KR102470622B1 - Tertiary amine derivatives and organic electroluminescent device including the same - Google Patents

Abstract

(상기 화학식 1에서 각 치환기들은 발명의 상세한 설명에서 정의한 바와 같다.)Provided is a tertiary amine derivative that effectively absorbs high-energy external light sources in the UV region and minimizes damage to organic materials inside the organic light emitting device, thereby contributing to a substantial improvement in lifespan of the organic light emitting device.
An organic electroluminescent device according to the present invention includes a first electrode; a second electrode; one or more organic material layers disposed between the first electrode and the second electrode; and a capping layer, wherein the capping layer includes a tertiary amine derivative represented by Formula 1 below.
[Formula 1]

(Each substituent in Formula 1 is as defined in the detailed description of the invention.)

Description

Tertiary amine derivatives and organic electroluminescent device including the same {Tertiary amine derivatives and organic electroluminescent device including the same}

The present invention relates to a tertiary amine derivative and an organic electroluminescent device including the same, wherein an organic electroluminescent device including a capping layer by the tertiary amine derivative has high refractive index characteristics and UV absorption 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, basic mechanisms such as charge injection, recombination, exciton generation, and light emission in organic materials and electroluminescence characteristics have been understood and studied.

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 consists of a multi-layer structure of ETL) and a cathode, and has a sandwich structure in which an organic multi-layer 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 organic materials. 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 therebetween. 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, an electron injection layer, and the like.

When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, 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 material 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 material 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 being 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 the organic light emitting diode itself has emerged.

Since the organic light emitting element is exposed to an external light source for a long time, it is in an environment where it is exposed to high-energy ultraviolet light. 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 in order 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, considerable deviations occur depending on the viewing angles. 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 an organic light emitting diode 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. In order to increase external luminous efficiency and prevent various problems that may be caused when exposed to daylight for a long time, development of a new functional capping layer (CPL) compound is required. In particular, there is a need to develop a capping layer (CPL) material having an excellent ability to absorb light in a UV wavelength range among CPL functions.

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 Publication No. 2019-0140233 (title of invention: organic light emitting compound and organic light emitting device including the same) Republic of Korea Patent Registration No. 10-1251455 (Title of Invention: Compounds Containing Quinoline Derivatives and Organic Electric Devices Using the Same, and Their Terminals)

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.

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 tertiary amine derivative represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1,

X ₁ and X ₂ are CH or N;

n, m, p and q are 0 or 1;

Ar ₁ and Ar ₂ are the same as or different from each other, and each independently a cyano group; an aryl group substituted with a cyano group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted pyridine group; A substituted or unsubstituted quinoline group; A substituted or unsubstituted quinoxaline group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted benzoxazole group; A substituted or unsubstituted benzthiazole group; And a substituted or unsubstituted benzimidazole group; which one is selected from (However, when X ₁ and X ₂ are CH at the same time, Ar ₁ to Ar ₂ exclude an unsubstituted naphthyl group.)

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

The compound according to the present invention exhibits UV absorption characteristics, thereby minimizing damage to organic materials in an organic light emitting device caused by an external light source, and improving efficiency, low driving voltage, and/or lifespan characteristics of an organic light emitting device.

In addition, in an organic light emitting device using the compound described in this specification as a capping layer, it is possible to significantly improve color purity due to improvement in light emitting efficiency and decrease in half width of the emission spectrum.

The compound according to the present invention can be used as a material for a capping layer (light efficiency improvement layer) that can improve the viewing angle and light efficiency of light extracted into the air due to the characteristic of exhibiting a high refractive index by introducing a cyano group.

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.
2 is a graph of light refraction and absorption characteristics when a tertiary amine derivative according to an embodiment of the present invention is used.

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. have. 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, the tertiary amine derivative compound used for the organic material layer and/or the capping layer will be described.

A tertiary amine derivative compound according to an embodiment of the present invention is represented by Formula 1 below

[Formula 1]

In Formula 1,

X ₁ and X ₂ are CH or N;

n, m, p and q are 0 or 1;

Ar ₁ and Ar ₂ are the same as or different from each other, and each independently a cyano group; an aryl group substituted with a cyano group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted pyridine group; A substituted or unsubstituted quinoline group; A substituted or unsubstituted quinoxaline group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted benzoxazole group; A substituted or unsubstituted benzthiazole group; And a substituted or unsubstituted benzimidazole group; which one is selected from (However, when X ₁ and X ₂ are CH at the same time, Ar ₁ to Ar ₂ exclude an unsubstituted naphthyl group.)

In one embodiment of the present invention, the tertiary amine derivative represented by Formula 1 may be any one selected from compounds represented by Formula 2 below, and the following compounds may be further substituted.

[Formula 2]

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 diode according to an exemplary embodiment of the present invention. Referring to FIG. 1 , an organic light emitting device according to an exemplary 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. The 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. have. 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 °C 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. At °C, the deposition rate can be freely adjusted to around 1 Å/s, and is not limited to specific conditions. In the case of forming the hole injection layer 210 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-styrene sulfonate)), 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 lifetime within a range in which the 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; cyano group-containing compounds; and the like, but is 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 may use a material having a high T1 value to block electrons moving to the hole transport region and prevent excitons formed in the light emitting layer 220 from being 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. 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 plays two roles as a host and a dopant. Eggplant is made 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. have. 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, and 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-permeable 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, the hard material may be soda lime glass, alkali-free glass, or alumino silicate 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. .

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 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 . Other lights that contact the second electrode 120 at a greater angle than the critical angle are totally reflected or reflected and are 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. Accordingly, the capping layer 300 is important from both viewpoints of protecting the inside of the organic light emitting device and simultaneously improving device characteristics. 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. have.

An 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 materials used.

Hereinafter, an example will be described in detail to describe the present specification in detail. 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 the present application are provided to more completely explain the present specification to those skilled in the art.

[Example]

intermediate synthesis example 1: synthesis of intermediate (1)

2-bromonaphthalene 20.0 g (96.6 mmol), benzophenone imine 19.3 g (106.3 mmol), Pd (dba) ₂ 1.7 g (2.9 mmol), BINAP 3.6 g (5.8 mmol) A mixture of 18.6 g (193.2 mmol) of , tert -butoxysodium and 500 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 chloroform solution through a celite pad, it was concentrated under reduced pressure. After the obtained compound was suspended in 300 mL of tetrahydrofuran, 15 mL of 6N hydrochloric acid was slowly added thereto, followed by stirring at 50 °C for 1 hour. After cooling to room temperature, the obtained solid was filtered under reduced pressure and washed with acetone. The filtered wet body was suspended in 300 mL of water, and the pH was adjusted to 8 or higher with saturated sodium carbonate solution, followed by stirring at room temperature for 4 hours. The obtained precipitate was filtered under reduced pressure, washed with water, and dried under reduced pressure to obtain 5.0 g (yield: 36%) of the compound (intermediate (1)) as a white solid.

intermediate synthesis example 2: synthesis of intermediate (3)

(Synthesis of Intermediate (2))

4-bromo-1-iodobenzene 10.0 g (35.3 mmol), dibenzofuran-4-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 (2)).

(Synthesis of intermediate (3))

Intermediate (2) 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 (3)) as a yellow solid.

intermediate synthesis example 3: synthesis of intermediate (4)

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 stirred at reflux for 3 hours. After cooling the reaction mixture to room temperature, it was washed with 326 mL of distilled water. The organic layer was separated, 100 mL of 6 N HCl was added, and the mixture was stirred at room temperature for 3 hours. The resulting solid was filtered, the filtered wet body was suspended in 300 mL of water, the pH was adjusted to 8 or higher with a saturated sodium carbonate solution, and 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 n-hexane to obtain 13.9 g (yield: 90%) of the compound (intermediate (4)) as a pale orange solid.

intermediate synthesis example 4: synthesis of intermediate (6)

(Synthesis of Intermediate (5))

3-quinolineboronic acid 50.0 g (289.1 mmol), 1-Bromo-4-iodobenzene 89.9 g (317.8 mmol), Pd (PPh ₃ ) ₄ 10.0 g (8.7 mmol), 99.8 g (722.1 mmol) of potassium carbonate, 1000 mL of toluene, 500 mL of ethanol and 500 mL of water were stirred at reflux for 12 hours. The reaction mixture was diluted with dichloromethane, washed with water, and the organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated. The concentrated mixture was purified by column chromatography to obtain 63.1 g (yield: 77%) of a white solid compound (intermediate (5)).

(Synthesis of Intermediate (6))

Intermediate (5) 25.0 g (88.0 mmol), Benzophenone imine 17.6 g (97.2 mmol), Pd (dba) ₂ 1.5 g (2.6 mmol), BINAP 3.2 g (5.3 mmol), tert -butoxysodium A mixture of 18.6 g (193.5 mmol) and 300 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 the obtained compound was suspended in 400 mL of tetrahydrofuran, 100 mL of 6N hydrochloric acid was slowly added thereto, followed by stirring at room temperature for 1 hour. The resulting precipitate was filtered under reduced pressure and then washed with tetrahydrofuran. The filtered wet body was suspended in 300 mL of water, and the pH was adjusted to 8 or higher with saturated sodium carbonate solution, followed by stirring at room temperature for 1 hour. The obtained precipitate was filtered under reduced pressure and washed with water to obtain 7.6 g (yield: 40%) of a white solid compound (intermediate (6)).

intermediate synthesis example 5: synthesis of intermediate (8)

(Synthesis of Intermediate (7))

2-bromo-1- (4-bromophenyl) ethanone [2-bromo-1- (4-bromophenyl) ethanone] 50.0 g (179.9 mol), benzene-1,2-diamine (benzene-1,2 -diamine) 19.5 g (179.9 mol) and 1000 mL of ethanol were added and stirred under reflux for 12 hours. The reaction mixture was cooled to room temperature, concentrated under reduced pressure, and then 200 mL of methanol was added. The resulting precipitate was filtered and washed with water. The layers were separated by extraction with chloroform. The separated chloroform layer was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 23.7 g (yield: 46%) of the compound (intermediate (7)) as a yellow solid.

(Synthesis of Intermediate (8))

Intermediate (7) 23.7 g (83.1 mmol), Benzophenone imine 16.6 g (91.4 mmol), Pd (dba) ₂ 1.4 g (2.5 mmol), BINAP 3.1 g (5.0 mmol), tert -butoxysodium A mixture of 16.0 g (166.2 mmol) and 300 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 300 mL of tetrahydrofuran, 50 mL of concentrated hydrochloric acid was slowly added, followed by stirring at 50 °C for 1 hour. The resulting precipitate was filtered under reduced pressure and then washed with tetrahydrofuran. The filtered wet body was suspended in 300 mL of water, and the pH was adjusted to 8 or higher with saturated sodium carbonate solution, followed by stirring at room temperature for 1 hour. The obtained precipitate was filtered under reduced pressure and washed with water to obtain 9.3 g (yield: 51%) of a yellow solid compound (Intermediate (8)).

intermediate synthesis example 6: synthesis of intermediate (11)

(Synthesis of Intermediate (10))

2-aminophenol (2-aminophenol) 10.0 g (91.6 mmol), 4-bromobenzaldehyde (4-Bromobenzaldehyde) 16.9 g (91.6 mmol) and ethanol 114 mL were added and stirred at room temperature for 6 hours. The reaction mixture was concentrated under reduced pressure and dried to obtain crude intermediate (9).

After dissolving intermediate (9) in 370 mL of dichloromethane, 2,3-dichloro-5,6-dicyano-p-benzoquinone (2,3-Dichloro-5,6-dicyano-p- 22.8 g (100.4 mmol) of benzoqui-none, DDQ) was added slowly. After stirring overnight, it was purified by column chromatography to obtain 30.5 g (yield: 94%) of a white solid compound (Intermediate (10)).

(Synthesis of Intermediate (11))

Intermediate (10) 10.0 g (36.5 mmol), Benzophenone imine 7.9 g (43.8 mmol), Pd (dba) ₂ 1.1 g (1.8 mmol), BINAP 2.3 g (3.7 mmol), cesium carbonate 35.7 g ( 109.6 mmol) and 243 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 the obtained compound was suspended in 182 mL of tetrahydrofuran, 30 mL of concentrated 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 5.9 g (yield: 78%) of the compound (intermediate (11)) as a yellow solid.

intermediate synthesis example 7: synthesis of intermediate (12)

2-bromodibenzo[b,d]thiophene 50.0 g (190.0 mmol), benzophenone imine 37.8 g (208.6 mmol), Pd (dba) ₂ 5.5 g (9.5 mmol), 11.8 g (19.0 mmol) of BINAP, 45.6 g (474.5 mmol) of sodium tert -butoxy and 800 mL of toluene were 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 the obtained compound was suspended in 600 mL of tetrahydrofuran, 30 mL of concentrated 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 300 mL of water, the pH was adjusted to 8 or higher with saturated sodium carbonate solution, and then 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 25.6 g (yield: 68%) of the compound (intermediate (12)) as a yellow solid.

Intermediate Synthesis Example 8: Synthesis of Intermediate (15)

(Synthesis of Intermediate (13))

In a one-neck 250 mL flask, 30.0 g (134.5 mmol) of 6-bromonaphthalen-2-ol, 19.3 g (215.2 mmol) of CuCN, 75 N,N-dimethylformamide (DMF) mL was added together and stirred under heating reflux all day. When the reaction was completed, it was cooled to room temperature, and 180 mL of 10% sodium hydroxide (NaOH) was added and stirred. After stirring for 20 to 30 minutes, pass through a celite pad, pass the filtered filtrate through a celite pad again, and wash with water. While stirring the filtrate, the pH was adjusted to 2-3 with 2N HCl and stirred for 3-4 hours. After stirring, the solid obtained by filtration was washed with water and washed with 50 mL of hexane to obtain 18.5 g (yield: 81.1%) of the compound (intermediate (13)) as a slightly brown solid.

(Synthesis of Intermediate (14))

18.5 g (109.4 mmol) of intermediate (13) and 550 mL of dichloromethane were added to a 1-necked 1000 mL flask, and while stirring, 34.6 g (437.4 mmol) of pyridine was added and anhydrous trifluoromethane sulfonic acid ( 46.3 g (164.0 mmol) of trifluoromethanesulfonic anhydride) was slowly added, the temperature was raised to room temperature, and the mixture was stirred throughout the day. After the reaction was completed, water was added at 0 ° C., extracted with dichloromethane, and the separated organic phase was dried with anhydrous MgSO ₄ , and purified by column chromatography (DCM) to obtain a white solid compound (intermediate (14) 20.5 g (yield) : 62.1%) was obtained.

(Synthesis of Intermediate (15))

20.5 g (68.1 mmol) of intermediate (14), 13.6 g (74.9 mmol) of benzophenone imine, 13.1 g (136.1 mmol) of NaOtBu, and 340 mL of toluene were added to a 500 mL 1-necked flask, stirred, and Pd (dba ) ₂ 1.2 g (2.0 mmol) and 2.5 g (4.1 mmol) of BINAP were added, and the mixture was stirred under reflux heating throughout the day. After the reaction was completed, it was cooled to room temperature, the solvent was removed, water was added, extracted with dichloromethane, and the separated organic phase was dried with anhydrous MgSO ₄ , passed through a celite pad with chloroform, and the solvent was removed by distillation under reduced pressure. . To obtain a compound of a slightly brown liquid, 500 mL of tetrahydrofuran was added and stirred, and the mixture was adjusted to pH 2 or higher with 4N HCl and stirred at 50 ° C. for 4 hours. When the reaction was completed, the solvent was removed, and 100 mL of acetone was added to the obtained solid, stirred for 30 minutes, and then filtered to obtain a red solid. The solid was adjusted to pH 8 or higher with NaOH, stirred for 30 minutes, extracted with dichloromethane, and the solvent was removed and purified by column chromatography (Hex/CHCl ₃ ) to obtain a slightly reddish solid compound (Intermediate (15)) 3.1 g ( Yield: 27.0%) was obtained.

intermediate synthesis example 9: synthesis of intermediate (16)

In a one-necked 500 mL flask, 13.6 g (48.2 mmol) of 1-bromo-4-iodobenzene, dibenzo[b,d]thiophen- 2-ylboronic acid) 10.0 g (43.8 mmol), Pd (PPh ₃ ) ₄ 1.5 g (1.3 mmol), and toluene 150 mL were added together and stirred, followed by 70 mL of ethanol, K ₂ CO ₃ 9.1 g (65.8 mmol), and 70 mL of water. was added and stirred for 8 hours under heating reflux. After the reaction was completed, it was cooled to room temperature, the solvent was blown off, water was added, extracted with dichloromethane, and the separated organic phase was dried over anhydrous MgSO ₄ , purified by column chromatography (DCM), and a slightly yellow solid compound (intermediate (16) ) 9.3 g (yield: 62.6%) was obtained.

intermediate synthesis example 10: synthesis of intermediate (18)

(Synthesis of Intermediate (17))

2-Bromodibenzofuran 20.0 g (80.9 mmol), bis (pinacolato) diboron 24.6 g (97.1 mmol), Pd (dppf) Cl ₂ CH ₂ Cl A mixture of 3.3 g (145 mmol) of ₂ , 14.3 g (145 mmol) of potassium acetate (KOAc), and 400 mL of 1,4-dioxane was stirred at 90°C for 12 hours. The reaction mixture was cooled to room temperature and concentrated. The concentrated residue was dissolved in dichloromethane, washed with water, and the organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated. The concentrated mixture was purified by column chromatography to obtain 19.8 g (yield: 83.1%) of a white solid compound (intermediate (17)).

(Synthesis of Intermediate (18))

Intermediate (17) 19.8 g (67.3 mmol), 4-bromo-1-iodobenzene 28.5 g (100 mmol), Pd (PPh ₃ ) ₄ 3.8 g (3.37 mmol), 2M A mixture of 67 mL (134 mmol) of sodium carbonate, 224 mL of toluene and 112 mL of ethanol was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, it was diluted with 200 mL of toluene and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrated mixture was purified by column chromatography to obtain 15.3 g (yield: 70.3%) of the compound (intermediate (18)) as a solid.

intermediate synthesis example 11: synthesis of intermediate (20)

(Synthesis of Intermediate (19))

In a one-neck 1000 mL flask, 20.0 g (76.0 mmol) of 4-bromodibenzo[b,d]thiophene, 15.3 mL (91.2 mmol) of benzophenone imine, and ₂ Pd (dba) 4.4 g (7.6 mmol), BINAP 9.5 g (15.2 mmol), Cs ₂ CO ₃ 74.3 g (228.0 mmol), and 380 mL of toluene were added and mixed, followed by reflux stirring for 17 hours. The reaction was terminated, cooled to room temperature, filtered through celite, and then concentrated. To obtain 49.9 g (yield: 100.0%) of a precipitated black liquid compound (intermediate (19)), the next reaction was carried out without further purification.

(Synthesis of Intermediate (20))

49.9 g (76.0 mmol) of intermediate (19) was added to 253 mL of tetrahydrofuran (THF) in a 500 mL one-necked flask to dissolve it, and then 101 mL (608.0 mmol) of 6 N hydrochloric acid solution was slowly added thereto. After stirring at room temperature for 17 hours, NaHCO ₃ was slowly added to neutralize, and the reaction was terminated after stirring for 30 minutes. After adding 400 mL of dichloromethane and 200 mL of distilled water, the organic layer was separated, and the separated organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. After purification by silica gel column chromatography (Hex:DCM:EA), recrystallization was performed with methanol and hexane to obtain 10.9 g (yield: 72.2%) of yellow solid compound (20).

intermediate synthesis example 12: synthesis of intermediate (21)

In a one-neck 250 mL flask, 2.4 g (16.8 mmol) of intermediate (1), 10.4 g (36.9 mmol) of 1-Bromo-4-iodobenzene, and 0.5 g of Pd (dba) ₂ (0.8 mmol), 0.9 g (1.7 mmol) of DPPF, 4.8 g (50.3 mmol) of NaOtBu, and 80 mL of toluene were refluxed and stirred for 6 hours. After cooling to room temperature, impurities were removed through celite filtration. After removing the solvent, it was purified by silica gel column chromatography (EA:HEX) to obtain 4.31 g (yield: 56.7%) of the compound (Intermediate (21)) as a white liquid.

intermediate synthesis example 13: synthesis of intermediate (23)

(Synthesis of Intermediate (22))

In a 1-necked 1 L flask, 22.9 g (76.0 mmol) of intermediate (14), 23.2 g (91.2 mmol) of PIN ₂ B ₂ , 3.1 g (3.8 mmol) of Pd(dppf)Cl ₂ DCM, 22.4 g (228 mmol) of KOAc were added. and 300 mL of 1,4-dioxane were refluxed and stirred for one day. After cooling at room temperature, impurities were removed through celite filtration. After completely removing the solvent, it was purified by silica gel column chromatography (DCM:HEX). The obtained solid was filtered with hexane to obtain 17.7 g (yield: 83.5%) of the compound (intermediate (22)) as a white solid.

(Synthesis of Intermediate (23))

In a one-neck 500 mL flask, 8.0 g (28.7 mmol) of intermediate (22), 9.9 g (57.3 mmol) of 4-bromoaniline, 3.3 g (2.9 mmol) of Pd (PPh ₃ ) ₄ , 2M K ₂ 58 mL (115 mmol) of CO ₃ , 110 mL of toluene and 55 mL of ethanol were refluxed and stirred for one day. After cooling to room temperature, extraction was performed using ethyl acetate. After removing moisture and solvent, the mixture was dissolved in chloroform (300 mL) and purified by silica gel column chromatography (EA:CHCl ₃ ). The obtained solid was filtered with a mixed solution (acetone/hexane) to obtain 3.87 g (yield: 55.4%) of the compound (intermediate (23)) as a yellow solid.

intermediate synthesis example 14: synthesis of intermediate (24)

In a one-necked 1 L flask, 10.0 g (58.8 mmol) of 4- (pyridin-4-yl) aniline (4- (pyridin-4-yl) aniline), 1-bromo-4-iodobenzene (1-bromo- After mixing 36.7 g (129.2 mmol) of 4-iodobenzene, 3.4 g (5.9 mmol) of Pd (dba) ₂ , 6.5 g (11.8 mmol) of DPPF, 16.9 g (176.3 mmol) of NaOtBu, and 294 mL of toluene, 17 It was refluxed and stirred for an hour. The reaction was terminated, cooled to room temperature, and filtered through Celite. The filtrate was concentrated and then purified by silica gel column chromatography (DCM:EA) to obtain 6.5 g (yield: 23.0%) of the compound (Intermediate (24)) as a beige solid.

intermediate synthesis example 15: synthesis of intermediate (25)

In a one-neck 250 mL flask, 4.3 g (17.6 mmol) of intermediate (23), 11.0 g (38.7 mmol) of 1-bromo-4-iodobenzene, 1.0 g of Pd (dba) ₂ (1.8 mmol), 2.0 g (3.5 mmol) of DPPF, 5.1 g (52.8 mmol) of NaOtBu, and 88 mL of toluene were mixed, followed by refluxing and stirring for 17 hours. The reaction was terminated, cooled to room temperature, and filtered through Celite. The filtrate was concentrated and then purified by silica gel column chromatography (Hex:DCM) to obtain 7.2 g (yield: 73.8%) of the compound (Intermediate (25)) as a beige solid.

intermediate synthesis example 16: synthesis of intermediate (26)

In a one-necked 250 mL flask, 2.8 g (16.5 mmol) of intermediate (15), 14.0 g (49.4 mmol) of 1-bromo-4-iodobenzene, and 1.0 g of Pd (dba) ₂ (1.6 mmol), 1.8 g (3.3 mmol) of DPPF, 4.7 g (49.4 mmol) of NaOtBu, and 82 mL of toluene were mixed, followed by refluxing and stirring for 17 hours. The reaction was terminated, cooled to room temperature, and filtered through Celite. The filtrate was concentrated and purified by silica gel column chromatography (Hex:DCM) to obtain 2.5 g (yield: 31.6%) of the compound (Intermediate (26)) as a beige solid.

intermediate synthesis example 17: synthesis of intermediate (27)

Intermediate (4) 5.0 g (22.8 mmol), 2- (4-bromophenyl) naphthalene (2- (4-bromophenyl) naphthalene) 6.5 g (22.8 mmol), NaOtBu 2.4 g (25.1 mmol) in a one-necked 250 mL flask ), and 150 mL of xylene were added together, followed by stirring, 0.4 g (0.7 mmol) of Pd(dba) ₂ and 0.3 mL (1.4 mmol) of P(t-Bu) ₃ were added, and the mixture was stirred under heating and reflux for 4 hours. When the reaction is complete, cool to room temperature, remove the solvent, add methanol, stir for 30 minutes, filter to obtain a solid, add acetone, stir for 30 minutes, filter to obtain a solid, dissolve with hot N-methyl-2-pyrrolidinone, and celite After passing through the pad, acetone was added dropwise, stirred for 3 to 4 hours, and filtered to obtain a solid, which was repeated twice to obtain 6.3 g (yield: 65.3%) of a light brown solid compound (Intermediate (27)).

intermediate synthesis example 18: synthesis of intermediate (28)

In a one-neck 500 mL flask, 10.0 g (50.2 mmol) of intermediate (12), 14.2 g (50.2 mmol) of 2- (4-bromophenyl) naphthalene, and Pd (dba) ₂ 1.4 g (2.5 mmol), S-Phos 2.1 g (5.0 mmol), NaOtBu 9.6 g (100.4 mmol), and xylene 200 mL 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 200 mL of dichlorobenzene, filtered through celite, and washed with acetone to obtain 10.3 g (yield: 51.2%) of a beige solid compound (Intermediate (28)).

intermediate synthesis example 19: synthesis of intermediate (30)

(Synthesis of Intermediate (29))

In a one-necked 1000 mL flask, 37.2 g (131.5 mmol) of 1-bromo-4-iodobenzene, dibenzo[b,d]thiophen-4-ylboronic acid (dibenzo[b ,d] thiophen-4-ylboronic acid) 30.0 g (131.5 mmol), Pd (PPh ₃ ) ₄ 4.6 g (3.9 mmol), and toluene 400 mL were added together and stirred, followed by ethanol 200 mL, K ₂ CO ₃ 27.3 g (197.3 mmol)/200 mL of water was added and stirred under heating reflux for 8 hours. After the reaction was completed, it was cooled to room temperature, the solvent was removed, water was added, extracted with dichloromethane, the organic phase was dried over anhydrous MgSO ₄ , and purified by column chromatography (DCM) to obtain a slightly yellow solid compound (intermediate (29)). ) 29.1 g (yield: 65.3%) was obtained.

(Synthesis of Intermediate (30))

5.0 g (22.8 mmol) of intermediate (4), 8.5 g (25.1 mmol) of intermediate (29), 2.4 g (25.1 mmol) of NaOtBu, and 150 mL of xylene were added to a 250 mL 1-necked flask, and stirred, and Pd (dba) ₂ 0.4 g (0.7 mmol) and 0.3 ml (1.4 mmol) of P(t-Bu) ₃ were added, and the mixture was stirred under reflux heating for 4 hours. When the reaction was completed, the mixture was cooled to room temperature, the solvent was removed, chloroform was passed through a celite pad, and the solvent was removed by distillation under reduced pressure. It was purified by column chromatography (Hex:CHCl ₃ ) to obtain 6.6 g (yield: 60.2%) of the compound (intermediate (30)) as a slightly red solid.

intermediate synthesis example 20: synthesis of intermediate (31)

In a one-neck 250 mL flask, 3.0 g (13.7 mmol) of intermediate (4), 8.5 g (30.1 mmol) of 1-Bromo-4-iodobenzene, and 0.4 g of Pd (dba) ₂ (0.7 mmol), 0.8 g (1.4 mmol) of DPPF, 3.9 g (41.0 mmol) of NaOtBu, and 70 mL of toluene were refluxed and stirred for 4 hours. After cooling at room temperature, impurities were removed through celite filtration. After removing the solvent, it was dissolved in dichloromethane and purified by silica gel column chromatography (DCM:HEX) to obtain 6.1 g (yield: 84.9%) of the compound (Intermediate (31)) as a white solid.

intermediate synthesis example 21: synthesis of intermediate (32)

In a one-neck 1000 mL flask, 51.1 g (198.0 mmol) of 4'-bromo-[1.1'-biphenyl]-4-carbonitrile, benzophenone 39.5 g (217.8 mmol) of Benzophenone imine, 57.1 g (593.9 mmol) of NaOtBu, and 500 mL of toluene were added together and stirred, and then 3.4 g (5.9 mmol) of Pd (dba) ₂ and 7.4 g (11.9 mmol) of BINAP were added. It was stirred all day under heating reflux. After the reaction was completed, the mixture was cooled to room temperature, the solvent was evaporated, water was added, extracted with dichloromethane, the organic phase was dried with anhydrous MgSO ₄ , chloroform was passed through a celite pad, and the solvent was removed by distillation under reduced pressure. The obtained slightly brown liquid compound was added to 500 mL of tetrahydrofuran, stirred, adjusted to pH 2 with 4N HCl, and stirred at 50° C. for 4 hours. When the reaction was completed, the solvent was removed, and acetone was added to the obtained solid, followed by stirring for 30 minutes, followed by filtration to obtain a red solid. The solid was adjusted to pH 8 or higher with NaOH, stirred for 30 minutes, extracted with dichloromethane, the solvent was removed, and purified by column chromatography (Hex:CHCl ₃ ) to obtain a slightly reddish solid compound (intermediate (32)) 12.0 g ( Yield: 31.1%) was obtained.

intermediate synthesis example 22: synthesis of intermediate (33)

Intermediate (29) 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 n-hexane to obtain 28.0 g (yield: 58%) of the compound (intermediate (33)) as a yellow solid.

intermediate synthesis example 23: synthesis of intermediate (35)

(Synthesis of Intermediate (34))

37.3 g (149 mmol) of 6-Bromo-2-naphthoic acid, 9.3 mL of DMF, and 240 mL of thionyl chloride (SOCl ₂ ) were added to a one-necked 1 L flask at 70°C for one day. while stirring. After confirming the reaction, the solvent was completely removed using toluene. It proceeded to the next reaction without treatment.

While stirring with 240 mL of dichloromethane, 120 mL of 25% NH ₄ OH and 120 mL of H ₂ O were slowly added dropwise at 0 °C. The mixture was stirred at room temperature for 1 hour or more, and after confirming the reaction, the resulting solid was filtered. The solid was washed with distilled water and a small amount of ethyl acetate to obtain 32.7 g (yield: 88.0%) of the compound (Intermediate (34)) as a white solid.

(Synthesis of Intermediate (35))

32.7 g (131 mmol) of intermediate (34), 21 mL (262 mmol) of Pyridine, and 260 mL of 1,4-dioxane were stirred in a 1-necked 1 L flask. 36 mL (262 mmol) of trifluoroacetic anhydride was slowly added dropwise at 0°C, and the mixture was stirred at room temperature for 5 hours. The reaction was terminated by adding distilled water, and extracted using ethyl acetate. After removing water and solvent, the mixture was filtered with a mixed solution (dichloromethane/methanol) to obtain 28.1 g (yield: 92.9%) of the compound (Intermediate (35)) as a white solid.

intermediate synthesis example 24: synthesis of intermediate (36)

15.0 g (72.5 mmol) of 4-bromophthalonitrile (4-Bromophthalonitrile), 22.1 g (86.9 mmol) of PIN ₂ B _{2 ,} 5.9 g (7.2 mmol) of Pd(dppf)Cl ₂ DCM, 35.6 g (362 mmol) of KOAc and 300 mL of 1,4-dioxane were refluxed and stirred for one day. After cooling at room temperature, impurities were removed through celite filtration. After completely removing the solvent, it was purified by silica gel column chromatography (DCM:HEX). The obtained solid was filtered with hexane to obtain 13.7 g (yield: 74.6%) of the compound (intermediate (36)) as a white solid.

intermediate synthesis example 25: synthesis of intermediate (37)

8.0 g (38.6 mmol) of 5-Bromo-1,3-benzenedicarbonitrile, 11.8 g (46.4 mmol) of PIN ₂ B ₂ , Pd ( dppf)Cl ₂ . DCM 3.2 g (3.9 mmol) _, KOAc 19.0 g (193 mmol) and 1,4-dioxane 160 mL were refluxed and stirred for one day. After cooling at room temperature, impurities were removed through celite filtration. After completely removing the solvent, it was purified by silica gel column chromatography (EA:DCM). The obtained solid was filtered with hexane to obtain 8.2 g (yield: 84.2%) of the compound (intermediate (37)) as a brown solid.

intermediate synthesis example 26: synthesis of intermediate (38)

In a one-necked 250 mL flask, 6.6 g (23.6 mmol) of intermediate (22), 6.7 g (23.6 mmol) of 1-bromo-4-iodobenzene, and Pd (PPh ₃ ) ₄ 0.8 g (0.7 mmol) and 80 mL of toluene were added together and stirred, then 40 mL of ethanol, 4.9 g (35.5 mmol) of K ₂ CO ₃ and 40 mL of water were added, and the mixture was stirred under reflux heating throughout the day. After the reaction was completed, it was cooled to room temperature, the solvent was evaporated, water was added, extracted with dichloromethane, the separated organic phase was dried over anhydrous MgSO ₄ , and purified by column chromatography (Hex:CHCl ₃ ) to form a yellow solid compound (intermediate (38)) 2.3 g (yield: 32.1%) was obtained.

Using the synthesized intermediate compound, various tertiary amine derivatives were synthesized as follows.

Example 1: Synthesis of compound 2-3 (LT19-30-309)

Intermediate (4) 2.0 g (9.1 mmol), 2-bromodibenzo [b, d] thiophene (2-bromodibenzo- [b, d] thiophene) 3.5 g (19.1 mmol), Pd (dba) ₂ 0.26 g ( A mixture of 0.45 mmol), 4.4 g (45.6 mmol) of tert -butoxysodium, 0.74 g (3.7 mmol, 50 wt% toluene solution) of tri- tert -butylphosphine and 20 mL of xylene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 80 mL of methanol was added. The resulting semi-solid precipitate was separated and purified by column chromatography to obtain 3.0 g (yield: 56%) of beige solid compound 2-3 (LT19-30-309).

Example 2: Synthesis of Compound 2-4 (LT19-30-272)

Intermediate (4) 1.2 g (5.3 mmol), Intermediate (5) 3.2 g (11.2 mmol), Pd (dba) ₂ 0.3 g (0.52 mmol), tert - butoxysodium 3.1 g (32.1 mmol), tri-tert- A mixture of 0.9 g of butylphosphine (2.1 mmol, 50 wt% toluene solution) and 50 mL of toluene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 500 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 1.4 g (yield: 41%) of yellow fluorescent solid Compound 2-4 (LT19-30-272).

Example 3: Synthesis of compound 2-5 (LT19-30-298)

Intermediate (4) 2.0 g (9.1 mmol), Intermediate (7) 5.2 g (18.2 mmol), Pd (dba) ₂ 0.3 g (0.5 mmol), tert - butoxysodium 2.6 g (27.4 mmol), tri-tert- A mixture of 0.4 g of butylphosphine (0.9 mmol, 50 wt% toluene solution) and 20 mL of xylene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 120 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 3.1 g (yield: 54%) of yellow solid compound 2-5 (LT19-30-298).

Example 4: Synthesis of compound 2-6 (LT19-30-201)

Intermediate (4) 3.0 g (13.7 mmol), Intermediate (2) 8.8 g (27.4 mmol), Pd (dba) ₂ 0.8 g (1.4 mmol), tri- tert -butylphosphine (50 wt% toluene solution) 1.1 g ( 2.8 mmol), 5.3 g (55.2 mmol) of tert -butoxysodium and 134 mL of toluene were stirred at reflux for 4 hours. The reaction mixture was cooled to room temperature, washed with water, and the organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated. The concentrated mixture was purified by column chromatography to obtain 3.5 g (yield: 36%) of compound 2-6 (LT19-30-201) as a white solid.

Example 5: Synthesis of Compound 2-15 (LT19-30-333)

Intermediate (6) 2.3 g (10.4 mmol), 2- (4-bromophenyl) naphthalene (2- (4-bromophenyl) naphthalene) 6.2 g (21.9 mmol), Pd (dba) ₂ 0.6 g (1.0 mmol), A mixture of 0.8 g (2.1 mmol) of tri- tert -butylphosphine (50 wt% toluene solution), 3.0 g (31.2 mmol) of sodium tert -butoxy and 104 mL of toluene was stirred at reflux for 4 hours. The reaction mixture was cooled to room temperature, washed with water, and the organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated. The concentrated mixture was purified by column chromatography to obtain 2.8 g (yield: 43%) of compound 2-15 (LT19-30-333) as a white solid.

Example 6: Synthesis of compound 2-16 (LT19-30-285)

Intermediate (6) 1.5 g (6.8 mmol), Intermediate (5) 4.1 g (14.3 mmol), Pd (dba) ₂ 0.4 g (0.7 mmol), tert - butoxysodium 3.9 g (40.6 mmol), tri-tert- A mixture of 1.1 g of butylphosphine (2.7 mmol, 50 wt% toluene solution) and 50 mL of toluene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 400 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 2.1 g (yield: 49%) of compound 2-16 (LT19-30-285) as a yellow fluorescent solid.

Example 7: Synthesis of compound 2-17 (LT19-30-281)

Intermediate (6) 2.0 g (9.1 mmol), Intermediate (7) 5.7 g (20.0 mmol), Pd (dba) ₂ 0.3 g (0.6 mmol), tert - butoxysodium 2.6 g (27.2 mmol), tri-tert- A mixture of 0.3 g of butylphosphine (0.7 mmol, 50 wt% toluene solution) and 50 mL of xylene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 100 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 3.0 g (yield: 53%) of compound 2-17 (LT19-30-281) as a yellow solid.

Example 8: Synthesis of compound 2-18 (LT19-30-231)

Intermediate (6) 2.3 g (10.6 mmol), Intermediate (2) 6.9 g (21.3 mmol), Pd (dba) ₂ 0.6 g (1.1 mmol), tert -butoxysodium 6.1 g (63.6 mmol), tri- tert - A mixture of 1.7 g of butylphosphine (4.2 mmol, 50 wt% toluene solution) and 100 mL of xylene was stirred at reflux for 16 hours. The reaction mixture was cooled to room temperature, washed with 300 mL of water, and the organic layer was separated. The separated organic layer was concentrated and purified by column chromatography to obtain 5.4 g (yield: 71%) of compound 2-18 (LT19-30-231) as a yellow solid.

Example 9: Synthesis of Compound 2-21 (LT319-30-228)

Intermediate (6) 3.0 g (13.6 mmol), Intermediate (10) 7.5 g (27.2 mmol), Pd (dba) ₂ 0.8 g (1.4 mmol), tert -butoxysodium 7.8 g (81.6 mmol), tri- tert - A mixture of 2.2 g of butylphosphine (5.4 mmol, 50 wt% toluene solution) and 100 mL of xylene was stirred at reflux for 16 hours. The reaction mixture was cooled to room temperature, washed with 300 mL of water, and the organic layer was separated. After concentrating the separated organic layer, it was purified by column chromatography to obtain 4.5 g (yield: 54%) of yellow solid compound 2-21 (LT19-30-228).

Example 10: Synthesis of compound 2-24 (LT19-35-121)

Intermediate (11) 2.0 g (9.5 mmol), Intermediate (5) 6.0 g (20.9 mmol), Pd (dba) ₂ 0.3 g (0.6 mmol), tert - butoxysodium 2.7 g (28.5 mmol), tri-tert- A mixture of 0.3 g of butylphosphine (0.8 mmol, 50 wt% toluene solution) and 50 mL of xylene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 100 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 1.8 g (yield: 31%) of yellow solid compound 2-24 (LT19-35-121).

Example 11: Synthesis of compound 2-25 (LT19-35-122)

4-aminobenzonitrile (4-aminobenzonitrile) 1.0 g (8.5 mmol), intermediate (5) 5.1 g (17.8 mmol), Pd (dba) ₂ 0.5 g (0.8 mmol), tri- tert -butylphosphine 1.4 g ( A mixture of 3.4 mmol, 50 wt% toluene solution), 4.9 g (50.7 mmol) of sodium tert -butoxy and 50 mL of xylene was stirred at reflux for 20 hours. After cooling the reaction mixture to room temperature, 400 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 2.5 g (yield: 56%) of yellow fluorescent solid compound 2-25 (LT19-35-122).

Example 12: Synthesis of compound 2-26 (LT19-30-296)

Intermediate (12) 1.1 g (8.4 mmol), Intermediate (5) 3.2 g (11.2 mmol), Pd (dba) ₂ 0.3 g (0.5 mmol), tert - butoxysodium 3.1 g (31.9 mmol), tri-tert- A mixture of 0.9 g of butylphosphine (2.1 mmol, 50 wt% toluene solution) and 50 mL of toluene was stirred at reflux for 18 hours. The reaction mixture was cooled to room temperature, diluted with 100 mL of chloroform, and washed with water. The organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated. The concentrated mixture was purified by column chromatography to obtain 1.0 g (yield: 31%) of compound 2-26 (LT19-30-296) as a yellow solid.

Example 13: Synthesis of compound 2-27 (LT19-30-279)

4- (dibenzofuran-4-yl) aniline (4- (dibenzo [b, d] furan-4-yl) aniline) 2.0 g (7.7 mmol), intermediate (5) 4.5 g (15.8 mmol), Pd ( dba) ₂ A mixture of 0.4 g (0.8 mmol), 4.4 g (46.2 mmol) of tert -butoxysodium, 1.2 g (3.1 mmol, 50 wt% toluene solution) of tri- tert -butylphosphine and 100 mL of toluene was added for 18 hours. while stirring at reflux. The reaction mixture was cooled to room temperature, diluted with 100 mL of chloroform, and washed with water. The organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated. The concentrated mixture was purified by column chromatography to obtain 3.0 g (yield: 58%) of compound 2-27 (LT19-30-279) as a beige solid.

Example 14: Synthesis of compound 2-29 (LT19-30-017)

Intermediate (11) 2.0 g (9.5 mmol), 2- (4-bromophenyl) naphthalene (2- (4-bromophenyl) naphthalene) 5.6 g (19.9 mmol), Pd (dba) ₂ 0.6 g (1.0 mmol), A mixture of 5.5 g (57.2 mmol) of tert -butoxysodium, 1.5 g (3.7 mmol, 50 wt% toluene solution) of tri- tert -butylphosphine and 100 mL of xylene was stirred at reflux for 16 hours. After cooling the reaction mixture to room temperature, 300 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by chromatography to obtain 2.9 g (yield: 50%) of yellow fluorescent solid compound 2-29 (LT19-30-019).

Example 15: Synthesis of compound 2-33 (LT19-30-284)

Intermediate (8) 2.0 g (9.0 mmol), Intermediate (7) 5.7 g (19.9 mmol), Pd (dba) ₂ 0.3 g (0.5 mmol), tert - butoxysodium 2.6 g (27.1 mmol), tri-tert- A mixture of 0.3 g of butylphosphine (0.7 mmol, 50 wt% toluene solution) and 50 mL of xylene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 100 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 1.9 g (yield: 33%) of compound 2-33 (LT19-30-284) as a yellow solid.

Example 16: Synthesis of compound 2-35 (LT19-30-301)

Intermediate (8) 2.0 g (9.0 mmol), Intermediate (5) 5.1 g (18.1 mmol), Pd (dba) ₂ 0.3 g (0.5 mmol), tert - butoxysodium 2.6 g (27.1 mmol), tri-tert- A mixture of 0.4 g of butylphosphine (0.9 mmol, 50 wt% toluene solution) and 20 mL of toluene was stirred at reflux for 12 hours. The reaction mixture was cooled to room temperature, diluted with 60 mL of chloroform, and washed with water. The organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated. The concentrated mixture was purified by column chromatography to obtain 2.7 g (yield: 48%) of yellow solid compound 2-35 (LT19-30-301).

Example 17: Synthesis of compound 2-36 (LT19-30-225)

Intermediate (8) 1.4 g (6.3 mmol), Intermediate (2) 4.5 g (13.9 mmol), Pd (dba) ₂ 0.2 g (0.4 mmol), tert -butoxysodium 1.8 g (19.0 mmol), tri- tert - A mixture of 0.2 g of butylphosphine (0.5 mmol, 50 wt% toluene solution) and 50 mL of xylene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 100 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 1.5 g (yield: 34%) of compound 2-36 (LT19-30-225) as a yellow solid.

Example 18: Synthesis of compound 2-37 (LT19-30-222)

Intermediate (8) 1.2 g (5.4 mmol), Intermediate (10) 3.3 g (11.9 mmol), Pd (dba) ₂ 0.2 g (0.3 mmol), tert -butoxysodium 1.6 g (16.3 mmol), tri- tert - A mixture of 0.2 g of butylphosphine (0.5 mmol, 50 wt% toluene solution) and 50 mL of xylene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 100 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 1.0 g (yield: 30%) of compound 2-37 (LT19-30-222) as a yellow solid.

Example 19: synthesis of compound 2-39 (LT19-30-300)

4-aminobenzonitrile (4-aminobenzonitrile) 1.0 g (8.5 mmol), intermediate (7) 4.8 g (16.9 mmol), Pd (dba) ₂ 0.2 g (0.4 mmol), tert -butoxysodium 2.4 g (25.4 mmol) ), a mixture of 0.3 g of tri- tert -butylphosphine (0.8 mmol, 50 wt% toluene solution) and 10 mL of toluene was stirred at reflux for 12 hours. The reaction mixture was cooled to room temperature, diluted with 40 mL of chloroform, and washed with water. The organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated. The concentrated mixture was purified by column chromatography to obtain 2.7 g (yield: 61%) of compound 2-39 (LT19-30-300) as a yellow solid.

Example 20: synthesis of compound 2-41 (LT19-30-256)

Intermediate (3) 2.0 g (7.7 mmol), Intermediate (8) 4.8 g (17.0 mmol), Pd (dba) ₂ 0.3 g (0.5 mmol), tert -butoxysodium 2.2 g (23.1 mmol), tri- tert - A mixture of 0.2 g of butylphosphine (0.6 mmol, 50 wt% toluene solution) and 50 mL of xylene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 100 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 3.0 g (yield: 58%) of yellow solid compound 2-41 (LT19-30-256).

Example 21: synthesis of compound 2-42 (LT19-30-260)

Intermediate (11) 1.6 g (7.6 mmol), Intermediate (8) 4.8 g (16.7 mmol), Pd (dba) ₂ 0.3 g (0.5 mmol), tert - butoxysodium 2.2 g (22.8 mmol), tri-tert- A mixture of 0.3 g of butylphosphine (0.6 mmol, 50 wt% toluene solution) and 50 mL of xylene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 100 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 2.0 g (yield: 43%) of compound 2-42 (LT19-30-260) as a yellow solid.

Example 22: synthesis of compound 2-45 (LT19-30-261)

Intermediate (12) 1.7 g (8.5 mmol), Intermediate (8) 5.4 g (18.8 mmol), Pd (dba) ₂ 0.3 g (0.5 mmol), tert - butoxysodium 2.5 g (25.6 mmol), tri-tert- A mixture of 0.3 g of butylphosphine (0.7 mmol, 50 wt% toluene solution) and 50 mL of xylene was stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 100 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 2.6 g (yield: 50%) of yellow solid compound 2-45 (LT19-30-261).

Example 23: synthesis of compound 2-46 (LT19-30-318)

Intermediate (8) 2.0 g (9.0 mmol), 2-bromodibenzo [b, d] thiophene (2-bromodibenzo [b, d] thiophene) 3.5 g (18.9 mmol), Pd (dba) ₂ 0.25 g (0.43 mmol), 4.3 g (44.7 mmol) of tert -butoxysodium, 0.73 g (1.8 mmol, 50 wt% toluene solution) of tri- tert -butylphosphine and 20 mL of xylene were stirred at reflux for 12 hours. After cooling the reaction mixture to room temperature, 80 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified by column chromatography to obtain 2.8 g (yield: 52%) of compound 2-46 (LT19-30-318) as a beige fluorescent solid.

Example 24: synthesis of compound 2-47 (LT20-30-203)

In a 1-neck 100 mL flask, 1.5 g (8.9 mmol) of intermediate (15), 5.3 g (18.7 mmol) of 2-(4-bromophenyl)naphthalene, and 0.5 Pd (dba) ₂ After mixing g (0.9 mmol), 0.8 mL (1.8 mmol) of P (tBu) ₃ , 2.6 g (26.7 mmol) of NaOtBu, and 36 mL of xylene, the mixture was heated to 130 ° C and stirred for 1 hour. After the reaction was terminated and cooled to room temperature, 100 mL of hexane was added and the mixture was stirred for 30 minutes. After filtering the precipitated solid compound, it was dissolved by adding dichloromethane and filtered through celite. After purification by silica gel column chromatography (Hex:DCM) and recrystallization with acetone, 1.3 g (yield: 25.5%) of Compound 2-47 (LT20-30-203) was obtained as a yellow solid.

Example 25: Synthesis of compound 2-52 (LT20-30-159)

In a one-necked 250 mL flask, 1.5 g (10.5 mmol) of intermediate (1), 4'-bromo[1,1'-biphenyl]-4-carbonitrile (4'-Bromo[1,1'-biphenyl]- 4-carbonitrile) 5.5 g (21.5 mmol), Pd (dba) ₂ 0.6 g (1.0 mmol), 50% P (t-Bu) ₃ 1.0 mL (2.1 mmol), NaOtBu 3.0 g (31.4 mmol) and xylene 40 mL was refluxed and stirred for 20 minutes. After cooling at room temperature, impurities were removed through celite filtration. After removing the solvent, it was dissolved in chloroform and purified by silica gel column chromatography (CHCl ₃ ). The obtained solid was filtered with a mixed solution (dichloromethane/acetone) to obtain 3.2 g (yield: 62.1%) of Compound 2-52 (LT20-30-159) as a yellow solid.

Example 26: synthesis of compound 2-53 (LT20-30-280)

In a one-neck 250 mL flask, 3.8 g (8.4 mmol) of intermediate (21), 5.3 g (21.0 mmol) of intermediate (36), 0.5 g (0.8 mmol) of Pd (dba) ₂ , 0.8 g (1.7 mmol) of XPhos, and 2M K ₃ PO ₄ 16 mL (33.5 mmol) and 40 mL of 1,4-dioxane were stirred at 85 °C for 3 hours. After cooling at room temperature, the resulting solid was filtered and washed with ethanol. The solid was dissolved in dichloromethane and purified through silica gel column chromatography (DCM:HEX). The resulting solid was filtered with a mixed solution (hexane/acetone) to obtain 4.0 g (yield: 87.7%) of Compound 2-53 (LT20-30-280) as an orange solid.

Example 27: synthesis of compound 2-54 (LT20-30-279)

In a one-necked 250 mL flask, 3.8 g (8.4 mmol) of intermediate (21), 5.3 g (21.0 mmol) of intermediate (37), 0.5 g (0.8 mmol) of Pd (dba) ₂ , 0.8 g (1.7 mmol) of XPhos, and 2M K ₃ PO ₄ 16 mL (33.5 mmol) and 40 mL of 1,4-dioxane were stirred at 85 °C for 3 hours. After cooling at room temperature, the resulting solid was filtered and washed with ethanol. After boiling the solid in chloroform (200 mL), it was purified through silica gel column chromatography (EA:CHCl ₃ ). The resulting solid was filtered with acetone to obtain 3.6 g (yield: 78.9%) of Compound 2-54 (LT20-30-279) as a yellow solid.

Example 28: synthesis of compound 2-55 (LT20-30-177)

In a one-neck 250 mL flask, 2.0 g (11.9 mmol) of intermediate (15), 4'-bromo-[1.1'-biphenyl]-4-carbonitrile (4'-bromo-[1.1'-biphenyl]-4- carbonitrile) 6.4 g (25.0 mmol), NaOtBu 2.3 g (35.7 mmol), and xylene 150 mL were added together and stirred, and Pd (dba) ₂ 0.4 g (0.7 mmol), P (t-Bu) ₃ 0.2 mL (1.0 mmol) ) was added and stirred under heating reflux all day. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed, chloroform was passed through a celite pad, and the solvent was removed by distillation under reduced pressure. It was purified by column chromatography (Hex:CHCl ₃ ) to obtain 2.0 g (yield: 32.1%) of Compound 2-55 (LT20-30-177) as a yellow solid.

Example 29: synthesis of compound 2-57 (LT20-30-311)

5.4 g (11.3 mmol) of intermediate (26), 6.3 g (24.8 mmol) of intermediate (37), 1.3 g (1.1 mmol) of Pd (PPh ₃ ) ₄ , and 80 mL of toluene were added to a 250 mL one-necked flask, stirred, and ethanol 40 mL of K ₂ CO ₃ 4.7 g (33.9 mmol) and 40 mL of water were added, and the mixture was stirred under reflux heating for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed, chloroform was passed through a celite pad, and the solvent was removed by distillation under reduced pressure. It was purified by column chromatography (Hex:CHCl ₃ ) to obtain 2.0 g (yield: 31.1%) of Compound 2-57 (LT20-30-311) as a yellow solid.

Example 30: synthesis of compound 2-59 (LT20-30-248)

4.0 g (8.9 mmol) of intermediate (21), 5.2 g (18.7 mmol) of intermediate (22), 0.5 g (0.9 mmol) of Pd (dba) ₂ , 0.9 g (1.8 mmol) of X-Phos, After mixing 7.6 g (35.6 mmol) of K ₃ PO ₄ and 45 mL of dioxane, the mixture was heated to 85° C. and stirred for 17 hours. The reaction was terminated, cooled to room temperature, and filtered while washing with dioxane. The filtrate was concentrated, and the precipitated solid compound was washed with ethanol and filtered. After purification by silica gel column chromatography (Hex:DCM) and washing with acetone, 1.9 g (yield: 36.6%) of compound 2-59 (LT20-30-248) was obtained as a yellow solid.

Example 31: synthesis of compound 2-60 (LT20-30-301)

In a 1-neck 100 mL flask, 1.0 g (6.0 mmol) of intermediate (15), 2.9 g (12.5 mmol) of intermediate (14), 0.3 g (0.6 mmol) of Pd (dba) ₂ , 0.5 g (1.2 mmol) of S-Phos, After mixing 3.8 g (17.8 mmol) of K ₃ PO ₄ and 24 mL of xylene, the mixture was heated to 130 °C and stirred for 2 hours. The reaction was terminated, cooled to room temperature, dissolved by adding dichloromethane, and filtered through celite. After purification by silica gel column chromatography (Hex:DCM), recrystallization with acetone and ethanol yielded 1.1 g (yield: 39.3%) of Compound 2-60 (LT20-30-301) as a yellow solid.

Example 32: synthesis of compound 2-61 (LT20-30-192)

1.2 g (7.1 mmol) of intermediate (15), 4.6 g (15.0 mmol) of intermediate (38), 2.1 g (21.4 mmol) of NaOtBu, and 150 mL of xylene were added to a 250 mL 1-necked flask, stirred, and Pd (dba) ₂ 0.3 g (0.4 mmol) and 0.1 mL (0.5 mmol) of P(t-Bu) ₃ were added, and the mixture was stirred under reflux heating for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed, chloroform was passed through a celite pad, and the solvent was removed by distillation under reduced pressure. Column chromatographyHex:CHCl ₃ ) yielded 1.3 g (yield: 29.3%) of Compound 2-61 (LT20-30-192) as a yellow solid.

Example 33: synthesis of compound 2-62 (LT20-30-210)

Put 2.0 g (11.9 mmol) of intermediate (15), 8.5 g (26.2 mmol) of intermediate (2), 3.4 g (35.7 mmol) of NaOtBu, and 150 mL of xylene in a 250 mL 1-necked flask, stir, and then add Pd (dba) ₂ 0.4 g (0.7 mmol) and 0.2 mL (1.0 mmol) of P(t-Bu) ₃ were added, and the mixture was stirred under reflux for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed, chloroform was passed through a celite pad, and the solvent was removed by distillation under reduced pressure. It was purified by column chromatography (Hex:CHCl ₃ ) to obtain 3.0 g (yield: 38.7%) of Compound 2-62 (LT20-30-210) as a yellow solid.

Example 34: synthesis of compound 2-64 (LT20-30-188)

2.0 g (11.9 mmol) of intermediate (15), 8.5 g (26.2 mmol) of intermediate (18), 3.4 g (35.7 mmol) of NaOtBu, and 150 mL of xylene were added to a 250 mL 1-necked flask, and while stirring, Pd (dba) ₂ 0.4 g (0.7 mmol) and 0.2 mL (1.0 mmol) of P(t-Bu) ₃ were added, and the mixture was stirred under reflux heating throughout the day. After the reaction was completed, 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 2.6 g (yield: 33.2%) of Compound 2-64 (LT20-30-188) as a yellow solid.

Example 35: synthesis of compound 2-89 (LT20-30-229)

In a one-neck 250 mL flask, 1.6 g (6.6 mmol) of intermediate (23), 4'-bromo [1,1'-biphenyl] -4-carbonitrile (4'-Bromo [1,1'-biphenyl] - 4-carbonitrile) 3.5 g (13.4 mmol), Pd (dba) ₂ 0.4 g (0.7 mmol), 50% P (t-Bu) ₃ 0.6 mL (1.3 mmol), NaOtBu 1.9 g (19.6 mmol) and xylene 26 mL was refluxed and stirred for 40 minutes. After cooling at room temperature, impurities were removed through celite filtration. After removing the solvent, it was purified by silica gel column chromatography (EA:HEX). The obtained solid was filtered with a mixed solution (dichloromethane/ethanol) to obtain 1.1 g (yield: 28.4%) of Compound 2-89 (LT20-30-229) as a yellow solid.

Example 36: synthesis of compound 2-92 (LT20-30-209)

Tris (4-bromophenyl) amine (Tis (4-bromophenyl) amine) 3.4 g (7.1 mmol), intermediate (22) 6.5 g (23.3 mmol), Pd (dba) ₂ 0.8 g ( 1.4 mmol), 1.4 g (2.8 mmol) of XPhos, 20 mL (42.3 mmol) of 2M K ₃ PO ₄ and 35 mL of 1,4-dioxane were stirred at 85° C. for one day. After cooling at room temperature, the resulting solid was filtered and washed with ethanol. After boiling the solid with chloroform, it was purified through silica gel column chromatography (EA:CHCl ₃ ). The obtained solid was filtered with a mixed solution (dichloromethane/acetone) to obtain 4.5 g (yield: 92.0%) of Compound 2-92 (LT20-30-209) as a yellow solid.

Example 37: synthesis of compound 2-94 (LT20-30-269)

4.0 g (8.3 mmol) of intermediate (24), 4.9 g (17.5 mmol) of intermediate (22), 0.5 g (0.8 mmol) of Pd (dba) ₂ , 0.8 g (1.7 mmol) of X-Phos, After mixing 7.1 g (33.3 mmol) of K ₃ PO ₄ and 45 mL of dioxane, the mixture was refluxed and stirred for 2 hours. The reaction was terminated, cooled to room temperature, and filtered while washing with dichloromethane. After concentrating the filtrate and adding dichloromethane and distilled water, the organic layer was extracted. After drying the extracted organic layer with anhydrous magnesium sulfate, the solvent was removed under reduced pressure. After purification by silica gel column chromatography (DCM:EA) and washing with acetone, 2.3 g (yield: 45.2%) of compound 2-94 (LT20-30-269) as a yellow solid was obtained.

Example 38: synthesis of compound 2-95 (LT20-30-281)

In a one-neck 100 mL flask, 3.8 g (6.8 mmol) of intermediate (25), 2.1 g (17.1 mmol) of pyridin-4-ylboronic acid, 0.4 g (0.7 mmol) of Pd (dba) ₂ After mixing 0.6 g (1.4 mmol) of S-Phos, 5.8 g (27.4 mmol) of K ₃ PO ₄ , 22 mL of toluene, and 11 mL of distilled water, the mixture was refluxed and stirred for 4 hours. The reaction was terminated, cooled to room temperature, dichloromethane and distilled water were added, and the organic layer was extracted. After drying the extracted organic layer with anhydrous magnesium sulfate, the solvent was removed under reduced pressure. It was purified by silica gel column chromatography (DCM:EA) to obtain 2.0 g (yield: 52.6%) of Compound 2-95 (LT20-30-281) as a yellow solid.

Example 39: synthesis of compound 2-96 (LT20-30-282)

In a one-necked 250 mL flask, 2.8 g (16.5 mmol) of intermediate (26), 14.0 g (49.4 mmol) of 1-bromo-4-iodobenzene, and 1.0 g of Pd (dba) ₂ (1.6 mmol), DPPF 1.8 g (3.3 mmol), NaOtBu 4.7 g (49.4 mmol), and toluene (Toluene) 82 mL were mixed and refluxed and stirred for 17 hours. The reaction was terminated, cooled to room temperature, and filtered through Celite. The filtrate was concentrated and then purified by silica gel column chromatography (Hex:DCM) to obtain 2.5 g (yield: 31.6%) of compound 2-96 (LT20-30-282) as a beige solid.

Example 40: synthesis of compound 2-97 (LT20-30-226)

In a one-necked 250 mL flask, 1.8 g (8.2 mmol) of intermediate (4), 4.0 g (17.2 mmol) of intermediate (35), 0.5 g (0.8 mmol) of Pd (dba) ₂ , 0.8 g (0.8 mmol) of 50% P (t-Bu) ₃ mL (1.6 mmol), 2.4 g (24.6 mmol) of NaOtBu and 35 mL of xylene were stirred at reflux for 20 minutes. After cooling at room temperature, impurities were removed through celite filtration. After removing the solvent, it was dissolved in chloroform and purified by silica gel column chromatography (EA:CHCl ₃ ). The obtained solid was filtered with a mixed solution (dichloromethane/acetone) to obtain 1.4 g (yield: 33.2%) of Compound 2-97 (LT20-30-226) as a yellow solid.

Example 41: synthesis of compound 2-98 (LT20-30-237)

In a one-neck 250 mL flask, 1.8 g (7.4 mmol) of intermediate (23), 3.6 g (15.5 mmol) of intermediate (35), 0.4 g (0.7 mmol) of Pd (dba) ₂ , 0.7 g (0.7 mmol) of 50% P (t-Bu) ₃ mL (1.5 mmol), 2.1 g (22.1 mmol) of NaOtBu and 36 mL of xylene were refluxed and stirred for 30 minutes. After cooling at room temperature, impurities were removed through celite filtration. After removing the solvent, it was purified by silica gel column chromatography (EA:DCM). The obtained solid was filtered with a mixed solution (acetone/ethanol) to obtain 1.7 g (yield: 41.5%) of Compound 2-98 (LT20-30-237) as a yellow solid.

Example 42: synthesis of compound 2-102 (LT20-30-234)

5.0 g (11.9 mmol) of intermediate (27), 3.7 g (17.8 mmol) of 5-bromoisophthalonitrile, 2.3 g (23.7 mmol) of NaOtBu, and 150 mL of xylene were added to a 250 mL one-necked flask. After stirring, 0.2 g (0.4 mmol) of Pd(dba) ₂ and 0.2 mL (0.7 mmol) of P(t-Bu) ₃ were added, followed by stirring under reflux for 4 hours. When the reaction is complete, it is cooled to room temperature, the solvent is blown off, and the solvent is removed by distillation under reduced pressure after passing through a celite pad with chloroform. Purification was performed by column chromatography (Hex:CHCl ₃ ) to obtain 2.2 g (yield: 34.2%) of Compound 2-102 (LT20-30-234) as a pale yellow solid.

Example 43: synthesis of compound 2-104 (LT20-30-146)

In a one-necked 250 mL flask, 3.5 g (7.7 mmol) of intermediate (21), 4.6 g (19.3 mmol) of dibenzothiophene-2-boronic acid, 0.4 g (0.8 mmol) of Pd (dba) ₂ mmol), XPhos 0.7 g (1.5 mmol), 2M K ₃ PO ₄ 15 mL (30.9 mmol) and 40 mL of 1,4-dioxane were stirred at 85° C. for 3 hours. After cooling at room temperature, the resulting solid was filtered and washed with ethanol. After boiling the solid with chloroform, it was purified through silica gel column chromatography (CHCl ₃ :HEX). After boiling the resulting solid in dichloromethane, it was cooled and filtered to obtain 2.8 g (yield: 54.5%) of Compound 2-104 (LT20-30-146) as a white solid.

Example 44: synthesis of compound 2-105 (LT20-30-124)

In a one-neck 250 mL flask, 2.0 g (10.1 mmol) of intermediate (20), 6.0 g (21.3 mmol) of 2- (4-bromophenyl) naphthalene, and 0.6 Pd (dba) ₂ After mixing g (1.1 mmol), P (tBu) ₃ 1.0 mL (2.2 mmol), NaOtBu 2.9 g (30.3 mmol), and 40 mL of xylene, the mixture was heated to 130 ° C and stirred for 1 hour. After the reaction was terminated and cooled to room temperature, methanol was added and stirred for 30 minutes. The precipitated solid compound was filtered, washed with methanol, and filtered through Celite. After purification by silica gel column chromatography (Hex:DCM), the product was recrystallized with dichloromethane and hexane to obtain 2.3 g (yield: 37.7%) of compound 2-105 (LT20-30-124) as a white solid.

Example 45: synthesis of compound 2-106 (LT20-30-126)

In a one-neck 250 mL flask, 4.0 g (10.0 mmol) of intermediate (28), 3.5 g (11.0 mmol) of intermediate (2), 0.3 g (0.5 mmol) of Pd (dba) ₂ , 0.5 mL (1.0 mmol) of P (tBu) ₃ ), NaOtBu 1.9 g (19.9 mmol), and xylene 50 mL were mixed, heated to 130 ° C, and stirred for 17 hours. After the reaction was terminated and cooled to room temperature, methanol was added and stirred for 30 minutes. The precipitated solid compound was filtered, washed with methanol, and filtered through Celite. Purification was performed by silica gel column chromatography (Hex:DCM) to obtain 2.2 g (yield: 34.4%) of compound 2-106 (LT20-30-126) as a white solid.

Example 46: synthesis of compound 2-107 (LT20-30-143)

In a one-neck 250 mL flask, 3.1 g (7.7 mmol) of intermediate (28), 2.9 g (8.5 mmol) of intermediate (16), 0.2 g (0.4 mmol) of Pd (dba) ₂ , 0.4 mL (0.8 mmol) of P (tBu) ₃ ), NaOtBu 1.5 g (15.4 mmol), and xylene (Xylene) 31 mL were mixed, heated to 130 ° C, and stirred for 1 hour. After the reaction was terminated and cooled to room temperature, hexane was added and stirred for 30 minutes. The precipitated solid compound was filtered, washed with hexane, and filtered through Celite. Purification was performed by silica gel column chromatography (Hex:DCM) to obtain 1.3 g (yield: 25.5%) of Compound 2-107 (LT20-30-143) as a white solid.

Example 47: synthesis of compound 2-108 (LT20-30-164)

5.0 g (10.5 mmol) of intermediate (30), 2-bromodibenzo [b, d] furan (2-bromodibenzo [b, d] furan) 2.8 g (11.5 mmol), NaOtBu 2.0 g ( 20.9 mmol) and 150 mL of xylene were added together and stirred, then 0.2 g (0.3 mmol) of Pd(dba) ₂ and 0.2 mL (0.6 mmol) of P(t-Bu) ₃ were added, followed by heating under reflux for 4 hours. After the reaction was completed, 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. Purification was performed by column chromatography (Hex:CHCl ₃ ) to obtain 2.4 g (yield: 35.6%) of Compound 2-108 (LT20-30-164) as a pale yellow solid.

Example 48: synthesis of compound 2-109 (LT20-30-233)

In a one-neck 250 mL flask, 3.2 g (6.1 mmol) of intermediate (31), 3.7 g (13.3 mmol) of intermediate (22), 0.4 g (0.6 mmol) of Pd (dba) ₂ , 0.6 g (1.2 mmol) of XPhos, and 2M K ₃ PO ₄ 12 mL (24.2 mmol) and 30 mL of 1,4-dioxane were stirred at 85 °C for 3 hours. After cooling at room temperature, the resulting solid was filtered and washed with ethanol. The solid was dissolved in dichloromethane and purified through silica gel column chromatography (DCM). The resulting solid was filtered with acetone to obtain 3.6 g (yield: 87.3%) of Compound 2-109 (LT20-30-233) as a yellow solid.

Example 49: synthesis of compound 2-110 (LT20-30-208)

2.0 g (10.3 mmol) of intermediate (32), 6.7 g (21.6 mmol) of intermediate (38), 3.0 g (30.9 mmol) of NaOtBu, and 150 mL of xylene were added to a 250 mL 1-necked flask, and while stirring, Pd (dba) ₂ 0.4 g (0.6 mmol) and 0.2 ml (0.8 mmol) of P(t-Bu) ₃ were added, and the mixture was stirred under reflux for 4 hours. After the reaction was completed, 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 2.3 g (yield: 35.1%) of Compound 2-110 (LT20-30-208) as a yellow solid.

Example 50: synthesis of compound 2-111 (LT20-30-260)

In a 1-neck 100 mL flask, 2.5 g (9.6 mmol) of intermediate (3), 4.7 g (20.2 mmol) of intermediate (35), 0.5 g (1.0 mmol) of Pd (dba) ₂ , 0.9 mL (1.9 mmol) of P (tBu) ₃ ), NaOtBu 2.8 g (28.9 mmol), and xylene (Xylene) 39 mL were mixed, heated to 130 ° C, and stirred for 30 minutes. The reaction was terminated, cooled to room temperature, dichloromethane and distilled water were added, and the organic layer was extracted. The extracted organic layer was dried over anhydrous magnesium sulfate and filtered through Celite. The filtrate was concentrated under reduced pressure, purified by silica gel column chromatography (Hex:DCM), and washed with acetone to obtain 2.6 g (yield: 48.1%) of Compound 2-111 (LT20-30-260) as a yellow solid.

Example 51: synthesis of compound 2-112 (LT20-30-271)

In a 1-neck 100 mL flask, 2.5 g (9.1 mmol) of intermediate (33), 4.4 g (19.1 mmol) of intermediate (35), 0.5 g (0.9 mmol) of Pd (dba) ₂ , 0.8 mL (1.8 mmol) of P (tBu) ₃ ), NaOtBu 2.6 g (27.2 mmol), and xylene (Xylene) 36 mL were mixed, heated to 130 ° C, and stirred for 1 hour. The reaction was terminated, cooled to room temperature, dichloromethane and distilled water were added, and the organic layer was extracted. The extracted organic layer was dried over anhydrous magnesium sulfate and filtered through celite. The filtrate was concentrated under reduced pressure, purified by silica gel column chromatography (Hex:DCM), and recrystallized with acetone and methanol to obtain 2.6 g (yield: 51.0%) of compound 2-112 (LT20-30-271) as a pale yellow solid. got it

<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 a single film was fabricated by depositing the compound on the glass substrate at 800 Å.

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. A single film is prepared by depositing the compound at a rate of 1 Å/sec in a vacuum of ^{9×10 -7 Torr} .

Comparative Test Example 1 (REF01) Comparative Test Example 2 (REF02) Test Example 36 (Compound (2-92))

<Test Examples 1 to 51>

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.

Table 1 shows the optical properties of the compounds according to Comparative Test Examples and Test Examples 1 to 51.

The optical properties are the refractive index constant at 450 nm and 620 nm wavelength and the absorption coefficient constant at 380 nm wavelength.

division compound n(450nm, 620nm) k(380nm) Comparative test example 1 REF01 2.000, 1.846 0.193 Comparative test example 2 REF02 2.184, 1.964 0.718 Test Example 1 2-3
(LT19-30-309) 2.063, 1.915 0.312 Test Example 2 2-4
(LT19-30-272) 2.277, 2.015 0.751 Test Example 3 2-5
(LT19-30-298) 2.703, 2.114 0.663 Test Example 4 2-6
(LT19-30-201) 2.203, 2.002 0.654 Test Example 5 2-15
(LT19-30-333) 3.030, 2.177 0.754 Test Example 6 2-16
(LT19-30-285) 2.333, 2.037 0.825 Test Example 7 2-17
(LT19-30-281) 2.794, 2.144 0.768 Test Example 8 2-18
(LT19-30-231) 2.235, 2.013 0.754 Test Example 9 2-21
(LT19-30-228) 2.340, 2.008 1.099 Test Example 10 2-24
(LT19-35-121) 2.245, 1.976 0.850 Test Example 11 2-25
(LT19-35-122) 2.794, 2.144 0.768 Test Example 12 2-26
(LT19-30-296) 2.227, 1.982 0.548 Test Example 13 2-27
(LT19-30-279) 2.306, 2.046 0.747 Test Example 14 2-29
(LT19-30-017) 2.245, 1.976 0.850 Test Example 15 2-33
(LT19-30-284) 3.030, 2.177 0.754 Test Example 16 2-35
(LT19-30-301) 2.605, 2.102 0.792 Test Example 17 2-36
(LT19-30-225) 2.470, 2.067 0.427 Test Example 18 2-37
(LT19-30-222) 2.541, 2.033 1.063 Test Example 19 2-39
(LT19-30-300) 2.561, 2.046 0.900 Test Example 20 2-41
(LT19-30-256) 2.810, 2.146 0.617 Test Example 21 2-42
(LT19-30-260) 2.829, 2.103 0.905 Test Example 22 2-45
(LT19-30-261) 2.638, 2.080 0.523 Test Example 23 2-46
(LT19-30-318) 2.352, 1.985 0.297 Test Example 24 2-47
(LT20-30-203) 2.274, 1.995 0.516 Test Example 25 2-52
(LT20-30-159) 2.274, 1.974 0.835 Test Example 26 2-53
(LT20-30-280) 2.701, 2.121 0.780 Test Example 27 2-54
(LT20-30-279) 2.302, 2.010 0.721 Test Example 28 2-55
(LT20-30-177) 2.274, 1.974 0.835 Test Example 29 2-57
(LT20-30-311) 2.417, 2.074 0.908 Test Example 30 2-59
(LT20-30-248) 2.603, 2.113 0.886 Test Example 31 2-60
(LT20-30-301) 2.396, 2.043 0.946 Test Example 32 2-61
(LT20-30-192) 2.693, 2.156 0.993 Test Example 33 2-62
(LT20-30-210) 2.209, 2.044 0.537 Test Example 34 2-64
(LT20-30-188) 2.294, 2.033 0.432 Test Example 35 2-89
(LT20-30-229) 2.588, 2.107 1.112 Test Example 36 2-92
(LT20-30-209) 2.822, 1.969 0.989 Test Example 37 2-94
(LT20-30-269) 2.659, 2.153 1.116 Test Example 38 2-95
(LT20-30-281) 2.419, 2.073 0.853 Test Example 39 2-96
(LT20-30-282) 2.287, 2.003 0.745 Test Example 40 2-97
(LT20-30-226) 2.364, 2.032 0.686 Test Example 41 2-98
(LT20-30-237) 2.535, 2.109 0.901 Test Example 42 2-102
(LT20-30-234) 2.053, 1.897 0.099 Test Example 43 2-104
(LT20-30-146) 2.197, 2.016 0.406 Test Example 44 2-105
(LT20-30-124) 2.062, 1.907 0.391 Test Example 45 2-106
(LT20-30-126) 2.120, 1.948 0.501 Test Example 46 2-107
(LT20-30-143) 2.183, 1.993 0.396 Test Example 47 2-108
(LT20-30-164) 2.117, 1.942 0.371 Test Example 48 2-109
(LT20-30-233) 2.658, 2.143 0.907 Test Example 49 2-110
(LT20-30-208) 2.726, 2.158 1.117 Test Example 50 2-111
(LT20-30-260) 2.616, 2.014 0.671 Test Example 51 2-112
(LT20-30-271) 2.335, 2.042 0.647

As can be seen from Table 1, the results of comparing Comparative Test Example 2 (REF02) and Test Example 36 (Compound (2-92)) have similar chemical structures, but the refractive index depending on whether or not a cyano group is introduced. (2.822 compared to 2.184) was confirmed to be higher.

The n value at 450 nm of Comparative Test Example 1 (REF01) was 2.000, whereas most of the Example compounds were found to have a refractive index generally higher than 2.000. This satisfies the high refractive index value required to secure a high viewing angle in the blue region.

In addition, it was confirmed that most of the example compounds had high k values at 380 nm corresponding to the beginning of the UV region. This may contribute to substantially improving the lifespan of the organic light emitting device by effectively absorbing a high-energy external light source in the UV region and minimizing damage to organic materials inside the organic light emitting device.

<Example>

device fabrication

For device fabrication, ITO, a transparent electrode, was used as the anode layer, 2-TNATA 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, and Liq was the electron injection layer. , Mg:Ag was used as the negative electrode. The structures of these compounds are as follows.

Comparative Example: ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / Alq ₃ (30 nm) / Liq (2 nm) / Mg: Ag (1:9, 10 nm) / REF01 (60 nm)

Blue fluorescent organic light emitting device is ITO (180 nm) / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: Pyrene-CN 10% (30 nm) / Alq ₃ (30 nm) / Liq (2 nm) / Mg:Ag (1:9, 10 nm) / REF (60 nm) in 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.

REF01 REF02

<Examples 1 to 51>

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

Table 2 shows the electrical emission characteristics of the organic light emitting diodes prepared in Comparative Example and Examples 1 to 51.

division compound Driving voltage [V] Efficiency [cd/A] life span(%) Comparative Example 1 REF01 4.50 5.10 88.92 Comparative Example 2 REF02 4.47 5.57 96.12 Example 1 2-3
(LT19-30-309) 4.23 5.35 97.12 Example 2 2-4
(LT19-30-272) 4.42 5.83 97.32 Example 3 2-5
(LT19-30-298) 4.43 5.99 97.10 Example 4 2-6
(LT19-30-201) 4.45 5.88 97.66 Example 5 2-15
(LT19-30-333) 4.51 5.68 98.12 Example 6 2-16
(LT19-30-285) 4.47 6.52 98.13 Example 7 2-17
(LT19-30-281) 4.45 6.13 97.45 Example 8 2-18
(LT19-30-231) 4.38 6.23 97.40 Example 9 2-21
(LT19-30-228) 4.40 6.10 97.32 Example 10 2-24
(LT19-35-121) 4.42 6.00 98.00 Example 11 2-25
(LT19-35-122) 4.49 5.99 95.61 Example 12 2-26
(LT19-30-296) 4.44 6.12 97.98 Example 13 2-27
(LT19-30-279) 4.45 6.05 97.56 Example 14 2-29
(LT19-30-017) 4.44 6.01 97.55 Example 15 2-33
(LT19-30-284) 4.44 6.52 97.98 Example 16 2-35
(LT19-30-301) 4.51 6.12 97.47 Example 17 2-36
(LT19-30-225) 4.40 6.10 97.32 Example 18 2-37
(LT19-30-222) 4.40 6.22 98.11 Example 19 2-39
(LT19-30-300) 4.42 6.11 97.54 Example 20 2-41
(LT19-30-256) 4.40 6.25 97.42 Example 21 2-42
(LT19-30-260) 4.41 6.23 97.55 Example 22 2-45
(LT19-30-261) 4.41 6.25 97.44 Example 23 2-46
(LT19-30-318) 4.51 5.82 97.33 Example 24 2-47
(LT20-30-203) 4.51 5.68 98.12 Example 25 2-52
(LT20-30-159) 4.40 6.25 97.42 Example 26 2-53
(LT20-30-280) 4.51 5.68 98.12 Example 27 2-54
(LT20-30-279) 4.40 6.22 98.11 Example 28 2-55
(LT20-30-177) 4.49 5.99 95.61 Example 29 2-57
(LT20-30-311) 4.41 6.23 97.55 Example 30 2-59
(LT20-30-248) 4.45 5.88 97.66 Example 31 2-60
(LT20-30-301) 4.38 6.23 97.40 Example 32 2-61
(LT20-30-192) 4.40 6.25 97.42 Example 33 2-62
(LT20-30-210) 4.40 6.10 97.32 Example 34 2-64
(LT20-30-188) 4.41 6.23 97.55 Example 35 2-89
(LT20-30-229) 4.44 6.52 97.98 Example 36 2-92
(LT20-30-209) 4.51 5.68 98.12 Example 37 2-94
(LT20-30-269) 4.42 6.11 97.54 Example 38 2-95
(LT20-30-281) 4.40 6.10 97.32 Example 39 2-96
(LT20-30-282) 4.44 6.12 97.98 Example 40 2-97
(LT20-30-226) 4.42 6.11 97.54 Example 41 2-98
(LT20-30-237) 4.44 6.52 97.98 Example 42 2-102
(LT20-30-234) 4.42 5.83 97.32 Example 43 2-104
(LT20-30-146) 4.43 5.99 97.10 Example 44 2-105
(LT20-30-124) 4.45 5.88 97.66 Example 45 2-106
(LT20-30-126) 4.51 5.68 98.12 Example 46 2-107
(LT20-30-143) 4.51 5.82 97.33 Example 47 2-108
(LT20-30-164) 4.51 5.68 98.12 Example 48 2-109
(LT20-30-233) 4.44 6.01 97.55 Example 49 2-110
(LT20-30-208) 4.42 6.00 98.00 Example 50 2-111
(LT20-30-260) 4.38 6.23 97.40 Example 51 2-112
(LT20-30-271) 4.40 6.25 97.42

From the results of Table 2, the tertiary 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 can have efficiency, driving voltage , it can be seen that excellent properties such as stability are exhibited. In particular, the compound according to the present invention has excellent micro-cavity ability and exhibits high efficiency.

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

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

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 Formula 1, it can have properties suitable for use in organic electroluminescent devices.

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 (3)

A tertiary amine derivative for a capping layer of an organic electroluminescent device represented by Formula 1 below.
[Formula 1]

In Formula 1,
n, m, and q are 0 or 1;
Ar ₁ and Ar ₂ are the same as or different from each other, and each independently a cyano group; an aryl group substituted with a cyano group; Substituted naphthyl group; A substituted or unsubstituted pyridine group; A substituted or unsubstituted quinoline group; A substituted or unsubstituted quinoxaline group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted benzoxazole group; A substituted or unsubstituted benzthiazole group; And a substituted or unsubstituted benzimidazole group; which one is selected from According to claim 1,
Formula 1 is a tertiary amine derivative for a capping layer of an organic electroluminescent device selected from compounds represented by Formula 2 below.
[Formula 2]

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 capping layer is an organic electroluminescent device comprising the tertiary amine derivative according to any one of claims 1 to 2.

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