KR102252493B1 - Benzazole derivatives and organic electroluminescent device including the same - Google Patents

Abstract

Provided is a benzazole derivative which effectively absorbs a high-energy external light source in the UV region and thus minimizes damage to organic materials in an organic electroluminescent device, thereby contributing to a substantial improvement in the service life of the organic electroluminescent device. An organic electroluminescent device according to the present invention comprises: a first electrode; a second electrode; at least one organic layer disposed between the first electrode and the second electrode; and a capping layer, wherein the organic layer or the capping layer comprises a benzazole derivative represented by chemical formula 1 (each of the substituents in the chemical formula 1 is the same as defined in the detailed description of the invention).

Description

Benzazole derivatives and organic electroluminescent device including the same}

The present invention relates to a benzazole derivative and an organic electroluminescent device including the same, wherein the organic electroluminescent device including a capping layer is made to have a low refractive index characteristic by the benzazole derivative.

OLED (Organic Light Emitting Diodes) is attracting attention as a display using the self-luminous phenomenon in the display industry.

In OLED, in 1963, Pope et al. first attempted a study of carrier injection type electroluminescence (EL) using a single crystal of anthracene aromatic hydrocarbon. 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 luminous efficiency, various approaches such as structural change of devices and material development have been taken [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 (ETL). ), and a multilayer structure of a cathode, and a sandwich structure in which an electronic organic multilayer film is formed between two electrodes.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. An organic light-emitting device using the 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 made of a multilayer structure made of different materials in order 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. In the structure of such an organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls into a state, it glows. These organic light emitting devices are 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 can 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, according to their functions.

Light-emitting materials include blue, green, and red light-emitting materials and yellow and orange light-emitting materials necessary to realize better natural colors according to the light-emitting color. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a luminescent material. The principle is that when a small amount of a dopant having an energy band gap smaller than that of a host mainly constituting the light emitting layer and having excellent light emission efficiency is mixed in a light emitting layer, excitons generated from 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 of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.

In order to sufficiently express the excellent characteristics of the above-described organic light emitting device, materials that form 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 recognized by products.

However, as the organic light-emitting device is commercialized and time passes, the need for other characteristics other than the light-emitting characteristics of the organic light-emitting device itself has emerged.

In most cases, the organic light emitting device is exposed to an external light source, so it is in an environment exposed to ultraviolet rays having high energy. Accordingly, there is a problem that the organic material constituting the organic light emitting device is continuously affected. In order to prevent exposure to such a high-energy light source, the problem can be solved by applying a capping layer having ultraviolet absorption characteristics to the organic light-emitting device.

In general, it is known that the viewing angle characteristics of organic light-emitting devices are wide, but from the viewpoint of the light source spectrum, considerable variation occurs depending on the viewing angle. This is due to the total refractive index of the glass substrate, organic material, and electrode material constituting the organic light-emitting device and the emission wavelength of the organic light-emitting device. This is due to the occurrence of a deviation between the appropriate refractive indices.

In general, the higher the required refractive index value of blue and the longer the wavelength, the smaller the required refractive index value. Accordingly, it is necessary to develop a material forming a capping layer that simultaneously satisfies the above-mentioned ultraviolet absorption characteristics and an appropriate refractive index.

The efficiency of an organic light-emitting device can be generally 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 in order to perform light conversion.

External luminous efficiency refers to the efficiency in which light generated in the organic layer is emitted to the outside of the organic light-emitting device.

In order to improve overall efficiency, it is necessary to increase not only the internal luminous efficiency but also the external luminous efficiency. There is a need to develop a capping layer (CPL) material having an excellent ability to increase external luminous efficiency.

Republic of Korea Patent Publication No. 2016-0062307 (name of the invention: organic light emitting display device including a high refractive index capping layer)

It is an object of the present invention 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.

It is an object of the present invention to provide a highly efficient and long-life organic electroluminescent device including a capping layer having improved refractive index and 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 material layer; And a capping layer disposed on the second electrode, wherein the organic material layer or the capping layer provides an organic electroluminescent device including a benzazole derivative represented by Formula 1 below.

[Formula 1]

In Formula 1,

Z ₁ is O or S,

X ₁ , X ₂ , X _3, X ₄ and X ₅ are each independently CH or N,

R ₁ to R ₆ are the same as or different from each other, and are at least any one selected from hydrogen, a methyl group, a tert-butyl group, a trimethylsilyl group, a fluoro group, a trifluoromethyl group, and a cyano group.

The compounds described herein can be used as a material for an organic material layer of an organic light-emitting device.

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

In addition, in an organic light-emitting device using the compound described in the present specification as a capping layer, it is possible to remarkably improve the color purity according to the improvement of luminous efficiency and reduction of the half width of the emission spectrum.

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

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

In the present invention, various modifications may be made and various forms may be applied, and specific embodiments will be illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

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

In the present application, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance the possibility of the presence or addition. Further, 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 the other part is "directly above" but also the case where another part is in the middle.

In the present specification, “substituted or unsubstituted” refers to a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a hydroxy group, a silyl group, a boron group, a phosphine oxide group, a phosphine sulfide group, an alkyl group, an alkoxy group, an alke It may mean substituted or unsubstituted with one or more substituents selected from the group consisting of a nil group, an aryl group, a hetero aryl group, and a heterocyclic group. In addition, each of the substituents exemplified above may be substituted or unsubstituted. For example, the biphenyl group may be interpreted as an aryl group, or may be interpreted as a phenyl group substituted with a phenyl group.

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

In the present specification, the alkyl group may be linear, branched or cyclic. The number of carbon atoms in 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-oxy 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-trico A group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, and n-triacontyl group, etc. are mentioned, It is not limited to these.

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

In the present 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 aryl groups include phenyl group, naphthyl group, fluorenyl group, anthracenyl group, phenanthryl group, biphenyl group, terphenyl group, quarterphenyl group, quincphenyl group, sexyphenyl group, triphenylenyl group, pyrenyl group, peryleneyl group, naphtha Although a senyl group, a pyrenyl group, a benzofluoranthenyl 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 including one or more of O, N, P, Si, and S as heterogeneous elements. The N and S atoms may be oxidized in some cases, and the N atom(s) may be quaternized in some cases. 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 thiophene group, furan group, pyrrole group, imidazole group, pyrazolyl group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridine group, bipyridine group, pyrimidine group, triazine group , Tetrazine group, triazole group, tetrazole group, acridyl group, pyridazine group, pyrazinyl group, quinoline group, quinazoline group, quinoxaline group, phenoxazine group, phthalazine group, pyrido pyrimidine group, pyrido pyrazino Pyrazine group, isoquinoline group, cinnoly group, indole group, isoindole group, indazole group, carbazole group, N-aryl carbazole group, N-heteroaryl carbazole group, N-alkyl carbazole group, benzoxazole group, benzoimidazole group , Benzothiazole group, benzocarbazole group, benzothiophene group, benzothiophene group, benzoisothiazolyl, benzoisoxazolyl, dibenzothiophene group, thienothiophene group, benzofuran group, phenanthroline group, phenanthridine group , Thiazole group, isoxazole group, oxadiazole group, thiadiazole group, isothiazole group, isoxazole group, phenothiazine group, benzodioxole group, dibenzosilol group and dibenzofuran group, isobenzofuran group, etc. It is not limited to these. In addition, there are N-oxide aryl groups corresponding to the monocyclic hetero aryl group or polycyclic hetero aryl group, for example, quaternary salts such as a pyridyl N-oxide group and a quinolyl N-oxide group. Not limited.

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

In the present 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, trimethyl boron group, triethyl boron group, t-butyldimethyl boron group, triphenyl boron group, diphenyl boron group, and phenyl boron group.

In the present specification, the alkenyl group may be linear or branched. The number of carbon atoms 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, 1-butenyl group, 1-pentenyl group, 1,3-butadienyl aryl group, styrenyl group, and 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, and 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, and 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 group, 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, an arylheteroarylamine group means 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 where the corresponding substituent is substituted, another substituent substituted on an atom where the corresponding substituent is substituted, or a substituent that is three-dimensionally adjacent to the substituent. have. For example, in 1,2-dimethylbenzene, two methyl groups can be interpreted as "adjacent groups", and in 1,1-diethylcyclopentene, 2 The two ethyl groups can be interpreted as “adjacent groups” to each other.

Hereinafter, the benzazole derivative compound used in the organic material layer and/or the capping layer will be described.

The benzazole derivative compound according to an embodiment of the present invention is represented by the following formula (1).

[Formula 1]

In Formula 1,

Z ₁ is O or S,

X ₁ , X ₂ , X _3, X ₄ and X ₅ are each independently CH or N,

R ₁ to R ₆ are the same as or different from each other, and are at least any one selected from hydrogen, a methyl group, a tert-butyl group, a trimethylsilyl group, a fluoro group, a trifluoromethyl group, and a cyano group.

In an embodiment of the present invention, the benzazole derivative represented by Formula 1 may be any one selected from compounds represented by Formula 2 and Formula 3, and the following compounds may be further substituted.

[Formula 2]

[Formula 3]

Hereinafter, an embodiment of the present invention will be described with reference to FIGS. 1 and 2.

1 is a schematic cross-sectional view of an organic light-emitting device according to an embodiment of the present invention. Referring to FIG. 1, in an organic light emitting diode according to an embodiment, a first electrode 110, a hole injection layer 210, a hole transport layer 215, a light emitting layer 220, and an electron are sequentially stacked on a substrate 100. 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 to face 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, a light emitting 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 Formula 1 of the present invention.

In the organic light-emitting device of the exemplary embodiment illustrated 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 on the substrate 100 by using an electrode material deposition method, an electron beam evaporation method, or a sputtering method. 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 front emission, and thus, 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), and Mg-Ag (magnesium-silver), which are not oxides. 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 a hole transport region 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 The electron transport regions 230 to 235 disposed on the 220 may be included.

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

The 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). It plays a role and generally has a thicker thickness than the electron transport region because the hole mobility is faster than the electron mobility.

The hole transport regions 210 to 215 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.

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 made 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 a 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 / electron Although it may have a structure of the blocking layer (EBL), 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, and an LB method. When the hole injection layer 210 is formed by vacuum deposition, the deposition conditions are 100 to 500 depending on the compound used as the material of the hole injection layer 210 and the structure and thermal characteristics of the hole injection layer 210. The deposition rate at °C can be freely controlled by 1Å/s before and after, and is not limited to a specific condition. In the case of forming the hole injection layer 210 by the spin coating method, the coating conditions are different depending on the characteristics between the compound used as the material of the hole injection layer 210 and the layers formed as the interface, but the coating speed and coating are used for even film formation. After the solvent is removed, heat treatment or the like 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, and TCTA. (4,4',4"-tris(N-carbazolyl)triphenylamine (4,4',4"-tris(Ncarbazolyl) triphenylamine)), Pani/DBSA (Polyaniline/Dodecylbenzenesulfonic acid: polyaniline/dodecylbenzene) Sulfonic acid), PEDOT/PSS (Poly(3,4-ethylenedioxythiophene) /Poly(4-styrene sulfonate):poly(3,4-ethylenedioxythiophene) /poly(4-styrenesulfonate)), Pani/CSA ( Polyaniline/Camphor sulfonic acid: polyaniline/camphor sulfonic 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 the corresponding organic layers of each hole transport region 210 to 215 are not limited to the same thickness. For example, if the thickness of the hole injection layer 210 is 50 Å, the thickness of the hole transport layer 215 may be 1000 Å, and the thickness of the electron blocking layer may be 500 Å. The thickness condition of the hole transport regions 210 to 215 may be set to a degree that satisfies the efficiency and lifetime within a range in which the increase in the driving voltage of the organic light emitting device does not increase. The organic layer 200 is a hole injection layer 210, a hole transport layer 215, a functional layer having a hole injection function and a hole transport function at the same time, a buffer layer, an electron blocking layer, a light emitting layer 220, a hole blocking layer, an electron transport layer It may include one or more layers selected from the group consisting of 230, an electron injection layer 235, and a functional layer having an electron transport function and an electron injection function at the same time.

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

The charge-generating material is generally composed of a material having very low HOMO and LUMO. For example, the LUMO of the charge-generating material has a similar value to that of the hole transport layer 215 material. Due to such a low LUMO, the electrons of the LUMO are vacant, and holes are easily transferred to the adjacent hole transport layer 215 to improve 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 tetracyanoquinonedimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane Quinone derivatives such as phosphorus (F4-TCNQ) and the like; Metal oxides such as tungsten oxide and molybdenum oxide; And a cyano group-containing compound such as Compound 2-22 and the like, but are not limited thereto.

In addition to the aforementioned materials, the hole transport regions 210 to 215 may further include a charge generating material to improve conductivity. The charge generating material may be uniformly or non-uniformly dispersed in the hole transport regions 210 to 215. The charge generating material may be, for example, a p-dopant. The p-dopant may be one of a quinone derivative, a metal oxide, and a cyano group-containing compound, but is not limited thereto. For example, non-limiting examples of p-dopants include quinone derivatives such as TCNQ (Tetracyanoquinodimethane) and F4-TCNQ (2,3,5,6-tetracyanoquinodimethane), metal oxides such as tungsten oxide and molybdenum oxide, and the like. However, it 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 emission layer 220. As a material included in the hole buffer layer, a material capable of being 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 to the hole transport regions 210 to 215. The electron blocking layer may use a material having a high T1 value so as not only to block electrons moving to the hole transport region, but also to prevent the excitons formed in the light emitting layer 220 from diffusing into the hole transport regions 210 to 215. For example, in general, _{a host of the light emitting layer 220 having a high T 1} value may be used as a material for the electron blocking layer.

The emission layer 220 is provided on the hole transport regions 210 to 215. The emission 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 emission layer 220 may have a single layer made of a single material, a single layer made of a plurality of different materials, or a multilayer structure having a plurality of layers made of a plurality of different materials.

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

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

The dopant of the emission layer 220 according to an embodiment may be an organic metal complex. The content of a general dopant may be selected from 0.01 to 20%, and is not limited thereto in some cases.

The electron transport regions 230 to 235 are provided on the emission 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 is not limited thereto.

The electron transport regions 230 to 235 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.

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 made of an electron injection material and an electron transport material. have. In addition, the electron transport regions 230 to 235 have a single layer structure made of a plurality of different materials, or an electron transport layer 230 / electron injection layer 235 sequentially stacked from the light emitting layer 220, and hole blocking. The layer/electron transport layer 230/electron injection layer 235 may have a 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 are various such as vacuum evaporation method, spin coating method, cast method, LB method (Langmuir-Blodgett), inkjet printing method, laser printing method, laser induced thermal imaging (LITI), etc. 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 compound. However, the present invention 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), It may include ADN (9,10-di(naphthalene-2-yl)anthracene) and a mixture thereof.

Since the electron transport layer 230 is selected as a material having a fast electron mobility or a slow electron mobility according to the structure of the organic light emitting device, it is necessary to select a variety of materials, and in some cases, the following Liq or Li may be doped.

The electron transport layers 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 above-described range, satisfactory electron transport characteristics can be obtained without a substantial increase in driving voltage.

When the electron transport regions 230 to 235 include the electron injection layer 235, the electron transport regions 230 to 235 select a metal material that facilitates injection of electrons, and LiF, LiQ (Lithium quinolate), Lanthanum group metals such as Li ₂ O, BaO, NaCl, CsF, and Yb, or halogenated metals such as RbCl and RbI may be used, but are not limited thereto.

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

As mentioned 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 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), and Balq It can be, 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 used in combination with a metal having a relatively low work function, an electroconductive compound, an alloy, and 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 a semi-transmissive film formed of the material and a transparent conductive film formed of indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium tin zinc oxide (ITZO), etc. Can be

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

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

In the organic light emitting diode, as voltages are applied to the first electrode 110 and the second electrode 120, respectively, holes injected from the first electrode 110 pass through the hole transport regions 210 to 215 and the emission layer The electrons are moved to 220, and electrons injected from the second electrode 120 are transferred to the emission layer 220 through the electron transport regions 230 to 235. The electrons and holes recombine in the emission layer 220 to generate excitons, and the excitons fall from the excited state to the ground state to emit light.

The light path generated in the light emitting layer 220 may exhibit very different trends depending on the refractive indexes of organic and inorganic materials constituting the organic light emitting device. Light passing through the second electrode 120 may pass only light transmitted at an angle smaller than the critical angle of the second electrode 120. In addition, light that contacts the second electrode 120 greater than the critical angle is totally reflected or reflected, and thus cannot be emitted to the outside of the organic light-emitting device.

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

The capping layer 300 is positioned on the outermost side of the organic light-emitting device, and does not affect the driving of the device at all and has a profound effect on device characteristics. Therefore, the capping layer 300 is important from both viewpoints of improving device characteristics as well as an internal protection role of the organic light-emitting device. Organic materials absorb light energy in a specific wavelength region, which depends on the energy band gap. If this energy band gap is adjusted for the purpose of absorbing the UV region that may 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 properties. have.

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

Hereinafter, examples will be described in detail in order to describe the present specification in detail. However, the 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 describe the present specification to those having average instructions in the art.

[Example]

Intermediate Synthesis example 1: Synthesis of intermediate (3)

(Synthesis of intermediate (1))

6-bromonaphthalen-2-ol 10.0 g (44.8 mmol), 4-fluorophenylboronic acid 6.3 g (44.8 mmol), Pd ( PPh ₃ ) ₄ 1.6 g (1.3 mmol), K ₃ PO ₄ 28.6 g (134.5 mmol), 150 mL of toluene, 30 mL of ethanol, and 30 mL of water were mixed and stirred under reflux for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CHCl ₃ ) and solidified with a mixed solution (DCM/Hex) to obtain 8.1 g (yield: 76.0%) of a white solid compound (intermediate (1)).

(Synthesis of intermediate (2))

8.1 g (34.1 mmol) of the intermediate compound (1) was dissolved in 170 mL of dichloromethane (DCM), 8.2 mL (102.2 mmol) of pyridine was added dropwise, and the temperature was lowered to 0°C. Tf ₂ O (Trifluoromethanesulfonic anhydride) 6.9 mL (40.9 mmol) was slowly added dropwise, the temperature was raised to room temperature, and the mixture was reacted for 12 hours. After washing the reaction product with 100 mL of water, the separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography (CHCl ₃ ) to form a yellow liquid compound (intermediate (2)) 12.6 g (yield: 100). %).

(Synthesis of intermediate (3))

In a 1-neck 500 mL flask, intermediate (2) 12.6 g (34.0 mmol), pinacolato diboron 13.0 g (51.0 mmol), Pd (dppf) Cl ₂ -CH ₂ Cl ₂ 556 mg (680.5) μmol), KOAc 10.0 g (102.1 mmol) and 170 mL of 1,4-dioxane were mixed, and then stirred at 100° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction product was passed through a pad of Celite and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl ₃ ) to obtain 7.55 g (yield: 63.7%) of a white solid compound (intermediate (3)).

Intermediate Synthesis example 2: Synthesis of intermediate (6)

(Synthesis of intermediate (4))

6-bromonaphthalen-2-ol (6-bromonaphthalen-2-ol) 50.0 g (224.2 mmol), 3,5-bistrifluoromethylphenylboronic acid ((3,5-bis(trifluoromethyl)phenyl) boronic acid) 57.8 g (224.2 mmol), Pd (PPh ₃ ) ₄ 7.8 g (6.7 mmol), K ₃ PO ₄ 142.7 g (672.5 mmol), toluene 600 mL, ethanol 200 mL, and water 200 mL were mixed, and then 12 Stir at reflux for hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CHCl ₃ ) and solidified with a mixed solution (DCM/Hex) to obtain 57.2 g (yield: 71.6%) of a white solid compound (intermediate (4)).

(Synthesis of intermediate (5))

57.2 g (160.6 mmol) of the intermediate compound (4) was dissolved in 800 mL of dichloromethane (DCM), 38.8 mL (481.7 mmol) of pyridine was added dropwise, and the temperature was lowered to 0°C. After slowly adding 32.4 mL (192.7 mmol) of Tf ₂ O dropwise, the temperature was raised to room temperature and reacted for 12 hours. After washing the reaction product with water (500 mL), the separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography (CHCl ₃ ) to form a yellow solid compound (intermediate (5)) 78.0 g (yield : 100%).

(Synthesis of intermediate (6))

In a 1-neck 2 L flask, intermediate (5) 78.0 g (159.7 mmol), pinacolato diboron 60.8 g (239.6 mmol), Pd (dppf) Cl ₂ -CH ₂ Cl ₂ 2.6 g (3.2 mmol), KOAc 47.0 g (479.2 mmol) and 800 mL of 1,4-dioxane were mixed, and then stirred at 100° C. for 5 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction product was passed through a pad of Celite and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl ₃ ) to obtain 57.0 g (yield: 76.5%) of a white solid compound (intermediate (6)).

Intermediate Synthesis example 3: Synthesis of intermediate (8)

(Synthesis of intermediate (7))

6-Bromonaphthalen-2-ol 15.0 g (67.2 mmol), 4- (trifluoromethyl) phenyl boronic acid 12.8 g (67.2) mmol), Pd(PPh ₃ ) ₄ 2.3 g (2.0 mmol), 2M sodium carbonate 67.2 mL (134.5 mmol), 700 mL of toluene, and 350 mL of ethanol were stirred under reflux for 12 hours. After the reaction mixture was cooled to room temperature, the solvent was removed, water was added, and 1000 mL of dichloromethane was added to separate the organic layer, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a slightly white solid compound (Intermediate (7). )) 12.1 g (yield: 62.4%) was obtained.

(Synthesis of intermediate (8))

Intermediate (7) 12.1 g (42.0 mmol) and 400 mL of dichloromethane were added, stirred, and 5.0 g (63.0 mmol) of pyridine was added, followed by 17.8 g (Trifluoromethanesulfonic anhydride) at 0 °C. 63.0 mmol) was slowly added, the temperature was raised to room temperature, and the mixture was stirred throughout the day. When the reaction is complete, add water and 500 mL of dichloromethane at 0 °C. The organic layer is separated, dried over anhydrous magnesium sulfate, and the obtained compound is purified by silica gel column chromatography to obtain a pale brown solid compound (intermediate (8)) 8.7 g (yield : 49.3%) was obtained.

Intermediate Synthesis example 4: Synthesis of intermediate (10)

(Synthesis of intermediate (9))

6-Bromonaphthalen-2-ol (6-Bromonaphthalen-2-ol) 15.0 g (67.2 mmol), phenyl boronic acid 8.2 g (67.2 mmol), Pd (PPh ₃ ) ₄ 2.3 g (2.0 mmol), 67.2 mL (134.5 mmol) of 2M sodium carbonate, 700 mL of toluene, and 350 mL of ethanol were stirred under reflux for 12 hours. After the reaction mixture was cooled to room temperature, the solvent was removed, water was added, and 1000 mL of dichloromethane was added to separate the organic layer, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a slightly white solid compound (Intermediate (9). )) 12.1 g (yield: 81.7%) was obtained.

(Synthesis of intermediate (10))

Intermediate (9) 12.1 g (42.0 mmol) and 400 mL of dichloromethane were added, stirred, and 5.0 g (63.0 mmol) of pyridine was added, followed by 17.8 g (Trifluoromethanesulfonic anhydride) at 0 °C. 63.0 mmol) was slowly added, the temperature was raised to room temperature, and the mixture was stirred all day. Upon completion of the reaction, water and 500 mL of dichloromethane were added at 0°C, and the organic layer was separated and dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a pale brown solid compound (intermediate (10)) 12.3 g (yield : 83.1%) was obtained.

Intermediate Synthesis example 5: Synthesis of intermediate (14)

(Synthesis of intermediate (11))

In a 1-neck 3000 mL flask, 6-bromonaphthalen-2-ol 120.0 g (537.9 mmol), bis (pinacolato) diboron} 150.3 g (591.7) mmol), Pd(dppf)Cl ₂ -DCM 17.6 g (21.5 mmol), potassium acetate 211.2 g (1.1 mol), and 2000 mL of Dioxane were added together and refluxed at 100° C. for the entire day under nitrogen. Upon completion of the reaction, the solvent was _{removed, water was added, extracted with CHCl 3} , and the separated organic layer was dried over anhydrous MgSO ₄ and purified by column chromatography to form a pale yellow solid compound (intermediate (11)) 102.2 g (yield: 70.3%) was obtained.

(Synthesis of intermediate (12))

1-bromo-2,3,4,5,6-pentafluorobenzene (1-bromo-2,3,4,5,6-pentafluorobenzene) 20.0 g (81.3 mmol), intermediate (11) 21.9 g ( 81.3 mmol), Pd(PPh ₃ ) ₄ 2.8 g (2.4 mmol), potassium carbonate 28.1 g (203.2 mmol), 300 mL of toluene, 150 mL of ethanol, and 150 mL of water were stirred under reflux for 12 hours. 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 20.0 g (yield: 79.3%) of a white solid compound (intermediate (12)).

(Synthesis of intermediate (13))

A mixture of 20.0 g (64.5 mmol) of intermediate (12), 7.6 mL (96.7 mmol) of pyridine, 16.2 mL (96.7 mmol) of dichloromethane, and 500 mL of dichloromethane was added for 16 hours. Stirred. After cooling the reaction mixture to 0 °C, water was added. The solid compound thus obtained was filtered to obtain 21.5 g (yield: 75.4%) of a white solid compound (intermediate (13)).

(Synthesis of intermediate (14))

Intermediate (13) 10.0 g (22.6 mmol), PIN ₂ B ₂ 11.5 g (45.2 mmol), Pd (dppf) ₂ DCM 735.0 mg (0.9 mmol), potassium acetate 4.4 g (45.2 mmol) and a mixture of dioxane 300 mL. Stir at reflux for 12 hours. The obtained compound was filtered through a Silica pad and then solidified to obtain 7.5 g (yield: 79.0%) of a brown solid compound (intermediate (14)).

Intermediate Synthesis example 6: Synthesis of intermediate (17)

(Synthesis of intermediate (15))

In a 1-neck 500 mL flask, 2-(4-bromophenyl)benzooxazole (2-(4-bromophenyl)benzo[d]oxazole) 10.0 g(36.5 mmol), Bis(pinacolato)diboron 10.2 g(40.1 mmol) , Pd(dppf)Cl ₂ ·CH ₂ Cl ₂ 1.2 g (1.5 mmol), potassium acetate (KOAc) 7.2 g (73.0 mmol) and dioxane 300 mL were added together, and the mixture was stirred under reflux all day at 100°C. . When the reaction was completed, the solvent was removed, and the obtained compound was purified by silica gel column chromatography to obtain 8.6 g (yield: 73.4%) of a slightly white solid compound (intermediate (15)).

(Synthesis of intermediate (16))

In a one neck 250 mL flask, intermediate (15) 8.9 g (27.8 mmol), 2,6-dichloroquinoline (2,6-dichloroquinoline) 5.0 g (25.2 mmol), tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ ) 1.5 g (1.3 mmol), toluene/ethanol (EtOH) = 2/1) 168 mL and 2M potassium carbonate (2M K ₂ CO ₃ ) 25.2 mL were mixed, and then stirred under reflux for 3 hours. . After confirming the completion of the reaction by thin layer chromatography (TLC), the mixture was cooled to room temperature and stirred for 1 hour. The resulting solid was filtered, washed with toluene, distilled water, and acetone, and dried to obtain 7.5 g (yield: 83.4%) of a solid compound (intermediate (16)).

(Synthesis of intermediate (17))

In a 1-neck 250 mL flask, intermediate (16) 3.5 g (9.8 mmol), bis (pinacolato) diboron) 5.0 g (19.6 mmol), bis (dibenzylideneacetone) palladium (Pd( dba) ₂ ) 1.1 g (1.9 mmol), P(cy) ₃ BF ₄ 1.4 g (3.9 mmol), potassium acetate (KOAc) 3.8 g (39.2 mmol) and dioxane 50 mL were added together, and 100°C The mixture was stirred under reflux for 2 hours. After confirming the completion of the reaction by thin film chromatography (TLC), the reaction product was cooled to room temperature and the solvent was removed under reduced pressure. The resulting solid was dissolved in dichloromethane (DCM), filtered with Celite, and washed with dichloromethane (DCM). After removing the solvent under reduced pressure, it was solidified with methanol (MeOH) and filtered to obtain a solid compound (intermediate (17) 4.0 g (yield: 91.0%)).

Intermediate Synthesis example 7: Synthesis of intermediate (20)

(Synthesis of intermediate (18))

Dissolve 50.0 g (335.1 mmol) of 4-tibutylaniline (4-(tert-butyl)aniline) in 1.1 L of acetonitrile in a 1-neck 3 L flask. After cooling to 0°C, 59.6 g (335.1 mmol) of NBS was added and the temperature was raised to room temperature. After stirring for 12 hours, 800 mL of water was added, extracted with dichloromethane, and the solvent was concentrated under reduced pressure. 700 mL of dichloromethane was added, washed with 2N NaOH 400 mL, filtered with a silica pad, and the solvent was concentrated under reduced pressure to obtain 76.0 g (yield: 99.4%) of a yellow liquid compound (intermediate (18)).

(Synthesis of intermediate (19))

In a 2-neck 2 L flask, 76.0 g (333.2 mmol) of the intermediate (18) was dissolved in 500 mL of NMP. After diluting 76.8 g (349.8 mmol) of 4-bromobenzoyl chloride in 170 mL of NMP, it was slowly added dropwise at room temperature and reacted for 12 hours. 500 mL of water was added, and when a solid precipitated, it was filtered and washed with water and methanol to give 133.0 g (yield: 97.1%) of a white solid compound (intermediate (19)).

(Synthesis of intermediate (20))

In a 2-neck 3 L flask, intermediate (19) 133.0 g (323.5 mmol), CuI 6.2 g (32.4 mmol), 1,10-phenanthroline (1,10-Phenanthroline) 11.7 g (64.7 mmol), Cs ₂ CO ₃ 316.0 g (970.5 mmol) and 1000 mL of DME were added and reacted at 90° C. for one day. After the reaction was completed, the mixture was cooled to room temperature, filtered with a pad of Celite, and the reaction solvent was concentrated under reduced pressure. The reaction mixture was filtered with a silica pad, and the solvent was concentrated under reduced pressure. It was solidified with a mixed solution (DCM/MeOH) to obtain 95.4 g (yield: 89.3%) of a white solid compound (intermediate (20)).

Intermediate Synthesis example 8: Synthesis of intermediate (22)

(Synthesis of intermediate (21))

To a 1-neck 2 L flask, add 13.7 g (108.1 mmol) of 2-amino-5-fluorophenol and 20.0 g (108.1 mmol) of 4-bromobenzaldehyde with ethanol. After mixing in 540 mL, the mixture was stirred at 70° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction mixture was distilled under reduced pressure to obtain 31.8 g (crude) of a brown solid compound (intermediate (21)).

(Synthesis of intermediate (22))

In a 1-neck 2 L flask, 31.8 g (108.1 mmol) of the intermediate (21) was dissolved in 540 mL of dichloromethane (DCM). After adding 43.9 g (129.7 mmol) of DDQ. It was stirred at room temperature for 12 hours. The reaction mixture _{was filtered through a pad of Celite (CHCl 3} ) and solidified with a mixed solution (DCM/EtOH) to obtain 24.2 g (yield: 76.7%) of a yellow solid compound (intermediate (22)).

Intermediate Synthesis example 9: Synthesis of intermediate (24)

(Synthesis of intermediate (23))

In a 2-neck 2 L flask, dissolve 100.0 g (507.5 mmol) of 4-amino-3-bromobenzonitrile in 800 mL of NMP. After diluting 117.0 g (532.9 mmol) of 4-bromobenzoyl chloride in 200 mL of NMP, it was slowly added dropwise at room temperature and reacted for 12 hours. 500 mL of water was added, and when a solid precipitated, it was filtered and washed with water and methanol to obtain 177.7 g (yield: 92.1%) of a white solid compound (intermediate (23)).

(Synthesis of intermediate (24))

In a 1-neck 3 L flask, intermediate (23) 181.8 g (478.4 mmol), Cu 15.2 g (239.2 mmol), K ₂ CO ₃ 132.2 g (956.8 mmol), Na ₂ SO ₄ 135.9 g (956.8 mmol) and nitrobenzene 1500 mL was mixed and then stirred under reflux for 2 days. After the reaction was completed, it was passed through a pad of Celite, concentrated under reduced pressure, and solidified with a mixed solution (DCM/MeOH) to obtain 119.0 g (yield: 83.2%) of a yellow solid compound (intermediate (24)).

Intermediate Synthesis example 10: Synthesis of intermediate (26)

(Synthesis of intermediate (25))

In a 1-neck 2 L flask, 20.0 g (183.3 mmol) of 2-aminophenol and 34.1 g (183.3 mmol) of 6-bromopicolinaldehyde were mixed with 900 mL of ethanol, and then 70°C. The mixture was stirred for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction mixture was distilled under reduced pressure to obtain 50.8 g (crude) of a brown solid compound (intermediate (25)).

(Synthesis of intermediate (26))

In a 1-neck 2 L flask, 50.8 g (183.3 mmol) of the intermediate (25) was dissolved in 900 mL of dichloromethane (DCM). After adding 49.9 g (220.0 mmol) of DDQ. It was stirred at room temperature for 12 hours. The reaction mixture was filtered through a pad of Celite (CHCl3) and solidified with a mixed solution (DCM/EtOH) to obtain 42.0 g (yield: 83.3%) of a yellow solid compound (intermediate (26)).

Intermediate Synthesis example 11: Synthesis of intermediate (28)

(Synthesis of intermediate (27))

In a 1-neck 2 L flask, 2-aminophenol 17.6 g (161.3 mmol) and 5-bromopicolinaldehyde 30.0 g (161.3 mmol) were mixed with 800 mL of ethanol, and then 70°C. The mixture was stirred for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction mixture was distilled under reduced pressure to obtain 45.0 g (crude) of a brown solid compound (intermediate (27)).

(Synthesis of Intermediate (28))

In a 1-neck 2 L flask, 45.0 g (161.3 mmol) of the intermediate (27) was dissolved in 800 mL of dichloromethane. After adding 43.9 g (193.5 mmol) of DDQ. Stirred at 40° C. for 12 hours. The reaction mixture _{was filtered through celite (CHCl 3} ) and solidified with a mixed solution (DCM/EtOH) to obtain 36.2 g (yield: 81.6%) of a pink solid compound (intermediate (28)).

Intermediate Synthesis example 12: Synthesis of intermediate (29)

To a 1-neck 500 mL flask, add 20.0 g (181.6 mmol) of 2-aminopyridin-3-ol and 45.0 g (181.6 mmol) of 4-iodobenzoic acid. _{After mixing well, 140 mL of POCl 3} was added slowly and carefully at 0°C, followed by stirring. After raising the temperature to 90 ℃ reacted for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reactant was slowly added dropwise to ice. After neutralization with an aqueous Na ₂ CO ₃ solution, the solid was filtered, washed with water and methanol, and dried to obtain 43.0 g (yield: 73.5%) of a white solid compound (intermediate (29)).

Intermediate Synthesis example 13: Synthesis of Intermediate (30)

To a 1-neck 500 mL flask, 20.0 g (181.6 mmol) of 2-aminopyridin-3-ol and 36.7 g (181.6 mmol) of 5-bromopicolinic acid were added. After mixing well, _{180 mL of POCl 3} was slowly and carefully added at 0° C. and stirred. After raising the temperature to 100 ℃ reacted for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the above reactant was slowly added dropwise to ice. After neutralizing the reaction with a solution in which 500 g of K ₂ CO ₃ was dissolved in 3 L of water, chloroform was added and stirred. Filtered through a pad of Celite, extracted with chloroform, and distilled under reduced pressure. Purified by silica gel column chromatography (CHCl ₃ :EA=20:1) and solidified with hot methanol to give 23.0 g (yield: 45.9%) of a yellow solid compound (intermediate (30)).

Intermediate Synthesis example 14: Synthesis of intermediate (33)

(Synthesis of intermediate (31))

2-(4-bromophenyl)benzo[d]thiazole (2-(4-bromophenyl)benzo[d]thiazole) 30.0 g(103.4 mmol), bis(pinacolato)diboron ) A mixture of 31.5 g (124.0 mmol), Pd(dppf)Cl ₂ 3.4 g (4.1 mmol), potassium acetate 20.3 g (206.8 mol), and 300 mL of 1,4-dioxane was stirred at 90° C. for 12 hours. After the reaction mixture was concentrated under reduced pressure, 600 mL of dichloromethane was added, followed by stirring for 30 minutes. The insoluble precipitate was removed by filtration through a pad of celite and concentrated under reduced pressure. 200 mL of methanol was added to the concentrated residue and stirred for 1 hour. The resulting precipitate was filtered, washed with methanol, and dried in vacuo to give 25.0 g (yield: 72.1%) of a pale yellow solid compound (intermediate (31)).

(Synthesis of intermediate (32))

Intermediate (31) 18.6 g (55.2 mmol), 2,6-dichloroquinoxaline (2,6-dichloroquinoxaline) 10.0 g (50.1 mmol), Pd (PPh ₃ ) ₄ 1.7 g (1.5 mmol), 2M sodium carbonate solution 25.1 mL (75.2 mmol), a mixture of 350 mL of toluene and 170 mL of ethanol was stirred under reflux for 12 hours. After the reaction mixture was cooled to room temperature, the solvent was removed, water was added, 500 mL of dichloromethane was added to separate the organic layer, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a yellow solid compound (intermediate (32). )) 12.5 g (yield: 66.7%) was obtained.

(Synthesis of intermediate (33))

Intermediate (32) 6.0 g (16.1 mmol), Bis (pinacolato) diboron 8.2 g (32.1 mmol), Pd (dba) ₂ 1.9 g (3.2 mmol), potassium acetate (KOAc) 6.3 g (64.2 mmol), tricyclohexyl Phosphine tetrafluoroborate (tricyclohexylphosphine tetrafluoroborate, P(Cy) ₃ ·HBF ₄ ) 2.4 g (6.4 mmol) and 300 mL of dioxane were added together, and the mixture was stirred under reflux for 4-5 days at 100°C. When the reaction was completed, the solvent was removed, and the obtained reaction product was purified by silica gel column chromatography to obtain 3.4 g (yield: 45.1%) of a pale yellow solid compound (intermediate (33)).

Intermediate Synthesis example 15: Synthesis of intermediate (35)

(Synthesis of intermediate (34))

2-(4-bromophenyl)benzothiazole (2-(4-bromophenyl)benzo[d]thiazole) 60.0 g (206.7 mmol), intermediate (11) 55.9 g (206.7 mmol), Pd (PPh ₃ ) ₄ A mixture of 7.1 g (6.2 mmol), 2M sodium carbonate 155.1 mL (310.2 mmol), 700 mL of toluene, and 350 mL of ethanol was stirred under reflux for 12 hours. After the reaction mixture was cooled to room temperature, the solvent was removed, water was added, and 1000 mL of dichloromethane was added to extract and separate the organic layer, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a yellow solid compound (intermediate (intermediate (intermediate)). 34)) 35.1 g (yield: 48.0%) was obtained.

(Synthesis of intermediate (35))

Intermediate (34) 15.0 g (42.4 mmol) and dichloromethane 400 mL were added together, pyridine 5.1 mL (63.6 mmol) was added, and trifluoromethanesulfonic anhydride 18.0 g (63.6) was added at 0 °C. mmol) was slowly added, the temperature was raised to room temperature, and the mixture was stirred throughout the day. When the reaction was completed, water was added at 0°C, 500 mL of dichloromethane, and the organic layer was separated, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a slightly white solid compound (intermediate (35)) 17.1 g (Yield: 83.1%) was obtained.

Various benzazole derivatives were synthesized as follows using the synthesized intermediate compound.

Example 1: Synthesis of compound 2-10 (LT19-30-535)

2-(4-bromophenylbenzoxazole) 3.2 g (11.5 mmol), intermediate (3) 4.0 g (11.5 mmol), Pd (PPh ₃ ) ₄ 664 mg (574.4 μmol), K ₃ PO ₄ 6.1 g (28.7 mmol) 40 mL of toluene, 10 mL of ethanol, and 10 mL of water were mixed and stirred under reflux for 4 hours After the reaction was terminated, the mixture was cooled to room temperature, and the solid was dissolved. The resulting solid mixture was purified by silica gel column chromatography (CHCl ₃ ) and solidified with chloroform, followed by filtration, washing with water and ethanol, and 3.1 g of white solid compound 2-10 (LT19-30-535) (yield: 64.9%) was obtained.

Example 2: Synthesis of compound 2-13 (LT19-35-102)

2-(4-bromophenyl)benzoxazole (2-(4-bromophenyl)benzo[d]oxazole) 3.0 g (10.9 mmol), intermediate (14) 4.6 g (10.9 mmol), Pd (PPh ₃ ) ₄ A mixture of 0.4 g (0.3 mmol), potassium carbonate 3.8 g (27.4 mmol), toluene 80 mL, ethanol 40 mL, and water 40 mL was stirred under reflux for 12 hours. After cooling the reaction mixture to room temperature, 200 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified with a silica gel/Celite pad to obtain 2.5 g (yield: 46.7%) of a solid compound 2-13 (LT19-35-102) exhibiting yellow fluorescence.

Example 3: Synthesis of compound 2-14 (LT19-30-174)

Intermediate (15) 4.2 g (13.1 mmol), intermediate (8) 5.0 g (11.9 mmol), Pd (PPh ₃ ) ₄ 0.4 g (0.4 mmol), 2M sodium carbonate 8.9 mL (17.8 mmol), toluene 70 mL and ethanol 35 mL of the mixture was stirred at reflux for 12 hours. After the reaction mixture was cooled to room temperature, the solvent was removed, water was added, and 300 mL of dichloromethane was added to separate the organic layer, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a pale yellow solid compound 2-14 ( LT19-30-174) 3.0 g (yield: 54.2%) was obtained.

Example 4: Synthesis of compound 2-15 (LT19-30-153)

Intermediate (5) 4.0 g (8.2 mmol), Intermediate (15) 2.89 g (9.0 mmol), Pd (PPh ₃ ) ₄ 0.28 g (0.25 mmol), 2M K ₂ CO ₃ 8 mL (16 mmol), Toluene 20 mL And a mixture of 8 mL of ethanol was stirred under reflux for 12 hours. After cooling the reaction mixture to room temperature, the resulting precipitate was filtered under reduced pressure and washed with toluene, water and methanol. The filtered precipitate was dissolved in 120 mL of tetrahydrofuran, and the insoluble precipitate was removed by filtration through a celite pad, and washed with 40 mL of tetrahydrofuran. 160 mL of methanol was added to the filtrate and allowed to stand for 3 hours. The resulting precipitate was filtered, washed with methanol, and dried in vacuo to give 3.50 g (yield: 80.0%) of a white solid compound 2-15 (LT19-30-153).

Example 5: Synthesis of compound 2-30 (LT19-30-480)

Intermediate (20) 2.0 g (6.1 mmol), Intermediate (6) 2.8 g (6.1 mmol), Pd (PPh ₃ ) ₄ 350 mg (302.8 mmol), K ₃ PO ₄ 3.2 g (15.1 mmol), toluene 30 mL, After mixing 5 mL of ethanol and 5 mL of water, the mixture was stirred under reflux for 12 hours. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained compound was dissolved by heating in 200 mL of chloroform, purified by column chromatography, and recrystallized with acetone and methanol to obtain 2.3 g (yield: 63.3%) of a white solid compound 2-30 (LT19-30-480).

Example 6: Synthesis of compound 2-45 (LT19-30-481)

Intermediate (22) 2.0 g (6.9 mmol), Intermediate (6) 3.2 g (6.9 mmol), Pd (PPh ₃ ) ₄ 395 mg (342.3 μmol), K ₃ PO ₄ 3.6 g (17.1 mmol) Toluene 30 mL, ethanol 5 mL and 5 mL of water were mixed and then stirred under reflux for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. The obtained solid mixture was purified by silica gel column chromatography (CHCl ₃ ) and solidified with a mixed solution (DCM/Acetone) to obtain 2.1 g (yield: 56.7%) of compound 2-45 (LT19-30-481) as a white solid. .

Example 7: Synthesis of compound 2-75 (LT19-30-524)

Intermediate (24) 2.5 g (8.4 mmol), intermediate (6) 4.3 g (9.2 mmol), Pd (PPh ₃ ) ₄ 0.9 g (0.8 mmol), 2M cesium carbonate solution 13.0 mL (25.1 mmol), toluene 42 mL and A mixture of 21 mL of ethanol was stirred at reflux for 2 hours. After cooling the reaction mixture to room temperature, the precipitated solid was filtered under reduced pressure and washed with water and methanol. The filtered solid was dissolved by heating in 400 mL of chloroform, purified by column chromatography, and recrystallized from chloroform and acetone to give 4.0 g (yield: 86.8%) of a white solid compound 2-75 (LT19-30-524).

Example 8: Synthesis of compound 2-87 (LT19-30-532)

Intermediate (6) 5.1 g (10.9 mmol), intermediate (28) 2.5 g (9.1 mmol), Pd (OAc) ₂ 0.2 g (0.9 mmol), triphenylphosphine 0.7 g (2.7 mmol), cesium carbonate 11.8 g ( 36.4 mmol), 45 mL of 1,4-dioxane and 9 mL of water were stirred at 85° C. for 4 hours. The reaction mixture was cooled to room temperature, water was added, and then extracted twice with 60 mL of dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained compound was purified by column chromatography and recrystallized with chloroform to give 3.8 g (yield: 78.3%) of a yellow solid compound 2-87 (LT19-30-532).

Example 9: Synthesis of compound 2-90 (LT19-30-489)

Intermediate (26) 2.0 g (7.3 mmol), Intermediate (6) 3.4 g (7.3 mmol), Pd (PPh ₃ ) ₄ 420 mg (363.5 μmol), K ₃ PO ₄ 3.9 g (18.2 mmol), toluene 30 mL, After mixing 5 mL of ethanol and 5 mL of water, the mixture was stirred under reflux for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solid was filtered, washed with water and methanol, and dried. The obtained solid mixture was purified by silica gel column chromatography (CHCl ₃ ) and solidified with a mixed solution (DCM/Acetone) to obtain 3.1 g (yield: 80.3%) of compound 2-90 (LT19-30-489) as a white solid. .

Example 10: Synthesis of compound 2-105 (LT19-30-522)

Intermediate (29) 2.5 g (7.8 mmol), intermediate (6) 4.0 g (8.5 mmol), Pd (PPh ₃ ) ₄ 0.4 g (0.4 mmol), 2M cesium carbonate solution 12.0 mL (23.3 mmol), toluene 40 mL and A mixture of 20 mL of ethanol was stirred at reflux for 16 hours. The reaction mixture was cooled to room temperature, water was added, and extracted twice with 100 mL of chloroform. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained compound was dissolved by heating in 200 mL of chloroform, purified by column chromatography, and recrystallized from chloroform and acetone to give 3.1 g (yield: 69.1%) of a yellow solid compound 2-105 (LT19-30-522).

Example 11: Synthesis of compound 2-120 (LT19-30-165)

In a 1-neck 250 mL flask, intermediate (17) 4.0 g (8.9 mmol), 1-bromo-3,5-bis (trifluoromethyl) benzene (1-bromo-3,5-bis (trifluoromethyl) benzene) 2.6 g (8.9 mmol), tetrakis (triphenylphosphine) palladium (Pd(PPh ₃ ) ₄ ) 0.5 g (0.45 mmol), mixed solution (Toluene/ethanol (EtOH) = 2/1) 45 mL and After mixing with 9 mL of 2M potassium carbonate (2M K ₂ CO ₃ ), the mixture was stirred under reflux for 12 hours. After confirming the completion of the reaction by membrane chromatography (TLC), the reaction product was cooled to room temperature. After distilled water was added _{and extracted with chloroform (CHCl 3} ), the separated organic layer was dried over anhydrous sodium sulfate (Na ₂ SO ₄ ), and the solvent was removed under reduced pressure. It was dissolved by refluxing the resulting solid in chloroform (CHCl3), and washed with Celite (Celite), filtered and chloroform (CHCl _3). After removing the solvent under reduced pressure, it was solidified with ethyl acetate (EtOAc) to obtain 2.5 g (yield: 52.6%) of a solid compound 2-120 (LT19-30-165).

Example 12: Synthesis of compound 2-138 (LT19-30-504)

Intermediate (30) 2.0 g (7.3 mmol), Intermediate (6) 3.4 g (7.3 mmol), Pd (PPh ₃ ) ₄ 420 mg (363.5 μmol), Cs ₂ CO ₃ 5.9 g (18.2 mmol) Toluene 30 mL, ethanol 5 mL, and 5 mL of water were mixed and then stirred under reflux for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the solid was filtered, washed with water and methanol, and dried. The obtained solid mixture was purified by silica gel column chromatography (CHCl ₃ ) and solidified with a mixed solution (DCM/Acetone) to obtain 1.5 g (yield: 38.7%) of a white solid compound 2-138 (LT19-30-504). .

Example 13: Synthesis of compound 3-1 (LT19-30-379)

Intermediate (31) 3.0 g (8.9 mmol), Intermediate (10) 3.0 g (8.5 mmol), Pd (PPh ₃ ) ₄ 0.30 g (0.26 mmol), 2M K ₂ CO ₃ 9.0 mL (18.0 mmol), Toluene 23 mL And a mixture of 9 mL of ethanol was stirred under reflux for 12 hours. After cooling the reaction mixture to room temperature, the resulting precipitate was filtered under reduced pressure and washed with toluene, water and methanol. The filtered precipitate was dissolved by heating in 120 mL of monochlorobenzene, and the insoluble precipitate was removed by filtration through a celite pad, and washed with 40 mL of monochlorobenzene. The filtrate was cooled to room temperature and stirred for 2 hours. The resulting precipitate was filtered, washed with dichloromethane, and dried in vacuo to give 2.3 g (yield: 65.1%) of a white solid compound 3-1 (LT19-30-379).

Example 14: Synthesis of compound 3-2 (LT19-30-486)

Intermediate (35) 6.0 g (12.4 mmol), p-Tolyl boronic acid 1.9 g (13.6 mmol), Pd (PPh ₃ ) ₄ 0.4 g (0.4 mmol), 2M sodium carbonate 9.3 mL (18.5 mmol) ), a mixture of 70 mL of toluene and 35 mL of ethanol was stirred under reflux for 12 hours. After the reaction mixture was cooled to room temperature, the solvent was removed, water was added, and 300 mL of dichloromethane was added to separate the organic layer, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a white solid compound 3-2 (LT19). -30-486) 3.0 g (yield: 56.8%) was obtained.

Example 15: Synthesis of compound 3-6 (LT19-35-111)

Intermediate (35) 4.3 g (8.8 mmol), ((4-tert-butyl) phenyl) boronic acid ((4-(tert-butyl) phenyl) boronic acid) 1.7 g (9.7 mmol), Pd (PPh ₃ ) ₄ A mixture of 0.3 g (2.6 mmol), potassium carbonate 3.0 g (21.9 mmol), toluene 80 mL, ethanol 40 mL, and water 40 mL was stirred under reflux for 12 hours. After cooling the reaction mixture to room temperature, 200 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified with a silica gel/Celite pad to obtain 2.1 g (yield: 50.9%) of a solid compound 3-6 (LT19-35-111) exhibiting yellow fluorescence.

Example 16: Synthesis of compound 3-8 (LT19-30-457)

Intermediate (35) 10.0 g (20.6 mmol), (4- (trimethylsilyl) phenyl) boronic acid (4- (trimethylsilyl) phenyl) boronic acid) 4.3 g (22.6 mmol), Pd (PPh ₃ ) ₄ 1.4 g (1.2 mmol), potassium carbonate 14.2 g (102.7 mmol), 100 mL of toluene, 50 mL of ethanol, and 50 mL of water were stirred under reflux for 12 hours. After cooling the reaction mixture to room temperature, 200 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified with a silica gel/Celite pad to obtain 5.5 g (yield: 54.6%) of a solid compound 3-8 (LT19-30-457) exhibiting yellow fluorescence.

Example 17: Synthesis of compound 3-10 (LT19-35-115)

Intermediate (35) 10.0 g (20.6 mmol), (4-fluorophenyl) boronic acid ((4-fluorophenyl) boronic acid) 3.1 g (22.6 mmol), Pd (PPh ₃ ) ₄ 1.4 g (1.2 mmol), carbonic acid A mixture of potassium 14.2 g (102.7 mmol), toluene 100 mL, ethanol 50 mL, and water 50 mL was stirred under reflux for 12 hours. After cooling the reaction mixture to room temperature, 200 mL of methanol was added. The resulting precipitate was filtered and washed with methanol. The filtered precipitate was purified with a silica gel/Celite pad to obtain 4.1 g (yield: 46.2%) of a solid compound 3-10 (LT19-35-115) exhibiting yellow fluorescence.

Example 18: Synthesis of compound 3-14 (LT19-35-115)

Intermediate (35) 4.3 g (8.8 mmol), ((4-(trifluoromethyl) phenyl) boronic acid ((4-(trifluoromethyl) phenyl) boronic acid) 1.8 g (9.7 mmol), Pd(PPh ₃ ) ₄ A mixture of 0.3 g (2.6 mmol), potassium carbonate 3.0 g (21.9 mmol), 80 mL of toluene, 40 mL of ethanol and 40 mL of water was stirred under reflux for 12 hours The reaction mixture was cooled to room temperature and 200 mL of methanol was added. The resulting precipitate was filtered and washed with methanol The filtered precipitate was purified with a silica gel/Celite pad to obtain 2.1 g (yield: 50.0%) of a solid compound 3-14 (LT19-35-118) exhibiting yellow fluorescence. .

Example 19: Synthesis of compound 3-15 (LT19-30-173)

Intermediate (31) 3.0 g (8.9 mmol), Intermediate (5) 4.0 g (8.2 mmol), Pd (PPh ₃ ) ₄ 0.3 g (0.2 mmol), 2M sodium carbonate 6.1 mL (12.1 mmol), toluene 70 mL and ethanol 35 mL of the mixture was stirred at reflux for 12 hours. After the reaction mixture was cooled to room temperature, the solvent was removed, water was added, 300 mL of dichloromethane was added to separate the organic layer, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a slightly yellow solid compound 3-15. (LT19-30-173) 3.0 g (yield: 67.5%) was obtained.

Example 20: Synthesis of compound 3-16 (LT19-30-443)

Intermediate (35) 6.0 g (12.4 mmol), 4-cyanophenyl boronic acid 2.0 g (13.6 mmol), Pd (PPh ₃ ) ₄ 0.4 g (0.4 mmol), 2M sodium carbonate 9.3 mL ( 18.5 mmol), 70 mL of toluene and 35 mL of ethanol were stirred under reflux for 12 hours. After the reaction mixture was cooled to room temperature, the solvent was removed, water was added, and 300 mL of dichloromethane was added to separate the organic layer, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a pale red solid compound 3-16. (LT19-30-443) 3.0 g (yield: 55.4%) was obtained.

Example 21: Synthesis of compound 3-120 (LT19-30-196)

Intermediate (33) 2.8 g (6.0 mmol), 1-bromo-3,5-bis (trifluoromethyl) benzene {1-bromo-3,5-bis (trifluoromethyl) benzene} 2.1 g (7.2 mmol), A mixture of Pd(PPh ₃ ) ₄ 0.2 g (0.2 mmol), 2M sodium carbonate 4.5 mL (9.0 mmol), toluene 70 mL, and ethanol 35 mL was stirred under reflux throughout the day. After the reaction mixture was cooled to room temperature, the solvent was removed, water was added, and 300 mL of dichloromethane was added to separate the organic layer, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a slightly yellow solid compound 3-120 ( LT19-30-196) 1.0 g (yield: 30.2%) was obtained.

<Test Example>

For the compound of the present invention, J.A. Using WOOLLAM's Ellipsometer, n (refractive index) and k (extinction coefficient) were measured.

Production of a single film for the test example:

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

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

The optical characteristic device was fabricated by depositing REF01 (80nm) on the glass. Before depositing the compound Glass is 2 × 10 ^- was for 2 minutes in the oxygen plasma treatment ² Torr to 125 W. Compound 9 × 10 ^- deposited at a vacuum degree of ⁷ Torr at a rate of 1Å / sec it was produced by danmak.

<Test Examples 1 to 21>

In the Comparative Test Example, a single membrane was manufactured 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 21.

Optical properties are refractive index constants at 460nm and 620nm wavelengths.

division compound n(460nm) n(620nm) Comparative test example REF01 1.986 1.846 Test Example 1 2-10
(LT19-30-535) 1.468 1.443 Test Example 2 2-13
(LT19-35-102) 1.425 1.418 Test Example 3 2-14
(LT19-30-174) 1.439 1.424 Test Example 4 2-15
(LT19-30-153) 1.417 1.405 Test Example 5 2-30
(LT19-30-480) 1.446 1.439 Test Example 6 2-45
(LT19-30-481) 1.483 1.453 Test Example 7 2-72
(LT19-30-524) 1.427 1.415 Test Example 8 2-87
(LT19-30-532) 1.468 1.443 Test Example 9 2-90
(LT19-30-489) 1.425 1.418 Test Example 10 2-105
(LT19-30-522) 1.483 1.453 Test Example 11 2-120
(LT19-30-165) 1.427 1.415 Test Example 12 2-138
(LT19-30-504) 1.468 1.443 Test Example 13 3-1
(LT19-30-379) 1.621 1.593 Test Example 14 3-2
(LT19-30-486) 1.583 1.551 Test Example 15 3-6
(LT19-35-111) 1.591 1.563 Test Example 16 3-8
(LT19-30-457) 1.468 1.443 Test Example 17 3-10
(LT19-35-115) 1.468 1.443 Test Example 18 3-14
(LT19-35-118) 1.425 1.418 Test Example 19 3-15
(LT19-30-173) 1.446 1.439 Test Example 20 3-16
(LT19-30-443) 1.620 1.590 Test Example 21 3-135
(LT19-30-196) 1.425 1.411

As can be seen in Table 1, n values in the blue region (460 nm) and red region (620 nm) of Comparative Test Example (REF01) were 1.986 and 1.846, respectively, whereas most of the compounds according to the present invention were As a result, it was confirmed to have a lower refractive index than the Comparative Test Example compound (REF01) in the blue region, green region, and red region. This is satisfied with the low refractive index value required to secure a high viewing angle in the blue region.

<Example>

Device fabrication

For device fabrication, ITO, a transparent electrode, was used as the anode layer, 2-TNATA was used as the hole injection layer, NPB was the hole transport layer, αβ-ADN was the host of the emission layer, Pyrene-CN was the blue fluorescent dopant, and Liq was the electron injection layer. , Mg:Ag was used as a negative electrode. The structures of these compounds are as shown in the following formula.

Comparative Example 1 (Capping layer consists of one layer): 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(80nm)

Comparative Example 2 (Capping layer consists of two layers): 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) / REF02(20nm) / REF01(60nm)

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) / capping layer was deposited in this order to fabricate a device. Before depositing the organic substance is applied to the ITO electrodes 2 × 10 ^- was for 2 minutes plasma treatment to 125W at ² Torr. Organics are 9 × 10 ^- were deposited at a vacuum degree of ⁷ Torr, Liq was 0.1 Å / sec, αβ-ADN is 0.18 Å / on the basis of sec Pyrene-CN was co-deposited with 0.02 Å / sec, all the remaining organics were 1 It was deposited at a rate of Å/sec. The cappim layer material used in the experiment was selected as REF01 (high refractive index) and REF02 (low refractive index). After the device was manufactured, the device was sealed in a glove box filled with nitrogen gas to prevent contact with air and moisture. After forming a partition wall with 3M's adhesive tape, barium oxide, a moisture absorbent that can remove moisture, was added and a glass plate was attached.

<Examples 1 to 21>

In Comparative Example 1, a multilayer having a high refractive index layer (60 nm) formed on a low refractive index layer (20 nm) as a capping layer instead of REF01, and the REF01 compound was added to the high refractive index layer as shown in Table 2 below. A device was manufactured in the same manner as in Comparative Example, except that the compound of was used.

Table 2 shows the electroluminescence characteristics of the organic light emitting devices prepared in Comparative Example 1 and Examples 1 to 21.

division compound Driving voltage
[V] efficiency
[cd/A] life span
(%) Comparative Example 1 REF01 alone 4.50 5.10 88.92 Example 1 2-10
(LT19-30-535) 4.42 6.11 97.54 Example 2 2-13
(LT19-35-102) 4.47 6.52 98.13 Example 3 2-14
(LT19-30-174) 4.45 6.13 97.45 Example 4 2-15
(LT19-30-153) 4.38 6.23 97.40 Example 5 2-30
(LT19-30-480 4.40 6.10 97.32 Example 6 2-45
(LT19-30-481) 4.41 6.23 97.55 Example 7 2-72
(LT19-30-524) 4.42 6.00 98.00 Example 8 2-87
(LT19-30-532) 4.49 5.99 95.61 Example 9 2-90
(LT19-30-489) 4.40 6.22 98.11 Example 10 2-105
(LT19-30-522) 4.42 6.11 97.54 Example 11 2-120
(LT19-30-165) 4.40 6.25 97.42 Example 12 2-138
(LT19-30-504) 4.41 6.23 97.55 Example 13 3-1
(LT19-30-379) 4.51 5.31 95.61 Example 14 3-2
(LT19-30-486) 4.49 5.43 95.55 Example 15 3-6
(LT19-35-111) 4.50 5.36 95.67 Example 16 3-8
(LT19-30-457) 4.41 6.23 97.55 Example 17 3-10
(LT19-35-115) 4.40 6.22 98.11 Example 18 3-14
(LT19-35-118) 4.45 6.13 97.45 Example 19 3-15
(LT19-30-173) 4.38 6.23 97.40 Example 20 3-16
(LT19-30-443) 4.50 5.21 97.32 Example 21 3-135
(LT19-30-196) 4.41 6.23 97.55

From the results of Table 2, the specific benzazole derivative compound according to the present invention can be used as a material for a low refractive index capping layer of organic electronic devices including organic light emitting devices, and organic electronic devices including organic light emitting devices using the same , It can be seen that it exhibits excellent characteristics in terms of driving voltage, stability, etc. In particular, the compound according to the present invention exhibited high efficiency characteristics due to excellent micro-cavity phenomenon.

The compound of Formula 1 has surprisingly desirable properties for use as a low refractive index capping layer in OLED.

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

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

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 (4)

A benzazole derivative for an organic electroluminescent device represented by the following formula (1).
[Formula 1]

In Formula 1,
Z ₁ is O or S,
X ₁ , X ₂ and X ₃ are each independently CH or N,
R ₁ is any one selected from hydrogen, methyl group, tert-butyl group, fluoro group and trifluoromethyl group,
R ₂ to R ₆ are the same as or different from each other, and each is any one selected from a trimethylsilyl group, a fluoro group, and a trifluoromethyl group. The method of claim 1,
Formula 1 is a benzazole derivative for an organic electroluminescent device selected from compounds represented by the following Formulas 2 and 3.
[Formula 2]

[Formula 3]

A first electrode;
An organic material layer formed of a plurality of organic material layers disposed on the first electrode;
A second electrode disposed on the organic material layer; And
Including; a capping layer disposed on the second electrode,
The organic material layer or the capping layer is an organic electroluminescent device comprising the benzazole derivative of claim 1 or 2. The method of claim 3,
The organic material layer is an organic light emitting device comprising a light emitting layer and an electron transport layer.

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