'-biphenyl]-4-yl)boraneyl)-3',5'- dimethyl-[1,1'-biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (27.9 g, 59 %) was obtained.

Ethyl 3-aminopicolinate (100 g, 602 mmole) and o-methoxyphenylacetylchloride (180 g, 974.6 mmole) were dissolved in pyridine and stirred under reflux for 30 minutes. When the reaction is complete, it is cooled to room temperature, and then extracted with water and chloroform. The resulting orange layer was washed with water and dried over _{MgSO 4 .} After concentration of the dried compound, silica gel column and recrystallization were performed to obtain ethyl 3-(2-(2-methoxyphenyl) acetamido) picolinate (142 g, 75%).

Ethyl 3-(2-(2-methoxyphenyl)acetamido)picolinate (140 g, 462.2 mmole) and sodium ethoxide (anhydrous ethanol and 30 g of Na metal) were dissolved in benzene and stirred under reflux for 5 hours. After the reaction is completed, it is cooled to room temperature, and neutralized by adding water and acetic acid. The precipitate was recrystallized from acetic acid and ethanol to obtain colorless 4-hydroxy-3-(2-methoxyphenyl)-1,5-naphthyridin-2(1H)-one (87.2 g, 73%).

Excess phosphoryl chloride was added to 4-hydroxy-3-(2-methoxyphenyl)-1,5-naphthyridin-2(1H)-one (80 g, 280 mmole) and stirred under reflux for 6 hours. When the reaction is complete, after cooling, water and ammonia are added, and then extracted with chloroform. The organic layer was washed with brine, _{dried over MgSO 4} and concentrated. The obtained compound was purified by silica gel column to obtain 2,4-dichloro-3-(2-methoxyphenyl)-1,5-naphthyridine (72 g, 79%).

2,4-dichloro-3-(2-methoxyphenyl)-1,5-naphthyridine (70 g, 229.37 mmole) was dissolved in anhydrous dichloromethane, cooled to -78 °C with stirring, and excess boron tribromide dissolved in dichloromethane was slowly added dropwise. do. After the mixture was stirred at room temperature for 2 hours, water was added and the mixture was extracted with ethyl acetate. The organic layer is dried over MgSO ₄ and concentrated. After dissolving the resulting compound in acetone, add K2CO3 and stir under reflux at 60-70 °C for 3-4 hours. When the reaction is complete, the solvent is removed and extracted with water and chloroform. The resulting orange layer _{was dried over MgSO 4} and concentrated, and the resulting compound was purified by silicagel column to obtain 11-chlorobenzofuro[2,3-b][1,5]naphthyridine (39.2 g, 93%).

2-(4'-(di([1,1'-biphenyl]-4-yl)boraneyl)-3',5'-dimethyl-[1,1'-biphenyl]-4-yl)-4,4 After dissolving ,5,5-tetramethyl-1,3,2-dioxaborolane (27.9 g, 44.7 mmol) in THF, 11-chlorobenzofuro[2,3-b][1,5]naphthyridine (12.5 g, 49.2 mmol) , Pd(PPh ₃ ) ₄ (1.5 g, 1.3 mmol), K ₂ CO ₃ (18.5 g, 134.1 mmol), and water were added, followed by stirring under reflux at 100° C. for 3 hours. When the reaction was completed, the organic layer was extracted with EA and water, dried over MgSO ₄ , concentrated, and the resulting organic material was separated and purified by silicagel column to obtain 23.4 g (yield: 73%) of the final compound.

(26) compound 6-2-3

2,5-dibromo-1,3-dimethylbenzene (68.4 g, 259 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere , cooled to -78°C, and n- BuLi (13 g, 199 mmol) was added dropwise. Stirred for 3 hours. _{Et 2} O in which bis(3,5-dimethyl-[1,1'-biphenyl]-4-yl)fluoroborane (78.1 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column (4-bromo-2,6-dimethylphenyl)bis(3,5-dimethyl-[1,1'-biphenyl]-4 -yl)borane (98.2 g, 68%) was obtained.

(4-bromo-2,6-dimethylphenyl)bis(3,5-dimethyl-[1,1'-biphenyl]-4-yl)borane (98.2 g, 176.1 mmol) was dissolved in DMF in a round bottom flask, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (67.1 g, 264.2 mmol), Pd(dppf)Cl ₂ (3.9 g, 5.3 mmol) and KOAc (51.8 g, 528.3 mmol) were added, and the mixture was stirred under reflux at 130 °C for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column to 2-(4-(bis(3,5-dimethyl-[1,1'-biphenyl]-4-yl)boraneyl)-3 ,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (71.3 g, 67 %) was obtained.

3-Chlorobenzo[b]thiophene-2-carbonyl chloride (15.2g, 65.8mmol) and pyridin-3-amine (6.2g, 65.8mmol) were dissolved in benzene, and triethylamine (9.4ml, 67.8mmol) was added thereto for 1 hour. Stir under reflux. After completion of the reaction, benzene was removed under reduced pressure, extracted with MC and water, dried over MgSO4, concentrated, and the resulting organic material was recrystallized from ethanol to produce 3-chloro-N-(pyridin-3-yl)benzo[b]thiophene- 15.2 g of 2-carboxamide (yield: 80%) was obtained.

3-chloro-N-(pyridin-3-yl)benzo[b]thiophene-2-carboxamide (12.9g, 44.6mmol) was dissolved in benzene, stirred, and triethylamine (4.7g, 4.64mmol) was added dropwise, followed by 450watt A high-pressure mercury lamp is irradiated for 10 hours. When the reaction is complete, benzene is removed by distillation under reduced pressure, and the solid is washed several times with water and dried to 9.4 g of benzo[4,5]thieno[2,3-c][1,7]naphthyridin-6(5H)-one (Yield: 83%) was obtained.

Phosphorus oxychloride was added to benzo[4,5]thieno[2,3-c][1,7]naphthyridin-6(5H)-one (10.0g, 39.6mmol) and stirred under reflux for 4 hours. When the reaction is complete, distillation under reduced pressure removes Phosphorus oxychloride, and after adding ice water, the mixture is stirred. Ammonium hydroxide is added dropwise to basify to pH 9. The resulting brown solid was filtered, washed several times with water, and recrystallized from benzene to obtain 7.8 g (yield: 73%) of 6-chlorobenzo[4,5]thieno[2,3-c][1,7]naphthyridine.

2-(4-(bis(3,5-dimethyl-[1,1'-biphenyl]-4-yl)boraneyl)-3,5-dimethylphenyl)-4,4,5,5-tetramethyl-1,3 After dissolving ,2-dioxaborolane (71.3 g, 118.0 mmol) in THF, 6-chlorobenzo[4,5]thieno[2,3-c][1,7]naphthyridine (35.1 g, 129.8 mmol), Pd(PPh) ₃ ) ₄ (4.1 g, 3.5 mmol), K ₂ CO ₃ (48.9 g, 354.0 mmol), and water were added, and the mixture was stirred under reflux at 100° C. for 3 hours. After completion of the reaction, extraction with EA and water was performed, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 60.6 g of a final compound (yield: 72%).

(27) compound 6-4-1

4,4'-dibromo-1,1'-biphenyl (80.8 g, 259 mmol) was added _{to degassed Et 2} O under a nitrogen atmosphere, and after cooling to -78 ° C, n- BuLi (13 g, 199 mmol) was added. It was added dropwise and stirred for 3 hours. _{Et 2} O in which bis(3,5-dimethyl-[1,1'-biphenyl]-4-yl)fluoroborane (78.1 g, 199 mmol) was dissolved was added dropwise to the mixture and stirred at room temperature overnight. After the reaction, Et ₂ O is additionally added, and the _{compound is extracted with a saturated NH 4} Cl aqueous solution and water. The organic layer was dried over Na ₂ SO ₄ and concentrated, and the resulting compound was purified by silicagel column (4'-bromo-[1,1'-biphenyl]-4-yl)bis(3,5-dimethyl-[1). ,1'-biphenyl]-4-yl)borane (105.1 g, 67 %) was obtained.

(4'-bromo-[1,1'-biphenyl]-4-yl)bis(3,5-dimethyl-[1,1'-biphenyl]-4-yl)borane (105.1 g, 173.5 mmol) After dissolving in DMF in a bottom flask, 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (66.1 g, 260.3) mmol), Pd(dppf)Cl ₂ (3.8 g, 5.2 mmol), and KOAc (51.1 g, 520.5 mmol) were added and the mixture was stirred under reflux at 130° C. for 4 hours. When the reaction was completed, DMF was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column and 2-(4'-(bis(3,5-dimethyl-[1,1'-biphenyl]-4-yl)boraneyl)- [1,1'-biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (74.7 g, 66 %) was obtained.

2-(4'-(bis(3,5-dimethyl-[1,1'-biphenyl]-4-yl)boraneyl)-[1,1'-biphenyl]-4-yl)-4,4,5 After dissolving ,5-tetramethyl-1,3,2-dioxaborolane (74.7 g, 114.5 mmol) in THF, 6-bromobenzo[h]quinoline (32.5 g, 126.0 mmol), Pd(PPh ₃ ) ₄ (4.0 g, 3.4 mmol), K ₂ CO ₃ (47.5 g, 343.5 mmol), and water were added and the mixture was stirred under reflux at 100° C. for 3 hours. After completion of the reaction, extraction with EA and water was performed, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was separated and purified by a silicagel column to obtain 54.0 g of a final compound (yield: 67%).

Other compounds can be synthesized in the same manner.

[abandonment electric field light emitting element production example ]

Example 1-18 (blue organic electric field light emitting device to the electron transport layer Application example )

A corning 15Ω/cm 2 (1200 Å) ITO glass substrate was placed in distilled water in which a dispersant was dissolved and washed with ultrasonic waves. The detergent used was a product of Fischer Co., and the distilled water was manufactured by Millipore Co. Secondary filtered distilled water was used as a filter of the product. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.

A hole injection layer having a thickness of 60 nm was formed by vacuum deposition of 2-TNATA on the ITO anode layer, and 4,4'-bis[N-(1-naphthyl)-N-phenylamino] ratio was formed on the hole injection layer. Phenyl (hereinafter, NPB) was vacuum-deposited to form a 30 nm-thick hole transport layer.

On the hole transport layer, ADN as a host and 4,4'-bis[2-(4-(N,N-diphenylamino)phenyl)vinyl]biphenyl) as a dopant were co-deposited at a weight ratio of 98:2 to a thickness of 30 nm. of the light emitting layer was formed.

After vacuum deposition of one of the compounds of Formula 1 on the light emitting layer to form an electron transport layer with a thickness of 30 nm, vacuum deposition of LiF on the electron transport layer to form an electron injection layer with a thickness of 1 nm, and then the electron transport layer By vacuum-depositing Al on the injection layer to form a 300 nm-thick cathode, an organic electroluminescent device was manufactured.

comparative example One

An organic electroluminescent device was prepared in the same manner as in Experimental Example except that ET1 below was used instead of the compound represented by Formula 1 of the present invention as the electron transport layer material.

<ET1> Alq ₃

As can be seen from the measurement results in Table 2, the blue organic electroluminescent device (OLED) using the compounds of the present invention is used as an electron transport layer material and exhibits lower driving voltage and higher efficiency than ET1, which is _{Alq 3 , which has been widely used in the past.} It was.

Examples 19 to 26 (Example of application to electron transport auxiliary layer of blue organic electroluminescent device)

A corning 15Ω/cm 2 (1200 Å) ITO glass substrate was placed in distilled water in which a dispersant was dissolved and washed with ultrasonic waves. The detergent used was a product of Fischer Co., and the distilled water was manufactured by Millipore Co. Secondary filtered distilled water was used as a filter of the product. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.

A hole injection layer having a thickness of 60 nm was formed by vacuum deposition of 2-TNATA on the ITO anode layer, and 4,4'-bis[N-(1-naphthyl)-N-phenylamino] ratio was formed on the hole injection layer. Phenyl (hereinafter, NPB) was vacuum-deposited to form a 30 nm-thick hole transport layer.

On the hole transport layer, ADN as a host and 4,4'-bis[2-(4-(N,N-diphenylamino)phenyl)vinyl]biphenyl) as a dopant were co-deposited at a weight ratio of 98:2 to a thickness of 30 nm. of the light emitting layer was formed.

After vacuum deposition of one of the compounds of Formula 1 on the light emitting layer to form an electron transport auxiliary layer with a thickness of 5 nm, Alq ₃ was vacuum deposited on the electron transport auxiliary layer to form an electron transport layer with a thickness of 25 nm . On that, LiF was vacuum deposited to form an electron injection layer with a thickness of 1 nm, and then Al was vacuum deposited on the electron injection layer to form a 300 nm thick cathode, thereby manufacturing an organic electroluminescent device.

Comparative Example 2

An organic electroluminescent device was manufactured in the same manner as in the above example, except that the electron transport auxiliary layer was not included and Alq _{3 was deposited to a thickness of 30 nm as the electron transport layer.}

Comparative Example 3

An organic electroluminescent device was fabricated in the same manner as in the above Example, except that BCP below was used instead of the compound represented by Formula 1 of the present invention as the electron transport auxiliary layer material.

As can be seen from the measurement results in Table 3, in the case of the blue organic electroluminescent device of Example using the compound of the present invention as an electron transport auxiliary layer material, the blue organic electroluminescence of Comparative Example 2 without using the electron transport auxiliary layer The driving voltage is slightly better than that of the device, but the current efficiency is greatly improved. In addition, compared to Comparative Example 3 in which BCP was used as an electron transport auxiliary layer, it showed better performance in both current efficiency and driving voltage.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present specification are intended to illustrate, not to limit the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (8)

1. A compound represented by the following formula (1).

   

   Here, Ar ₁ , Ar ₂ are each independently, a substituted or unsubstituted C ₆ ~ C ₆₀ aryl group; Or a substituted or unsubstituted C9~ C60 condensed polycyclic group,

   L is a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted C9~ C60 condensed polycyclic group,

   A1 is represented by any one of the following structures,

   

   X1 is C or N.
2. According to claim 1,

   Ar1, Ar2 are each independently a substituted or unsubstituted C ₆ ~ C ₆₀ aryl group,

   L is a direct bond; or a substituted or unsubstituted arylene group.
3. According to claim 1,

   The compound of Formula 1 is any one of the following compounds.

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
4. a first electrode;

   a second electrode opposite to the first electrode; and

   An organic layer interposed between the first electrode and the second electrode,

   The organic electroluminescent device comprising the compound of claim 1 in the organic layer.
5. 5. The method of claim 4,

   The first electrode is an anode,

   the second electrode is a cathode;

   the organic layer,

   i) a light emitting layer;

   ii) a hole transport region interposed between the first electrode and the light emitting layer and including at least one of a hole injection layer, a hole transport layer, and an electron blocking layer, and

   iii) an organic electroluminescent device interposed between the light emitting layer and the second electrode and including an electron transport region including at least one of a hole blocking layer, an electron transport layer, and an electron injection layer.
6. The organic electroluminescent device of claim 5 , wherein the electron transport region comprises the compound of claim 1 .
7. The organic electroluminescent device of claim 6 , wherein the electron transport layer comprises the compound of claim 1 .
8. A display device comprising the organic electroluminescent element of claim 4 and a thin film transistor connected to the organic electroluminescent element, wherein a first electrode of the organic electroluminescent element is electrically connected to a source electrode or a drain electrode of the thin film transistor.

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