KR20230028821A - Heteroaryl amine derivatives substituted with cyano group and organic electroluminescent device including the same - Google Patents

Abstract

Provided is a cyano group-substituted heteroaryl amine derivative which effectively absorbs high-energy external light source in the UV region to minimize damage to organic materials inside an organic electroluminescent device, thus contributing to substantial improvement in the lifespan of the organic electroluminescent device. The organic electroluminescent device according to the present invention comprises: a first electrode; a second electrode; at least one organic material layer provided between the first electrode and the second electrode; and a capping layer. The capping layer includes a cyano group-substituted heteroaryl amine derivative represented by chemical formula 1 according to the present invention. In the chemical formula 1, each substituent is as defined in the detailed description of the invention.

Description

Heteroaryl amine derivatives substituted with cyano group and organic electroluminescent device including the same}

The present invention relates to a heteroaryl amine derivative substituted with a cyano group and an organic electroluminescent device including the heteroaryl amine derivative substituted with a cyano group, wherein the organic electroluminescent device including a capping layer exhibits high refractive index characteristics and UV absorption to have both characteristics at the same time.

In the display industry, demand for a flat display device having a small space occupancy is increasing according to the size of the display device. A liquid crystal display (LCD) has a limited viewing angle and has disadvantages in that a separate light source is required because it is not self-luminous. For this reason, OLED (Organic Light Emitting Diodes) is attracting attention as a display using a self-luminous phenomenon.

In OLED, research on carrier injection type electroluminescence (EL) using a single crystal of anthracene aromatic hydrocarbon was first attempted by Pope et al. in 1963. From these studies, a lot of understanding and research on the basic mechanisms of charge injection, recombination, exciton generation, and light emission in organic materials and electroluminescent properties began.

In particular, in order to increase the luminous efficiency, various approaches such as structural changes and material development of devices have been made [Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007)/Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364].

The basic structure of an OLED display is generally an anode, a hole injection layer (HIL), a hole transporting layer (HTL), an emission layer (EML), an electron transporting layer, It is composed of a multilayer structure of ETL) and a cathode, and has a sandwich structure in which an organic multilayer film is formed between two electrodes.

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer between them. Here, the organic material layer is often composed of a multi-layer structure composed of different materials to increase the efficiency and stability of the organic light emitting device, and may include, 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 this organic light emitting device structure, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and when the injected holes and electrons meet, excitons are formed. When it falls to the ground state, it emits light. Such an organic light emitting device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

Materials used as the organic layer in the organic light emitting device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their functions.

Light-emitting materials include blue, green, and red light-emitting materials according to light-emitting colors, and yellow and orange light-emitting materials required to realize better natural colors. In addition, in order to increase color purity and increase light emitting efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a small amount of a dopant having a smaller energy band gap and higher luminous efficiency than the host constituting the light emitting layer is mixed in the light emitting layer in a small amount, excitons generated in the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength range of the dopant, light of a desired wavelength can be obtained according to the type of dopant used.

In order to fully express the excellent characteristics of the organic light emitting device described above, materials constituting the organic layer in the device, such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. have been developed. The performance of organic light emitting devices is recognized by products.

However, as organic light emitting diodes are commercialized and time passes, the need for other characteristics in addition to the light emitting properties of organic light emitting diodes themselves has emerged.

Since the organic light emitting device is exposed to an external light source for a long time, it is in an environment where it is exposed to high-energy ultraviolet rays. Accordingly, there is a problem in that organic materials constituting the organic light emitting device are continuously affected. The problem can be solved by applying a capping layer having UV absorption characteristics to the organic light emitting device to prevent exposure to such a high-energy light source.

In general, it is known that the viewing angle characteristics of organic light emitting diodes are wide, but from the viewpoint of the light source spectrum, significant deviations occur depending on the viewing angle, which affects the total refractive index of the organic light emitting diode, such as the glass substrate, organic material, and electrode material, and the emission wavelength of the organic light emitting diode. This is due to the occurrence of deviations between appropriate refractive indices according to the

In general, as the refractive index value required for blue is large and the wavelength becomes longer, the required refractive index value becomes smaller. Accordingly, it is necessary to develop a material constituting the capping layer that simultaneously satisfies the above-mentioned UV absorption characteristics and appropriate refractive index.

Efficiency of organic light emitting diodes can generally be divided into internal luminescent efficiency and external luminescent efficiency. The internal luminous efficiency is related to the efficiency of the formation of excitons in the organic layer for light conversion to take place.

The external light emitting efficiency refers to the efficiency with which light generated in the organic layer is emitted to the outside of the organic light emitting device.

In order to improve the overall efficiency, it is necessary to increase the external luminous efficiency as well as the internal luminous efficiency. Therefore, it is required to develop a capping layer (CPL, light efficiency improvement layer) material capable of increasing the external luminous efficiency.

On the other hand, compared to the bottom element structure of the non-resonant structure, the top element structure of the resonance structure is reflected by the anode, which is a reflective film, and comes out toward the cathode. big.

Therefore, one of the important methods for improving the shape and efficiency of the EL spectrum is to use a light efficiency improving layer (capping layer) on the top cathode.

In general, in SPP, four types of metals, Al, Pt, Ag, and Au, are mainly used for electron emission, and surface plasmons are generated on the surface of metal electrodes. For example, when Ag is used as the cathode, the emitted light is quenched by SPP (light energy loss due to Ag) and the efficiency is reduced.

On the other hand, when a capping layer (light efficiency improvement layer) is used, SPP occurs at the interface between the MgAg electrode and the organic material. At this time, when the organic material has high refractive index (eg n>1.69 @ 620), TE (Transverse electric) polarized light is dissipated on the surface of the capping layer (light efficiency improvement layer) in the vertical direction by evanescent waves, and TM (Transverse magnetic) polarized light moving along the cathode and capping layer generates surface plasma resonance (Surface Plasma Resonance). Wavelength amplification occurs by plasma resonance, which increases the intensity of the peak, enabling high efficiency and effective color purity control.

However, there is still a demand for development of materials and structures necessary for improvement of various characteristics in a balanced manner along with improvement of efficiency and color purity in organic light emitting devices.

Republic of Korea Patent Publication No. 2016-0062307 (title of invention: organic light emitting display device including high refractive index capping layer) Republic of Korea Patent Registration No. 2060645 (title of invention: tertiary amine derivative and organic electroluminescent device including the same)

An object of the present invention is to provide a capping layer material for an organic light emitting device, which can improve luminous efficiency and lifetime and at the same time improve viewing angle characteristics.

An object of the present invention is to provide a high-efficiency and long-life organic electroluminescent device including a capping layer having a high refractive index and high heat resistance in order to improve the light extraction rate of the organic electroluminescent device.

In order to achieve the above object, the present inventors conducted an example of research as shown below.

That is, a material having a higher refractive index was selected by introducing a cyano group from a tertiary amine compound having dibenzofuran and dibenzothiophene (Prior Patent No. 2060645) having a high refractive index. Then, an organic light emitting device using this material as a capping layer was manufactured, and characteristics of the device were evaluated as an example.

The present invention is a first electrode; an organic material layer disposed on the first electrode; a second electrode disposed on the organic layer; and a capping layer disposed on the second electrode, wherein the organic material layer or the capping layer includes a cyano group-substituted heteroaryl amine derivative represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1,

L ₁ , L ₂ and L ₃ are each independently a direct bond; A substituted or unsubstituted arylene group; And it is selected from a substituted or unsubstituted heteroarylene group,

A represents a monovalent group having as a binding site one of R ₁ to R ₄ represented by the following formula (2);

B and C are each independently an aryl group in which a cyano group is substituted or unsubstituted; and a heteroaryl group in which a cyano group is substituted or unsubstituted; is selected from

a, b and c are integers from 0 to 5;

When a, b, and c are 0, it is a direct bond.

[Formula 2]

In Formula 2,

R ₁ to R ₄ are linking groups as binding sites;

Z- ₁ is O, S or NR _{5 ;}

R ₅ is a phenyl group unsubstituted or substituted with a cyano group; and a naphthyl group in which a cyano group is substituted or unsubstituted; are selected from

The compounds described in this specification can be used as a material for an organic material layer of an organic light emitting device.

The compound according to at least one exemplary embodiment may exhibit ultraviolet ray absorption characteristics to minimize damage to organic matter in the organic light emitting device by an external light source, and improve efficiency, low driving voltage and/or lifespan characteristics of the organic light emitting device. there is.

In addition, in an organic light emitting device using the compound described in this specification as a capping layer, color purity can be remarkably improved by improving luminous efficiency and reducing the half-width of the luminous spectrum.

The compound according to the present invention exhibits an unexpectedly high refractive index due to the introduction of a cyano group into a conventional compound, and as a result, the heteroarylamine compound substituted with a cyano group having a high refractive index has a viewing angle and light efficiency of light extracted into the air. It can be used as a material for a capping layer (light efficiency improvement layer) that can improve

1 shows a first electrode 110, a hole injection layer 210, a hole transport layer 215, a light emitting layer 220, an electron transport layer 230, and an electron injection layer on a substrate 100 according to an embodiment of the present invention. 235, the second electrode 120, and the capping layer 300 are sequentially stacked to show an example of an organic light emitting device.
2 is a graph of light refraction and absorption characteristics when using a cyano group-substituted heteroaryl amine derivative according to an embodiment of the present invention.

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

Since the present invention may have various changes and various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, it should be understood that this is not intended to limit the present invention to the specific disclosed form, and includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Like reference numerals have been used for like elements throughout the description of each figure. In the accompanying drawings, the dimensions of the structures are shown enlarged than actual for clarity of the present invention. Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. These terms are only used for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element, without departing from the scope of the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this application, the terms "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. In addition, when a part such as a layer, film, region, plate, etc. is said to be “on” another part, this includes not only the case where it is “directly on” the other part, but also the case where another part is present in the middle.

In this specification, “substituted or unsubstituted” means a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a hydroxyl group, a silyl group, a boron group, a phosphine oxide group, a phosphine sulfide group, an alkyl group, an alkoxy group, an alkene It may mean substituted or unsubstituted with one or more substituents selected from the group consisting of a yl group, an aryl group, a heteroaryl group, and a heterocyclic group. In addition, each of the substituents exemplified above may be substituted or unsubstituted. For example, a biphenyl group may be interpreted as an aryl group or a phenyl group substituted with a phenyl group.

In this specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In this specification, the alkyl group may be straight chain, branched chain or cyclic. The number of carbon atoms of the alkyl group is 1 or more and 50 or less, 1 or more and 30 or less, 1 or more and 20 or less, 1 or more and 10 or less, or 1 or more and 6 or less. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, i-butyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group , n-pentyl group, i-pentyl group, neopentyl group, t-pentyl group, cyclopentyl group, 1-methylpentyl group, 3-methylpentyl group, 2-ethylpentyl group, 4-methyl-2-pentyl group , n-hexyl group, 1-methylhexyl group, 2-ethylhexyl group, 2-butylhexyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-t-butylcyclohexyl group, n-heptyl group, 1 -Methylheptyl group, 2,2-dimethylheptyl group, 2-ethylheptyl group, 2-butylheptyl group, n-octyl group, t-octyl group, 2-ethyloctyl group, 2-butyloctyl group, 2-hexyl Siloctyl group, 3,7-dimethyloctyl group, cyclooctyl group, n-nonyl group, n-decyl group, adamantyl group, 2-ethyldecyl group, 2-butyldecyl group, 2-hexyldecyl group, 2-ox Tyldecyl group, n-undecyl group, n-dodecyl group, 2-ethyldodecyl group, 2-butyldodecyl group, 2-hexyldodecyl group, 2-octyldodecyl group, n-tridecyl group, n-tetradecyl group, n -Pentadecyl group, n-hexadecyl group, 2-ethylhexadecyl group, 2-butylhexadecyl group, 2-hexylhexadecyl group, 2-octylhexadecyl group, n-heptadecyl group, n-octadecyl group , n- nonadecyl group, n- icosyl group, 2-ethyl icosyl group, 2-butyl icosyl group, 2-hexyl icosyl group, 2-octyl icosyl group, n-henicosyl group, n- docosyl group, n-tricot practical group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, and n-triacontyl group; not limited to these

In this specification, a hydrocarbon ring group means any functional group or substituent derived from an aliphatic hydrocarbon ring. The hydrocarbon ring group may be a saturated hydrocarbon ring group having 5 to 20 ring carbon atoms.

In this specification, an aryl group means any functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. The number of ring carbon atoms in the aryl group may be 6 or more and 30 or less, 6 or more and 20 or less, or 6 or more and 15 or less. Examples of the aryl group include a phenyl group, a naphthyl group, a fluorenyl group, anthracenyl group, a phenanthryl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a quinquephenyl group, a sexyphenyl group, a triphenylenyl group, a pyrenyl group, a peryleneyl group, and a naphtha group. Although a cenyl group, a pyrenyl group, a benzo fluoranthenyl group, a chrysenyl group, etc. can be illustrated, it is not limited to these.

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

In the present specification, the heteroaryl group may be a heteroaryl group containing one or more of O, N, P, Si, and S as heterogeneous elements. The N and S atoms may optionally be oxidized, and the N atom(s) may optionally be quaternized. The number of ring carbon atoms in the heteroaryl group is 2 or more and 30 or less, or 2 or more and 20 or less. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The polycyclic heteroaryl group may have, for example, a bicyclic or tricyclic structure.

Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a pyrazolyl group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridine group, a bipyridine group, a pyrimidine group, and a triazine group. , tetrazine group, triazole group, tetrazole group, acridyl group, pyridazine group, pyrazinyl group, quinoline group, quinazoline group, quinoxaline group, phenoxazine group, phthalazine group, pyridopyrimidine group, pyridopyrazino Pyrazine group, isoquinoline group, synol group, indole group, isoindole group, indazole group, carbazole group, N-arylcarbazole group, N-heteroarylcarbazole group, N-alkylcarbazole group, benzooxazole group, benzoimidazole group , Benzothiazole group, benzocarbazole group, benzothiophene group, benzothiophene group, benzoisothiazolyl group, benzoisoxazolyl group, dibenzothiophene group, thienothiophene group, benzofuran group, phenanthroline group, phenanthridine group , Thiazole group, isoxazole group, oxadiazole group, thiadiazole group, isothiazole group, isoxazole group, phenothiazine group, benzodioxol group, dibenzosilol group and dibenzofuran group, isobenzofuran group, etc. not limited to these In addition, there are N-oxide aryl groups corresponding to the monocyclic heteroaryl group or polycyclic heteroaryl group, for example, quaternary salts such as pyridyl N-oxide group and quinolyl N-oxide group, but these Not limited.

In this specification, the silyl group includes an alkyl silyl group and an aryl silyl group. Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group. Not limited.

In this specification, the boron group includes an alkyl boron group and an aryl boron group. Examples of the boron group include, but are not limited to, trimethylboron, triethylboron, t-butyldimethylboron, triphenylboron, diphenylboron, and phenylboron.

In this specification, an alkenyl group may be straight-chain or branched-chain. The carbon number is not particularly limited, but is 2 or more and 30 or less, 2 or more and 20 or less, or 2 or more and 10 or less. Examples of the alkenyl group include, but are not limited to, a vinyl group, a 1-butenyl group, a 1-pentenyl group, a 1,3-butadienyl aryl group, a styrenyl group, and a styrylvinyl group.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, may include a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the aryl amine group include phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 3-methyl-phenylamine group, 4-methyl-naphthylamine group, 2-methyl-biphenylamine group, 9-methyl-anthracenylamine group, diphenyl amine group, phenyl naphthylamine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine groups, but are not limited thereto.

In the present specification, examples of the heteroallylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroaryl group in the heteroarylamine group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. The heteroarylamine group including two or more heterocyclic groups may include a monocyclic heterocyclic group, a polycyclic heterocyclic group, or a monocyclic heterocyclic group and a polycyclic heterocyclic group at the same time.

In the present specification, the arylheteroarylamine group refers to an amine group substituted with an aryl group and a heterocyclic group.

In the present specification, “adjacent group” may mean a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, another substituent substituted on the atom on which the substituent is substituted, or a substituent sterically closest to the substituent. there is. For example, two methyl groups in 1,2-dimethylbenzene can be interpreted as “adjacent groups” to each other, and 2 methyl groups in 1,1-diethylcyclopentene Two ethyl groups can be interpreted as "adjacent groups".

Hereinafter, a cyano group-substituted heteroaryl amine derivative compound used in the organic layer and/or the capping layer will be described.

A cyano group-substituted heteroaryl amine derivative compound according to an embodiment of the present invention is represented by Formula 1 below.

[Formula 1]

In Formula 1,

L ₁ , L ₂ and L ₃ are each independently a direct bond; A substituted or unsubstituted arylene group; And it is selected from a substituted or unsubstituted heteroarylene group,

A represents a monovalent group having as a binding site one of R ₁ to R ₄ represented by the following formula (2);

B and C are each independently an aryl group in which a cyano group is substituted or unsubstituted; and a heteroaryl group in which a cyano group is substituted or unsubstituted; is selected from

a, b and c are integers from 0 to 5;

When a, b, and c are 0, it is a direct bond.

[Formula 2]

In Formula 2,

R ₁ to R ₄ are linking groups as binding sites;

Z- ₁ is O, S or NR _{5 ;}

R ₅ is a phenyl group unsubstituted or substituted with a cyano group; and a naphthyl group in which a cyano group is substituted or unsubstituted; are selected from

In the present invention, Formula 1 is represented by any one of Formulas 3 to 5.

[Formula 3]

[Formula 4]

[Formula 5]

L ₁ , L ₂ and L ₃ are each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted pyridylene group, a substituted or unsubstituted dibenzofuran group, or a substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted benzoxazole group; and a substituted or unsubstituted benzthiazole group; is selected from

Ar ₁ and Ar ₂ are each independently a phenyl group unsubstituted or substituted with a cyano group; a naphthyl group in which a cyano group is substituted or unsubstituted; Dibenzofuran group; Dibenzothiophene group; A benzofuran group in which a cyano group is substituted or unsubstituted; A benzothiophene group in which a cyano group is substituted or unsubstituted; a fluorene group in which a cyano group is substituted or unsubstituted; A benzoxazole group in which a cyano group is substituted or unsubstituted; a benzthiazole group in which a cyano group is substituted or unsubstituted; is selected from

Z ₁ is as defined in Formula 2 above.

In one embodiment of the present invention, the cyano group-substituted heteroaryl amine derivative represented by Formula 1 may be any one compound selected from compounds represented by Formulas 6 to 8 below, and the following compounds are further can be substituted.

[Formula 6]

[Formula 7]

[Formula 8]

An embodiment of the present invention will be described with reference to FIGS. 1 and 2 below.

1 is a schematic cross-sectional view of an organic light emitting device according to an exemplary embodiment of the present invention. Referring to FIG. 1 , an organic light emitting diode according to an embodiment includes a first electrode 110 sequentially stacked on a substrate 100, a hole injection layer 210, a hole transport layer 215, a light emitting layer 220, and electrons. A transport layer 230 , an electron injection layer 235 , a second electrode 120 , and a capping layer 300 may be included.

The first electrode 110 and the second electrode 120 are disposed facing each other, and the organic material layer 200 may be disposed between the first electrode 110 and the second electrode 120 . The organic material layer 200 may include a hole injection layer 210 , a hole transport layer 215 , an emission layer 220 , an electron transport layer 230 , and an electron injection layer 235 .

Meanwhile, the capping layer 300 presented in the present invention is a functional layer deposited on the second electrode 120 and includes an organic material according to Chemical Formula 1 of the present invention.

In the organic light emitting diode according to an embodiment shown in FIG. 1 , the first electrode 110 has conductivity. The first electrode 110 may be formed of a metal alloy or a conductive compound. The first electrode 110 is generally an anode, but its function as an electrode is not limited.

The first electrode 110 may be formed by depositing an electrode material on the substrate 100, electron beam evaporation, or sputtering. A material of the first electrode 110 may be selected from materials having a high work function to facilitate injection of holes into the organic light emitting device.

The capping layer 300 proposed in the present invention is applied when the emission direction of the organic light emitting device is top emission, and therefore, the first electrode 110 uses a reflective electrode. These materials include Mg (magnesium), Al (aluminum), Al-Li (aluminum-lithium), Ca (calcium), Mg-In (magnesium-indium), Mg-Ag (magnesium-silver) and It can also be made using the same metal. Recently, carbon substrate flexible electrode materials such as CNT (carbon nanotube) and Graphene (graphene) may be used.

The organic material layer 200 may be formed of a plurality of layers. When the organic material layer 200 is a plurality of layers, the organic material layer 200 includes hole transport regions 210 to 215 disposed on the first electrode 110, a light emitting layer 220 disposed on the hole transport region, and the light emitting layer. Electron transport regions 230 to 235 disposed on 220 may be included.

The capping layer 300 according to an embodiment includes an organic compound represented by Chemical Formula 1 described below.

Hole transport regions 210 to 215 are provided on the first electrode 110 . The hole transport regions 210 to 215 may include at least one of a hole injection layer 210 , a hole transport layer 215 , a hole buffer layer, and an electron blocking layer (EBL), and provide smooth injection and transport of holes into the organic light emitting device. Since the hole mobility is faster than the electron mobility, it has a thicker thickness than the electron transport area.

The hole transport regions 210 to 215 may have a single layer structure made of a single material, a single layer made of a plurality of different materials, or a multilayer structure having a plurality of layers made of a plurality of different materials.

For example, the hole transport regions 210 to 215 may have a single layer structure of the hole injection layer 210 or the hole transport layer 215, or may have a single layer structure composed of a hole injection material and a hole transport material. there is. In addition, the hole transport regions 210 to 215 have a single layer structure made of a plurality of different materials, or the hole injection layer 210 / hole transport layer 215 sequentially stacked from the first electrode 110, Hole injection layer 210 / hole transport layer 215 / hole buffer layer, hole injection layer 210 / hole buffer layer, hole transport layer 215 / hole buffer layer, or hole injection layer 210 / hole transport layer 215 / electrons It may have a structure of the blocking layer (EBL), but the embodiment is not limited thereto.

Among the hole transport regions 210 to 215 , the hole injection layer 210 may be formed on the anode by various methods such as a vacuum deposition method, a spin coating method, a cast method, or an LB method. When the hole injection layer 210 is formed by the vacuum deposition method, the deposition conditions are 100 to 500 Å depending on the compound used as the material for the hole injection layer 210, the structure and thermal characteristics of the hole injection layer 210 as a target, and the like. The deposition rate can be freely adjusted at around 1 Å/s, and is not limited to specific conditions. When the hole injection layer 210 is formed by the spin coating method, the coating conditions vary depending on the properties of the compound used as the material for the hole injection layer 210 and the layers formed as the interface, but the coating speed and coating for uniform film formation. After that, heat treatment for solvent removal is required.

The hole transport regions 210 to 215 are, for example, m-MTDATA, TDATA, 2-TNATA, NPB, β-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated-NPB, TAPC, HMTPD, TCTA (4,4',4"-tris(N-carbazolyl)triphenylamine (4,4',4"-tris(Ncarbazolyl) triphenylamine)), Pani/DBSA (Polyaniline/Dodecylbenzenesulfonic acid: polyaniline/dodecylbenzene sulfonic acid), PEDOT/PSS (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrene sulfonate):Poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate)), Pani/CSA ( Polyaniline/Camphor sulfonicacid: polyaniline/camphorsulfonic acid), PANI/PSS (Polyaniline)/Poly(4-styrenesulfonate): polyaniline)/poly(4-styrenesulfonate)), and the like.

The hole transport regions 210 to 215 may have a thickness of about 100 to about 10,000 Å, and corresponding organic layers of each hole transport region 210 to 215 are not limited to the same thickness. For example, if the hole injection layer 210 has a thickness of 50 Å, the hole transport layer 215 may have a thickness of 1000 Å and the electron blocking layer may have a thickness of 500 Å. Thickness conditions of the hole transport regions 210 to 215 may be determined to a degree that satisfies efficiency and lifespan within a range in which an increase in driving voltage of the organic light emitting device is not increased. The organic layer 200 includes a hole injection layer 210, a hole transport layer 215, a functional layer having both a hole injection function and a hole transport function, a buffer layer, an electron blocking layer, a light emitting layer 220, a hole blocking layer, an electron transport layer ( 230), an electron injection layer 235, and at least one layer selected from the group consisting of a functional layer having both an electron transport function and an electron injection function.

The hole transport regions 210 to 215 may be doped to improve characteristics like the light emitting layer 220, and doping of a charge-generating material into the hole transport regions 210 to 215 can improve the electrical characteristics of the organic light emitting device. can

The charge-generating material is generally made of a material having very low HOMO and LUMO. For example, the LUMO of the charge-generating material has a similar value to the HOMO of the hole transport layer 215 material. Due to such a low LUMO, holes are easily transferred to the adjacent hole transport layer 215 by using the characteristic that electrons of the LUMO are empty, thereby improving electrical characteristics.

The charge-generating material may be, for example, a p-dopant. The p-dopant may be one of a quinone derivative, a metal oxide, and a cyano group-containing compound, but is not limited thereto. For example, non-limiting examples of the p-dopant include tetracyanoquinondimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinondimethane quinone derivatives such as phosphorus (F4-TCNQ); metal oxides such as tungsten oxide and molybdenum oxide; and cyano group-containing compounds such as the following compound 2-22, etc., but are not limited thereto.

In addition to the aforementioned materials, the hole transport regions 210 to 215 may further include a charge generating material to improve conductivity.

The charge generating material may be uniformly or non-uniformly dispersed in the hole transport regions 210 to 215 . The charge generating material may be, for example, a p-dopant. The p-dopant may be one of a quinone derivative, a metal oxide, and a compound containing a cyano group, but is not limited thereto. For example, non-limiting examples of the p-dopant include quinone derivatives such as TCNQ (Tetracyanoquinodimethane) and F4-TCNQ (2,3,5,6-tetrafluoro-tetracyanoquinodimethane), metal oxides such as tungsten oxide and molybdenum oxide, and the like. It may include, but is not limited thereto.

As described above, the hole transport regions 210 to 215 may further include at least one of a hole buffer layer and an electron blocking layer in addition to the hole injection layer 210 and the hole transport layer 215 . The hole buffer layer may increase light emission efficiency by compensating for a resonance distance according to a wavelength of light emitted from the light emitting layer 220 . As a material included in the hole buffer layer, a material that may be included in the hole transport regions 210 to 215 may be used.

The electron blocking layer is a layer that serves to prevent injection of electrons from the electron transport regions 230 to 235 into the hole transport regions 210 to 215 . The electron blocking layer not only blocks electrons moving to the hole transport region, but also may use a material having a high T ₁ value so that excitons formed in the light emitting layer 220 are not diffused into the hole transport regions 210 to 215 . For example, a host of the light emitting layer 220 having a generally high T ₁ value may be used as the electron blocking layer material.

The light emitting layer 220 is provided on the hole transport regions 210 to 215 . The light emitting layer 220 may have a thickness of, for example, about 100 Å to about 1000 Å or about 100 Å to about 300 Å. The light emitting layer 220 may have a single layer made of a single material, a single layer made of a plurality of different materials, or a multilayer structure having a plurality of layers made of a plurality of different materials.

The light-emitting layer 220 is a region where holes and electrons meet to form excitons, and the material constituting the light-emitting layer 220 must have a high light-emitting property and an appropriate energy band gap to exhibit a desired light-emitting color, and generally has two roles as a host and a dopant. It consists of two materials, but is not limited thereto.

The host may include at least one of the following TPBi, TBADN, ADN (also referred to as “DNA”), CBP, CDBP, TCP, and mCP, and the material is not limited thereto if the properties are appropriate.

A dopant of the light emitting layer 220 according to an embodiment may be an organic metal complex. The content of a typical dopant may be selected from 0.01 to 20%, but is not limited thereto.

Electron transport regions 230 to 235 are provided on the light emitting layer 220 . The electron transport regions 230 to 235 may include at least one of a hole blocking layer, an electron transport layer 230 and an electron injection layer 235, but are not limited thereto.

The electron transport regions 230 to 235 may have a single-layer structure made of a single material, a single-layer structure made of a plurality of different materials, or a multi-layer structure having a plurality of layers made of a plurality of different materials.

For example, the electron transport regions 230 to 235 may have a single layer structure of the electron injection layer 235 or the electron transport layer 230, or may have a single layer structure composed of an electron injection material and an electron transport material. there is. In addition, the electron transport regions 230 to 235 have a structure of a single layer made of a plurality of different materials, or the electron transport layer 230/electron injection layer 235 sequentially stacked from the light emitting layer 220, the hole blocking It may have a layer/electron transport layer 230/electron injection layer 235 structure, but is not limited thereto. The thickness of the electron transport regions 230 to 235 may be, for example, about 1000 Å to about 1500 Å.

The electron transport regions 230 to 235 may be formed by various methods such as a vacuum deposition method, a spin coating method, a cast method, a Langmuir-Blodgett (LB) method, an inkjet printing method, a laser printing method, a laser induced thermal imaging (LITI) method, and the like. It can be formed using a method.

When the electron transport regions 230 to 235 include the electron transport layer 230 , the electron transport region 230 may include an anthracene-based compound. However, it is not limited thereto, and the electron transport region is, for example, Alq3 (Tris(8-hydroxyquinolinato)aluminum),1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene,2 ,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine,2-(4-(N-phenylbenzoimidazolyl-1-ylphenyl)-9,10 -dinaphthylanthracene,TPBi(1,3,5-Tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl),BCP(2,9-Dimethyl-4,7-diphenyl-1,10- phenanthroline), Bphen(4,7-Diphenyl-1,10-phenanthroline),TAZ(3-(4-Biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole),NTAZ(4 -(Naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole),tBu-PBD(2-(4-Biphenylyl)-5-(4-tert-butylphenyl)-1, 3,4-oxadiazole),BAlq(Bis(2-methyl-8-quinolinolato-N1,O8)-(1,1'-Biphenyl-4-olato)aluminum),Bebq2(berylliumbis(benzoquinolin-10-olate), ADN (9,10-di (naphthalene-2-yl) anthracene) and mixtures thereof may be included.

Since the electron transport layer 230 is selected from a material having fast electron mobility or slow electron mobility according to the structure of the organic light emitting device, various materials need to be selected. In some cases, Liq or Li may be doped.

The electron transport layer 230 may have a thickness of about 100 Å to about 1000 Å, for example, about 150 Å to about 500 Å. When the thickness of the electron transport layers 230 satisfies the aforementioned range, satisfactory electron transport characteristics may be obtained without a substantial increase in driving voltage.

When the electron transport regions 230 to 235 include the electron injection layer 235, a metal material that facilitates electron injection is selected for the electron transport regions 230 to 235, and LiF, lithium quinolate (LiQ), A lanthanide metal such as Li ₂ O, BaO, NaCl, CsF, or Yb, or a metal halide such as RbCl or RbI may be used, but is not limited thereto.

The electron injection layer 235 may also be made of a mixture of an electron transport material and an insulating organometal salt. The organometallic salt may be a material having an energy band gap of about 4 eV or more. Specifically, for example, the organometallic salt may include metal acetate, metal benzoate, metal acetoacetate, metal acetylacetonate or metal stearate. can The electron injection layers 235 may have a thickness of about 1 Å to about 100 Å or about 3 Å to about 90 Å. When the thickness of the electron injection layers 235 satisfies the aforementioned range, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.

As described above, the electron transport regions 230 to 235 may include a hole blocking layer. The hole blocking layer includes, for example, at least one of BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), and Balq. It can be done, but is not limited thereto.

The second electrode 120 is provided on the electron transport regions 230 to 235 . The second electrode 120 may be a common electrode or a cathode. The second electrode 120 may be a transmissive electrode or a transflective electrode. Unlike the first electrode 110 , the second electrode 120 may be a combination of a metal having a relatively low work function, an electrically conductive compound, an alloy, or the like.

The second electrode 120 is a transflective electrode or a reflective electrode. The second electrode 120 is Li (lithium), Mg (magnesium), Al (aluminum), Al-Li (aluminum-lithium), Ca (calcium), Mg-In (magnesium-indium), Mg-Ag (magnesium -silver) or a compound or mixture containing them (eg, a mixture of Ag and Mg). Alternatively, a plurality of layer structures including a reflective film or semi-transmissive film formed of the above material and a transparent conductive film formed of indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium tin zinc oxide (ITZO), or the like. can be

Although not shown, the second electrode 120 may be connected to an auxiliary electrode. When the second electrode 120 is connected to the auxiliary electrode, resistance of the second electrode 120 may be reduced.

An electrode and an organic material layer are formed on the illustrated substrate 100. At this time, a hard or soft material may be used as the material of the substrate 100, for example, soda lime glass, alkali-free glass, and alumino silicate as the hard material. Glass, etc. can be used, and PC (polycarbonate), PES (polyethersulfone), COC (cyclic olefin copolymer), PET (polyethylene terephthalate), PEN (polyethylene naphthalate), etc. can be used as soft materials. there is.

In the organic light emitting device, as voltage is applied to the first electrode 110 and the second electrode 120, holes injected from the first electrode 110 pass through the hole transport regions 210 to 215 to the light emitting layer. 220 , and electrons injected from the second electrode 120 are transferred to the light emitting layer 220 via the electron transport regions 230 to 235 . Electrons and holes recombine in the light emitting layer 220 to generate excitons, and as the excitons fall from an excited state to a ground state, they emit light.

An optical path generated in the light emitting layer 220 may exhibit very different tendencies depending on the refractive indices of organic and inorganic materials constituting the organic light emitting device. Light passing through the second electrode 120 may pass only through an angle smaller than the critical angle of the second electrode 120 . In addition, light contacting the second electrode 120 greater than the critical angle is totally reflected or reflected and is not emitted to the outside of the organic light emitting device.

If the refractive index of the capping layer 300 is high, it contributes to the improvement of luminous efficiency by reducing the total reflection or reflection phenomenon, and also contributes to the improvement of high efficiency and color purity by maximizing the micro-cavity phenomenon when the capping layer 300 has an appropriate thickness. .

The capping layer 300 is located at the outermost part of the organic light emitting device, and has a great influence on device characteristics without affecting the driving of the device at all. Therefore, the capping layer 300 serves to protect the inside of the organic light emitting device and at the same time helps to efficiently emit light generated from the organic light emitting layer 220 toward the outside. Organic materials absorb light energy in a specific wavelength range, which depends on the energy band gap. If this energy bandgap is adjusted for the purpose of absorbing the UV region that can affect organic materials inside the organic light emitting device, the capping layer 300 can be used for the purpose of protecting the organic light emitting device including improving optical characteristics. there is. And the capping layer 300 including such a tertiary amine compound has a high refractive index of 1.9 or more. For example, the capping layer may have a refractive index in the range of 1.9 to 3.0. When the refractive index of the capping layer 300 is high, light may be reflected at the interface of the capping layer 300 and thus light resonance may occur.

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

Hereinafter, the following examples will be described in detail in order to specifically describe the present specification. However, embodiments according to the present specification may be modified in various other forms, and the scope of the present application is not construed as being limited to the embodiments described below. The embodiments of this application are provided to more completely explain the present disclosure to those of ordinary skill in the art.

[Example]

Intermediate Synthesis Example 1: Synthesis of Intermediate (3)

(Synthesis of Intermediate (1))

In a one-neck 2000 mL flask, 50.0 g (235.8 mmol) of 4-bromo-3-methoxybenzonitrile, 4-chloro-2-fluorophenylboronic acid (4-chloro-2 -fluorophenylboronic acid) 45.2 g (259.4 mmol), Pd (PPh ₃ ) ₄ 8.2 g (7.1 mmol), and toluene 800 mL were mixed and stirred, followed by ethanol 400 mL, K ₂ CO ₃ 65.2 g (471.6 mmol) and distilled water 400 mL. was added and stirred under heating reflux throughout the day. After confirming that the reaction was complete, the mixture was cooled to room temperature and the solvent was removed. The organic layer separated by extraction with ethyl acetate and distilled water was distilled under reduced pressure to remove the solvent. It was purified by column chromatography (Hex:CHCl ₃ ) to obtain 43.2 g (yield: 70.0%) of the compound (intermediate (1)) as a yellow solid.

(Synthesis of Intermediate (2))

After mixing and stirring 43.2 g (165.1 mmol) of intermediate (1) and 850 mL of dichloromethane in a 2000 mL one-necked flask, 23.9 mL (247.6 mmol) of boron tribromide (BBr ₃ ) was slowly added dropwise at 0 ° C. Then, the temperature was raised to room temperature and stirred for 5 days. After confirming the completion of the reaction, distilled water was slowly added dropwise at 0 ° C, followed by extraction with dichloromethane. The separated organic layer was dried with MgSO ₄ and purified by column chromatography (DCM) to obtain a red solid compound (intermediate (2)) 27.2 g (yield: 66.5%) was obtained

(Synthesis of intermediate (3))

27.2 g (109.8 mmol) of intermediate (2), 45.5 g (329.5 mmol) of K ₂ CO ₃ , and 300 mL of N,N-dimethylformamide (DMF) were mixed in a 500 mL one-necked flask, and then kept at 105°C for one day. Stir. After confirming the completion of the reaction, it was cooled to room temperature, distilled water was added, and the resulting solid was filtered. The obtained reaction mixture was added with methanol and hexane, stirred at room temperature for 1 hour, and filtered to obtain 15.8 g (yield: 63.3%) of a red solid compound (intermediate (3)).

Intermediate Synthesis Example 2: Synthesis of Intermediate (5)

(Synthesis of intermediate (4))

In a one-neck 500 mL flask, 20.0 g (116.3 mmol) of 4-bromoaniline, 36.2 g (127.9 mmol) of 1-bromo-4-iodobenzene, NaO ^t Bu 12.3 g (127.9 mmol) and 150 mL of xylene were added together and stirred while Pd (dba) ₂ 1.3 g (2.3 mmol), Xanphos 2.7 g (4.7 mmol) was added and stirred under heating reflux throughout the day. After confirming the completion of the reaction, the mixture was cooled to room temperature, the solvent was removed, and chloroform was passed through a celite pad, and then the solvent was removed by distillation under reduced pressure. It was purified by column chromatography (Hex:CHCl ₃ ) to obtain 23.6 g (yield: 62.1%) of the compound (intermediate (4)) as a slightly red solid.

(Synthesis of Intermediate (5))

10.0 g (30.6 mmol) of intermediate (4), 9.3 g (76.5 mmol) of phenylboronic acid, 1.8 g (1.5 mmol) of Pd (PPh ₃ ) ₄ , and 120 mL of toluene were added to a 1000 mL one-necked flask. While stirring, 60 mL of ethanol and 61 mL (122.3 mmol) of 2M K ₂ CO ₃ were added, and the mixture was stirred under reflux heating throughout the day. After confirming the completion of the reaction, the solvent was removed, distilled water was added, and extraction was performed with chloroform. The organic layer was separated and the solvent was removed. Acetone was added to the concentrate, and the mixture was stirred for 30 minutes and filtered to obtain 5.3 g (yield: 53.9%) of the compound (intermediate (5)) as a dark green solid.

Intermediate Synthesis Example 3: Synthesis of Intermediate (6)

23.6 g (72.2 mmol) of intermediate (4), 31.8 g (216.5 mmol) of 4-cyanophenylbononic acid, _5.0 g (4.3 mmol) of Pd (PPh ₃ ) 4, While stirring with 400 mL of toluene, 200 mL of ethanol, 49.9 g (360.8 mmol) of K ₂ CO ₃ and 200 mL of distilled water were added, and the mixture was stirred under reflux heating throughout the day. After confirming the completion of the reaction, the solvent was removed. Distilled water was added to the concentrate and extracted with chloroform. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. After adding acetone to the concentrate, the mixture was stirred for 30 minutes and filtered to obtain 14.8 g (yield: 55.1%) of the compound (intermediate (6)) as a dark green solid.

Intermediate Synthesis Example 4: Synthesis of Intermediate (9)

(Synthesis of Intermediate (7))

5.0 g (23.5 mmol) of 5-bromobenzo[b]thiophene, 2.5 g (28.2 mmol) of CuCN, and 15 mL of DMF were mixed and stirred under reflux at 160°C for 3 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, 2N NaOH aqueous solution was added, and the mixture was stirred for 30 minutes. The mixed solution was extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and concentrated. The concentrate was purified through column chromatography (EA:HEX) to obtain 2.3 g (yield: 62.1%) of the compound (intermediate (7)) as a yellow solid.

(Synthesis of Intermediate (8))

To a solution of 2.3 g (14.5 mmol) of intermediate (7) in 83 mL of anhydrous THF, 10.2 mL (17.3 mmol, 1.7 M in pentane) of n-BuLi was slowly added dropwise at -78°C and stirred for 15 minutes. After slowly adding 43.0 mL (385.7 mmol) of trimethylborate dropwise, the mixture was stirred at -78°C for 15 minutes and then stirred at room temperature for 2 hours. After confirming the completion of the reaction, 1M HCl aqueous solution was slowly added dropwise and concentrated. Distilled water was added to the concentrate and extracted with ethyl acetate. The separated organic layer was dried over anhydrous sodium sulfate, filtered and concentrated. The concentrate was purified by column chromatography (MeOH/CHCl ₃ ) to obtain 1.2 g (yield: 40.9%) of the compound (Intermediate (8)) as an off-white solid.

(Synthesis of Intermediate (9))

2.0 g (7.1 mmol) of 1-Bromo-4-iodobenzene, 1.2 g (5.7 mmol) of intermediate (18), Pd (PPh ₃ ) ₄ 0.2 g (0.2 mmol) 2M K ₂ CO ₃ Aqueous solution of 7.1 mL (14.1 mmol), 14 mL of toluene and 7 mL of ethanol were mixed and stirred under reflux for 2 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature to separate an organic layer. The separated organic layer was filtered through a pad of silica and celite and washed with toluene. The filtrate was concentrated under reduced pressure and slurried with a mixed solution (DCM/HEX) to obtain 1.1 g (yield: 49.5%) of the compound (Intermediate (9)) as a pale yellow solid.

Intermediate Synthesis Example 5: Synthesis of Intermediate (10)

After adding 10.0 g (59.1 mmol) of biphenylamine, 18.6 g (59.1 mmol) of intermediate (9) and 100 mL of Xylene, stirring at 50 ° C., 1.7 g (3.0 mmol) of Pd (dba) ₂ and NaO After adding 11.4 g (118.2 mmol) of t- Bu and 2.4 g (5.9 mmol, 50 wt% in toluene) of P( t- Bu) ₃ , the mixture was stirred at 125-130 °C all day. After confirming the completion of the reaction, the reaction mixture was cooled to room temperature, passed through a celite pad, washed with chloroform, and distilled under reduced pressure to remove the solvent. The obtained compound was solidified with hexane to obtain a yellow solid, and then with CHCl ₃ After melting by heating, charcoal was added and stirred for 30 minutes. After passing the mixed solution (Hot CHCl ₃ :EA) through Celite and SiO ₂ pad, the solvent was removed by distillation under reduced pressure. The obtained compound was purified by SiO ₂ column chromatography (EA:CHCl ₃ :HEX). Slurry with a mixed solution (DCM/HEX) to obtain 11.2 g (yield: 47.1%) of the compound (intermediate (10)) as a yellow solid.

Intermediate Synthesis Example 6: Synthesis of Intermediate (11)

In a one-necked 1000 mL flask, 10.0 g (36.5 mmol) of 2-(4-bromophenyl)benzo[d]oxazole, 7.9 g (43.8 g) of benzophenone imine mmol) and toluene 243 mL were added, and then 1.1 g (1.8 mmol) of Pd (dba) ₂ , 2.3 g (3.7 mmol) of BINAP, and 35.7 g (109.4 mmol) of Cs ₂ CO ₃ were added, and the mixture was stirred at 110 °C all day. After the reaction was completed, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using chloroform under reduced pressure, and the solvent was removed by distillation under reduced pressure. After diluting the obtained compound in 182 mL of THF, 30 mL of concentrated hydrochloric acid was slowly added to acidify (pH<2), and the mixture was stirred at room temperature all day. After filtering the precipitated solid, it was washed with chloroform. The filtered solid was basicized (pH>8) using a saturated Na ₂ CO ₃ solution, extracted with chloroform, dried with MgSO ₄ , and distilled under reduced pressure to remove the solvent. The obtained compound was slurryed with DCM and Hexane to obtain 5.9 g (yield: 78.2%) of the compound (intermediate (11)) as a yellow solid.

Intermediate Synthesis Example 7: Synthesis of Intermediate (12)

In a one-neck 500 mL flask, 10.0 g (47.6 mmol) of intermediate (11), 2- (4-bromophenyl) benzo [di] oxazole {2- (4-bromophenyl) benzo [d] oxazole} 13.0 g (47.6 mmol) mmol), NaO ^t Bu 6.9 g (71.3 mmol) and 300 mL of toluene were added and stirred, then Pd (dba) ₂ 0.8 g (1.4 mmol) and P (t-Bu) ₃ 0.7 mL (2.9 mmol, 50 wt% in toluene) were added and heated to reflux. was stirred throughout the day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Methanol was added to the concentrated solution, stirred for 30 minutes, and then filtered. The obtained solid was dissolved in hot monochlorobenzene, passed through a celite pad, and the solvent was removed by distillation under reduced pressure. After adding acetone, the mixture was stirred for 30 minutes and filtered to obtain 13.6 g (yield: 71.1%) of the compound (intermediate (12)) as a light green solid.

Intermediate Synthesis Example 8: Synthesis of Intermediate (13)

In a one-neck 1000 mL flask, 26.6 g (91.7 mmol) of 2-(4-bromophenyl)benzo[d]thiazole, 19.9 Benzophenone imine After adding g (110.0 mmol) and toluene 270 mL, 2.6 g (4.6 mmol) of Pd (dba) ₂ , 5.7 g (9.2 mmol) of BINAP, and 89.6 g (275.0 mmol) of Cs ₂ CO ₃ were added and kept at 110 ° C all day. Stir. After the reaction was completed, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using chloroform under reduced pressure, and the solvent was removed by distillation under reduced pressure. After diluting the obtained compound in 300 mL of THF, 30 mL of concentrated hydrochloric acid was slowly added to acidify it (pH<2), and the mixture was stirred at room temperature all day. After filtering the precipitated solid, it was washed with chloroform. The filtered solid was basicized (pH>8) using a saturated Na ₂ CO ₃ solution, extracted with chloroform, dried with MgSO ₄ , and distilled under reduced pressure to remove the solvent. The obtained compound was slurried with DCM and Hexane to obtain 17.8 g (yield: 85.8%) of the compound (intermediate (13)) as a yellow solid.

Intermediate Synthesis Example 9: Synthesis of Intermediate (14)

10.0 g (44.2 mmol) of intermediate (13), 2- (4-bromophenyl) benzo [di] thiazole {2- (4-bromophenyl) benzo [d] thiazole} 12.8 g (44.2 mmol) in a one-neck 250 mL flask mmol), NaO ^t Bu 4.7 g (48.6 mmol) and 150 mL of xylene were added and stirred, then 0.8 g (1.3 mmol) of Pd (dba) ₂ and 0.6 mL (2.7 mmol) of P (t-Bu) ₃ were added and stirred under heating and reflux all day. did After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Methanol was added to the concentrated solution, stirred for 30 minutes, and then filtered. The solid thus obtained was dissolved in hot monochlorobenzene, passed through a celite pad, and the solvent was removed by distillation under reduced pressure. Acetone was added to the concentrated residue, stirred for 30 minutes, and filtered to obtain 13.5 g (yield: 70.3%) of the compound (Intermediate (14)) as a light green solid.

Intermediate Synthesis Example 10: Synthesis of Intermediate (15)

23.4 g (84.3 mmol) of 1-Bromo-4-iodobenzene, 10.0 g (56.2 mmol) of benzo[b]thiophen-2-ylboronic acid ), Pd(PPh ₃ ) ₄ 1.9 g (0.7 mmol) 2M K ₂ CO ₃ aqueous solution 84.3 mL (168.6 mmol), toluene 187 mL and ethanol 94 mL were mixed and stirred under reflux for 2 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature to separate an organic layer. The separated organic layer was filtered through a pad of silica and celite and washed with toluene. The filtrate was concentrated under reduced pressure and slurried with a mixed solution (DCM/HEX) to obtain 10.0 g (yield: 61.7%) of the compound (Intermediate (15)) as a white solid.

Intermediate Synthesis Example 11: Synthesis of Intermediate (17)

(Synthesis of Intermediate (16))

1-Bromo-4-nitrobenzene 5.0 g (24.8 mmol), benzo[b]thiophen-2-ylboronic acid 5.3 g (29.8 mmol) ), Pd(PPh ₃ ) ₄ 0.8 g (0.7 mmol) 2M K ₂ CO ₃ aqueous solution 37.2 mL (74.4 mmol), toluene 83 mL and ethanol 41 mL were mixed and stirred under reflux for 4 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature and methanol was added dropwise. The precipitate formed was filtered off. After dissolving the solid in chloroform, it was filtered through celite and a silica pad and washed with chloroform. The filtrate was concentrated under reduced pressure and slurried with methanol to obtain 4.5 g (yield: 68.3%) of the compound (intermediate (16)) as a yellow solid.

(Synthesis of Intermediate (17))

After slowly adding 5 mL of concentrated hydrochloric acid (conc. HCl) dropwise to 50 mL of ethanol, 4.5 g (17.6 mmol) of intermediate (16) and 2.9 g (52.8 mmol) of iron (Fe) were added and refluxed at 90 ° C for 8 hours. Stir. After confirming the completion of the reaction, it was cooled to room temperature, filtered through a celite pad, and washed with dichloromethane (DCM). The filtrate was concentrated, diluted with dichloromethane, adjusted to pH 10 with saturated sodium carbonate solution, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated. The concentrate was recrystallized from a mixed solution (DCM/HEX) to obtain 1.7 g (yield: 42.5%) of the compound (intermediate (17)) as an ivory solid.

Intermediate Synthesis Example 12: Synthesis of Intermediate (18)

5.0 g (23.8 mmol) of intermediate (17), 6.5 g (23.8 mmol) of intermediate (15), 0.4 g (0.7 mmol) of Pd (dba) _2, 0.6 g (1.4 mmol) of S-Phos, After mixing 4.6 g (47.6 mmol) of NaOtBu and 100 mL of xylene, the mixture was heated to 130° C. and stirred for 40 minutes. After the reaction was terminated and cooled to room temperature, the precipitated solid compound was filtered while washing with distilled water, toluene, and hexane. The solid compound was dissolved by heating in dichlorobenzene, filtered through Celite, and washed with acetone to obtain 6.2 g (yield: 64.6%) of the compound (Intermediate (18)) as a beige solid.

Intermediate Synthesis Example 13: Synthesis of Intermediate (19)

2-bromodibenzo[b,di]furan (2-bromodibenzo[b,d]furan) 10.0 g (40.5 mmol), benzophenone imine 8.1 g (44.7 mmol), Pd (dba) ₂ 0.7 g (1.2 mmol), 1.5 g (2.5 mmol) of BINAP, 11.7 g (121.7 mmol) of tert -butoxysodium and 200 mL of toluene were stirred at 110° C. throughout the day. The reaction mixture was cooled to room temperature, passed through a celite pad, and the solvent was removed by distillation under reduced pressure. After dissolving the obtained compound in 100 mL of tetrahydrofuran, it was slowly acidified (pH<2) with 4N hydrochloric acid solution and stirred at 50°C for 4 hours. After cooling to room temperature, tetrahydrofuran was removed by distillation under reduced pressure, and then diethyl ether was added and stirred. The resulting solid was filtered under reduced pressure, the filtered wet body was suspended in 200 mL of water, and the acidity was adjusted to 8 or higher with a saturated sodium carbonate solution, followed by stirring for 1 hour. The resulting solid was filtered, washed with water and dried under reduced pressure. The obtained compound was purified by column chromatography to obtain 5.0 g (yield: 67.0%) of the compound (intermediate (19)).

Intermediate Synthesis Example 14: Synthesis of Intermediate (20)

In a one-neck 500 mL flask, 10.0 g (54.6 mmol) of intermediate (19), 13.5 g (54.6 mmol) of 3-bromodibenzo [b, d] furan, NaO ^t Bu 5.8 g (60.0 mmol) and 300 mL of toluene were added together and stirred while adding 0.9 g (1.6 mmol) of Pd (dba) ₂ and 0.8 mL (3.3 mmol, 50 wt% in toluene) of P (t-Bu) ₃ and heating to reflux. was stirred all day under After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Methanol was added to the concentrate, stirred for 30 minutes, and filtered. The solid thus obtained was dissolved in hot monochlorobenzene, passed through a celite pad, and the solvent was removed by distillation under reduced pressure. Acetone was added to the concentrated solution, and the mixture was stirred for 30 minutes and filtered to obtain 11.8 g (yield: 62.1%) of a pale red solid compound (Intermediate (20)).

Intermediate Synthesis Example 15: Synthesis of Intermediate (21)

2-bromodibenzo[b,d]thiophene 6.0 g (22.8 mmol), Benzophenone imine 4.6 mL (27.4 mmol), Pd ₂ (dba) ₃ A mixture of 1.0 g (1.1 mmol), 1.4 g (2.3 mmol) of BINAP, 22.3 g (68.4 mmol) of cesium carbonate and 110 mL of toluene was stirred at reflux for 12 hours. The reaction mixture was cooled to room temperature, filtered through a celite pad, and the filtrate was concentrated under reduced pressure. After dissolving the filtered wet body in tetrahydrofuran, 30 mL of 6N hydrochloric acid aqueous solution was added and stirred for 1 hour. The mixture was basified (pH 7-8) with saturated sodium carbonate solution and then extracted with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and then purified by column chromatography to obtain 2.7 g (yield: 59.9%) of the compound (Intermediate (21)) as a brown solid.

Intermediate Synthesis Example 16: Synthesis of Intermediate (22)

In a one-neck 500 mL flask, 11.5 g (57.7 mmol) of intermediate (21), 15.2 g (57.7 mmol) of 2-bromodibenzo[b,d]thiophene, NaO ^t Bu 6.1 g (63.5 mmol) and 300 mL of toluene were added and stirred, then Pd (dba) ₂ 1.0 g (1.7 mmol) and P (t-Bu) ₃ 0.8 mL (3.5 mmol, 50 wt% in toluene) were added and heated to reflux. was stirred throughout the day. After confirming the completion of the reaction, it was cooled to room temperature and the solvent was distilled off. Methanol was added to the concentrate, stirred for 30 minutes, and filtered. The solid thus obtained was dissolved in hot monochlorobenzene, passed through a celite pad, and the solvent was removed by distillation under reduced pressure. Acetone was added to the concentrated residue, and the mixture was stirred for 30 minutes and filtered to obtain 14.4 g (yield: 65.3%) of a pale red solid compound (Intermediate (22)).

Intermediate Synthesis Example 17: Synthesis of Intermediate (26)

(Synthesis of Intermediate (23))

After dissolving 30.0 g (177.3 mmol) of 6-hydroxy-2-naphthonitrile in 700 mL of dichloromethane, adding 42.9 mL (531.9 mmol) of pyridine, the temperature was reduced to 0 ° C. lowered After slowly adding 35.7 mL (212.8 mmol) of Tf ₂ O dropwise, the temperature was raised to room temperature and reacted for 12 hours. After washing the reactant with 500 mL of distilled water, the separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography (CHCl ₃ ) to obtain 53.0 g of the compound (intermediate (23)) as a yellow solid (yield: 99.2) %) was obtained.

(Synthesis of Intermediate (24))

In a one-necked 2 L flask, 53.0 g (175.9 mmol) of intermediate (23), 67.0 g (263.9 mmol) of pinacol diboron (Bis (pinacolato) diboron), Pd (dppf) Cl ₂ -CH ₂ Cl ₂ 2.9 g (3.5 mmol), KOAc 51.8 g (527.8 mmol) and 1,4-dioxane 800 mL were mixed, and then stirred at 100°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, passed through a celite pad, and then concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl ₃ ) and solidified with a mixed solvent (DCM/MeOH) to obtain 38.0 g (yield: 77.4%) of the compound (Intermediate (24)) as a white solid.

(Synthesis of Intermediate (25))

4.3 g (15.4 mmol) of intermediate (24), 21.8 g (77.0 mmol) of 1-bromo-4-iodobenzene, 0.5 g of Pd (PPh ₃ ) ₄ (0.5 mmol), 2M aqueous solution of K ₂ CO ₃ 15.4 mL (30.8 mmol), 102 mL of toluene and 51 mL of ethanol, and then stirred at 80 ^° C for 3 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, and distilled water was added dropwise. After extracting the reactant with dichloromethane and drying the separated organic layer over anhydrous sodium sulfate, the solvent was removed under reduced pressure. The obtained reaction product was purified by silica gel column chromatography (Hexanes/DCM) to obtain 3.4 g (yield: 72.3%) of the compound (Intermediate (25)) as a white solid.

(Synthesis of Intermediate (26))

Intermediate (25) 3.4 g (11.0 mmol), Benzophenone imine 2.4 g (13.2 mmol), Pd (dba) ₂ 190.3 mg (0.3 mmol), BINAP 206.1 g (0.3 mmol), NaO t Bu 7.2 g (22.1 mmol) and 50 mL of toluene were mixed and stirred at 100°C for 3 hours. After the reaction was completed, it was cooled to room temperature, and the reaction mixture was filtered through a celite pad and distilled under reduced pressure. 50 mL of THF and 50 mL of 6N HCl aqueous solution were added and stirred for one day. After filtering the formed solid, it was washed with chloroform. The solid thus obtained was diluted with distilled water, neutralized with Na ₂ CO ₃ solution, and extracted with chloroform. After concentrating the dried organic layer, it was completely dissolved in DCM and solidified while slowly adding hexane dropwise to obtain 2.5 g (yield: 92.7%) of the compound (Intermediate (26)) as a yellow solid.

Intermediate Synthesis Example 18: Synthesis of Intermediate (29)

(Synthesis of Intermediate (27))

50.0 g (253.8 mmol) of 4-amino-3-bromobenzonitrile, 55.7 g (253.8 mmol) of 4-Bromobenzoyl chloride and 500 pyridine mL was added and stirred under reflux for 12 hours or longer. After confirming the completion of the reaction, the solvent was distilled under reduced pressure. It was solidified with diisopropyl ether (IPE) to obtain 75.6 g (yield: 78.3%) of a pale yellow solid compound (Intermediate (27)).

(Synthesis of Intermediate (28))

In a one-necked 1 L flask, 75.6 g (251.1 mmol) of intermediate (27), 2.39 g (12.6 mmol) of CuI, 4.5 g (25.1 mmol) of 1,10-Phenanthroline, 148.7 g (456.6 mmol) of Cs ₂ CO ₃ and nitrobenzene (Nitrobenzene) 800 mL was refluxed and stirred throughout the day. After the reaction was complete, DCM was passed through a celite pad. After solvent removal, the solid was dissolved in chloroform and purified using column chromatography (CHCl ₃ ). Solidified with methanol to obtain 42.3 g (yield: 56.3%) of a pale yellow solid compound (intermediate (28)).

(Synthesis of Intermediate (29))

5.0 g (16.7 mmol) of intermediate (28), 4.5 g (25.1 mmol) of benzophenone imine, 961.0 mg (1.7 mmol) of Pd (dba) ₂ , 2.1 g (3.3 mmol) of BINAP in a one-necked 500 mL flask , NaO t Bu 4.8 g (50.2 mmol) and toluene 80 mL were mixed, and then stirred at 100° C. for 3 hours. After the reaction was completed, it was cooled to room temperature, and the reaction mixture was filtered through a celite pad and distilled under reduced pressure. 50 mL of THF and 50 mL of 6N HCl aqueous solution were added and stirred for one day. After filtering the formed solid, it was washed with chloroform. The solid thus obtained was diluted with distilled water, neutralized with Na ₂ CO ₃ solution, and extracted with chloroform. After concentrating the dried organic layer, it was completely dissolved in DCM, and solidified while slowly adding hexane dropwise to obtain 3.3 g (yield: 85.0%) of the compound (Intermediate (29)) as a yellow solid.

Intermediate Synthesis Example 19: Synthesis of Intermediate (30)

After adding 4.0 g (17.8 mmol) of intermediate (17), 5.3 g (17.8 mmol) of intermediate (28) and 80 mL of Xylene, stirring at 50 ° C., 0.3 g (0.5 mmol) of Pd (dba) ₂ and NaO t- After adding 3.4 g (35.5 mmol) of Bu and _0.4 g (1.1 mmol, 50 wt% in toluene) of P( t- Bu) 3 , the mixture was stirred at 125-130 °C all day. After confirming the completion of the reaction, the reaction mixture was cooled to room temperature, passed through a celite pad, washed with chloroform, and distilled under reduced pressure to remove the solvent. The obtained compound was solidified with hexane to obtain a yellow solid, and then with CHCl ₃ After melting by heating, charcoal was added and stirred for 30 minutes. After passing the mixed solution (Hot CHCl ₃ :EA) through Celite and SiO ₂ pad, the solvent was removed by distillation under reduced pressure. The obtained compound was purified by SiO ₂ column chromatography (EA:CHCl ₃ :HEX). Slurry with a mixed solution (DCM/HEX) to obtain 2.7 g (yield: 34.3%) of the compound (intermediate (30)) as a yellow solid.

Intermediate Synthesis Example 20: Synthesis of Intermediate (31)

3.0 g (12.8 mmol) of intermediate (29), 3.7 g (12.8 mmol) of 2-(4-bromophenyl)benzo[d]thiazole, and 60 mL of Xylene were added. After stirring at 50 ° C., 0.2 g (0.4 mmol) of Pd (dba) ₂ , 2.5 g (25.5 mmol) of NaO t- Bu and _0.3 g (0.8 mmol, 50 wt% in toluene) of P ( t- Bu) 3 were added. After addition, it was stirred all day at 125 ~ 130 ℃. After confirming the completion of the reaction, the reaction mixture was cooled to room temperature, passed through a celite pad, washed with chloroform, and distilled under reduced pressure to remove the solvent. The obtained compound was solidified with hexane to obtain a yellow solid, and then with CHCl ₃ After melting by heating, charcoal was added and stirred for 30 minutes. After passing the mixed solution (Hot CHCl ₃ :EA) through Celite and SiO ₂ pad, the solvent was removed by distillation under reduced pressure. The obtained compound was purified by SiO ₂ column chromatography (EA:CHCl ₃ :HEX). Slurry with a mixed solution (DCM/HEX) to obtain 2.0 g (yield: 35.1%) of the compound (intermediate (31)) as a yellow solid.

Intermediate Synthesis Example 21: Synthesis of Intermediate (32)

In a one-neck 250 mL flask, 10.0 g (40.9 mmol) of intermediate (26), 11.8 g (40.9 mmol) of intermediate (15), 1.2 g (2.1 mmol) of Pd (dba) ₂ , 1.7 g (4.1 mmol) of S-Phos, After mixing 7.9 g (81.9 mmol) of NaOtBu and 200 mL of xylene, the mixture was heated to 130° C. and stirred for 40 minutes. After the reaction was terminated and cooled to room temperature, the precipitated solid compound was filtered while washing with distilled water, toluene, and hexane. The solid compound was dissolved by heating in dichlorobenzene, filtered through Celite, and washed with acetone to obtain 10.1 g (yield: 54.5%) of a beige solid compound (Intermediate (32)).

Intermediate Synthesis Example 22: Synthesis of Intermediate (33)

60.0 g (175.4 mmol) of 3,7-dibromo-dibenzo[b,d]thiophene, 23.6 g (263.1 mmol) of CuCN, 900 mL of N,N-dimethylformamide (DMF) was added and stirred under heating and reflux all day. After confirming the completion of the reaction, the mixture was cooled to room temperature, passed through a celite pad, and the filtrate was concentrated, adjusted to pH 2-3 with 2N aqueous hydrochloric acid, and stirred for 4 hours. After stirring, the solid obtained by filtration was washed with water, dried over anhydrous MgSO ₄ , and purified by column chromatography (Hex/CHCl ₃ ) to obtain 8.2 g (yield: 16.2%) of the compound (Intermediate (33)) as a white solid.

Intermediate Synthesis Example 23: Synthesis of Intermediate (35)

(Synthesis of Intermediate (34))

4-bromo-1-iodobenzene 10.0 g (35.3 mmol), dibenzofuran-3-ylboronic acid 8.2 g (38.9 mmol), Pd ( A mixture of 0.2 g (1.1 mmol) of PPh ₃ ) ₄ , 36.0 mL (72.0 mmol) of 2M sodium carbonate solution, 90 mL of toluene and 36 mL of ethanol was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, it was diluted with 100 mL of toluene and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 10.7 g (yield: 93%) of a solid compound (intermediate (34)).

(Synthesis of Intermediate (35))

Intermediate (34) 60.0 g (185.7 mmol), Benzophenone imine 37.0 g (204.2 mmol), Pd (dba) ₂ 5.3 g (9.3 mmol), BINAP 11.5 g (18.5 mmol), tert -butoxysodium A mixture of 44.6 g (464.1 mmol) in 600 mL of toluene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, it was dissolved in chloroform. After passing this solution through a celite pad, it was concentrated under reduced pressure. After dissolving the obtained compound in 500 mL of tetrahydrofuran, 80 mL of 6N hydrochloric acid was slowly added thereto, followed by stirring overnight at room temperature. The resulting precipitate was filtered under reduced pressure and then washed with chloroform. The filtered wet body was suspended in 600 mL of water, the pH was adjusted to 8 or higher with saturated sodium carbonate solution, and the layers were separated by extraction with chloroform. The separated chloroform layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The concentrated residue was slurried with dichloromethane and normal hexane to obtain 28.0 g (yield: 58%) of the compound (intermediate (35)) as a yellow solid.

Intermediate Synthesis Example 24: Synthesis of Intermediate (36)

In a 1-neck 250 mL flask, 10.0 g (38.6 mmol) of intermediate (35), 9.0 g (38.6 mmol) of biphenyl bromide, 1.1 g (1.9 mmol) of Pd (dba) ₂ , 1.6 g (3.9 mmol) of S-Phos mmol), 7.4 g (77.1 mmol) of NaOtBu, and 200 mL of xylene were mixed, heated to 130 °C, and stirred for 40 minutes. After the reaction was terminated and cooled to room temperature, the precipitated solid compound was filtered while washing with distilled water, toluene, and hexane. The solid compound was dissolved by heating in dichlorobenzene, filtered through celite, and washed with acetone to obtain 9.6 g (yield: 60.5%) of a beige solid compound (Intermediate (36)).

Intermediate Synthesis Example 25: Synthesis of Intermediate (38)

(Synthesis of intermediate (37))

In a one-necked 500 mL flask, 15.8 g (69.4 mmol) of intermediate (3), 19.4 g (76.3 mmol) of bis (pinacolato) diboron}, 1.7 g (2.1 mmol) of Pd (dppf)Cl ₂ ), potassium acetate (KOAc) 13.6 g (138.8 mmol), and 300 mL of dioxane were added, and then refluxed under nitrogen for a day at 100 ° C. After confirming the completion of the reaction, it was concentrated, distilled water was added, and then extracted with chloroform. The extracted organic layer was dried over anhydrous MgSO ₄ and then purified by column chromatography (Hex/CHCl ₃ ) to obtain 13.8 g (yield: 62.1%) of the compound (Intermediate (37)) as a white solid.

(Synthesis of Intermediate (38))

4-bromo-1-iodobenzene 18.4 g (64.9 mmol), intermediate (37) 13.8 g (43.2 mmol), Pd (PPh ₃ ) ₄ 2.5 g (2.2 mmol), 2M A mixture of 43 mL (86.5 mmol) of sodium carbonate solution, 90 mL of toluene and 40 mL of ethanol was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, it was diluted with toluene and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 10.7 g (yield: 93%) of a solid compound (intermediate (38)).

Intermediate Synthesis Example 26: Synthesis of Intermediate (39)

In a one-neck 1000 mL flask, 4.5 g (48.7 mmol) of biphenylamine, 10.0 g (32.5 mmol) of intermediate (25), NaO ^t Bu 6.2 g (64.9 mmol) and 200 mL of toluene were added together and stirred while Pd (dba) ₂ 932.9 mg (1.6 mmol), DPPF 1.8 g (3.2 mmol) was added and stirred under heating reflux throughout the day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. After adding distilled water, it was extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:CHCl ₃ ) to obtain 5.8 g (yield: 55.8%) of the compound (Intermediate (39)) as a slightly red solid.

Intermediate Synthesis Example 27: Synthesis of Intermediate (40)

2- (4-bromophenyl) naphthalene (2- (4-bromophenyl) naphthalene) 20.0 g (70.6 mmol), benzophenone imine 12.8 g (70.6 mmol), Pd (dba) ₂ 2.0 g (3.5 mmol) ), 4.4 g (7.1 mmol) of BINAP, 13.6 g (141.3 mmol) of tert -butoxysodium, and 326 mL of toluene were refluxed and stirred for 3 hours, and the reaction mixture was cooled to room temperature and washed with 326 mL of distilled water. The organic layer was separated, 100 mL of 6 N HCl was added, and stirred at room temperature for 3 hours.The resulting solid was filtered, the filtered wet body was suspended in 300 mL of water, and the pH was adjusted to 8 or more with saturated sodium carbonate solution. The layers were separated by extraction with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated by column chromatography. The concentrated mixture was crystallized with dichloromethane and normal hexane to obtain a pale orange solid compound (intermediate (40)) 13.9 g (yield: 90%) was obtained.

Intermediate Synthesis Example 28: Synthesis of Intermediate (41)

In a one-neck 1000 mL flask, 4.5 g (48.7 mmol) of biphenylamine, 11.5 g (32.5 mmol) of intermediate (38), NaO ^t Bu 6.2 g (64.9 mmol) and 200 mL of toluene were added together and stirred while Pd (dba) ₂ 932.9 mg (1.6 mmol), DPPF 1.8 g (3.2 mmol) was added and stirred under heating reflux throughout the day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. After adding distilled water, it was extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:CHCl ₃ ) to obtain 7.0 g (yield: 50.0%) of the compound (Intermediate (41)) as a slightly red solid.

Intermediate Synthesis Example 29: Synthesis of Intermediate (43)

(Synthesis of Intermediate (42))

In a one-neck 1000 mL flask, 10.0 g (107.4 mmol) of aniline, 91.1 g (322.1 mmol) of 1-bromo-4-iodobenzene, NaO ^t Bu 31.0 g (322.1 mmol) and 600 mL of toluene were added and stirred while Pd (dba) ₂ 3.7 g (6.4 mmol), DPPF 7.1 g (12.9 mmol) was added and stirred under heating reflux throughout the day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. After adding distilled water, extraction was performed with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:CHCl ₃ ) to obtain 23.9 g (yield: 55.3%) of the compound (Intermediate (42)) as a slightly red solid.

(Synthesis of Intermediate (43))

In a one-neck 500 mL flask, 23.9 g (59.3 mmol) of intermediate (42), 45.2 g (177.9 mmol) of bis (pinacolato) diboron, 2.9 g (3.6 mmol) of Pd (dppf) Cl ₂ ), potassium acetate (KOAc) 17.5 g (177.9 mmol), and 350 mL of dioxane were added together and refluxed at 100 ° C for a day. After confirming the completion of the reaction, the solvent was removed. After adding distilled water, extraction was performed with chloroform. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:CHCl ₃ ) to obtain 21.0 g (yield: 71.1%) of the compound (Intermediate (43)) as a pale red sticky liquid.

Intermediate Synthesis Example 30: Synthesis of Intermediate (44)

Intermediate (38) 20.0 g (57.4 mmol), Benzophenone imine 15.6 g (86.2 mmol), Pd (dba) ₂ 1.7 g (2.9 mmol), BINAP 3.6 g (5.7 mmol), Cs ₂ CO ₃ 37.4 A mixture of g (114.9 mmol) and 400 mL of toluene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, it was dissolved in chloroform. After passing this solution through a celite pad, it was concentrated under reduced pressure. After dissolving the obtained compound in 400 mL of tetrahydrofuran, 80 mL of 6N hydrochloric acid was slowly added thereto, followed by stirring overnight at room temperature. The resulting precipitate was filtered under reduced pressure and then washed with chloroform. The filtered wet body was suspended in 600 mL of water, the pH was adjusted to 8 or higher with saturated sodium carbonate solution, and the layers were separated by extraction with chloroform. The separated chloroform layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The concentrated residue was slurried with dichloromethane and n-hexane to obtain 10.2 g (yield: 62.5%) of the compound (intermediate (44)) as a yellow solid.

Various cyano group-substituted heteroaryl amine derivatives were synthesized as follows using the synthesized intermediate compound.

Preparation Example 1: Synthesis of Compound 3-2 (LT21-35-002)

In a 1-necked 100 mL flask, 5.0 g (15.6 mmol) of intermediate (5), 3.5 g (15.6 mmol) of intermediate (3), 258.4 mg (0.5 mmol) of Pd (dba) ₂ , S-Phos 383.2 mg (0.9 mmol), K ₃ PO ₄ 6.6 g (31.1 mmol) and 50 mL of xylene were added together and stirred under heating and reflux for 2 to 3 days. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrate was purified by column chromatography (Hex:EA) to obtain 1.2 g (yield: 15.1%) of Compound 3-2 (LT21-35-002) as a light green solid.

Preparation Example 2: Synthesis of Compound 3-43 (LT21-35-043)

In a 1-neck 100 mL flask, 5.0 g (12.4 mmol) of intermediate (10), 2.8 g (12.4 mmol) of intermediate (3), 357.1 mg (0.6 mmol) of Pd (dba) ₂ , S-Phos 510.0 mg (1.2 mmol), K ₃ PO ₄ 5.3 g (24.8 mmol) and 50 mL of xylene were added together and stirred under heating and reflux for 2 to 3 days. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrate was purified by column chromatography (Hex:EA) to obtain 1.5 g (yield: 20.3%) of compound 3-43 (LT21-35-043) as a pale yellow solid.

Preparation Example 3: Synthesis of Compound 3-47 (LT21-30-083)

. In a one-neck 100 mL flask, 5.0 g (13.5 mmol) of intermediate (6), 3.4 g (14.8 mmol) of intermediate (3), 0.2 g (0.4 mmol) of Pd (dba) ₂ , S-Phos 0.3 g (0.8 mmol), K ₃ PO ₄ 8.6 g (40.4 mmol), and 70 mL of xylene were added together and stirred under heating and reflux for 2 to 3 days. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. Purification was performed by column chromatography (Hex:EA) to obtain 2.4 g (yield: 32.1%) of Compound 3-47 (LT21-30-083) as a light green solid.

Preparation Example 4: Synthesis of Compound 3-56 (LT21-30-165)

In a one-necked 250 mL flask, 4.5 g (11.2 mmol) of intermediate (12), 2.5 g (11.2 mmol) of intermediate (3), 0.2 g (0.3 mmol) of Pd (dba) ₂ , S-Phos 0.3 g (0.7 mmol), K ₃ PO ₄ 4.7 g (22.3 mmol), and 110 mL of xylene were added together, and the mixture was stirred under heating and reflux all day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:EA) to obtain 2.6 g (yield: 39.3%) of Compound 3-56 (LT21-30-165) as a yellow solid.

Preparation Example 5: Synthesis of Compound 3-57 (LT21-30-180)

In a one-neck 250 mL flask, 3.5 g (8.0 mmol) of intermediate (14), 2.0 g (8.8 mmol) of intermediate (3), 0.1 g (0.2 mmol) of Pd (dba) ₂ , S-Phos 0.2 g (0.5 mmol), K ₃ PO ₄ 5.1 g (24.1 mmol), and 70 mL of xylene were added together, and the mixture was stirred under reflux heating throughout the day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:EA) to obtain 1.8 g (yield: 35.7%) of compound 3-57 (LT21-30-180) as a light green solid.

Preparation Example 6: Synthesis of compound 3-59 (LT21-35-059)

5.0 g (11.5 mmol) of intermediate (18), 2.6 g (11.5 mmol) of intermediate (3), 331.6 mg (0.6 mmol) of Pd (dba) ₂ , 473.4 mg (1.2 mmol) of S-Phos, After mixing 4.9 g (23.1 mmol) of K ₃ PO ₄ and 50 mL of xylene, the mixture was heated to 130 °C and stirred for 40 minutes. After the reaction was terminated and cooled to room temperature, the precipitated solid compound was filtered while washing with distilled water, toluene, and hexane. The solid compound was dissolved by heating in dichlorobenzene, filtered through celite, and washed with acetone to obtain 1.3 g (yield: 18.0%) of compound 3-59 (LT21-35-059) as a pale yellow solid.

Preparation Example 7: Synthesis of Compound 3-66 (LT21-30-250)

In a one-neck 250 mL flask, 4.0 g (11.4 mmol) of intermediate (20), 2.9 g (12.6 mmol) of intermediate (3), 0.2 g (0.3 mmol) of Pd (dba) ₂ , S-Phos 0.3 g (0.7 mmol), K ₃ PO ₄ 4.9 g (22.9 mmol), and 110 mL of xylene were added together, and the mixture was stirred under reflux heating throughout the day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (CHCl ₃ ) to obtain 2.5 g (yield: 40.4%) of Compound 3-66 (LT21-30-250) as a pale yellow solid.

Preparation Example 8: Synthesis of Compound 3-68 (LT21-30-239)

In a one-neck 250 mL flask, 5.0 g (13.1 mmol) of intermediate (22), 3.3 g (14.4 mmol) of intermediate (3), 0.2 g (0.4 mmol) of Pd (dba) ₂ , S-Phos 0.3 g (0.8 mmol), K ₃ PO ₄ 5.6 g (26.2 mmol), and 110 mL of xylene were added together, and the mixture was stirred under heating and reflux all day. After confirming the completion of the reaction, it was cooled to room temperature and the solvent was distilled off. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (CHCl ₃ ) to obtain 3.0 g (yield: 40.0%) of compound 3-68 (LT21-30-239) as a light green solid.

Preparation Example 9: Synthesis of Compound 3-77 (LT21-35-077)

In a one-neck 250 mL flask, 5.0 g (11.2 mmol) of intermediate (31), 2.6 g (11.3 mmol) of intermediate (3), 321.9 mg (0.6 mmol) of Pd (dba) ₂ , S-Phos 459.7 mg (1.1 mmol), K ₃ PO ₄ 4.8 g (22.4 mmol), and 110 mL of xylene were added together, and the mixture was stirred under reflux heating throughout the day. After confirming the completion of the reaction, it was cooled to room temperature and the solvent was distilled off. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (CHCl ₃ ) to obtain 1.7 g (yield: 23.9%) of compound 3-77 (LT21-35-077) as a pale yellow solid.

Preparation Example 10: Synthesis of Compound 3-83 (LT21-35-083)

In a one-neck 250 mL flask, 5.0 g (11.3 mmol) of intermediate (30), 2.6 g (11.3 mmol) of intermediate (3), 324.1 mg (0.6 mmol) of Pd (dba) ₂ , S-Phos 462.8 mg (1.1 mmol), K ₃ PO ₄ 4.8 g (22.6 mmol), and 110 mL of xylene were added together and stirred under heating and refluxing all day. After confirming the completion of the reaction, it was cooled to room temperature and the solvent was distilled off. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (CHCl ₃ ) to obtain 2.0 g (yield: 28.0%) of compound 3-83 (LT21-35-083) as a pale yellow solid.

Preparation Example 11: Synthesis of Compound 3-108 (LT21-35-108)

In a one-neck 250 mL flask, 5.0 g (11.1 mmol) of intermediate (32), 2.5 g (11.1 mmol) of intermediate (3), 317.6 mg (0.6 mmol) of Pd (dba) ₂ , S-Phos 453.6 mg (1.1 mmol), K ₃ PO ₄ 4.7 g (22.1 mmol), and 110 mL of xylene were added together and stirred under heating and refluxing all day. After confirming the completion of the reaction, it was cooled to room temperature and the solvent was distilled off. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (CHCl ₃ ) to obtain 1.8 g (yield: 25.3%) of compound 3-108 (LT21-35-108) as a pale yellow solid.

Preparation Example 12: Synthesis of Compound 3-121 (LT21-35-121)

In a 1-neck 100 mL flask, 5.0 g (15.6 mmol) of intermediate (5), 4.5 g (15.6 mmol) of intermediate (33), 258.4 mg (0.5 mmol) of Pd (dba) ₂ , S-Phos 383.2 mg (0.9 mmol), K ₃ PO ₄ 6.6 g (31.1 mmol) and 50 mL of xylene were added together and stirred under heating and reflux for 2 to 3 days. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrate was purified by column chromatography (Hex:EA) to obtain 2.0 g (yield: 24.3%) of compound 3-121 (LT21-35-121) as a light green solid.

Preparation Example 13: Synthesis of Compound 3-131 (LT21-35-131)

In a one-neck 100 mL flask, 5.0 g (12.2 mmol) of intermediate (36), 3.5 g (12.2 mmol) of intermediate (33), 349.3 mg (0.6 mmol) of Pd (dba) ₂ , S-Phos 499.0 mg (1.2 mmol), K ₃ PO ₄ 5.2 g (24.3 mmol) and 50 mL of xylene were added together and stirred for 2 to 3 days under heating and reflux. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrate was purified by column chromatography (Hex:EA) to obtain 2.2 g (yield: 29.3%) of Compound 3-131 (LT21-35-131) as a light green solid.

Preparation Example 14: Synthesis of Compound 3-250 (LT21-35-251)

5.0 g (11.5 mmol) of intermediate (18), 4.0 g (11.5 mmol) of intermediate (38), 331.6 mg (0.6 mmol) of Pd (dba) ₂ , 473.4 mg (1.2 mmol) of S-Phos, After mixing 4.9 g (23.1 mmol) of K ₃ PO ₄ and 50 mL of xylene, the mixture was heated to 130 °C and stirred for 40 minutes. After the reaction was terminated and cooled to room temperature, the precipitated solid compound was filtered while washing with distilled water, toluene, and hexane. The solid compound was dissolved by heating in dichlorobenzene, filtered through celite, and washed with acetone to obtain 2.0 g (yield: 24.8%) of compound 3-250 (LT21-35-251) as a pale yellow solid.

Preparation Example 15: Synthesis of Compound 3-257 (LT21-35-390)

In a 1-neck 100 mL flask, 5.0 g (12.6 mmol) of intermediate (39), 4.4 g (12.6 mmol) of intermediate (38), 362.6 mg (0.6 mmol) of Pd (dba) ₂ , _517.7 mg (1.3 mmol) of S-Phos, K ₃ PO ₄ 5.4 g (25.2 mmol) and 50 mL of xylene were added together and stirred for 2 to 3 days under heating and reflux. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrate was purified by column chromatography (Hex:EA) to obtain 2.3 g (yield: 27.5%) of Compound 3-257 (LT21-35-390) as a light green solid.

Preparation Example 16: Synthesis of Compound 4-3 (LT21-30-193)

In a one-necked 250 mL flask, 2.0 g (11.8 mmol) of 4-aminobiphenyl, 5.9 g (26.0 mmol) of intermediate (3), 0.4 g (0.7 mmol) of Pd (dba) ₂ , S-Phos 0.6 g (1.4 mmol), K ₃ PO ₄ 7.5 g (35.5 mmol), and 100 mL of xylene were added together and stirred under heating and reflux all day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:EA) to obtain 2.5 g (yield: 38.6%) of Compound 4-3 (LT21-30-193) as a yellow solid.

Preparation Example 17: Synthesis of Compound 4-4 (LT21-30-189)

In a one-neck 250 mL flask, 3.0 g (13.7 mmol) of intermediate (40), 6.9 g (30.1 mmol) of intermediate (3), 0.5 g (0.8 mmol) of Pd (dba) ₂ , S-Phos 0.7 g (1.6 mmol), K ₃ PO ₄ 8.7 g (41.0 mmol), and 110 mL of xylene were added together and stirred under heating and reflux all day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:EA) to obtain 3.0 g (yield: 36.4%) of Compound 4-4 (LT21-30-189) as a yellow solid.

Preparation Example 18: Synthesis of Compound 4-5 (LT21-30-188)

In a one-neck 250 mL flask, 2.5 g (11.9 mmol) of intermediate (11), 6.0 g (26.2 mmol) of intermediate (3), 0.4 g (0.7 mmol) of Pd (dba) ₂ , S-Phos 0.6 g (1.4 mmol), K ₃ PO ₄ 7.6 g (35.7 mmol), and 100 mL of xylene were added together, and the mixture was stirred under reflux all day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:EA) to obtain 2.4 g (yield: 34.2%) of Compound 4-5 (LT21-30-188) as a yellow solid.

Preparation Example 19: Synthesis of Compound 4-8 (LT21-35-080)

In a one-neck 250 mL flask, 2.5 g (11.9 mmol) of intermediate (17), 6.0 g (26.2 mmol) of intermediate (3), 0.4 g (0.7 mmol) of Pd (dba) ₂ , S-Phos 0.6 g (1.4 mmol), K ₃ PO ₄ 7.6 g (35.7 mmol), and 100 mL of xylene were added together, and the mixture was stirred under reflux all day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:EA) to obtain 2.4 g (yield: 34.2%) of Compound 4-8 (LT21-35-080) as a yellow solid.

Preparation Example 20: Synthesis of Compound 4-9 (LT21-30-253)

In a one-necked 250 mL flask, 2.3 g (12.6 mmol) of intermediate (19), 6.0 g (26.4 mmol) of intermediate (3), 0.4 g (0.8 mmol) of Pd (dba) ₂ , X-Phos 0.7 g (1.5 mmol), K ₃ PO ₄ 8.0 g (37.7 mmol), and 120 mL of xylene were added together and stirred under heating and reflux for 5 days. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (CHCl ₃ ) to obtain 3.0 g (yield: 42.2%) of compound 4-9 (LT21-30-253) as a pale yellow solid.

Preparation Example 21: Synthesis of Compound 4-10 (LT21-30-246)

In a one-necked 250 mL flask, 1.5 g (7.5 mmol) of intermediate (21), 3.6 g (15.8 mmol) of intermediate (3), 0.3 g (0.5 mmol) of Pd (dba) ₂ , S-Phos 0.4 g (0.9 mmol), K ₃ PO ₄ 4.8 g (22.5 mmol), and 80 mL of xylene were added together and stirred under heating and reflux all day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:EA) to obtain 1.6 g (yield: 35.0%) of compound 4-10 (LT21-30-246) as a pale yellow solid.

Preparation Example 22: Synthesis of Compound 4-33 (LT21-30-196)

2.5 g (12.9 mmol) of 4-amino-[1,1'-biphenyl]-4-carbonitrile in a one-neck 250 mL flask, intermediate (3) 6.4 g (28.3 mmol), Pd (dba) ₂ 0.4 g (0.8 mmol), S-Phos 0.6 g (1.5 mmol), K ₃ PO ₄ 8.2 g (38.6 mmol), and 110 mL of xylene were added together and stirred under heating and reflux all day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:EA) to obtain 1.6 g (yield: 21.6%) of Compound 4-33 (LT21-30-196) as a yellow solid.

Preparation Example 23: Synthesis of Compound 4-57 (LT21-35-570)

In a one-neck 250 mL flask, 5.0 g (11.5 mmol) of intermediate (41), 2.6 g (11.5 mmol) of intermediate (3), 329.3 mg (0.6 mmol) of Pd (dba) ₂ , S-Phos 470.3 g (1.2 mmol), K ₃ PO ₄ 4.9 g (22.9 mmol), and 100 mL of xylene were added together, and the mixture was stirred under heating and reflux all day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (Hex:EA) to obtain 2.1 g (yield: 29.2%) of Compound 4-57 (LT21-35-570) as a pale yellow solid.

Preparation Example 24: Synthesis of Compound 4-178 (LT21-30-277)

In a one-neck 250 mL flask, 5.0 g (10.1 mmol) of intermediate (43), 4.8 g (21.1 mmol) of intermediate (3), 0.3 g (0.6 mol) of Pd (dba) ₂ , X-Phos 0.6 g (1.2 mmol) and 120 mL of dioxane were added and stirred while K ₃ PO ₄ 6.4 g (30.2 mmol) and 40 mL of distilled water were added, and the mixture was refluxed at 100° C. for 2 days. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. After adding distilled water, extraction was performed with chloroform. The separated organic layer was dried over anhydrous MgSO ₄ , filtered and concentrated. The concentrated residue was purified by column chromatography (CHCl ₃ ) to obtain 2.1 g (yield: 33.4%) of Compound 4-178 (LT21-30-277) as a pale yellow solid.

Preparation Example 25: Synthesis of Compound 5-5 (LT21-35-320)

5.0 g (17.6 mmol) of intermediate (44), 8.0 g (35.2 mmol) of intermediate (3), 505.6 mg (0.9 mmol) of Pd (dba) _2, 722.0 mg (1.8 mmol) of S-Phos, 14.9 g (70.3 mmol) of K ₃ PO ₄ and 200 mL of xylene were added together, and the mixture was stirred under heating and reflux all day. After confirming the completion of the reaction, the mixture was cooled to room temperature and the solvent was removed. Distilled water was added to the concentrate and extracted with dichloromethane. The separated organic layer was dried over anhydrous MgSO4, filtered and concentrated. The concentrated residue was purified by column chromatography (CHCl ₃ ) to obtain 2.1 g (yield: 17.9%) of Compound 5-5 (LT21-35-320) as a yellow solid.

<Test Example>

For the compounds of the present invention, J.A. Measure n (refractive index) and k (extinction coefficient) using WOOLLAM's Ellipsometer.

Fabrication of single film for test example:

To measure the optical properties of the compound, a glass substrate (0.7T) was washed with Ethanol, DI Water, and Acetone for 10 minutes each, and then the compound was deposited on the glass substrate to a thickness of 800 Å to form a single film.

Fabrication of single film for comparative test example (Glass/REF01 (80 nm)):

The optical characteristic element was fabricated by depositing REF01 (80nm) on Glass. Before depositing the compound, Glass was treated with oxygen plasma for 2 minutes at 2×10 ^-2 Torr at 125 W. The compound is deposited at a rate of 1 Å/sec in a vacuum of 9×10 ^-7 Torr to form a single film.

Comparative test example 1 (REF01) 3-47 (LT21-30-083)

3-56 (LT21-30-165) 4-5 (LT21-30-188)

<Test Examples 1 to 3>

In the Comparative Test Example, a single film was prepared in the same manner as in the Comparative Test Example, except that each compound shown in Table 1 was used instead of REF01.

Optical properties of the compounds for the Comparative Test Example and Test Examples 1 to 3 are shown in Table 1.

The optical properties are the refractive index (n) constants at 450 nm and 620 nm wavelengths.

As can be seen from Table 1, the results of comparing Comparative Test Example 2 (REF02) and Test Example 3 (Compounds (4-5)) show similar chemical structures, but the refractive index depending on whether or not a cyano group is introduced. (2.522 compared to 2.270) was confirmed to be higher.

It can be determined that as the refractive index increases, the effect of extracting light emitted from inside the electrode to the outside increases.

The n value at 450 nm of Comparative Test Example 2 (REF02) was 2.270, whereas most of the Example compounds were found to have refractive indices generally higher than 2.300. This satisfies the high refractive index value required to secure a high viewing angle in the blue region.

device fabrication

For device fabrication, ITO, a transparent electrode, was used as the anode layer, HT01 was the hole injection layer, NPB was the hole transport layer, αβ-ADN was the host of the light emitting layer, Pyene-CN was the blue fluorescent dopant, ET201 was the electron transport layer, and Liq was An electron injection layer, Mg:Ag, was used as a cathode. The structures of these compounds are as follows.

Comparative Example: ITO / HT01 (90 nm) / NPB (25 nm) / αβ-ADN: 5% Pyrene-CN (200 nm) / ET201: Liq (=1: 1, 40 nm) / Liq (2 nm) / Mg:Ag (1:9, 10 nm)/REF01 (60 nm)

Blue fluorescence organic light emitting device is ITO / HT01 (90 nm) / NPB (25 nm) / αβ-ADN:5% Pyrene-CN (200 nm) / ET201:Liq (=1:1, 40 nm) / Liq (2 nm) ) / Mg: Ag (1:9, 10 nm) / REF01 (60 nm) were deposited in the order to fabricate a device. Before depositing the organic material, the ITO electrode was treated with oxygen plasma for 2 minutes at 125 W at 2 × 10 ^-2 Torr. Organic materials were deposited at a vacuum of 9 × 10 ^-7 Torr, Liq was deposited at 0.1 Å/sec, αβ-ADN was 0.18 Å/sec, Pyrene-CN was deposited at 0.02 Å/sec, and all other organic materials were deposited at 1 It was deposited at a rate of Å/sec. The capping layer material used in the experiment was selected as REF01. After the device fabrication was completed, the device was sealed in a glove box filled with nitrogen gas to prevent contact with air and moisture. After forming a barrier with 3M's adhesive tape, barium oxide, a moisture absorbent that can remove moisture, was added and a glass plate was attached.

Comparative test example 1 (REF01)

<Examples 1 to 25>

In the Comparative Example, a device was fabricated in the same manner as in the Comparative Example, except that each compound shown in Table 2 was used instead of REF01.

Table 2 shows the electrical light emitting characteristics of the organic light emitting diodes prepared in Comparative Example and Examples 1 to 25.

From the results of Table 2, the cyano group-substituted heteroaryl amine derivative compound according to the present invention can be used as a material for a capping layer of an organic electronic device including an organic light emitting device, and an organic electronic device including an organic light emitting device using the same It can be seen that exhibits excellent characteristics in efficiency, driving voltage, stability, etc. In particular, the compound according to the present invention exhibited high efficiency characteristics due to its excellent ability of micro-cavity phenomenon.

The compound of Formula 1 has unexpectedly desirable properties for use as a capping layer in OLEDs.

The compound of the present invention can be applied to industrial organic electronic device products due to these characteristics.

However, the synthesis example described above is an example, and reaction conditions may be changed as needed. In addition, the compound according to one embodiment of the present invention can be synthesized to have various substituents using methods and materials known in the art. By introducing various substituents into the core structure represented by Chemical Formula 1, it can have properties suitable for use in an organic light emitting device.

Reference Numerals 100: substrate, 110: first electrode, 120: second electrode, 200: organic material layer, 210: hole injection layer, 215: hole transport layer, 220: light emitting layer, 230: electron transport layer, 235: electron injection layer, 300: capping layer

Claims (5)

A heteroaryl amine derivative substituted with a high refractive index (n>1.7) cyano group for an organic light emitting device, represented by Formula 1 below.
[Formula 1]

In Formula 1,
L ₁ , L ₂ and L ₃ are each independently a direct bond; A substituted or unsubstituted arylene group; And it is selected from a substituted or unsubstituted heteroarylene group,
A represents a monovalent group having as a binding site one of R ₁ to R ₄ represented by the following formula (2);
B and C are each independently an aryl group in which a cyano group is substituted or unsubstituted; and a heteroaryl group in which a cyano group is substituted or unsubstituted; is selected from
a, b and c are integers from 0 to 5;
When a, b, and c are 0, it is a direct bond.
[Formula 2]

In Formula 2,
R ₁ to R ₄ are linking groups as binding sites;
Z- ₁ is O, S or NR _{5 ;}
R ₅ is a phenyl group unsubstituted or substituted with a cyano group; and a naphthyl group in which a cyano group is substituted or unsubstituted; selected from. The heteroaryl amine derivative according to claim 1, wherein the cyano group represented by any one of Formulas 3 to 5 in Formula 1 is substituted.
[Formula 3]

[Formula 4]

[Formula 5]

L ₁ , L ₂ and L ₃ are each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted pyridylene group, a substituted or unsubstituted dibenzofuran group, or a substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted benzoxazole group; and a substituted or unsubstituted benzthiazole group; is selected from
Ar ₁ and Ar ₂ are each independently a phenyl group unsubstituted or substituted with a cyano group; a naphthyl group in which a cyano group is substituted or unsubstituted; Dibenzofuran group; Dibenzothiophene group; A benzofuran group in which a cyano group is substituted or unsubstituted; A benzothiophene group in which a cyano group is substituted or unsubstituted; a fluorene group in which a cyano group is substituted or unsubstituted; A benzoxazole group in which a cyano group is substituted or unsubstituted; a benzthiazole group in which a cyano group is substituted or unsubstituted; is selected from
Z ₁ is as defined in Formula 2 above. According to claim 1,
The compound represented by Chemical Formula 1 is any one compound selected from compounds represented by Chemical Formulas 6 to 8 below, and a cyano group-substituted heteroaryl amine derivative.
[Formula 6]

[Formula 7]

[Formula 8]

a first electrode;
an organic material layer composed of a plurality of organic material layers disposed on the first electrode;
a second electrode disposed on the organic layer; and
A capping layer disposed on the second electrode; includes,
The organic material layer or the capping layer includes the cyano group-substituted heteroaryl amine derivative according to any one of claims 1 to 3. An organic light emitting device. According to claim 4,
wherein the organic material layer includes a light emitting layer and a hole transport layer, and the hole transport layer includes a heteroaryl amine derivative in which the cyano group is substituted.

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