Heteroaryl amine derivative and organic electroluminescent device comprising same

Abstract

A heteroaryl amine derivative is provided that contributes to a substantial improvement in the lifespan of an organic electroluminescent device by effectively absorbing high-energy external light in the UV region to minimizes damages to organic materials inside the organic electroluminescent device. An organic electroluminescent device according to the present invention comprises: a first electrode; a second electrode; at least one organic material layer disposed between the first electrode and the second electrode; and a capping layer, wherein the capping layer contains a heteroaryl amine derivative represented by chemical formula 1 according to the present invention.

Description

Heteroaryl amine derivatives and organic electroluminescent devices containing the same

[0001] The present invention relates to a heteroaryl amine derivative and an organic electroluminescent device comprising the same, wherein the organic electroluminescent device including a capping layer formed by the heteroaryl amine derivative has both high refractive index characteristics and ultraviolet absorption characteristics.

[0002] In the display industry, OLED (Organic Light Emitting Diodes) is attracting attention as a display that utilizes the self-luminous phenomenon.

[0003] In OLEDs, the first attempt at carrier-injected electroluminescence (EL) using a single crystal of the aromatic hydrocarbon anthracene was made by Pope et al. in 1963. From this research, the basic mechanisms of charge injection, recombination, exciton generation, and luminescence in organic materials, as well as electroluminescence characteristics, have been understood and studied.

[0004] In particular, various approaches are being taken with regard to structural changes of devices and material development to increase luminous efficiency [Sun, S., Forrest, SR, Appl. Phys. Lett. 91, 263503 (2007) / Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364].

[0005] The basic structure of an OLED display is generally composed of a multilayer structure of an anode, a hole injection layer (HIL), a hole transporting layer (HTL), an emission layer (EML), an electron transporting layer (ETL), and a cathode, and the electro-organic multilayer film is formed in a sandwich structure between the two electrodes.

[0006] Generally, organic light emitting diodes (OLEDs) are devices that convert electrical energy into light energy using organic materials. Organic light emitting diodes (OLEDs) typically have a structure comprising an anode, a cathode, and an organic layer between them. These organic layers are often multilayered, composed of different materials, to enhance the efficiency and stability of the device. For example, they may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

[0007] In the structure of these organic light-emitting devices, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, excitons are formed, and when these excitons fall to the ground state, light is emitted. These organic light-emitting devices are known to have characteristics such as self-luminescence, high brightness, high efficiency, low operating voltage, wide viewing angle, high contrast, and high-speed response.

[0008] Materials used as organic layers in organic light-emitting devices can be classified, depending on their function, into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials.

[0009] Depending on the emission color, light-emitting materials include blue, green, and red light-emitting materials, as well as yellow and orange light-emitting materials required to realize better natural colors. In addition, a host / dopant system can be used as a light-emitting material to increase color purity and luminous efficiency through energy transfer. The principle is that when a small amount of a dopant with a smaller energy band gap and superior luminous efficiency than the host, which mainly constitutes the light-emitting layer, is mixed into the light-emitting layer, excitons generated in the host are transported to the dopant, resulting in efficient light emission. At this time, the wavelength of the host shifts to the wavelength of the dopant, so light of a desired wavelength can be obtained depending on the type of dopant used.

[0010] In order to realize the excellent characteristics of the organic light-emitting device described above, materials forming the organic layer within the device, such as hole injection materials, hole transport materials, luminescent materials, electron transport materials, and electron injection materials, have been developed, and as a result, the performance of organic light-emitting devices has been recognized through recently commercialized products.

[0011] However, after the commercialization of organic light-emitting devices, the need for other characteristics other than the light-emitting characteristics of the organic light-emitting devices themselves has emerged.

[0012] Organic light-emitting devices are often exposed to external light sources for extended periods of time, placing them in environments where they are exposed to high-energy UV rays. Consequently, the organic materials constituting the device are subject to continuous exposure. This problem can be addressed by applying a capping layer with UV-absorbing properties to the device to prevent exposure to these high-energy light sources.

[0013] While organic light-emitting diodes (OLEDs) are generally known to have a wide viewing angle, significant deviations occur depending on the viewing angle from a light source spectrum perspective. This is due to the discrepancy between the overall refractive index (including the glass substrate, organic materials, and electrode materials that make up the OLED) and the appropriate refractive index based on the OLED's emission wavelength.

[0014] Generally, the refractive index required for blue light is high, and as the wavelength increases, the required refractive index decreases. Therefore, there is a need to develop a capping layer material that simultaneously satisfies the aforementioned UV absorption characteristics and an appropriate refractive index.

[0015] The efficiency of organic light-emitting devices can generally be divided into internal luminescent efficiency and external luminescent efficiency. Internal luminescent efficiency is related to the efficiency of exciton formation in the organic layer for photoconversion.

[0016] External luminescence efficiency refers to the efficiency with which light generated in the organic layer is emitted outside the organic light-emitting device.

[0017] To improve overall efficiency, both internal and external luminescence efficiency must be enhanced. To increase external luminescence efficiency and prevent potential problems that may arise from prolonged exposure to sunlight, the development of new functional capping layer (CPL) compounds is required. In particular, among CPL functions, the development of capping layer (CPL) materials with superior absorption capabilities in the UV wavelength range is required.

[0018] Meanwhile, compared to the bottom element structure of the non-resonant structure, the top element structure of the resonant structure has a large optical energy loss due to SPP (Surface Plasmon Polariton) because the light formed is reflected by the anode, which is a reflective film, and comes out toward the cathode.

[0019] Therefore, one of the important methods for improving the shape and efficiency of the EL spectrum is to use a light efficiency improvement layer (capping layer) on the top cathode.

[0020] Typically, SPP emitters primarily use four metals: Al, Pt, Ag, and Au, and surface plasmons are generated on the surface of the metal electrode. For example, if Ag is used as the cathode, the emitted light is quenched by SPP (light energy loss due to Ag), reducing efficiency.

[0021] On the other hand, when a capping layer (light efficiency improvement layer) is used, SPP is generated at the interface between the MgAg electrode and the organic material. In this case, if the organic material has a high refractive index (e.g., n>1.69 @620), the TE (Transverse electric) polarized light is annihilated in the vertical direction at the capping layer plane (light efficiency improvement layer plane) by an evanescent wave, and the TM (Transverse magnetic) polarized light traveling along the cathode and the capping layer experiences wavelength amplification by surface plasma resonance, which increases the intensity of the peak, enabling high efficiency and effective color purity control.

[0022] However, there is still a need for the development of materials and structures necessary to improve various characteristics in a balanced manner along with improvements in efficiency and color purity in organic light-emitting devices.

[0023] An object of the present invention is to provide a capping layer material for an organic light-emitting device that can improve luminous efficiency and lifespan and at the same time improve viewing angle characteristics.

[0024] 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 heat resistance, particularly to improve the light extraction rate of the organic electroluminescent device.

[0025] In order to achieve the above purpose, the inventors conducted an example study as shown below.

[0026] That is, a material with a further improved refractive index was selected by introducing an aryl group, a cyano group-substituted aryl group, and a heteroaryl group from a tertiary amine compound having dibenzofuran and dibenzothiophene (prior Korean Patent No. 2060645) with high refractive index characteristics. Then, an organic light-emitting device was manufactured using this material as a capping layer, and the device's characteristics were evaluated as an example.

[0027] The present invention provides an organic electroluminescent device comprising: a first electrode; an organic 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 layer or the capping layer includes a heteroaryl amine derivative represented by the following chemical formula 1.

[0028] [Chemical Formula 1]

[0029]

[0030] In the above chemical formula 1,

[0031] L 1, L2 and L3 are each independently a direct bond; or a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group,

[0032] Z1 is O or S

[0033] Ar1, Ar2 and Ar3 are each independently selected from a phenyl group, a biphenyl group, a naphthyl group, a benzofuran group, a benzothiophene group, a benzoxazole group, a benzothiazole group, a dibenzofuran group, and a dibenzothiophene group, each of which is substituted or unsubstituted with a cyano group;

[0034] m is an integer of 0 or 1,

[0035] p, q and r are integers from 0 to 2,

[0036] If p, q, and r are 0, it is a direct combination.

[0037] The compound described herein can be used as a material of an organic layer of an organic light-emitting device.

[0038] The compound according to at least one embodiment exhibits ultraviolet 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 in the organic light-emitting device.

[0039] An organic light-emitting device using the compound described herein as a capping layer can have improved luminous efficiency and significantly improved color purity due to a reduction in the half-width of the luminous spectrum.

[0040] The compound of the present invention exhibits an unexpectedly high refractive index due to the introduction of a cyano group into a conventional compound. This improves the viewing angle and luminous efficiency of light extracted into the air in an organic light-emitting device, and thus, the compound of the present invention can be used as a material for a capping layer (luminous efficiency-improving layer).

[0041] FIG. 1 illustrates an example of an organic light-emitting device in which 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 (235), a second electrode (120), and a capping layer (300) are sequentially laminated on a substrate (100) according to one embodiment of the present invention.

[0042] Figure 2 is a graph of the refraction and absorption characteristics of light that appear when using an organic compound according to one embodiment of the present invention.

[0043] In this specification, “substituted or unsubstituted” may mean substituted or unsubstituted with one or more substituents selected from the group consisting of 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, a halogenated alkyl group, an alkoxy group, an alkenyl group, an aryl group, a heteroaryl group, and a heterocyclic group. In addition, each of the above-mentioned substituents may be substituted or unsubstituted. For example, a biphenyl group may be interpreted as an aryl group, or may be interpreted as a phenyl group substituted with a phenyl group.

[0044] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms.

[0045] In this specification, the alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is 1 to 50, preferably 1 to 6. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, i-butyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, i-pentyl, neopentyl, t-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl group, t-octyl group, 2-ethyloctyl group, 2-butyloctyl group, 2-hexyloctyl 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-octyldecyl 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, Examples thereof include, but are not limited to, n-octadecyl group, n-nonadecyl group, n-icosyl group, 2-ethylicosyl group, 2-butylicosyl group, 2-hexylicosyl group, 2-octylicosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, and n-triacontyl group.

[0046] 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-forming carbon atoms.

[0047] 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-forming carbon atoms of the aryl group may be 6 or more and 30 or less, preferably 6 or more and 15 or less. Examples of the aryl group include, but are not limited to, a phenyl group, a naphthyl group, a fluorenyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, a terphenyl group, a quarterphenyl group, a quincphenyl group, a sexiphenyl group, a triphenylenyl group, a pyrenyl group, a perylenyl group, a naphthacenyl group, a pyrenyl group, a benzofluoranthenyl group, and a chrysenyl group.

[0048] In this specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

[0049] In the present specification, a heteroaryl group may be a heteroaryl group containing at least one of O, N, P, Si, and S as a heteroatom. N and S atoms may be oxidized as needed, and N atom(s) may be quaternized as needed. The number of ring-forming carbon atoms of 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.

[0050] Examples of heteroaryl groups 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, pyridopyrimidine group, pyridopyrazino pyrazine group, isoquinoline group, cinnoline group, indole group, isoindole group, indazole group, carbazole group, N-arylcarbazole group, N-heteroarylcarbazole group, N-alkylcarbazole group, benzoxazole group, benzimidazole group, benzothiazole group, Examples thereof include, but are not limited to, a benzocarbazole group, a benzothiophene group, a benzoisothiazolyl group, a benzoisoxazolyl group, a dibenzothiophene group, a benzofuran group, a phenanthroline group, a phenanthridine group, a thiazole group, an isoxazole group, an oxadiazole group, a thiadiazole group, an isothiazole group, an isoxazole group, a phenothiazine group, a benzodioxole group, a dibenzosilole group, a dibenzofuran group, and an isobenzofuran group. In addition, examples thereof include, but are not limited to, a quaternary salt of a N-oxide aryl group corresponding to the monocyclic heteroaryl group or polycyclic heteroaryl group, such as a pyridyl N-oxide group, a quinolyl N-oxide group, and the like.

[0051] In the present specification, the alkenyl group may be straight-chain or branched. The number of carbon atoms is not particularly limited, but is 2 to 30, preferably 2 to 10. 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.

[0052] In this specification, “adjacent group” may mean a substituent substituted on an atom directly connected to the atom substituted by the substituent, another substituent substituted on the atom substituted by the substituent, or a substituent that is sterically closest to the substituent. For example, in 1,2-dimethylbenzene, two methyl groups may be interpreted as “adjacent groups,” and in 1,1-diethylcyclopentene, two ethyl groups may be interpreted as “adjacent groups.”

[0053]

[0054] Hereinafter, the heteroaryl amine derivative used in the organic layer and / or capping layer is described.

[0055] A heteroaryl amine derivative compound according to one embodiment of the present invention is represented by the following chemical formula 1.

[0056] [Chemical Formula 1]

[0057]

[0058] In the above chemical formula 1,

[0059] L 1, L2 and L3 are each independently a direct bond; or a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group,

[0060] Z1 is O or S

[0061] Ar1, Ar2 and Ar3 are each independently selected from a phenyl group, a biphenyl group, a naphthyl group, a benzofuran group, a benzothiophene group, a benzoxazole group, a benzothiazole group, a dibenzofuran group, and a dibenzothiophene group, each of which is substituted or unsubstituted with a cyano group;

[0062] m is an integer of 0 or 1,

[0063] p, q and r are integers from 0 to 2,

[0064] If p, q, and r are 0, it is a direct combination.

[0065] In one embodiment of the present invention, the compound of Chemical Formula 1 may be any one selected from compounds represented by Chemical Formulas 2 to 5 below.

[0066] [Chemical Formula 2]

[0067]

[0068] [Chemical Formula 3]

[0069]

[0070] [Chemical Formula 4]

[0071]

[0072] [Chemical Formula 5]

[0073]

[0074] In the above chemical formulas 2 to 5, L1, L2 and L3 are each independently selected from a direct bond; a substituted or unsubstituted phenylene group; a substituted or unsubstituted naphthylene group; a substituted or unsubstituted pyridylene group; a substituted or unsubstituted dibenzofuranylene group; and a substituted or unsubstituted dibenzothiophenylene group;

[0075] R 1, R2, R3, R4, R5 and R6 are each independently selected from a cyano group; a phenyl group with a substituted or unsubstituted cyano group; a biphenyl; a naphthyl group; a benzofuran group; a benzothiophene group; a benzoxazole group; a benzothiazole group; and a dibenzofuran group; a dibenzothiophene group.

[0076] Z 2, Z3, Z4 and Z5 are each independently O or S,

[0077] X1 and X2 are each independently CH or N,

[0078] a, b, c, d, e and f are each independently integers 0 or 1,

[0079] Z1, m, p, q, and r are as defined in the above chemical formula 1.

[0080] In one embodiment of the present invention, the compound of Chemical Formula 1 may be any one selected from compounds represented by Chemical Formulas 6 to 7 below, and may be further substituted with the following compounds.

[0081] [Chemical Formula 6]

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[0330] Hereinafter, embodiments of the present invention will be described with reference to FIGS. 1 and 2.

[0331] FIG. 1 is a cross-sectional view schematically illustrating an organic electroluminescent device according to one embodiment of the present invention. Referring to FIG. 1, an organic electroluminescent device according to one embodiment may include 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 (235), a second electrode (120), and a capping layer (300) sequentially stacked on a substrate (100).

[0332] The first electrode (110) and the second electrode (120) are arranged to face each other, and an organic layer (200) may be arranged between the first electrode (110) and the second electrode (120). The organic 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).

[0333] 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 the chemical formula 1 of the present invention.

[0334] In the organic electroluminescent device of one 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 thereto.

[0335] The first electrode (110) can be formed on the upper portion of the substrate (100) by using a deposition method, electron beam evaporation, sputtering method, or the like. The material of the first electrode (110) can be selected from among materials having a high work function to facilitate the injection of holes into the organic electroluminescent device.

[0336] The capping layer (300) proposed in the present invention is applied when the light emitting direction of the organic electroluminescent device is front emission, and therefore the first electrode (110) uses a reflective electrode. These materials can be manufactured using metals such as Mg (magnesium), Al (aluminum), Al-Li (aluminum-lithium), Ca (calcium), Mg-In (magnesium-indium), and Mg-Ag (magnesium-silver) rather than oxides. Recently, carbon substrate flexible electrode materials such as CNT (carbon nanotube) and Graphene can also be used.

[0337] The organic layer (200) may be formed of multiple layers. When the organic layer (200) is a plurality of layers, the organic layer (200) may include 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 an electron transport region (230 to 235) disposed on the light-emitting layer (220).

[0338] The above capping layer (300) includes an organic compound represented by the chemical formula 1 described below.

[0339] A hole transport region (210 to 215) is provided on the first electrode (110). The hole transport region (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 plays a role in smoothly injecting and transporting holes into the organic electroluminescent device. In general, since hole mobility is faster than electron mobility, the hole transport region has a thickness greater than that of the electron transport region.

[0340] The hole transport region (210-215) may have a multilayer structure having a single layer made of a single material, a single layer made of multiple different materials, or multiple layers made of multiple different materials.

[0341] For example, the hole transport region (210 to 215) may have a single-layer structure of a hole injection layer (210) or a hole transport layer (215), or may have a single-layer structure composed of a hole injection material and a hole transport material. In addition, the hole transport region (210 to 215) may have a single-layer structure composed of a plurality of different materials, or may have a structure of a hole injection layer (210) / hole transport layer (215), a hole injection layer (210) / hole transport layer (215) / hole buffer layer, a hole injection layer (210) / hole buffer layer, a hole transport layer (215) / hole buffer layer, or a hole injection layer (210) / hole transport layer (215) / electron blocking layer (EBL) sequentially stacked from the first electrode (110), but the embodiment is not limited thereto.

[0342] In the above hole transport region (210-215), the hole injection layer (210) can be formed on the anode by various methods such as vacuum deposition, spin coating, casting, and LB. When the hole injection layer (210) is formed by vacuum deposition, the deposition conditions can be freely adjusted at a deposition rate of about 1 Å / s at 100 to 500°C depending on the compound used as the hole injection layer (210) material and the structure and thermal characteristics of the target hole injection layer (210), and are not limited to specific conditions. When the hole injection layer (210) is formed by spin coating, the coating conditions vary depending on the characteristics between the compound used as the hole injection layer (210) material and the layers formed at the interface, but an appropriate coating speed, heat treatment for removing the solvent after coating, etc. are required for uniform film formation.

[0343]

[0344] The above hole transport region (210-215) is, for example, m-MTDATA, TDATA, 2-TNATA, NPB, β-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated-NPB, TAPC, HMTPD, TCTA(4,4',4"-tris(Ncarbazolyl) triphenylamine), Pani / DBSA(Polyaniline / Dodecylbenzenesulfonic acid), PEDOT / PSS(Poly(3,4-ethylenedioxythiophene) / Poly(4-styrene sulfonate)), Pani / CSA(Polyaniline / Camphor sulfonic acid: It may include polyaniline / camphorsulfonic acid), Pani / PSS (Polyaniline) / Poly(4-styrenesulfonate): polyaniline) / poly(4-styrenesulfonate)).

[0345]

[0346] The thickness of the above hole transport regions (210 to 215) can be formed to be 100 to 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) can be formed to be 1,000 Å, and the thickness of the electron blocking layer can be formed to be 500 Å. The thickness condition of the hole transport regions (210 to 215) can be determined to a degree that satisfies efficiency and lifespan within a range in which the driving voltage increase of the organic electroluminescent device does not increase significantly.

[0347] The above organic layer (200) may include at least one layer selected from the group consisting of 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 a functional layer having both an electron transport function and an electron injection function.

[0348] The hole transport region (210-215) can be doped to improve characteristics, similar to the light-emitting layer (220), and doping of a charge-generating material into the hole transport region (210-215) can improve the electrical characteristics of the organic electroluminescent device.

[0349] Charge-generating materials are generally composed of materials with very low HOMO and LUMO. For example, the LUMO of the charge-generating material has a value similar to the HOMO of the hole transport layer (215) material. Due to this low LUMO, the empty electron characteristic of the LUMO is utilized to easily transfer holes to the adjacent hole transport layer (215), thereby improving electrical properties.

[0350] The charge-generating material may be, for example, a p-dopant. The p-dopant may be, but is not limited to, one of a quinone derivative, a metal oxide, and a cyano group-containing compound. For example, non-limiting examples of the p-dopant include, but are not limited to, quinone derivatives such as tetracyanoquinonedimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4-TCNQ); metal oxides such as tungsten oxide and molybdenum oxide; and cyano group-containing compounds.

[0351]

[0352] The hole transport region (210-215) may further include a charge generating material to improve conductivity in addition to the materials mentioned above.

[0353] The charge-generating material may be uniformly or non-uniformly dispersed within the hole transport region (210-215). The charge-generating material may be, for example, a p-dopant. The p-dopant may be, but is not limited to, one of a quinone derivative, a metal oxide, and a cyano group-containing compound. For example, non-limiting examples of p-dopants include, but are not limited to, quinone derivatives such as TCNQ (Tetracyanoquinodimethane) and F4-TCNQ (2,3,5,6-tetrafluoro-tetracyanoquinodimethane), and metal oxides such as tungsten oxide and molybdenum oxide.

[0354] As described above, the hole transport region (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 the wavelength of light emitted from the light emitting layer (220). As a material included in the hole buffer layer, a material that can be included in the hole transport region (210 to 215) may be used.

[0355] The electron blocking layer is a layer that prevents electron injection from the electron transport region (230-235) to the hole transport region (210-215). The electron blocking layer not only blocks electrons moving to the hole transport region, but also uses a material having a high T1 value to prevent excitons formed in the light-emitting layer (220) from diffusing into the hole transport region (210-215). For example, a host of the light-emitting layer (220), which generally has a high T1 value, can be used as the electron blocking layer material.

[0356] The light-emitting layer (220) is provided on the hole transport region (210 to 215). The light-emitting layer (220) may have a thickness of, for example, 100 Å to 1000 Å or 100 Å to 300 Å. The light-emitting layer (220) may have a multilayer structure having a single layer made of a single material, a single layer made of multiple different materials, or multiple layers made of multiple different materials.

[0357] The light-emitting layer (220) is a region where holes and electrons meet to form excitons. The material forming the light-emitting layer (220) must have an appropriate energy band gap to exhibit high light-emitting characteristics and a desired light-emitting color, and is generally composed of two materials that have two roles as a host and a dopant, but is not limited thereto.

[0358] The above host may include at least one of, but is not limited to, TPBi, TBADN, ADN (also referred to as “DNA”), CBP, CDBP, TCP, mCP.

[0359]

[0360] The dopant of the light-emitting layer (220) of one embodiment may be an organic metal complex. The content of the general dopant may be selected from 0.01 to 20%, but is not limited thereto.

[0361] The electron transport region (230 to 235) is provided on the light-emitting layer (220). The electron transport region (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.

[0362] The electron transport region (230-235) may have a multilayer structure having a single layer made of a single material, a single layer made of multiple different materials, or multiple layers made of multiple different materials.

[0363] For example, the electron transport region (230 to 235) may have a single-layer structure of an electron injection layer (235) or an electron transport layer (230), or may have a single-layer structure composed of an electron injection material and an electron transport material. In addition, the electron transport region (230 to 235) may have a single-layer structure composed of a plurality of different materials, or may have a structure of an electron transport layer (230) / electron injection layer (235), a hole blocking layer / electron transport layer (230) / electron injection layer (235) sequentially stacked from the light emitting layer (220), but is not limited thereto. The thickness of the electron transport region (230 to 235) may be, for example, 1000 Å to 1500 Å.

[0364] The electron transport region (230-235) can be formed using various methods such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) method, inkjet printing, laser printing, and laser induced thermal imaging (LITI).

[0365] When the electron transport region (230-235) includes an electron transport layer (230), the electron transport region (230) may include an anthracene compound. However, the electron transport region is not limited thereto, and examples thereof include 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), It may include 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(beryllium bis(benzoquinolin-10-olate), ADN(9,10-di(naphthalene-2-yl)anthracene) and mixtures thereof.

[0366]

[0367] The electron transport layer (230) is selected from a material with fast or slow electron mobility depending on the structure of the organic light-emitting device, so a variety of materials must be selected, and in some cases, Liq or Li may be doped.

[0368] The thickness of the electron transport layers (230) may be 100 Å to 1000 Å, for example, 150 Å to 500 Å. When the thickness of the electron transport layers (230) satisfies the range described above, satisfactory electron transport characteristics can be obtained without a substantial increase in driving voltage.

[0369] When the electron transport region (230 to 235) includes an electron injection layer (235), the electron transport region (230 to 235) may include a metal material that facilitates electron injection, and lanthanide metals such as LiF, LiQ (lithium quinolate), Li2O, BaO, NaCl, CsF, Yb, or halogenated metals such as RbCl, RbI may be used, but are not limited thereto.

[0370] The electron injection layer (235) may also be formed of a material in which an electron transport material and an insulating organometallic 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. The thickness of the electron injection layer (235) may be 1 Å to 100 Å, preferably 3 Å to 90 Å. When the thickness of the electron injection layer (235) satisfies the range described above, satisfactory electron injection characteristics can be obtained without a substantial increase in driving voltage.

[0371] The electron transport region (230-235) may include a hole blocking layer, as mentioned above. The hole blocking layer may include, but is not limited to, at least one of BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), and Balq.

[0372] The second electrode (120) is provided on the electron transport region (230-235). The second electrode (120) may be a common electrode or a cathode. The second electrode (120) may be a transmissive electrode or a semi-transmissive electrode. Unlike the first electrode (110), the second electrode (120) may be formed by combining a metal, an electrically conductive compound, an alloy, or the like having a relatively low work function.

[0373] The second electrode (120) is a semi-transmissive electrode or a reflective electrode. The second electrode (120) may include 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 these (for example, a mixture of Ag and Mg). Alternatively, it may have a multi-layer structure including a reflective film or semi-transmissive film formed of the above materials and a transparent conductive film formed of ITO (indium tin oxide), IZO (indium zinc oxide), ZnO (zinc oxide), ITZO (indium tin zinc oxide), etc.

[0374] 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, the resistance of the second electrode (120) may be reduced.

[0375] An electrode and an organic layer are formed on the illustrated substrate (100), and at this time, a hard or soft material can be used as the substrate (100) material. For example, hard materials such as soda lime glass, alkali-free glass, and aluminosilicate glass can be used, and soft materials such as PC (polycarbonate), PES (polyethersulfone), COC (cyclic olefin copolymer), PET (polyethylene terephthalate), PEN (polyethylene naphthalate) can be used.

[0376] In an organic electroluminescent device, when voltage is applied to the first electrode (110) and the second electrode (120), holes injected from the first electrode (110) move to the light-emitting layer (220) through the hole transport region (210 to 215), and electrons injected from the second electrode (120) move to the light-emitting layer (220) through the electron transport region (230 to 235). Electrons and holes recombine in the light-emitting layer (220) to generate excitons, and light is emitted when the excitons drop from the excited state to the ground state.

[0377] The path of light generated from the light-emitting layer (220) may exhibit very different tendencies depending on the refractive index of the organic and inorganic materials constituting the organic electroluminescent element. Only light that passes through the second electrode (120) at an angle smaller than the critical angle of the second electrode (120) can pass through. Other light that contacts the second electrode (120) at an angle larger than the critical angle is totally reflected or reflected and is not emitted to the outside of the organic electroluminescent element.

[0378] If the refractive index of the capping layer (300) is high, it contributes to improving the luminous efficiency by reducing the total reflection or reflection phenomenon, and if it has an appropriate thickness, it also contributes to improving the efficiency and color purity by maximizing the micro-cavity phenomenon.

[0379] The capping layer (300) is located at the outermost part of the organic electroluminescent device, and has a significant influence on the device characteristics without affecting the operation of the device at all. Therefore, the capping layer (300) is important from both the perspective of protecting the inside of the organic electroluminescent device and improving the device characteristics. Organic materials absorb light energy in a specific wavelength range, which depends on the energy band gap. If this energy band gap is adjusted for the purpose of absorbing the UV range that can affect the organic materials inside the organic electroluminescent device, the capping layer (300) including the organic materials can be used for the purpose of protecting the organic electroluminescent device, including improving the optical characteristics.

[0380] And the capping layer (300) including such a tertiary amine compound has a high refractive index of 1.9 or more. For example, the capping layer may have a refractive index in the range of 1.9 to 3.0. When the refractive index of the capping layer (300) is high, light may be reflected at the interface of the capping layer (300), resulting in light resonance.

[0381] The organic light-emitting device according to the present specification may be a front-emitting, back-emitting or double-sided emitting device depending on the material used.

[0382] Hereinafter, an organic electroluminescent device according to one embodiment of the present invention and an organic compound according to one embodiment will be specifically described with reference to Examples and Comparative Examples. In addition, the Examples shown below are illustrative examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

[0383]

[0384] [Synthesis example]

[0385] Intermediate synthesis example 1: Synthesis of intermediate (1)

[0386]

[0387] 30.0 g (132.5 mmol) of 4-(benzo[d]thiazol-2-yl)aniline, 42.3 g (145.8 mmol) of 2-(4-bromophenyl)benzo[d]thiazole, 21.5 g (2.6 mmol) of Pd(dba), 3.0 g (5.3 mmol) of Xantphos, 31.8 g (331.4 mmol) of t-BuONa, and 500 mL of toluene were mixed and stirred at 70°C for 3 hours. After cooling to room temperature, the resulting solid was filtered and washed with toluene, distilled water, and methanol. The obtained solid was slurried with toluene and filtered to obtain 41.0 g (yield: 71.0%) of a light yellow solid compound (intermediate (1)).

[0388]

[0389] Intermediate synthesis example 2: Synthesis of intermediate (2)

[0390]

[0391] 3-Bromo-7-chlorodibenzo[b,d]furan (7.0 g, 24.9 mmol), phenylboronic acid (3.0 g, 24.9 mmol), Pd(PPh3) (4860.0 mg, 750.0 μmol), K2CO3 (10.3 g, 74.6 mmol), toluene (70 mL), distilled water (30 mL), and ethanol (30 mL) were added, and the mixture was refluxed overnight. After cooling to room temperature, the formed solid was filtered, washed with toluene and methanol, and dried. The solid thus obtained was recrystallized from a combination of dichloromethane and hexane to obtain 5.8 g (yield: 83.9%) of the compound (intermediate (2)) as a light gray solid.

[0392]

[0393] Intermediate synthesis example 3: Synthesis of intermediate (3)

[0394]

[0395] Bis(4-bromophenyl)amine (25.0 g, 76.4 mmol), (4-cyanophenyl)boronic acid (24.7 g, 168.0 mmol), Pd(PPh3) (43.5 g, 3.1 mmol), K2CO3 (42.3 g, 306.0 mmol), 375 mL toluene, 75 mL distilled water, and 75 mL ethanol) were added and stirred at 90°C overnight. After cooling to room temperature, the formed solid was filtered, washed with toluene, distilled water, and methanol, and dried. The obtained solid was slurried with hot dichloromethane to obtain 24.5 g (yield: 86.2%) of the compound (intermediate (3)) as a light brown solid.

[0396]

[0397] Intermediate synthesis example 4: Synthesis of intermediate (4)

[0398]

[0399] 20.0 g (95.0 mmol) of 4-(benzo[d]oxazol-2-yl)aniline, 26.0 g (95.0 mmol) of 2-(4-bromophenyl)benzo[d]oxazole, 21.0 g (1.9 mmol) of Pd(dba), 2.1 g (3.8 mmol) of Xantphos, 27.3 g (285.0 mmol) of NaOt-Bu, and 400 mL of toluene were mixed and stirred under reflux overnight at 80°C. The reaction was quenched with distilled water, cooled to room temperature, filtered under reduced pressure, washed with methanol, and dried to obtain 34.4 g (yield: 89.8%) of the compound (intermediate (4)) as a yellow solid.

[0400]

[0401] Intermediate synthesis example 5: Synthesis of intermediate (5)

[0402]

[0403] Bis(4-bromophenyl)amine (40.0 g, 122.0 mmol), benzofuran-2-ylboronic acid (43.5 g, 269.0 mmol), Pd(pph3) (42.8 g, 2.4 mmol), K2CO (50.5 g, 366.0 mmol), toluene (400 mL), ethanol (80 mL), and distilled water (80 mL) were mixed and stirred under reflux overnight. After quenching the reaction with distilled water, the mixture was cooled to room temperature, and the formed solid was filtered under reduced pressure, washed with methanol, and dried to obtain 32.2 g (yield: 65.8%) of a brown solid compound (intermediate (5)).

[0404]

[0405] Intermediate synthesis example 6: Synthesis of intermediate (6)

[0406]

[0407] 4-(benzo[d]oxazol-2-yl)aniline (10.0 g, 34.5 mmol), 2-(4-bromophenyl)benzo[d]thiazole (8.0 g, 37.9 mmol), Pd(dba) (2590 mg, 1.0 mmol), Xantphos (1.2 g, 2.1 mmol), t-BuONa (9.9 g, 103.0 mmol), and toluene (150 mL) were mixed and stirred at 100°C overnight. After cooling to room temperature, the formed solid was filtered, washed with toluene and methanol, and dried. The solid thus obtained was slurried with DCM to obtain 10.7 g (yield: 74.1%) of a light brown solid compound (intermediate (6)).

[0408]

[0409] Intermediate synthesis example 7: Synthesis of intermediate (7)

[0410]

[0411] 20.0 g (71.0 mmol) of 3-bromo-7-chlorodibenzo[b,d]furan, 15.7 g (106.6 mmol) of 4-cyanophenylboronic acid, 41.2 g (1.1 mmol) of Pd(PPh3), 29.7 g (213.1 mmol) of K2CO3, 300 mL of toluene, 60 mL of distilled water, and 60 mL of ethanol were mixed and stirred under reflux for 4 hours. After cooling to room temperature, the resulting solid was filtered, washed with toluene, distilled water, and methanol, and dried. The solid thus obtained was added to toluene, stirred under reflux for 1 hour, and then slowly cooled to room temperature. The solid was filtered and washed with toluene to obtain 15.3 g (yield: 70.9%) of a light yellow solid compound (intermediate (7)).

[0412]

[0413] Intermediate synthesis example 8: Synthesis of intermediate (8)

[0414]

[0415] Bis(4-bromophenyl)amine (20.0 g, 61.1 mmol), benzo[b]thiophen-2-ylboronic acid (27.2 g, 152.0 mmol), Pd(pph3) (41.4 g, 1.2 mmol), K2CO3 (25.3 g, 183.0 mmol), THF (300 mL), and distilled water (100 mL) were mixed and stirred under reflux overnight. After completion of the reaction, the reaction mixture was cooled to room temperature, and the formed solid compound was filtered under reduced pressure and dried. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM:EtOAc), and recrystallized with a mixed solvent (DCM:HEX) to obtain 19.5 g (yield: 73.5%) of an orange solid compound (intermediate (8)).

[0416]

[0417] Intermediate synthesis example 9: Synthesis of intermediate (9)

[0418]

[0419] 4-(benzo[d]oxazol-2-yl)aniline 10.0 g (47.6 mmol), 2-(4-bromophenyl)benzo[b]thiophene 13.8 g (47.6 mmol), NaO t Bu 9.1 g (95.1 mmol), 300 mL of toluene were mixed and stirred, and Pd (dba) 20.8 g (1.4 mmol), Xantphos 1.7 g (2.9 mmol) was added and stirred under reflux for a whole day. After confirming the completion of the reaction, the mixture was cooled to room temperature, the solvent was removed, methanol was added, stirred for 30 minutes, and the formed solid was filtered and dried. The solid thus obtained was dissolved in hot dichlorobenzene, filtered through a pad of Celite, and concentrated under reduced pressure. The concentrate was added to acetone, stirred for 30 minutes, and filtered to obtain 12.4 g (yield: 62.1%) of the compound (intermediate (9)) as a yellow solid.

[0420]

[0421] Intermediate synthesis example 10: Synthesis of intermediate (10)

[0422]

[0423] 3-Bromo-7-chlorodibenzo[b,d]furan (30.0 g, 106.6 mmol), naphthalen-2-ylboronic acid (18.7 g, 108.8 mmol), Pd(PPh3) (43.7 g, 3.2 mmol), 2M K2CO3 aqueous solution (160.0 mL, 319.8 mmol), toluene (340 mL), and ethanol (EtOH) (170 mL) were mixed, and then refluxed and stirred at 60°C for 18 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered and dried. The obtained solid was dissolved in hot monochlorobenzene and filtered through celite and silica gel pad. The filtrate was concentrated and then solidified with a mixed solution (CHCl3:MeOH) to obtain 28.0 g (yield: 80.0%) of a yellow solid compound (intermediate (10)).

[0424]

[0425] Intermediate synthesis example 11: Synthesis of intermediate (11)

[0426]

[0427] 4-(benzo[d]thiazol-2-yl)aniline 10.0 g (44.2 mmol), 2-(4-bromophenyl)benzo[b]thiophene 12.8 g (44.2 mmol), NaO t Bu 8.5 g (88.4 mmol) and 300 mL of toluene were mixed and stirred, and then 20.8 g (1.3 mmol) of Pd (dba), Xantphos 1.5 g (2.7 mmol) was added and stirred under reflux for a whole day. After confirming the completion of the reaction, it was cooled to room temperature and concentrated. Methanol was added to the concentrate and stirred for 30 minutes. The formed solid was filtered and dried. The solid thus obtained was dissolved in hot dichlorobenzene, filtered through a celite pad, and concentrated under reduced pressure. The concentrate was added to acetone, stirred for 30 minutes, and then filtered to obtain 11.9 g (yield: 62.1%) of the compound (intermediate (11)) as a light green solid.

[0428]

[0429] Intermediate synthesis example 12: Synthesis of intermediate (12)

[0430]

[0431] 20.0 g (71.0 mmol) of 3-bromo-7-chlorodibenzo[b,d]furan, 16.8 g (85.2 mmol) of [1,1'-biphenyl]-4-ylboronic acid, 40.8 g (0.7 mmol) of Pd(pph3), 29.4 g (213.0 mmol) of K2CO3, 300 mL of toluene, 60 mL of ethanol, and 60 mL of distilled water were added and stirred under reflux overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the formed solid was filtered and washed with methanol to obtain 23.7 g (yield: 94.4%) of the compound (intermediate (12)) as a gray solid.

[0432]

[0433] Intermediate synthesis example 13: Synthesis of intermediate (14)

[0434]

[0435] (Synthesis of intermediate (13))

[0436] 4-Bromoaniline (50.0 g, 290.6 mmol), benzofuran-2-ylboronic acid (56.5 g, 348.7 mmol), Pd(PPh3) (46.7 g, 5.8 mmol), 2M K2CO3 aqueous solution (436 mL, 871.8 mmol), toluene (800 mL), and ethanol (EtOH) (400 mL) were mixed and stirred under reflux for 3 hours. After the reaction was completed, the mixture was cooled to room temperature and concentrated, and the resulting solid was filtered and dried. The resulting solid was dissolved in chloroform by reflux, filtered through Celite and silica gel, and concentrated. The concentrate was solidified with hexane to obtain 33.6 g (yield: 55.3%) of the compound (intermediate (13)) as a yellow solid.

[0437] (Synthesis of intermediate (14))

[0438] Intermediate (13) 16.0 g (76.5 mmol), 2-(4-bromophenyl)benzo[d]thiophene 22.1 g (76.5 mmol), Pd(dba) 21.3 g (2.3 mmol), Xantphos 2.7 g (4.6 mmol), NaOtBu 22.1 g (229.5 mmol), and toluene 38 mL were mixed and stirred at 70°C for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, and the resulting solid was filtered, washed with distilled water, and dried to obtain 19.2 g (yield: 60.2%) of the compound (intermediate (14)) as a brown solid.

[0439]

[0440] Intermediate synthesis example 14: Synthesis of intermediate (15)

[0441]

[0442] 2-(4-bromophenyl)benzo[d]oxazole (30.0 g, 172.2 mmol), 4'-amino-[1,1'-biphenyl]-4-carbonitrile (47.2 g, 172.2 mmol), Pd(dba) (23.0 g, 5.2 mmol), Xantphos (6.0 g, 10.3 mmol), NaOtBu (49.7 g, 516.6 mmol), and toluene (860 mL) were mixed and stirred at 70°C for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, and distilled water was added. The resulting solid was filtered and dried. The solid thus obtained was dissolved by refluxing with toluene, cooled slowly, filtered and dried to obtain 22.0 g (yield: 32.9%) of a brown solid compound (intermediate (15)).

[0443]

[0444] Intermediate synthesis example 15: Synthesis of intermediate (16)

[0445]

[0446] Intermediate (13) 5.0 g (23.9 mmol), intermediate (10) 7.9 g (23.9 mmol), Pd(dba) 20.4 g (0.7 mmol), Xantphos 0.8 g (1.4 mmol), NaOtBu 9.5 g (98.7 mmol), and toluene 120 mL were mixed and stirred at 90°C for 18 hours. After the reaction was completed, it was cooled to room temperature. The resulting solid was filtered, washed with distilled water, and dried to obtain 6.2 g (yield: 51.7%) of compound (16) as a brown solid.

[0447]

[0448] Intermediate synthesis example 16: Synthesis of intermediate (17)

[0449]

[0450] 20.0 g (71.0 mmol) of 3-bromo-7-chlorodibenzo[b,d]furan, 11.5 g (71.0 mmol) of benzofuran-2-ylboronic acid, 42.5 g (2.1 mmol) of Pd(PPh3), 46.3 g (142.0 mmol) of Cs2CO3, 200 mL of THF, and 40 mL of distilled water were mixed and stirred at 70°C overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the formed solid was filtered, washed with THF, distilled water, and methanol, and dried. The solid thus obtained was refluxed with dichloromethane (DCM), cooled to room temperature, and filtered to obtain 18.7 g (yield: 82.6%) of a light yellow solid compound (intermediate (17)).

[0451]

[0452] Intermediate synthesis example 17: Synthesis of intermediate (18)

[0453]

[0454] Intermediate (13) 24.5 g (117.1 mmol), 2-(4-bromophenyl)benzo[d]oxazole 35.3 g (128.8 mmol), Pd(dba) 21.4 g (2.3 mmol), Xantphos 2.7 g (4.7 mmol), t-BuONa 38.8 g (292.7 mmol), and toluene 400 mL were mixed and stirred at 70°C for 3 hours. After cooling to room temperature, the resulting solid was filtered and washed with toluene, distilled water, and methanol. The solid thus obtained was slurried with toluene for 1 hour and filtered to obtain 30.0 g (yield: 63.7%) of the compound (intermediate (18)) as a brown solid.

[0455]

[0456] Intermediate synthesis example 18: Synthesis of intermediate (19)

[0457]

[0458] Intermediate (13) 7.5 g (38.7 mmol), intermediate (17) 8.9 g (42.6 mmol), Pd(dba)2 670.0 mg (1.2 mmol), Xantphos 1.0 g (2.3 mmol), t-BuONa 11.2 g (116.0 mmol), and toluene 100 mL were mixed and stirred at 95°C overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, the formed solid was filtered, washed with toluene and methanol, and dried. The solid thus obtained was slurried with dichloromethane and filtered to obtain 11.5 g (yield: 71.8%) of a brown solid compound (intermediate (19)).

[0459]

[0460] Intermediate synthesis example 19: Synthesis of intermediate (21)

[0461]

[0462] (Synthesis of intermediate (20))

[0463] 7-bromodibenzo[b,d]furan-3-amine (20.0 g, 76.0 mmol), benzofuran-2-ylboronic acid (14.8 g, 91.5 mmol), Pd(pph3) (41.7 g, 1.5 mmol), CS2CO3 (74.5 g, 228.0 mmol), THF (300 mL) and distilled water (100 mL) were mixed and stirred under reflux for 3 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the formed solid was filtered, washed with methanol and dried to obtain 20.1 g (yield: 88.5%) of a brown solid compound (intermediate (20)).

[0464] (Synthesis of intermediate (21))

[0465] Intermediate (20) 5.0 g (16.7 mmol), 2-(4-bromophenyl)benzo[d]oxazole 4.5 g (16.7 mmol), Pd(dba) 20.1 g (0.3 mmol), Xantphos 0.3 g (0.6 mmol), NaOt-Bu 4.8 g (50.0 mmol) and toluene 100 mL were mixed and stirred at 80°C overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the formed solid was filtered, washed with methanol and dried to obtain 5.8 g (yield: 70.7%) of the compound (intermediate (21)) as a brown solid.

[0466]

[0467] Intermediate synthesis example 20: Synthesis of intermediate (22)

[0468]

[0469] 3-Bromo-7-chlorodibenzo[b,d]furan (5.0 g, 17.7 mmol), benzo[b]thiophen-2-ylboronic acid (3.4 g, 19.5 mmol), Pd(pph3) (40.4 g, 0.3 mmol), K2CO3 (7.3 g, 53.1 mmol), toluene (50 mL), ethanol (15 mL), and distilled water (15 mL) were mixed and stirred under reflux overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the formed solid was filtered under reduced pressure, washed with methanol, and dried to obtain 3.5 g (yield: 59.3%) of a yellow solid compound (intermediate (22)).

[0470]

[0471] Intermediate synthesis example 21: Synthesis of intermediate (23)

[0472]

[0473] 4-(benzo[d]oxazol-2-yl)aniline 5.0 g (23.8 mmol), 7-chlorodibenzo[b,d]furan-3-carbonitrile 5.7 g (25.0 mmol), Pd(dba) 20.4 g (0.7 mmol), X-Phos 0.7 g (1.4 mmol), K3PO4 10.1 g (47.6 mmol) and 180 mL of xylene were mixed and refluxed overnight. After confirming the completion of the reaction, the reaction mass was cooled to room temperature and concentrated. The concentrate was added to methanol, stirred for 30 minutes, and filtered. The solid thus obtained was dissolved in dichlorobenzene while refluxing, filtered through a celite pad, and concentrated. Acetone was added to the concentrate, stirred for 30 minutes, and filtered to obtain 5.8 g (yield: 61.2%) of the compound (intermediate (23)) as a brown solid.

[0474]

[0475] Intermediate synthesis example 22: Synthesis of intermediate (25)

[0476]

[0477] (Synthesis of intermediate (24))

[0478] To a mixture of 20.0 g (71.0 mmol) of 3-bromo-7-chlorodibenzo[b,d]furan and 200 mL of tetrahydrofuran, 39.8 mL (2.5 M in hexane, 99.5 mmol) of n-BuLi was slowly added dropwise at -78°C. The reaction mixture was stirred at -78°C for 1 hour, then 11.0 mL (142.1 mmol) of DMF was slowly added dropwise and stirred for 1 hour. After confirming the completion of the reaction, distilled water was slowly added dropwise to the reaction mixture. The reaction mixture was distilled off tetrahydrofuran under reduced pressure, and the resulting solid was filtered, washed with methanol and distilled water, and dried. The solid thus obtained was slurried with a mixed solvent (DCM / HEX) and filtered to obtain 7.8 g (yield: 47.6%) of the compound (intermediate (24)) as a yellow solid.

[0479] (Synthesis of intermediate (25))

[0480] Intermediate (24) 7.8 g (33.8 mmol), 2-aminophenol 3.7 g (33.8 mmol), and 150 mL of ethanol were mixed and stirred at room temperature overnight. After confirming the completion of the reaction, the reaction mass was concentrated. 200 mL of dichloromethane (DCM) was added to the concentrate, and 8.4 g (37.2 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) was slowly added little by little, and the mixture was stirred at room temperature for 1 hour. The reactant was filtered through a silica gel pad, washed with dichloromethane (DCM), and concentrated. The concentrate was slurried with methanol and filtered. The solid thus obtained was recrystallized with a mixed solvent (DCM / MeOH) to obtain 4.8 g (yield: 44.4%) of the compound (intermediate (25)) as a brown solid.

[0481]

[0482] Intermediate synthesis example 23: Synthesis of intermediate (27)

[0483]

[0484] (Synthesis of intermediate (26))

[0485] 20.0 g (71.0 mmol) of 3-bromo-7-chlorodibenzo[b,d]furan, 27.1 g (106.6 mmol) of PIN2B, 1.2 g (1.4 mmol) of PdCl2dppf·DCM, 20.9 g (213.1 mmol) of KOAc, and 200 mL of dioxane were mixed and refluxed overnight. The reaction mixture was cooled to room temperature and concentrated. Distilled water and dichloromethane (DCM) were added to the concentrate, stirred, and the organic layer was separated. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrate was purified by silica gel column chromatography (DCM:HEX), slurried with hexane, and filtered to obtain 16.2 g (yield: 69.4%) of a yellow solid compound (intermediate (26)).

[0486] (Synthesis of intermediate (27))

[0487] Intermediate (26) 16.0 g (48.7 mmol), 2-chlorobenzo[d]thiazole 12.4 g (73.0 mmol), Pd(PPh3) 41.1 (974.0 μmol), K2CO3 20.3 g (146.1 mmol), toluene 160 mL, distilled water 40 mL, and ethanol 40 mL were mixed and stirred at 85°C overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, filtered, washed with toluene, distilled water, and methanol, and dried. The solid thus obtained was heated with chloroform, stirred for 1 hour, cooled to room temperature, filtered, and washed with hexane (Hex) to obtain 10.4 g (yield: 63.6%) of a yellow solid compound (intermediate (27)).

[0488]

[0489] Intermediate synthesis example 24: Synthesis of intermediate (28)

[0490]

[0491] 3-Bromo-7-chlorodibenzo[b,d]thiophene (5.0 g, 17.7 mmol), benzo[b]thiophen-2-ylboronic acid (3.4 g, 19.5 mmol), Pd(pph3) (40.4 g, 0.3 mmol), K2CO3 (7.3 g, 53.1 mmol), toluene (50 mL), ethanol (15 mL), and distilled water (15 mL) were mixed and stirred under reflux overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the formed solid was filtered under reduced pressure, washed with methanol, and dried to obtain 3.5 g (yield: 59.3%) of a yellow solid compound (intermediate (28)).

[0492]

[0493] Intermediate synthesis example 25: Synthesis of intermediate (29)

[0494]

[0495] 2-Bromo-7-chlorodibenzo[b,d]furan (20.0 g, 71.0 mmol), benzofuran-2-ylboronic acid (17.3 g, 106.6 mmol), Pd(PPh3) (41.2 g, 1.1 mmol), K2CO3 (29.7 g, 213.1 mmol), toluene (200 mL), ethanol (40 mL), and distilled water (40 mL) were mixed and stirred at 75°C for 2 days. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the mixture was stirred. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrate was purified by silica gel column chromatography (DCM:HEX), slurried with hexane (HEX) for 1 hour, and filtered to obtain 5.6 g (yield: 24.7%) of a white solid compound (intermediate (29)).

[0496]

[0497] Using the intermediate compound synthesized above, various organic compounds were synthesized as follows.

[0498]

[0499] Manufacturing Example 1: Synthesis of compound 6-3 (LT23-30-209)

[0500]

[0501] Intermediate (1) 5.0 g (11.5 mmol), 3-bromodibenzo[b,d]furan 3.4 g (13.8 mmol), Pd(dba) 20.2 g (0.3 mmol), X-Phos 0.3 g (0.7 mmol), K3PO4 4.9 g (23.0 mmol), and 180 mL of xylene were mixed and stirred under reflux for 2 to 3 days. After confirming the completion of the reaction, cool to room temperature, remove the solvent, add dichloromethane and distilled water, stir, and separate the organic layer. The separated organic layer was filtered over anhydrous magnesium sulfate, dried, and concentrated. The mixture was purified by column chromatography (HEX:EtOAc) to obtain 3.0 g (yield: 43.4%) of compound 6-3 (LT23-30-209) as a yellow solid.

[0502]

[0503] Manufacturing Example 2: Synthesis of compound 6-82 (LT23-30-192)

[0504]

[0505] Intermediate (3) 5.0 g (13.4 mmol), intermediate (2) 4.1 g (14.8 mmol), Pd(dba)2230.0 mg (400.0 μmol), SPhos 330.0 mg (810.0 μmol), t-BuONa 3.8 g (40.4 mmol) and xylene 100 mL were mixed and stirred under reflux for 24 hours. After concentrating the reaction solution, the mixture was dissolved in hot chloroform, filtered through a pad of Celite, and concentrated. The mixture was purified by silica gel column chromatography (DCM:HEX) and recrystallized with a mixed solvent (DCM / Acetone) to obtain 1.5 g (yield: 18.6%) of compound 6-82 (LT23-30-192) as a yellow solid.

[0506]

[0507] Manufacturing Example 3: Synthesis of compound 6-83 (LT23-30-208)

[0508]

[0509] Intermediate (4) 5.0 g (12.3 mmol), intermediate (2) 3.7 g (13.6 mmol), Pd (dba) 20.7 g (1.2 mmol), X-phos 1.1 g (2.4 mmol), NaOt-Bu 3.5 g (37.2 mmol) and xylene 100 mL were mixed and stirred under reflux overnight. After quenching the reaction with distilled water, the reaction solution was cooled to room temperature and the formed solid was filtered under reduced pressure. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM:EtOAc), and recrystallized with a mixed solvent (DCM:HEX) to obtain 6.7 g (yield: 84.8%) of compound 6-83 (LT23-30-208) as a yellow solid.

[0510]

[0511] Manufacturing Example 4: Synthesis of compound 6-85 (LT23-30-211)

[0512]

[0513] Intermediate (5) 2.8 g (7.1 mmol), intermediate (2) 2.0 g (7.1 mmol), Pd (dba) 20.4 g (0.7 mmol), X-phos 0.6 g (1.4 mmol), NaOt-Bu 2.0 g (21.5 mmol) and 60 mL of xylene were mixed and stirred under reflux overnight. After quenching the reaction with distilled water, the reaction solution was cooled to room temperature and the formed solid was filtered under reduced pressure. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM:HEX), and recrystallized with a mixed solvent (DCM:MeOH) to obtain 1.3 g (yield: 28.2%) of compound 6-85 (LT23-30-211) as a yellow solid.

[0514]

[0515] Manufacturing Example 5: Synthesis of compound 6-87 (LT23-30-157)

[0516]

[0517] Intermediate (6) 5.7 g (13.6 mmol), intermediate (2) 4.2 g (14.9 mmol), Pd(dba)2230 mg (0.4 mmol), SPhos 0.3 g (0.8 mmol), t-BuONa 3.9 g (40.8 mmol) and xylene 90 mL were mixed and stirred under reflux for 24 hours. The reaction solution was concentrated, dissolved in hot chloroform, and filtered through a Celite pad. The filtrate was purified by silica gel column chromatography (DCM:HEX) and recrystallized with a mixed solvent (DCM:Acetone) to obtain 7.1 g (yield: 75.8%) of compound 6-87 (LT23-30-157) as a yellow solid.

[0518]

[0519] Manufacturing Example 6: Synthesis of compound 6-164 (LT23-30-131)

[0520]

[0521] Intermediate (4) 4.0 g (9.9 mmol), intermediate (7) 3.6 g (11.9 mmol), Pd(OAc) 267.0 mg (297.0 μmol), Sphos 244.0 mg (595.0 μmol), K3PO4 2.9 g (29.7 mmol) and xylene 80 mL were mixed and stirred under reflux overnight. Cooled to room temperature, distilled water and dichloromethane were added, and the organic layer was extracted. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The mixture was purified by silica gel column chromatography (EtOAc:DCM) and recrystallized from a mixed solvent (DCM:Acetone) to obtain 3.7 g (yield: 56.2%) of compound 6-164 (LT23-30-131) as a yellow solid.

[0522]

[0523] Manufacturing Example 7: Synthesis of compound 6-166 (LT23-30-204)

[0524]

[0525] Intermediate (5) 5.0 g (12.4 mmol), intermediate (7) 4.1 g (13.6 mmol), Pd (dba) 20.7 g (1.2 mmol), X-phos 1.1 g (2.4 mmol), NaOt-Bu 3.5 g (37.2 mmol), and xylene 100 mL were mixed and stirred under reflux overnight. After quenching the reaction with distilled water, the mixture was cooled to room temperature, and the formed solid was filtered under reduced pressure. The solid thus obtained was purified by silica gel column chromatography (DCM:HEX) and recrystallized with a mixed solvent (DCM:HEX) to obtain 1.4 g (yield: 16.8%) of compound 6-166 (LT23-30-204) as a yellow solid.

[0526]

[0527] Manufacturing Example 8: Synthesis of compound 6-167 (LT23-30-147)

[0528]

[0529] Intermediate (8) 5.0 g (11.5 mmol), intermediate (7) 3.8 g (12.6 mmol), Pd (dba) 20.3 g (0.5 mmol), X-phos 0.5 g (1.1 mmol), NaOt-Bu 3.3 g (34.5 mmol) and toluene 100 mL were mixed and stirred under reflux overnight. After quenching the reaction with distilled water, the mixture was cooled to room temperature and the formed solid was filtered under reduced pressure and dried. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM), and recrystallized with a mixed solvent (DCM:HEX) to obtain 4.8 g (yield: 59.5%) of compound 6-167 (LT23-30-147) as a pale yellow solid.

[0530]

[0531] Manufacturing Example 9: Synthesis of compound 6-171 (LT23-30-150)

[0532]

[0533] Intermediate (9) 5.0 g (11.9 mmol), Intermediate (7) 4.4 g (14.3 mmol), Pd(OAc) 20.1 g (0.4 mmol), S-Phos 0.3 g (0.7 mmol), NaO t Bu 2.3 g (23.9 mmol) of 110 mL of xylene was mixed and stirred under reflux for a whole day. After confirming the completion of the reaction, it was cooled to room temperature and concentrated under reduced pressure. Dichloromethane and distilled water were added to the concentrate, stirred, and the organic layer was separated. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The mixture was purified by column chromatography (HEX:EtOAc) to obtain 2.0 g (yield: 24.4%) of compound 6-171 (LT23-30-150) as a pale yellow solid.

[0534]

[0535] Manufacturing Example 10: Synthesis of compound 6-251 (LT23-30-185)

[0536]

[0537] Intermediate (6) 6.0 g (14.3 mmol), intermediate (10) 6.1 g (18.6 mmol), Pd (dba) 20.2 g (0.4 mmol), X-Phos 0.4 g (0.9 mmol), K3PO4 9.1 g (42.9 mmol) and xylene 143 mL were mixed and stirred under reflux for 18 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, and distilled water and chloroform were added. The separated organic layer was distilled under reduced pressure, and the obtained mixture was purified by silica gel column chromatography (CHCl3) to obtain 4.6 g (yield: 45.1%) of compound 6-251 (LT23-30-185) as a yellow solid.

[0538]

[0539] Manufacturing Example 11: Synthesis of compound 6-252 (LT23-30-170)

[0540]

[0541] Intermediate (9) 6.0 g (14.3 mmol), intermediate (10) 6.1 g (18.6 mmol), Pd(dba) 20.2 g (0.4 mmol), X-Phos 0.4 g (0.9 mmol), K3PO4 9.1 g (42.9 mmol) and xylene 143 mL were mixed and stirred under reflux for 18 hours. After the reaction was completed, the mixture was cooled to room temperature and distilled water and chloroform were added. The separated organic layer was distilled under reduced pressure and purified by silica gel column chromatography (HEX:CHCl3) to obtain 7.4 g (yield: 72.5%) of compound 6-252 (LT23-30-170) as a yellow solid.

[0542]

[0543] Manufacturing Example 12: Synthesis of compound 6-254 (LT23-30-249)

[0544]

[0545] Intermediate (11) 4.5 g (10.4 mmol), Intermediate (10) 4.1 g (12.4 mmol), Pd(dba) 20.2 g (0.3 mmol), S-Phos 0.3 g (0.6 mmol), K3PO4 4.4 g (20.7 mmol) of 170 mL of xylene was mixed and stirred under reflux for 2 to 3 days. After confirming the completion of the reaction, it was cooled to room temperature and concentrated. 500 mL of dichloromethane and distilled water were added to the concentrate, and the organic layer was separated. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The mixture was purified by column chromatography (HEX:CHCl3) to obtain 3.0 g (yield: 39.8%) of compound 6-254 (LT23-30-249) as a yellow solid.

[0546]

[0547] Manufacturing Example 13: Synthesis of compound 6-255 (LT23-30-210)

[0548]

[0549] Intermediate (14) 7.0 g (16.8 mmol), intermediate (10) 6.6 g (20.1 mmol), Pd(dba) 20.3 g (0.5 mmol), X-Phos 0.5 g (1.0 mmol), K3PO4 10.7 g (50.4 mmol) and xylene 143 mL were mixed and stirred under reflux for 1 day. After the reaction was completed, the mixture was cooled to room temperature, distilled water and chloroform were added, and the organic layer was separated and concentrated. The concentrate was purified by silica gel column chromatography (HEX:CHCl3) to obtain 5.8 g (yield: 48.7%) of compound 6-255 (LT23-30-210) as a yellow solid.

[0550]

[0551] Manufacturing Example 14: Synthesis of compound 6-256 (LT23-30-163)

[0552]

[0553] Intermediate (15) 5.0 g (13.0 mmol), intermediate (10) 4.7 g (14.3 mmol), Pd(dba) 20.2 g (0.4 mmol), X-Phos 0.4 g (0.8 mmol), K3PO4 8.3 g (39.02 mmol) and xylene 70 mL were mixed and stirred under reflux for 18 hours. After the reaction was completed, the mixture was cooled to room temperature and distilled water was added. The resulting solid was filtered and dried. The solid thus obtained was purified by silica gel column chromatography (HEX:CHCl3) to obtain 3.5 g (yield: 39.8%) of compound 6-256 (LT23-30-163) as a yellow solid.

[0554]

[0555] Manufacturing Example 15: Synthesis of compound 6-258 (LT23-30-223)

[0556]

[0557] Intermediate (16) 6.1 g (12.4 mmol), 4'-bromo-[1,1'-biphenyl]-4-carbonitrile 3.8 g (14.9 mmol), Pd(dba) 20.2 g (0.4 mmol), X-Phos 0.4 g (0.7 mmol), K3PO4 7.9 g (37.2 mmol) and xylene 124 mL were mixed and stirred under reflux for 2 days. After the reaction was completed, the mixture was cooled to room temperature, and distilled water and chloroform were added. The separated organic layer was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (HEX:CHCl3) to obtain 4.7 g (yield: 56.0%) of compound 6-258 (LT23-30-223) as a yellow solid.

[0558]

[0559] Manufacturing Example 16: Synthesis of compound 6-407 (LT23-30-166)

[0560]

[0561] Intermediate (4) 5.0 g (12.4 mmol), intermediate (17) 4.4 g (13.6 mmol), Pd(dba) 20.2 g (0.4 mmol), SPhos 0.3 g (0.7 mmol), t-BuONa 3.6 g (37.2 mmol) and xylene 80 mL were mixed and stirred under reflux for 24 hours. After confirming the completion of the reaction, the reaction solution was concentrated. Chloroform was added, dissolved by reflux, filtered through a celite pad and concentrated. The concentrate was purified by silica gel column chromatography (DCM:HEX) and recrystallized with a mixed solvent (DCM / Acetone) to obtain 3.2 g (yield: 37.9%) of compound 6-407 (LT23-30-166) as a pale yellow solid.

[0562]

[0563] Manufacturing Example 17: Synthesis of compound 6-409 (LT23-30-197)

[0564]

[0565] Intermediate (5) 5.0 g (12.4 mmol), intermediate (17) 4.4 g (13.7 mmol), Pd(dba) 20.2 g (0.4 mmol), SPhos 0.3 g (0.8 mmol), t-BuONa 3.6 g (37.4 mmol) and xylene 100 mL were mixed and stirred under reflux for 24 hours. After confirming the completion of the reaction, the reaction solution was concentrated. Chloroform was added, refluxed to dissolve, filtered through a celite pad and concentrated. The concentrate was purified by silica gel column chromatography (DCM:HEX) and recrystallized with a mixed solvent (DCM / Acetone) to obtain 2.5 g (yield: 29.4%) of compound 6-409 (LT23-30-197) as a pale yellow solid.

[0566]

[0567] Manufacturing Example 18: Synthesis of compound 6-412 (LT23-30-198)

[0568]

[0569] Intermediate (18) 4.0 g (9.9 mmol), intermediate (17) 3.5 g (11.9 mmol), Pd(OAc) 267.0 mg (298.0 mmol), Sphos 245.0 mg (596.0 μmol), K3PO4 6.3 g (29.8 mmol) and xylene 80 mL were mixed and refluxed overnight. After cooling to room temperature, distilled water was added, and the organic layer was separated. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (DCM:HEX) and recrystallized from a mixed solvent (DCM / EtOAc) to obtain 3.5 g (yield: 51.7%) of compound 6-412 (LT23-30-198) as a yellow solid.

[0570]

[0571] Manufacturing Example 19: Synthesis of compound 6-413 (LT23-30-229)

[0572]

[0573] Intermediate (6) 5.0 g (11.9 mmol), intermediate (17) 4.2 g (13.1 mmol), Pd(dba) 20.2 g (0.4 mmol), SPhos 0.3 g (0.7 mmol), t-BuONa 3.4 g (35.8 mmol) and xylene 75 mL were mixed and stirred under reflux for 24 hours. After confirming the completion of the reaction, the reaction solution was concentrated. The concentrate was dissolved in chloroform while refluxing, filtered through a Celite pad and concentrated. The concentrate was purified by silica gel column chromatography (DCM:HEX) and recrystallized with a mixed solvent (DCM / Acetone) to obtain 5.5 g (yield: 66.0%) of compound 6-413 (LT23-30-229) as a yellow solid.

[0574]

[0575] Manufacturing Example 20: Synthesis of compound 6-414 (LT23-30-264)

[0576]

[0577] Intermediate (9) 5.0 g (11.9 mmol), intermediate (17) 4.2 g (13.1 mmol), Pd(dba) 20.2 g (0.4 mmol), SPhos 0.3 g (0.7 mmol), t-BuONa 3.4 g (35.8 mmol) and xylene 75 mL were mixed and stirred under reflux for 24 hours. After confirming the completion of the reaction, the reaction solution was concentrated. The concentrate was dissolved in chloroform while refluxing, filtered through a celite pad and concentrated. The concentrate was purified by silica gel column chromatography (DCM:HEX) and recrystallized with a mixed solvent (DCM / Acetone) to obtain 3.5 g (yield: 42.0%) of compound 6-414 (LT23-30-264) as a pale yellow solid.

[0578]

[0579] Manufacturing Example 21: Synthesis of compound 6-417 (LT23-30-195)

[0580]

[0581] Intermediate (14) 5.0 g (12.0 mmol), Intermediate (17) 4.2 g (13.2 mmol), Pd (dba) 20.2 g (0.4 mmol), X-Phos 0.3 g (0.7 mmol), K3PO4 5.1 g (24.0 mmol) of a solution and 110 mL of xylene were mixed and stirred under reflux for 2–3 days. After confirming the completion of the reaction, the mixture was cooled to room temperature and concentrated. Dichloromethane and distilled water were added to the concentrate, stirred, and the organic layer was separated. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrate was purified by column chromatography (HEX:CHCl3) to obtain 3.0 g (yield: 35.9%) of compound 6-417 (LT23-30-195) as a yellow solid.

[0582]

[0583] Manufacturing Example 22: Synthesis of compound 6-418 (LT23-30-239)

[0584]

[0585] Intermediate (15) 5.0 g (12.9 mmol), intermediate (17) 4.5 g (14.2 mmol), Pd(dba) 20.2 g (0.4 mmol), SPhos 0.3 g (0.8 mmol), t-BuONa 3.7 g (38.7 mmol) and xylene 90 mL were mixed and stirred under reflux for 24 hours. After confirming the completion of the reaction, the reaction solution was concentrated. The concentrate was dissolved in chloroform while refluxing, filtered through a Celite pad and concentrated. The concentrate was purified by silica gel column chromatography (DCM:HEX) and recrystallized with a mixed solvent (DCM / Acetone) to obtain 1.5 g (yield: 18.1%) of compound 6-418 (LT23-30-239) as a yellow solid.

[0586]

[0587] Manufacturing Example 23: Synthesis of compound 6-420 (LT23-30-257)

[0588]

[0589] Intermediate (19) 5.0 g (10.2 mmol), 4'-bromo-[1,1'-biphenyl]-4-carbonitrile 2.9 g (11.1 mmol), Pd(dba) 20.2 g (0.4 mmol), SPhos 0.3 g (0.8 mmol), t-BuONa 3.7 g (38.7 mmol) and xylene 100 mL were mixed and stirred under reflux for 24 hours. After confirming the completion of the reaction, the reactant was concentrated. The concentrate was dissolved by refluxing with chloroform, filtered through a celite pad and concentrated. The concentrate was purified by silica gel column chromatography (DCM:HEX) and recrystallized with a mixed solvent (DCM / Acetone) to obtain 3.1 g (yield: 45.6%) of compound 6-420 (LT23-30-257) as a yellow solid.

[0590]

[0591] Manufacturing Example 24: Synthesis of compound 6-489 (LT23-30-259)

[0592]

[0593] Intermediate (21) 5.8 g (11.7 mmol), 7-chlorodibenzo[b,d]furan-3-carbonitrile 2.9 g (12.9 mmol), Pd(dba) 20.6 g (1.1 mmol), X-phos 1.1 g (2.3 mmol), NaOt-Bu 3.3 g (35.1 mmol) and xylene 120 mL were mixed and stirred under reflux overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the formed solid was filtered. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM:HEX), and recrystallized with a mixed solvent (DCM / MeOH) to obtain 0.9 g (yield: 11.2%) of compound 6-489 (LT23-30-259) as a yellow solid.

[0594]

[0595] Manufacturing Example 25: Synthesis of compound 6-492 (LT23-30-263)

[0596]

[0597] Intermediate (20) 5.0 g (16.7 mmol), 7-chlorodibenzo[b,d]furan-3-carbonitrile 8.3 g (36.7 mmol), Pd(OAc) 20.3 g (1.6 mmol), X-phos 1.5 g (3.3 mmol), NaOt-Bu 4.8 g (50.1 mmol) and xylene 100 mL were mixed and stirred under reflux overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the formed solid was filtered. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM:HXE), and recrystallized with a mixed solvent (DCM / MeOH) to obtain 2.9 g (yield: 25.6%) of compound 6-492 (LT23-30-263) as a yellow solid.

[0598]

[0599] Manufacturing Example 26: Synthesis of compound 6-495 (LT23-30-135)

[0600]

[0601] Intermediate (4) 20.0 g (49.6 mmol), intermediate (22) 18.2 g (54.4 mmol), Pd(dba) 20.8 g (1.5 mmol), SPhos 1.2 g (3.0 mmol), t-BuONa 14.3 g (149.0 mmol) and xylene 300 mL were mixed and stirred under reflux for 24 hours. After confirming the completion of the reaction, the reaction solution was concentrated. The concentrate was dissolved in chloroform under reflux, filtered through a celite pad and concentrated. The concentrate was purified by silica gel column chromatography (DCM:HEX) and recrystallized with a mixed solvent (DCM / Acetone) to obtain 18.2 g (yield: 52.3%) of compound 6-495 (LT23-30-135) as a pale yellow solid.

[0602]

[0603] Manufacturing Example 27: Synthesis of compound 6-497 (LT23-30-201)

[0604]

[0605] Intermediate (5) 4.0 g (9.9 mmol), intermediate (22) 3.6 g (10.9 mmol), Pd (dba) 20.5 g (0.9 mmol), X-phos 0.9 g (1.9 mmol), NaOt-Bu 2.8 g (29.8 mmol) and xylene 80 mL were mixed and stirred under reflux overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the formed solid was filtered under reduced pressure. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM:HEX), and recrystallized with a mixed solvent (DCM / HEX) to obtain 1.5 g (yield: 21.5%) of compound 6-497 (LT23-30-201) as a yellow solid.

[0606]

[0607] Manufacturing Example 28: Synthesis of compound 6-499 (LT23-30-232)

[0608]

[0609] Intermediate (6) 5.0 g (11.9 mmol), intermediate (22) 4.4 g (13.1 mmol), Pd (dba) 20.6 g (1.1 mmol), X-phos 1.1 g (2.3 mmol), NaOt-Bu 3.4 g (35.7 mmol) and xylene 100 mL were mixed and stirred under reflux overnight. After confirming the completion of the reaction, it was cooled to room temperature, distilled water was added, and the formed solid was filtered under reduced pressure. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM:HEX), and recrystallized with a mixed solvent (DCM / MeOH) to obtain 5.1 g (yield: 59.7%) of compound 6-499 (LT23-30-232) as a yellow solid.

[0610]

[0611] Manufacturing Example 29: Synthesis of compound 6-500 (LT23-35-099)

[0612]

[0613] Intermediate (18) 5.0 g (12.4 mmol), intermediate (22) 4.6 g (13.7 mmol), Pd (dba) 20.7 g (1.2 mmol), X-phos 1.2 g (2.5 mmol), NaOt-Bu 3.6 g (37.3 mmol) and xylene 100 mL were mixed and stirred under reflux overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the formed solid was filtered under reduced pressure. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM:HEX), and recrystallized with a mixed solvent (DCM / MeOH) to obtain 3.9 g (yield: 44.8%) of compound 6-500 (LT23-35-099) as a yellow solid.

[0614]

[0615] Manufacturing Example 30: Synthesis of compound 6-502 (LT23-30-230)

[0616]

[0617] Intermediate (9) 5.0 g (11.9 mmol), intermediate (22) 4.4 g (13.1 mmol), Pd (dba) 20.6 g (1.1 mmol), X-phos 1.1 g (2.3 mmol), NaOt-Bu 3.4 g (35.7 mmol), and xylene 100 mL were mixed and stirred under reflux overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the formed solid was filtered under reduced pressure. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM:HEX1), and recrystallized with a mixed solvent (DCM / MeOH) to obtain 4.1 g (yield: 48.2%) of compound 6-502 (LT23-30-230) as a yellow solid.

[0618]

[0619] Manufacturing Example 31: Synthesis of compound 6-506 (LT23-30-240)

[0620]

[0621] Intermediate (15) 5.0 g (12.9 mmol), intermediate (22) 4.8 g (14.2 mmol), Pd(dba) 20.2 g (0.4 mmol), SPhos 0.3 g (0.8 mmol), t-BuONa 3.7 g (38.7 mmol) and xylene 90 mL were mixed and stirred under reflux for 24 hours. After confirming the completion of the reaction, the reaction solution was concentrated. The concentrate was dissolved in chloroform while refluxing, filtered through a Celite pad and concentrated. The concentrate was purified by silica gel column chromatography (DCM:HEX) and recrystallized with a mixed solvent (DCM / Acetone) to obtain 1.7 g (yield: 19.9%) of compound 6-506 (LT23-30-240) as a yellow solid.

[0622]

[0623] Manufacturing Example 32: Synthesis of compound 6-573 (LT23-30-262)

[0624]

[0625] Intermediate (23) 4.5 g (11.2 mmol), Intermediate (22) 4.5 g (13.5 mmol), Pd(dba) 20.2 g (0.3 mmol), X-Phos 0.3 g (0.7 mmol), K3PO4 4.8 g (22.4 mmol) and 180 mL of xylene were mixed and stirred under reflux for a whole day. After confirming the completion of the reaction, the reaction mass was cooled to room temperature and concentrated. Tetrahydrofuran and distilled water were added to the concentrate and stirred. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrate was purified by column chromatography (HEX:CHCl3) to obtain 3.0 g (yield: 38.3%) of compound 6-573 (LT23-30-262) as an orange solid.

[0626]

[0627] Manufacturing Example 33: Synthesis of compound 6-579 (LT23-30-164)

[0628]

[0629] Intermediate (4) 4.0 g (9.9 mmol), intermediate (25) 3.5 g (10.9 mmol), Pd(OAc) 267.0 mg (297.0 μmol), Sphos 244.0 mg (595.0 μmol), K3PO4 6.3 g (29.7 mmol) and xylene 80 mL were mixed and refluxed overnight. After confirming the completion of the reaction, distilled water and dichloromethane (DCM) were added to the reaction mixture, stirred, and the organic layer was separated. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrate was purified by silica gel column chromatography (EtOAc:DCM) and recrystallized from a mixed solvent (DCM / HEX) to obtain 3.5 g (yield: 51.7%) of compound 6-579 (LT23-30-164) as a yellow solid.

[0630]

[0631] Manufacturing Example 34: Synthesis of compound 6-581 (LT23-30-199)

[0632]

[0633] Intermediate (5) 5.0 g (12.5 mmol), Intermediate (25) 4.4 g (13.7 mmol), Pd (dba) 20.2 g (0.4 mmol), X-Phos 0.4 g (0.7 mmol), K3PO4 5.3 g (24.9 mmol) of acetonitrile and 110 mL of xylene were mixed and stirred under reflux for 2–3 days. After confirming the completion of the reaction, the reaction mass was cooled to room temperature and concentrated. Dichloromethane and distilled water were added to the concentrate, stirred, and the organic layer was separated. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrate was purified by column chromatography (CHCl3) to obtain 2.0 g (yield: 23.5%) of compound 6-581 (LT23-30-199) as a yellow solid.

[0634]

[0635] Manufacturing Example 35: Synthesis of compound 6-583 (LT23-30-252)

[0636]

[0637] Intermediate (6) 4.2 g (10.0 mmol), intermediate (25) 3.8 g (12.0 mmol), Pd(dba) 20.2 g (0.3 mmol), X-Phos 0.3 g (0.6 mmol), K3PO4 6.4 g (30.0 mmol) and xylene 100 mL were mixed and refluxed and stirred for 1 day. After the reaction was completed, it was cooled to room temperature, and distilled water and chloroform were added. The separated organic layer was distilled under reduced pressure, and the obtained mixture was purified by silica gel column chromatography (CHCl3:EtOAc) to obtain 3.9 g (yield: 49.3%) of compound 6-583 (LT23-30-252) as a yellow solid.

[0638]

[0639] Manufacturing Example 36: Synthesis of compound 6-586 (LT23-30-248)

[0640]

[0641] Intermediate (9) 5.5 g (13.0 mmol), intermediate (25) 5.0 g (15.6 mmol), Pd(dba) 20.2 g (0.4 mmol), X-Phos 0.4 g (0.8 mmol), K3PO4 8.3 g (39.0 mmol) and xylene 130 mL were mixed and refluxed and stirred for 3 days. After the reaction was completed, it was cooled to room temperature, and distilled water and chloroform were added. The separated organic layer was distilled under reduced pressure, and the obtained mixture was purified by silica gel column chromatography (CHCl3:EtOAc) to obtain 5.0 g (yield: 54.9%) of compound 6-586 (LT23-30-248) as a yellow solid.

[0642]

[0643] Manufacturing Example 37: Synthesis of compound 6-660 (LT23-30-158)

[0644]

[0645] Intermediate (4) 4.0 g (9.9 mmol), intermediate (27) 5.0 g (14.9 mmol), Pd(OAc) 245.0 mg (198.0 μmol), Sphos 163.0 mg (397.0 μmol), K3PO4 6.3 g (29.7 mmol) and xylene 80 mL were mixed and refluxed overnight. The reaction mixture was cooled to room temperature, distilled water and dichloromethane (DCM) were added, and the mixture was stirred. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrate was purified by silica gel column chromatography (EtOAc:DCM) and recrystallized from a mixed solvent (DCM / Acetone) to obtain 3.3 g (yield: 47.4%) of compound 6-660 (LT23-30-158) as a yellow solid.

[0646]

[0647] Manufacturing Example 38: Synthesis of compound 6-738 (LT23-35-107)

[0648]

[0649] Intermediate (4) 4.0 g (9.9 mmol), intermediate (29) 3.6 g (11.4 mmol), Pd(OAc) 267.0 mg (297.0 μmol), Sphos 244.0 mg (595.0 μmol), K3PO4 6.3 g (29.8 mmol) and xylene 80 mL were mixed and refluxed overnight. After confirming the completion of the reaction, it was cooled to room temperature, distilled water was added, and the mixture was stirred. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrate was purified by silica gel column chromatography (EtOAc:HEX) and recrystallized from a mixed solvent (DCM / HEX) to obtain 2.4 g (yield: 35.7%) of compound 6-738 (LT23-35-107) as a yellow solid.

[0650]

[0651] Manufacturing Example 39: Synthesis of compound 6-739 (LT23-30-247)

[0652]

[0653] 4-(benzo[d]oxazol-2-yl)aniline (4.0 g (19.0 mmol), intermediate (2) (11.6 g (41.8 mmol), Pd(dba) (21.0 g (1.9 mmol), X-phos (1.8 g (3.8 mmol), NaOt-Bu (57.0 mmol), and xylene (80 mL)) were mixed and stirred under reflux overnight. After confirming the completion of the reaction, the reaction solution was cooled to room temperature, distilled water was added, and the formed solid was filtered. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM:HEX), and recrystallized with a mixed solvent (DCM / MeOH) to obtain 6.0 g (yield: 45.4%) of compound 6-739 (LT23-30-427) as a yellow solid.

[0654]

[0655] Manufacturing Example 40: Synthesis of compound 6-740 (LT23-30-244)

[0656]

[0657] Intermediate (4) 4.6 g (11.4 mmol), intermediate (12) 4.0 g (11.4 mmol), Pd(dba) 20.6 g (1.1 mmol), X-phos 1.0 g (2.2 mmol), NaOt-Bu 3.2 g (34.2 mmol) and xylene 100 mL were mixed and stirred under reflux overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the formed solid was filtered. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM:EtOAc), and crystallized with a mixed solvent (DCM / HEX) to obtain 5.5 g (yield: 67.0%) of beige solid compound 6-740 (LT23-30-244).

[0658]

[0659] Manufacturing Example 41: Synthesis of compound 6-741 (LT23-30-246)

[0660]

[0661] Intermediate (6) 5.0 g (11.9 mmol), intermediate (12) 4.2 g (11.9 mmol), Pd (dba) 20.6 g (1.1 mmol), X-phos 1.1 g (2.3 mmol), NaOt-Bu 3.4 g (35.7 mmol), and xylene 100 mL were mixed and stirred under reflux overnight. After confirming the completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and the formed solid was filtered. The solid thus obtained was dissolved in dichloromethane, purified by silica gel column chromatography (DCM:EtOAc), and crystallized with a mixed solvent (DCM / HEX) to obtain 5.6 g (yield: 64.3%) of compound 6-741 (LT23-30-246) as a yellow solid.

[0662]

[0663] Manufacturing Example 42: Synthesis of Compound 7-3 (LT23-30-212)

[0664]

[0665] Intermediate (1) 5.0 g (11.5 mmol), 3-bromodibenzo[b,d]thiophene 3.6 g (13.8 mmol), Pd(dba) 20.2 g (0.3 mmol), X-Phos 0.3 g (0.7 mmol), K3PO4 4.9 g (23.0 mmol), and 180 mL of xylene were mixed and stirred under reflux for 2–3 days. After the reaction was completed, the reaction mixture was cooled to room temperature and concentrated. Dichloromethane and distilled water were added to the concentrate, and the mixture was stirred. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrate was purified by column chromatography (HEX:EtOAc) to obtain 3.0 g (yield: 42.3%) of compound 7-3 (LT23-30-212) as a yellow solid.

[0666]

[0667] Manufacturing Example 43: Synthesis of compound 7-495 (LT23-35-101)

[0668]

[0669] Intermediate (4) 4.0 g (9.9 mmol), intermediate (28) 5.2 g (14.9 mmol), Pd(OAc) 245.0 mg (198.0 μmol), Sphos 163.0 mg (397.0 μmol), K3PO4 6.3 g (29.7 mmol) and xylene 80 mL were mixed and refluxed overnight. The reaction mixture was cooled to room temperature, distilled water and dichloromethane (DCM) were added, and the mixture was stirred. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. The concentrate was purified by silica gel column chromatography (EtOAc:DCM) and recrystallized from a mixed solvent (DCM / Acetone) to obtain 2.7 g (yield: 39.0%) of compound 7-495 (LT23-35-101) as a yellow solid.

[0670]

[0671] <Example of an exam>

[0672] For the compound of the present invention, n (refractive index) and k (extinction coefficient) of a single film for evaluating optical properties are measured using an Ellipsometer from JA WOOLLAM.

[0673] Fabrication of single films for evaluating optical properties of compounds:

[0674] 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 2×10 - 2 Oxygen plasma treatment at 125 W for 2 minutes at Torr, 9×10 - 7 A single film is produced by depositing 800Å of the compound on a glass substrate at a rate of 1Å / sec under a vacuum of 1 Torr.

[0675] In the production of a single film for evaluating the above optical properties, REF01 was used as a compound for comparative testing.

[0676]

[0677] Comparative test example (REF01)

[0678] < Test Examples 1 to 43 >

[0679] In the production of a single film for evaluating the optical properties, each compound shown in Table 1 below was used.

[0680] The optical properties of the compounds manufactured in the above comparative test examples and test examples 1 to 43 are shown in Table 1.

[0681] The optical properties are the refractive index (n) constants at wavelengths of 450 nm and 620 nm.

[0682] Classification Compound n (450 nm) n (620 nm) Comparative Test Example REF012.2702.009 Test Example 16-3 (LT23-30-209) 2.3972.036 Test Example 26-82 (LT23-30-192) 2.3382.040 Test Example 36-83 (LT23-30-208) 2.3172.025 Test Example 46-85 (LT23-30-211) 2.3472.042 Test Example 56-87 (LT23-30-157) 2.3912.057 Test Example 66-164 (LT23-30-131) 2.4232.076 Test Example 76-166(LT23-30-204)2.4882.095 Test Example 86-167(LT23-30-147)2.5252.125 Test Example 96-171(LT23-30-150)2.4772.104 Test Example 106-251(LT23-30-185)2.4592.104 Test Example 116-252(LT23-30-170)2.4232.097 Test Example 126-254(LT23-30-249)2.5112.130 Test Example 136-255(LT23-30-210)2.4482.113 Test Example 146-256(LT23-30-163)2.4142.095 Test Example 156-258(LT23-30-223)2.4262.098 Test Example 166-407(LT23-30-166)2.4702.091 Test Example 176-409(LT23-30-197)2.5322.117 Test Example 186-412(LT23-30-198)2.5062.106 Test Example 196-413(LT23-30-229)2.5352.118 Test Example 206-414(LT23-30-264)2.5232.119 Test Example 216-417(LT23-30-195)2.5452.129 Test Example 226-418(LT23-30-239)2.5292.136 Test Example 236-420(LT23-30-257)2.5392.122 Test Example 246-489(LT23-30-259)2.5342.118 Test Example 256-492(LT23-30-263)2.5892.130 Test Example 266-495(LT23-30-135)2.4652.098 Test Example 276-497(LT23-30-201)2.5212.118 Test Example 286-499(LT23-30-232)2.5302.123Exam Example 296-500(LT23-35-099)2.5212.118Exam Example 306-502(LT23-30-230)2.5092.122Exam Example 316-506(LT23-30-240)2.5122.123Exam Example 326-573(LT23-30-262)2.5302.124Exam Example 336-579(LT23-30-164)2.4732.088Exam Example 346-581(LT23-30-199)2.5872.117Exam Example 356-583(LT23-30-252)2.5432.118Exam Example 366-586(LT23-30-248)2.5402.119 Test Example 376-660(LT23-30-158)2.5182.107 Test Example 386-738(LT23-35-107)2.3192.042 Test Example 396-739(LT23-30-247)2.3322.047 Test Example 406-740(LT23-30-244)2.3692.061 Test Example 416-741(LT23-30-246)2.4362.087 Test Example 427-3(LT23-30-212)2.4242.061 Test Example 437-495(LT23-35-101)2.5062.106.

[0683] As can be seen in Table 1 above, the results of comparing the comparative test example (REF01) and test example 1 (compound 6-3) with other test examples showed that although the chemical structure was similar, the refractive index increased depending on the presence or absence of the introduction of an aryl group and a benzazole group substituted with an aryl group and a cyano group using a dibenzofuran and dibenzothiophene group as a link.

[0684] As the refractive index increases, it can be judged that the effect of extracting light emitted from inside the electrode to the outside will increase.

[0685] The n value at 450 nm of the comparative test example (REF01) was 2.270, whereas most of the example compounds were found to have a refractive index generally higher than 2.300. This satisfies the high refractive index value required to secure a high viewing angle in the blue region.

[0686]

[0687] <Example>

[0688] Component fabrication

[0689] For the fabrication of the device, ITO, a transparent electrode, was used as an anode layer, 2-TNATA was used as a hole injection layer, NPB was used as a hole transport layer, αβ-ADN was used as a host for the light-emitting layer, Pyene-CN was used as a blue fluorescent dopant, Alq3 was used as an electron transport layer, Liq was used as an electron injection layer, and Mg:Ag was used as a cathode. The structures of these compounds are as shown in the following chemical formulas.

[0690]

[0691] Comparative examples: ITO / HT01 (90 nm) / NPB (25 nm) / αβ-ADN:5% Pyrene-CN (200 nm) / ET201:Liq (=1:1, 40 nm) / Liq (2 nm) / Mg:Ag (1:9, 10 nm) / REF01 (60 nm)

[0692] The blue fluorescent organic light-emitting device was fabricated by depositing ITO / HT01 (90 nm) / NPB (25 nm) / αβ-ADN:5% Pyrene-CN (200 nm) / ET201:Liq (=1:1, 40 nm) / Liq (2 nm) / Mg:Ag (1:9, 10 nm) / REF01 (60 nm) in that order.

[0693] Before depositing the organic material, the ITO electrode was 2 × 10 - 2 Oxygen plasma treatment was performed at 125 W for 2 minutes at Torr. Organic matter was 9 × 10 - 7 Deposition was performed under a vacuum of 10 Torr, Liq was simultaneously deposited at 0.1 Å / sec, αβ-ADN at 0.18 Å / sec, Pyrene-CN at 0.02 Å / sec, and the remaining organic materials were all deposited at a rate of 1 Å / sec.

[0694] After the device fabrication was complete, it was sealed in a glove box filled with nitrogen gas to prevent contact with air and moisture. A barrier was formed with 3M adhesive tape, and then barium oxide, a desiccant that removes moisture, was added, and a glass plate was attached.

[0695]

[0696] Comparative test example (REF01)

[0697] < Examples 1 to 43 >

[0698] In the above comparative example, a device was manufactured in the same manner as in the above comparative example, except that each compound shown in Table 2 below was used instead of REF01.

[0699] The electrical luminescence characteristics of the organic electroluminescent devices manufactured in the above comparative examples and examples 1 to 43 are shown in Table 2.

[0700] Classification Compound Driving Voltage [V] Efficiency [cd / A] Lifespan (%) Comparison Example REF 0 1 3.92 6.10 42 Example 16-3 (LT23-30-209) 3.90 6.31 45 Example 26-82 (LT23-30-192) 3.92 6.24 46 Example 36-83 (LT23-30-208) 3.93 6.20 43 Example 46-85 (LT23-30-211) 3.92 6.25 45 Example 56-87 (LT23-30-157) 3.90 6.31 45 Example 66-164 (LT23-30-131) 3.92 6.39 50 Example 76-166(LT23-30-204)3.916.5261Example 86-167(LT23-30-147)3.916.5862Example 96-171(LT23-30-150)3.916.5160Example 106-251(LT23-30-185)3.916.5060Example 116-252(LT23-30-170)3.926.3950Example 126-254(LT23-30-249)3.916.5562Example 136-255(LT23-30-210)3.916.4555Example 146-256(LT23-30-163)3.906.3145Example 156-258(LT23-30-223)3.926.3950Example 166-407(LT23-30-166)3.916.5160Example 176-409(LT23-30-197)3.916.6060Example 186-412(LT23-30-198)3.916.5460Example 196-413(LT23-30-229)3.916.6060Example 206-414(LT23-30-264)3.916.5862Example 216-417(LT23-30-195)3.906.6162Example 226-418(LT23-30-239)3.916.6060Example 236-420(LT23-30-257)3.906.6162Example 246-489(LT23-30-259)3.916.6060Example 256-492(LT23-30-263)3.926.6366Example 266-495(LT23-30-135)3.916.5060Example 276-497(LT23-30-201)3.916.5862Example 286-499(LT23-30-232)3.916.6060Example 296-500(LT23-35-099)3.916.5862Example 306-502(LT23-30-230)3.916.5562Example 316-506(LT23-30-240)3.916.5562Example 326-573(LT23-30-262)3.916.6060Example 336-579(LT23-30-164)3.916.5160Example 346-581(LT23-30-199)3.926.6366Example 356-583(LT23-30-252)3.906.6162Example 366-586(LT23-30-248)3.906.6162 Example 376-660(LT23-30-158)3.916.5862 Example 386-738(LT23-35-107)3.936.2043 Example 396-739(LT23-30-247)3.926.2445 Example 406-740(LT23-30-244)3.936.3047 Example 416-741(LT23-30-246)3.916.4555 Example 427-3(LT23-30-212)3.926.3950 Example 437-495(LT23-35-101)3.916.5460.

[0701] From the results in Table 2 above, it can be seen that the heteroaryl amine derivative compound according to the present invention can be used as a material for a capping layer of an organic electronic device, including an organic light-emitting device, and that the organic electronic device, including an organic light-emitting device, using the heteroaryl amine derivative compound exhibits excellent characteristics in terms of efficiency, driving voltage, stability, etc. In particular, the compound according to the present invention exhibited high efficiency characteristics due to its excellent ability for microcavity phenomenon.

[0702] The compound of formula 1 has unexpectedly desirable properties for use as a capping layer in OLEDs.

[0703] The compound of the present invention can be applied to industrial organic electronic device products due to these properties.

[0704] However, the above-described synthesis example is merely an example, and the reaction conditions may be modified as needed. Furthermore, compounds according to one embodiment of the present invention can be synthesized to have various substituents using methods and materials known in the art. By introducing various substituents into the core structure represented by Chemical Formula 1, the compound can have properties suitable for use in organic electroluminescent devices.

[0705] The organic compound according to the present invention can be used to improve the quality of an organic electroluminescent device by being used in an organic material layer and / or a capping layer of the organic electroluminescent device.

[0706] When the above compound is used in the capping layer, the organic electroluminescent device exhibits its original characteristics while at the same time improving its lifespan due to the optical properties of the compound.

Claims

1. A heteroaryl amine derivative for an organic electroluminescent device, represented by the following chemical formula 1. [Chemical Formula 1] In the above chemical formula 1, L 1, L 2 and L 3 are each independently a direct bond; or a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group, Z 1 is O or S Ar 1 , Ar 2 and Ar 3 are each independently selected from a phenyl group, a biphenyl group, a naphthyl group, a benzofuran group, a benzothiophene group, a benzoxazole group, a benzothiazole group, a dibenzofuran group and a dibenzothiophene group, each of which is substituted or unsubstituted with a cyano group; m is an integer of 0 or 1, p, q and r are integers from 0 to 2, If p, q, and r are 0, it is a direct connection.

2. In paragraph 1, The above chemical formula 1 is a heteroaryl amine derivative for an organic electroluminescent device selected from compounds of the following chemical formulas 2 to 5. [Chemical formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] In the above chemical formulas 2 to 5, L 1 , L 2 and L 3 are each independently selected from a direct bond; a substituted or unsubstituted phenylene group; a substituted or unsubstituted naphthylene group; a substituted or unsubstituted pyridylene group; a substituted or unsubstituted dibenzofuranylene group; and a substituted or unsubstituted dibenzothiophenylene group; R 1, R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from a cyano group; a phenyl group with a substituted or unsubstituted cyano group; a biphenyl; a naphthyl group; a benzofuran group; a benzothiophene group; a benzoxazole group; a benzothiazole group; and a dibenzofuran group; a dibenzothiophene group; Z 2, Z 3 , Z 4 and Z 5 are each independently O or S, X 1 and X 2 are each independently CH or N, a, b, c, d, e and f are each independently integers 0 or 1, Z 1 , m, p, q, and r are as defined in the above chemical formula 1.

3. In paragraph 1, The above chemical formula 1 is a heteroaryl amine derivative for an organic electroluminescent device selected from compounds of the following chemical formulas 6 to 7. [Chemical formula 6] [Chemical formula 7] 4. First electrode; An organic layer comprising a plurality of organic layers disposed on the first electrode; a second electrode disposed on the organic layer; and A capping layer disposed on the second electrode; An organic electroluminescent device, wherein the organic layer or capping layer comprises a heteroaryl amine derivative according to any one of claims 1 to 3.

5. In paragraph 4, An organic electroluminescent device, wherein the organic layer includes a light-emitting layer and a hole transport layer, and the hole transport layer includes the heteroarylamine derivative.

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