KR20200018006A - Organic luminescent compound, producing method of the same and organic electroluminescent device including the same - Google Patents

Abstract

Provided by the present invention is an organic light emitting compound represented by chemical formula 1. In chemical formula 1, each of R_1 to R_5 is independently cyano, halogen, or aryl of C_6-C_20 capable of being substituted, and alkyl of C_1-C_20 of a linear or branched shape capable of being substituted in a single bond; A_1 is at least one ring selected from a group consisting of a five-membered unsaturated or aromatic ring which may be substituted, a six-membered unsaturated or aromatic ring which may be substituted, a five-membered unsaturated or aromatic hetero ring which may be substituted, and a six-membered unsaturated or aromatic hetero ring which may be substituted or a polycyclic ring in which two or more rings selected from the group are combined; n is 0 or 1; the hetero ring includes at least one selected from a group consisting of N, O, and S; and the substitution is substituted by alkyl of C_1-C_6 or aryl of C_6-C_20. However, the invention is not limited thereto. The present invention is able to solve problems of efficiency reduction.

Description

Organic light-emitting compound, a method of manufacturing the same and an organic EL device comprising the same {ORGANIC LUMINESCENT COMPOUND, PRODUCING METHOD OF THE SAME AND ORGANIC ELECTROLUMINESCENT DEVICE INCLUDING THE SAME}

The present application relates to an organic light emitting compound, a method of manufacturing the same, and an organic electroluminescent device including the same.

Display has become an indispensable element of life, serving as a general information provider of life such as computer, television, and large commercials. Recently, with the development of the display and the improvement of the quality of life, research and development having a complex function for improving the quality of life as well as the existing simple information providing function is required. Accordingly, OLED (Organic Light-Emitting Diode) presents many possibilities and various indicators in future-oriented research such as flexible display and wearable display using thin and light materials. OLED display is a self-luminous display device that can be light and thin, has excellent contrast ratio and viewing angle, and has a fast response speed. In addition, OLED devices have many advantages in the fabrication of flexible and transparent devices, as there is no backlight that takes up a large volume in the LCD compared to liquid crystal display (LCD), which is an important material with OLED as a display material. .

In 1963, the first organic electroluminescent device (OLED) was produced using anthracene single crystal by Pope et al. [M. Pope, H. P. Kallmamm and P. Magnae. J. Chem. Phys. 38. 2042 (1963). Subsequently, in 1987, C. Tang and S. A. VanSlyke reported a bilayer thin film device using Alq3 and TPD as the light emitting layer and the charge transporting layer, respectively. At present, the development of low molecular weight OLED displays with improved efficiency and stability using a multi-layered EL device incorporating a charge injection layer and a transport layer is rapidly being made.

Currently, OLED devices have fabricated a multi-layered device incorporating a layer for injecting electrons and holes and a layer for transporting them, which has high efficiency and improved stability. Performance such as luminous efficiency and lifetime are determined by the light emitting materials (red, green, blue) used in such OLED devices. In order to realize the natural color of the light emitting material, red, green, and blue light emitting materials must have high thermal stability, efficiency, and color purity.

Luminescent materials are classified into fluorescent materials and phosphorescent materials according to the light emission principle. Basically, electrons are injected from the cathode to move through each layer's Low Unoccupied Molecular Orbital (LUMO) energy level, and holes are injected from the anode to transfer the highest Occupied Molecular Orbital (HOMO) energy level of each layer. It moves through to form excitons in the light emitting layer. The exciton formed falls to the ground state and emits light of red, green, and blue wavelengths according to respective energy differences. When electrons and holes are injected in an OLED device, they are divided into singlet excitons and triplet excitons according to the spin direction of the injected electrons, which are generated in a 1: 3 ratio. Fluorescent materials emit light with energy emitted by stabilizing singlet excitons, 25% of excitons to the ground state, and phosphorescent materials emitting energy with triplet excitons, 75% of excitons, stabilized to the ground state. Say substance.

Phosphors using heavy metals show a theoretical value of 100% internal quantum efficiency by converting singlet excitons to triplet excitons due to intersystem crossing by spin-orbit coupling. Therefore, in red and green, phosphors using heavy metals have excellent color purity and high efficiency and are used commercially. However, triplet excitons used by phosphors have lower energy levels than singlet excitons due to exchange energy stabilization, which results in relatively wider energy band gaps than red and green light emitting materials. There is a disadvantage in that blue light emission does not obtain good color purity and shortens the life of the device.

In order to develop a light emitting material that realizes a dark blue color, a lot of researches have been conducted on aromatic compounds such as anthracene, fluorene, and pyrene. In the case of phenanthrene, it is known that the flat and rigid molecular structure emits a wavelength of blue region and has thermal and electrochemical stability, and many studies have been conducted. However, due to its own flat structure, the interaction between molecules has a disadvantage in that the excimer is formed well, the concentration disappearance phenomenon and the stoke movement occur well. In order to solve this problem, studies have been conducted to supplement the structure of the flat phenanthrene by substituting different functional groups of the phenanthrene group. [J. Mater. Chem. C., (2016), 4, 9310-9315] In addition, bulky amine groups were introduced into indenophenanthrene to enable effective injection and transport of electric charges, as well as pure blue color through conversion to warped structures. A study on the development of a light emitter having color coordinates has been conducted. [Dyes and Pigments, (2017), 144, 9-16] In order to further improve the characteristics of the organic EL device, there is a continuing need for development of more stable and efficient materials that can be used in the organic EL device. .

In the case of phenanthroline (phenanthroline) is known as a blue light emitting material having excellent thermal stability, long fluorescence lifetime, high charge transport characteristics and good efficiency. However, the flat and rigid structure of phenanthroline can lead to crystallization and self-aggregation, leading to reduced efficiency.

In addition, although phenanthroline derivatives exhibit high efficiency light emission when used in an electron transport material, there is a problem that the thin film becomes cloudy due to crystallization by prolonged energization.

Korean Laid-Open Patent Publication No. 2007-0043825, which is a background technology of the present application, relates to a penalthroline derivative and a light emitting device and a light emitting device using the same. However, this publication does not mention compounds in which a substituent is introduced at the 2-position of imidazophenalthroline.

The present application is to solve the above-mentioned problems of the prior art, an object of the present invention to provide an organic light emitting device, a method for manufacturing the same and an organic electroluminescent device comprising the same.

However, the technical problem to be achieved by the embodiments of the present application is not limited to the technical problems as described above, and other technical problems may exist.

As a technical means for achieving the above technical problem, the first aspect of the present application provides an organic light emitting compound represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ to R ₅ are each independently a single bond, a linear or branched C ₁ -C ₂₀ alkyl that may be substituted, an aryl, halogen, C ₆ -C ₂₀ that may be substituted, Or cyano, and A ₁ is a 5-membered unsaturated or aromatic ring which may be substituted, a 6-membered unsaturated or aromatic ring which may be substituted, a 5-membered unsaturated or aromatic hetero ring which may be substituted and 6-substituted which may be substituted At least one ring selected from the group consisting of circularly unsaturated or aromatic hetero rings, or at least two rings selected from the group are fused polycyclic rings, n is 0 or 1, and the hetero rings are N, O and S It includes one or more selected from the group consisting of, the substitution may be substituted by C ₁ -C ₆ alkyl or C ₆ -C ₂₀ aryl, but is not limited thereto.

According to an embodiment of the present application, R ₁ to R ₅ are each independently a single bond, methyl, phenyl which may be substituted, biphenyl, chrysene, phenanthrene, naphthyl, fluorenyl, quinoline, phen It includes those selected from the group consisting of rylene, pyrene, halogen, cyano and combinations thereof, the substitution may be substituted by linear or branched C ₁ -C ₂₀ alkyl, but is not limited thereto. It is not.

According to an embodiment of the present disclosure, A ₁ is phenoxazine, phenoxyazine, dimethylacridin, diphenylacridine, carbazole, phenyl, biphenyl, naphthalene, fluorene, anthracene, phenanthrene, Selected from the group consisting of pyrene, fluoranthene, chrysene, benzofluoranthene, perylene, quinoline, indenoanthracene, indenophenanthrene, hydroanthracene, dibenzothiophene, dibenzofuran and combinations thereof It may be to include a substance, but is not limited thereto.

According to an embodiment of the present disclosure, the organic light emitting compound may include any one of the following compounds, but is not limited thereto:

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According to a second aspect of the present application, there is provided a method for producing an organic light emitting compound according to claim 1, comprising reacting a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, and a phenanthroline derivative in the presence of an ammonium salt. to provide.

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3, R ₁ to R ₅ are each independently a single bond, a linear or branched C ₁ -C ₂₀ alkyl which may be substituted, an aryl of C ₆ -C ₂₀ which may be substituted, Halogen, or cyano, and A ₁ is a 5-membered unsaturated or aromatic ring which may be substituted, a 6-membered unsaturated or aromatic ring which may be substituted, a 5-membered unsaturated or aromatic hetero ring which may be substituted and may be substituted At least one ring selected from the group consisting of 6-membered unsaturated or aromatic hetero rings, or at least two rings selected from the group fused to a polycyclic ring, n is 0 or 1, and the hetero ring is N, O And one or more selected from the group consisting of S, and the substitution may be substituted by C ₁ -C ₆ alkyl or C ₆ -C ₂₀ aryl, but is not limited thereto.

According to an embodiment of the present application, R ₁ to R ₅ are each independently a single bond, methyl, phenyl which may be substituted, biphenyl, chrysene, phenanthrene, naphthyl, fluorenyl, quinoline, phen It includes those selected from the group consisting of rylene, pyrene, halogen, cyano and combinations thereof, the substitution may be substituted by linear or branched C ₁ -C ₂₀ alkyl, but is not limited thereto. It is not.

According to an embodiment of the present disclosure, A ₁ is phenoxazine, phenoxyazine, dimethylacridin, diphenylacridine, carbazole, phenyl, biphenyl, naphthalene, fluorene, anthracene, phenanthrene, Selected from the group consisting of pyrene, fluoranthene, chrysene, benzofluoranthene, perylene, quinoline, indenoanthracene, indenophenanthrene, hydroanthracene, dibenzothiophene, dibenzofuran and combinations thereof It may be to include a substance, but is not limited thereto.

According to an embodiment of the present disclosure, the phenanthroline derivative may include 1,10-phenanthroline-5,6-dione (1,20-phenanthroline-5,6-dione), but is not limited thereto. It doesn't happen.

According to one embodiment of the present invention, the ammonium salt is a group consisting of ammonium acetate, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, ammonium cyanide, ammonium nitrate, ammonium sulfate, ammonium carbonate and combinations thereof It may be to include an ammonium salt selected from, but is not limited thereto.

According to one embodiment of the present application, the reaction may be performed under a solvent, but is not limited thereto.

According to one embodiment of the present application, the solvent is acetic acid, water, ethanol, methanol, propanol, butanol, hexane, methylene chloride, ethyl acetate, propylene glycol, butylene glycol, dipropylene glycol, glycerin, ketone, acetone, dimethyl sulfoxide But may include, but are not limited to, a solvent comprising side, dimethylformamide, toluene, tetrahydrofuran, dichloromethane, acetonitrile and combinations thereof.

The third aspect of the present application provides an organic electroluminescent device comprising the organic light emitting compound according to the present application.

The above-mentioned means for solving the problems are merely exemplary, and should not be construed as limiting the present application. In addition to the above-described exemplary embodiments, additional embodiments may exist in the drawings and detailed description of the invention.

According to the aforementioned problem solving means of the present invention, the organic light emitting compound according to the present invention is phenyl is connected to the 1- and 2-position of the imidazo [1,10] phenanthroline, HOMO (Highest Occupied Molecular Orbital) and LUMO ( The spatial separation of the Lowest Unoccupied Molecular Orbital can also have small singlet and triplet energy differences.

The organic light emitting compound according to the present invention has high thermal and electrochemical stability because it is based on imidazophenanthroline. For example, by introducing imidazophenanthroline, the organic light emitting compound has a high thermal decomposition temperature (T _d ) and a glass transition temperature (T _g ) to have high thermal stability.

In the organic light-emitting compound according to the present invention, a phenyl group is introduced at 1- and 2-positions of imidazophenanthroline, and in particular, a warp having a back angle close to 90 degrees due to the substitution of electron donors at the 2-position You have a structure. At the same time, the phenyl group having the alkyl group introduced at the 1-position may have a greater steric effect. This makes it possible to have more three-dimensional molecular orbital (molecular orbital) than in the planar molecule and to increase the mutual repulsion between molecules effectively prevent the intermolecular interaction. As the interaction between molecules is reduced, color purity and luminous efficiency can be improved by preventing the formation of excimers or self-extinction. The energy spacing can then be adjusted to a shorter conjugation length to induce an appropriate emission wavelength region, particularly a blue emission wavelength region, of the device.

The organic light emitting compound according to the present invention was applied to the device by controlling the energy state of the HOMO and LUMO of the molecule itself through nitrogen atoms introduced at the 1- and 10- positions of the imidazophenanthroline. At this time, the mobility of electrons and holes is adjusted to a similar level to facilitate the formation of exciton in the emission layer, thereby exhibiting high emission efficiency.

In addition, by having a distorted structure of the molecule, it is possible to efficiently separate the HOMO and LUMO energy levels of the molecule itself, thereby exhibiting the intrinsic properties of the material, and to prevent the phenomenon that the color purity of light due to the self-aggregation phenomenon in the solid state falls. have.

Furthermore, the organic light emitting compound may exhibit a better life due to the characteristics of delayed fluorescent light.

The organic light emitting compound according to the present invention can make a great contribution to the development of next-generation OLED materials by solving the problems of the prior art and providing an organic light emitting compound having excellent efficiency and color purity.

1 is a schematic diagram of an organic electroluminescent device according to an embodiment of the present disclosure.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure.

As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a part is "connected" to another part, this includes not only "directly connected" but also "electrically connected" with another element in between. do.

Throughout this specification, when a member is said to be located on another member "on", "upper", "top", "bottom", "bottom", "bottom", this means that any member This includes not only the contact but also the case where another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated.

As used herein, the terms "about", "substantially", and the like, are used at the numerical values of, or in the vicinity of, numerical values when manufacturing and material tolerances inherent in the meanings mentioned are provided to aid the understanding herein. In order to prevent an unscrupulous infringer from unfairly using the disclosed disclosure. In addition, throughout this specification, "step to" or "step of" does not mean "step for."

Throughout this specification, the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.

 Throughout this specification, description of "A and / or B" means "A or B, or A and B."

Throughout this specification, the term "aromatic ring" refers to a C _6-30 aromatic hydrocarbon ring group, for example, phenyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, perrylenyl Means an aromatic ring, such as chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzocrisenyl, anthracenyl, stilbenyl, pyrenyl, and the like. As an aromatic ring containing a hetero element, for example, pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindoleyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, Quinolyl groups, isoquinolyl, quinoxalinyl, carbazolyl, phenantridinyl, acridinyl, phenanthrolinyl, thienyl, and pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, triazine rings, Indole ring, quinoline ring, acridingo , Pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, piperazine ring, carbazole ring, furan ring, thiophene ring, oxazole ring, oxadiazole ring, benzoxazole ring, thiazole It is meant to include aromatic heterocyclic groups formed from rings, thiadiazole rings, benzothiazole rings, triazole rings, imidazole rings, benzoimidazole rings, pyran rings, dibenzofuran rings.

Throughout this specification, the term “fusion” means that, with respect to two or more rings, at least one pair or more adjacent atoms are included in two rings.

Throughout this specification, the term “alkyl” may include linear or branched, saturated or unsaturated C ₁ -C ₆ alkyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl or their It may be to include all possible isomers, but may not be limited thereto.

Throughout this specification, the term “halogen” is a Group 17 element of the periodic table, which may include, for example, F, Cl, Br, or I, but may not be limited thereto.

Hereinafter, the organic light emitting compound of the present application, a method for manufacturing the same, and an organic electroluminescent device including the same will be described in detail with reference to embodiments, examples, and drawings. However, the present application is not limited to these embodiments, examples, and drawings.

The 1st side of this application relates to the organic light emitting compound represented by following formula (1).

[Formula 1]

In Formula 1, R ₁ to R ₅ are each independently a single bond, a linear or branched C ₁ -C ₂₀ alkyl that may be substituted, an aryl, halogen, C ₆ -C ₂₀ that may be substituted, Or cyano, and A ₁ is a 5-membered unsaturated or aromatic ring which may be substituted, a 6-membered unsaturated or aromatic ring which may be substituted, a 5-membered unsaturated or aromatic hetero ring which may be substituted and 6-substituted which may be substituted At least one ring selected from the group consisting of circularly unsaturated or aromatic hetero rings, or at least two rings selected from the group are fused polycyclic rings, n is 0 or 1, and the hetero rings are N, O and S It includes one or more selected from the group consisting of, the substitution may be substituted by C ₁ -C ₆ alkyl or C ₆ -C ₂₀ aryl, but is not limited thereto.

According to an embodiment of the present application, R ₁ to R ₅ are each independently a single bond, methyl, phenyl which may be substituted, biphenyl, chrysene, phenanthrene, naphthyl, fluorenyl, quinoline, phen It includes those selected from the group consisting of rylene, pyrene, halogen, cyano and combinations thereof, the substitution may be substituted by linear or branched C ₁ -C ₂₀ alkyl, but is not limited thereto. It is not.

According to an embodiment of the present disclosure, A ₁ is phenoxazine, phenoxyazine, dimethylacridin, diphenylacridine, carbazole, phenyl, biphenyl, naphthalene, fluorene, anthracene, phenanthrene, Selected from the group consisting of pyrene, fluoranthene, chrysene, benzofluoranthene, perylene, quinoline, indenoanthracene, indenophenanthrene, hydroanthracene, dibenzothiophene, dibenzofuran and combinations thereof It may be to include a substance, but is not limited thereto.

The A ₁ may be bonded to ortho-, meta-, or para- positions of the phenyl group of the organic light emitting compound, but is not limited thereto.

The A ₁ may be to serve as an electron donor, but is not limited thereto.

The organic light emitting compound according to the present invention may be based on a light emitting compound of a derivative of imidazo [1,10] phenanthroline having phenyl bonded to 1- and 2-positions, but is not limited thereto.

In the organic light emitting compound according to the present invention, phenyl is connected to the 1- and 2-positions of imidazo [1,10] phenanthroline, so that the spatial separation between High Occupied Molecular Orbital (HOMO) and Low Unoccupied Molecular Orbital (LUMO) At the same time it may have small singlet and triplet energy differences.

The organic light emitting compound according to the present invention has high thermal and electrochemical stability because it is based on imidazophenanthroline. For example, by introducing imidazophenanthroline, the organic light emitting compound has a high thermal decomposition temperature (T _d ) and a glass transition temperature (T _g ) to have high thermal stability.

In the organic light-emitting compound according to the present invention, a phenyl group is introduced at 1- and 2-positions of imidazophenanthroline, and in particular, a warp having a back angle close to 90 degrees due to the substitution of an electron donor at the 2-position. You have a structure. At the same time, the phenyl group having the alkyl group introduced at the 1-position may have a greater steric effect. This makes it possible to have more three-dimensional molecular orbital (molecular orbital) than in the planar molecule and to increase the mutual repulsion between molecules effectively prevent the intermolecular interaction. As the interaction between molecules is reduced, color purity and luminous efficiency can be improved by preventing the formation of excimers or self-extinction. The energy spacing can then be adjusted to a shorter conjugation length to induce an appropriate emission wavelength region, particularly a blue emission wavelength region, of the device.

The organic light emitting compound according to the present invention was applied to the device by controlling the energy state of the HOMO and LUMO of the molecule itself through nitrogen atoms introduced at the 1- and 10- positions of the imidazophenanthroline. At this time, the mobility of electrons and holes is adjusted to a similar level to facilitate the formation of exciton in the emission layer, thereby exhibiting high emission efficiency.

In addition, by having a distorted structure of the molecule, it is possible to efficiently separate the HOMO and LUMO energy levels of the molecule itself, thereby exhibiting the intrinsic properties of the material, and to prevent the phenomenon that the color purity of light due to the self-aggregation phenomenon in the solid state falls. have.

Furthermore, the organic light emitting compound may exhibit a better life due to the characteristics of delayed fluorescent light.

The organic light emitting compound according to the present invention can make a great contribution to the development of next-generation OLED materials by solving the problems of the prior art and providing an organic light emitting compound having excellent efficiency and color purity.

The organic light emitting compound may contribute positively to the development of next generation displays such as flat panel displays and flexible displays.

According to an embodiment of the present disclosure, the organic light emitting compound may include any one of the following compounds, but is not limited thereto:

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With respect to the method for producing an organic light emitting compound according to the second aspect of the present application, detailed descriptions of the overlapping portions of the first side of the present application have been omitted, but the descriptions of the first aspect of the present application may be omitted. The same may be applied to the second aspect.

According to a second aspect of the present application, the second aspect of the present application includes reacting a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, and a phenanthroline derivative in the presence of an ammonium salt. A method for producing an organic light emitting compound.

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3, R ₁ to R ₅ are each independently a single bond, a linear or branched C ₁ -C ₂₀ alkyl which may be substituted, an aryl of C ₆ -C ₂₀ which may be substituted, Halogen, or cyano, and A ₁ is a 5-membered unsaturated or aromatic ring which may be substituted, a 6-membered unsaturated or aromatic ring which may be substituted, a 5-membered unsaturated or aromatic hetero ring which may be substituted and may be substituted At least one ring selected from the group consisting of 6-membered unsaturated or aromatic hetero rings, or at least two rings selected from the group are fused polycyclic rings, n is 0 or 1, and the hetero ring is N, It includes one or more selected from the group consisting of O and S, the substitution may be substituted by C ₁ -C ₆ alkyl or C ₆ -C ₂₀ aryl, but is not limited thereto.

According to an embodiment of the present application, R ₁ to R ₅ are each independently a single bond, methyl, phenyl which may be substituted, biphenyl, chrysene, phenanthrene, naphthyl, fluorenyl, quinoline, phen It includes those selected from the group consisting of rylene, pyrene, halogen, cyano and combinations thereof, the substitution may be substituted by linear or branched C ₁ -C ₂₀ alkyl, but is not limited thereto. It is not.

According to an embodiment of the present disclosure, A ₁ is phenoxazine, phenoxyazine, dimethylacridin, diphenylacridine, carbazole, phenyl, biphenyl, naphthalene, fluorene, anthracene, phenanthrene, Selected from the group consisting of pyrene, fluoranthene, chrysene, benzofluoranthene, perylene, quinoline, indenoanthracene, indenophenanthrene, hydroanthracene, dibenzothiophene, dibenzofuran and combinations thereof It may be to include a substance, but is not limited thereto.

The A ₁ may be to serve as an electron donor, but is not limited thereto.

According to an embodiment of the present disclosure, the phenanthroline derivative may include 1,10-phenanthroline-5,6-dione (1,20-phenanthroline-5,6-dione), but is not limited thereto. It doesn't happen.

The compound represented by Chemical Formula 3 may be one containing aniline, but is not limited thereto.

According to one embodiment of the present invention, the ammonium salt is ammonium acetate (ammonium acetate), ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, ammonium cyanide, ammonium nitrate, ammonium sulfate, ammonium carbonate and combinations thereof It may be to include an ammonium salt selected from the group consisting of, but is not limited thereto.

According to one embodiment of the present application, the reaction may be performed under a solvent, but is not limited thereto.

According to one embodiment of the present application, the solvent is acetic acid, water, ethanol, methanol, propanol, butanol, hexane, methylene chloride, ethyl acetate, propylene glycol, butylene glycol, dipropylene glycol, glycerin, ketone, acetone, dimethyl sulfoxide But may include, but are not limited to, a solvent comprising side, dimethylformamide, toluene, tetrahydrofuran, dichloromethane, acetonitrile and combinations thereof.

The reaction may be performed under a catalyst, but is not limited thereto.

The catalyst includes a metal selected from the group consisting of Pd, Pt, Ni, Rh, Ti, Zr, Hf, V, Ta, Cr, Mo, W, Fe, Ru, Os, Ir, and combinations thereof. May be, but is not limited thereto.

For the organic electroluminescent device according to the third aspect of the present application, detailed descriptions of portions overlapping with the first side of the present application have been omitted. However, the descriptions of the first aspect of the present disclosure may not be described in detail. The same can be applied to the side.

The third aspect of the present application provides an organic electroluminescent device comprising the organic light emitting compound according to the present application.

The organic electroluminescent device is, for example, ITO (180 nm) / N, N′-di (1-naphthyl) -N, N′-diphenyl- (1,1′-biphenyl) -4,4 ′ -Diamine (NPB, HIL) (50 nm) / tris (4-carbazoyl-9-ylphenyl) amine (TCTA, HTL) (10 nm) / the organic light emitting compound (EML) (20 nm) / 2, 2 ', 2' '-(1,3,5-benzintril) -tris (1-phenyl-1-H-benzoimidazole) (TPBi, ETL) (30 nm) / lithium quinolate (Liq, EIL) (2 nm) / Al (100 nm), but is not limited thereto.

The organic electroluminescent device can be applied to various fields such as indoor and outdoor lighting, photoelectric devices, solar power generation.

The organic electroluminescent device may be manufactured as follows: A transparent electrode indium-tin-oxide (ITO) thin film (sheet resistance 10 Ω / square) obtained from glass for organic EL is sequentially prepared using acetone, methanol, and distilled water. After ultrasonic cleaning, it is stored in isopropyl alcohol for 20 minutes and then used after treatment with oxygen plasma. The ITO substrate is placed in a substrate folder of a vacuum deposition apparatus, and N, N'-di (1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) is placed in a cell in the vacuum deposition apparatus. Add -4,4'-diamine (NPB), evacuate until the vacuum in the chamber reaches 5.0 x 10 ^-7 Torr, apply current to the cell to evaporate the NPB to about 50 on the ITO substrate. A nm thick hole injection layer is deposited. The tris (4-carbazoyl-9-ylphenyl) amine (TCTA) is then evaporated under similar conditions to deposit a 10 nm thick hole transport layer. The organic light emitting compound according to the present invention is evaporated at 1.0 kW / sec in the vacuum deposition equipment to deposit a light emitting layer having a thickness of about 20 nm on the hole transport layer. Then, under similar conditions, 2,2 ', 2''-(1,3,5-benzintril) -tris (1-phenyl-1-H-benzimidazole) (TPBi) and lithium quinolate (Liq) Are sequentially evaporated to deposit an electron transport layer and an electron injection layer having a thickness of about 30 nm and about 2 nm, respectively. Thereafter, an Al cathode having a thickness of 100 nm is deposited using another vacuum deposition apparatus to manufacture an organic EL device.

1 is a schematic diagram of an organic electroluminescent device according to an embodiment of the present disclosure.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present application.

EXAMPLE

Example 1 2- (4- (10H-vphenoxazin-10-yl) phenyl) -1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthroline (2- ( Synthesis of 4- (10H-phenoxazin-10-yl) phenyl) -1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthroline)

Example 1- (1): Synthesis of 10- (4-bromophenyl) -10H-phenoxazine (10- (4-bromophenyl) -10H-phenoxazine)

0.8 g (1.0 eq, 4.37 mmol) of 10-phenoxazine, 1.61 g (1.3 eq, 5.68 mmol) of 4-bromoioiobenzene, 0.144 g (0.52 eq, 2.27 mmol) of Cu powder , 18-crown-6 0.09 g (0.08 eq, 0.35 mmol) and potassium carbonate 2.41 g (4.0 eq, 17.47 mmol) were added to a reaction vessel and vacuum dried, followed by nitrogen gas. 11 ml of 1,2-dichlorobenzene was added to the reaction vessel to dissolve the compounds, and the mixture was stirred under reflux for 2 hours at a temperature of 190 ° C. After completion of the reaction, the organic layer was extracted with distilled water and ethyl acetate. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Thereafter, column chromatography gave 1.07 g (yield = 72.36%) of 10- (4-bromophenyl) -10H-phenoxazine through recrystallization with hexane. ( ¹ H NMR (DMSO-d6) d 7.84 (d, J ¼ 8.3, 2H), 7.54 (d, J ¼ 8.6, 2H), 6.75-6.62 (m, 6H), 5.87-5.84 (m, 2H) ppm ).

Example 1- (2): Synthesis of 4- (10H-phenoxazin-10-yl) benzaldehyde (4- (10H-phenoxazin-10-yl) benzaldehyde)

0.8 g (1.0 eq, 2.36 mmol) of 10- (4-bromophenyl) -10H-phenoxazine obtained in the above Example 1- (1) was placed in a reaction vessel and dried under vacuum and filled with nitrogen gas. 8 ml of tetrahydrofuran was added to the reaction vessel to dissolve the compound, and the temperature of the reaction vessel was adjusted to -78 ° C using dry ice. While maintaining the temperature, 2.22 ml (1.5 eq, 3.54 mmol) of 1.6 M n-butyllithium was slowly added dropwise to the reaction vessel, followed by stirring for 90 minutes. 0.272 ml (1.5 eq, 3.54 mmol) of dimethylformamide was added to the reaction vessel, followed by stirring at room temperature for 3 hours. After completion of the reaction, the organic layer was extracted with distilled water and ethyl acetate. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Then column chromatography gave 0.40 g (yield = 58.8%) of compound 4- (10H-phenoxazin-10-yl) benzaldehyde (4- (10H-phenoxazin-10-yl) benzaldehyde). ( ¹ H NMR (500 MHz, CDCl ₃ ) δ 10.11 (s, 1H), 8.14-8.09 (m, 2H), 7.58-7.51 (m, 2H), 6.71 (dtd, J = 9.3, 7.9, 1.6 Hz, 4H), 6.65-6.58 (m, 2H), 5.96 (dd, J = 8.0, 1.4 Hz, 2H))

Example 1- (3): Synthesis of 1,10-phenanthroline-5,6-dione (1,10-phenanthroline-5,6-dione)

3.0 g (1.0 eq, 11.1 mmol) of 1,10-phenanthroline and 3.09 g (1.56 eq, 17.3 mmol) of potassium bromide were added to a reaction vessel and cooled to a temperature of 0 ° C. 40 ml of a solution of 20 ml of sulfuric acid and 20 ml of nitric acid was slowly added dropwise to the reaction vessel, followed by stirring to dissolve the compound. The reaction vessel was stirred at reflux for 3 hours at a temperature of 100 ℃. After completion of the reaction, the mixture was neutralized with sodium carbonate. Washed with distilled water and extracted the organic layer with dichloromethane. Then dried over anhydrous magnesium sulfate, filtered through celite and the solvent was evaporated. Then recrystallization with dichloromethane and ethanol gave 2.59 g (yield = 73.4%) of 1,10-phenanthroline-5,6-dione. ( ¹ H-NMR: 9.13 (dd, J = 4.7, 1.8 Hz, 2H), 8.52 (dd, J = 7.9, 1.8 Hz, 2H), 7.60 (dd, J = 7.9, 4.7 Hz, 2H))

Example 1- (4): 2- (4- (10H-vphenoxazin-10-yl) phenyl) -1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthroline (2- (4- (10H-phenoxazin-10-yl) phenyl) -1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthroline) Synthesis

0.293 g (1.0 eq, 1.39 mmol) of 1,10-phenanthroline-5,6-dione obtained in Example 1- (3), 4- (10H-) obtained in Example 1- (2) Phenoxazine-10-yl) benzaldehyde 0.74 g (1.0 eq, 1.39 mmol), aniline 0.64 g (5.0 eq, 6.96 mmol), and 1.33 g (12.4 eq, 17.26 mmol) of ammonium acetate were placed in a reaction vessel and dried in vacuo. Filled with nitrogen gas. 9 ml of acetic acid was added to the reaction vessel to dissolve the compounds, and the mixture was stirred under reflux for 16 hours at a temperature of 130 ° C. After completion of the reaction, neutrality was adjusted using sodium carbonate, washed with distilled water, and the organic layer was extracted with dichloromethane. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Then, after column chromatography, the compound 2- (4- (10H-vphenoxazin-10-yl) phenyl) -1-phenyl-1H-imidazo [4,5-f] by recrystallization with isopropyl alcohol. 0.43 g (yield = 55.84%) of [1,10] phenanthroline were obtained. ( ¹ H-NMR: 9.22 (dd, J = 4.3, 1.8 Hz, 1H), 9.17 (dd, J = 8.1, 1,8 Hz, 1H), 9.08 (dd, J = 4.3, 1.6 Hz, 1H), 7.86-7.81 (m, 2H), 7.78 (dd, J = 8.1, 4.4 Hz, 1H), 7.76-7.68 (m, 3H), 7.64-7.59 (m, 2H), 7.48 (dd, J = 8.4, 1.6 Hz, 1H), 7.35-7.29 (m, 3H), 6.67 (dtd, J = 9.3, 7.8, 1.6 Hz, 4H), 6.61-6.56 (m, 2H), 5.90 (dd, J = 7.9, 1.4 Hz, 2H) .APCI-MS (m / z): 553 [M + 1 ⁺ ])

Example 2 2- (3- (10H-phenoxazin-10-yl) phenyl) -1-phenyl 1H imidazo [4,5f] [1,10] phenanthroline (2- (3- (10H- Synthesis of phenoxazin-10-yl) phenyl) -1-phenyl 1Himidazo [4,5f] [1,10] phenanthroline

Example 2- (1): Synthesis of 10- (3-bromophenyl) -10H-phenoxazine (10- (3-bromophenyl) -10H-phenoxazine)

0.59 g (1.3 eq, 3.22 mmol) of 10H-phenoxazine, 0.7 g (1.0 eq, 2.47 mmol) of 3-bromoiodobenzene, 0.081 g (0.52 eq, 1.29 mmol) of Cu powder, 0.052 g of 18-crown-6 ( 0.08 eq, 0.198 mmol) and 1.56 g (4.0 eq, 11.31 mmol) of potassium carbonate were placed in a reaction vessel and dried in vacuo to fill with nitrogen gas. 5 ml of 1,2-dichlorobenzene was added to the reaction vessel to dissolve the compounds, and the mixture was stirred under reflux for 3 hours at a temperature of 190 ° C. After completion of the reaction, the organic layer was extracted with distilled water and dichloromethane. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Then column chromatography gave 0.4 g (yield = 47.8%) of 10- (3-bromophenyl) -10H-phenoxazine.

Example 2- (2): Synthesis of 3- (10H-phenoxazin-10-yl) benzaldehyde (3- (10H-phenoxazin-10-yl) benzaldehyde)

0.4 g (1.0 eq, 1.183 mmol) of 10- (3-bromophenyl) -10H-phenoxazine obtained in the above Example 2- (1) was placed in a reaction vessel, and dried in vacuo and filled with nitrogen gas. 4 ml of tetrahydrofuran was added to the reaction vessel, and the temperature of the reaction vessel was adjusted to -78 ° C using dry ice. While maintaining the temperature, 1.11 ml (1.5 eq, 1.774 mmol) of 1.6 M n-butyllithium was slowly added dropwise to the reaction vessel, followed by stirring for 90 minutes. 0.14 ml (1.5 eq, 1.774 mmol) of dimethylformamide was added to the reaction vessel, followed by stirring at room temperature for 3 hours. After completion of the reaction, the organic layer was extracted with distilled water and ethyl acetate. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Then column chromatography gave 0.29 g (yield = 85.1%) of compound 3- (10H-phenoxazin-10-yl) benzaldehyde (4- (10H-phenoxazin-10-yl) benzaldehyde). ( ¹ H NMR (500 MHz, CDCl 3) δ 10.07 (s, 1H), 8.01 (dt, J = 7.7, 1.3 Hz, 1H), 7.90 (t, J = 1.7 Hz, 1H), 7.78 (t, J = 7.7, 1H), 7.66 (ddd, J = 7.8, 2.0, 1.2 Hz, 1H), 6.69 (dtd, J = 9.3, 7.9, 1.5 Hz, 4H). 6.61-6.57 (m, 2H), 5.87 (dd, J = 8.0, 1.4 Hz, 2H))

Example 2- (3): 2- (3- (10H-vphenoxazin-10-yl) phenyl) -1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthroline (2- (4- (10H-phenoxazin-10-yl) phenyl) -1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthroline) Synthesis

0.146 g (1.0 eq, 0.691 mmol) of 1,10-phenanthroline-5,6-dione obtained in Example 1- (3), 3- (10H-) obtained in Example 2- (2) Phenoxazine-10-yl) benzaldehyde 0.2 g (1.0 eq, 0.691 mmol), aniline 0.32 g (5.0 eq, 3.48 mmol), and 0.665 g (12.4 eq, 8.63 mmol) of ammonium acetate were placed in a reaction vessel and dried in vacuo. Filled with nitrogen gas. 4.4 ml of acetic acid was added to the reaction vessel to dissolve the compounds, and the mixture was stirred under reflux for 16 hours at a temperature of 130 ° C. After completion of the reaction, neutrality was adjusted using sodium carbonate, washed with distilled water, and the organic layer was extracted with dichloromethane. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Subsequently, after column chromatography, the compound 2- (3- (10H-vphenoxazin-10-yl) phenyl) -1-phenyl-1H-imidazo [4,5-f] [was recrystallized using ethyl acetate. 0.23 g (yield = 60.5%) of 1,10] phenanthroline were obtained. ( ¹ H-NMR: 9.20 (dd, J = 4.4, 1.8 Hz, 1H), 9.14 (dd, J = 8.1, 1.8 Hz, 1H), 9.06 (dd, J = 4.3, 1.6 Hz, 1H), 7.92- 7.87 (m, 1H), 7.76 (dt, J = 9.5, 4.7 Hz, 1H), 7.63 (t, J = 7.8 Hz, 1H), 7.61-7.57 (m, 3H), 7.53 (dt, J = 5.3, 3.7 Hz, 2H), 7.46 (dd, J = 8.4, 1.6 Hz, 1H), 7.38 (t, J = 1.7 Hz, 1H), 7.35 (ddd, J = 7.8, 1.9, 1.1 Hz, 1H), 7.30 ( dd, J = 8.4, 4.3 Hz, 1H), 6.66 (d, J = 1.8 Hz, 1H), 6.64 (ddd, J = 10.1, 9.3, 1.6 Hz, 3H), 6.53 (ddd, J = 8.0, 7.2, 1.8 Hz, 2H), 5.65 (dd, J = 8.0, 1.3 Hz, 2H) .APCI-MS (m / z): 553 [M + 1 ⁺ ])

Example 3: 2- (2- (10H-phenoxazin-10-yl) phenyl) -1-phenyl 1H imidazo [4,5f] [1,10] phenanthroline (2- (2- (10H- Synthesis of phenoxazin-10-yl) phenyl) -1-phenyl 1Himidazo [4,5f] [1,10] phenanthroline

Example 3- (1): Synthesis of 10- (2-bromophenyl) -10H-phenoxazine (10- (2-bromophenyl) -10H-phenoxazine)

0.5 g (1.3 eq, 2.729 mmol) 10H-phenoxazine, 1.54 g (2.0 eq, 5.46 mmol), 2-bromoiodobenzene, 0.26 g (0.5 eq, 1.36 mmol) Copper (I) iodide 0.754 g (2.0 eq, 5.46 mmol) of potassium carbonate was added to the reaction vessel, followed by vacuum drying, and nitrogen gas. 5 ml of xylene was added to the reaction vessel and stirred at reflux overnight at a temperature of 120 ° C. After completion of the reaction, the organic layer was extracted with distilled water and ethyl acetate. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Column chromatography then gave 0.61 g (yield = 66.1%) of 10- (2-bromophenyl) -10H-phenoxazine. ( ¹ H NMR (500 MHz, CDCl 3) δ 7.83 (dd, J = 8.0, 1.4 Hz, 1H), 7.53 (td, J = 7.6, 1.4 Hz, 1H), 7.43 (dd, J = 7.8, 1.6 Hz, 1H), 7.39-7.33 (m, 1H), 6.73-6.58 (m, 6H), 5.79 (dd, J = 7.9, 1.5 Hz, 2H))

Example 3- (2): Synthesis of 2- (10H-phenoxazin-10-yl) benzaldehyde (3- (10H-phenoxazin-10-yl) benzaldehyde)

0.6 g (1.0 eq, 1.7 mmol) of 10- (2-bromophenyl) -10H-phenoxazine obtained in the above Example 3- (1) was placed in a reaction vessel, and vacuum dried and filled with nitrogen gas. 25 ml of tetrahydrofuran was added to the reaction vessel, and the temperature of the reaction vessel was adjusted to -78 ° C using dry ice. While maintaining the temperature, 1.66 ml (1.5 eq, 2.6 mmol) of 1.6 M n-butyllithium was slowly added dropwise to the reaction vessel, followed by stirring for 90 minutes. 0.204 ml (1.5 eq, 2.6 mmol) of dimethylformamide was added to the reaction vessel, followed by stirring at room temperature for 3 hours. After completion of the reaction, the organic layer was extracted with distilled water and ethyl acetate. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Thereafter, recrystallization with hexane gave 0.5 g (yield = 98.0%) of compound 2- (10H-phenoxazin-10-yl) benzaldehyde (2- (10H-phenoxazin-10-yl) benzaldehyde). ( ¹ H NMR (500 MHz, CDCl 3) δ 10.29 (s, 1H), 8.17 (d, J = 7.8 Hz, 1H), 7.88 (td, J = 7.7, 1.1 Hz, 1H), 7.64 (t, J = 7.5 Hz, 1H), 7.44 (d, J = 7.8 Hz, 1H), 6.77-6.52 (m, 7H), 5.82 (d, J = 7.9 Hz, 1H))

Example 3- (3): 2- (2- (10H-phenoxazin-10-yl) phenyl) -1-phenyl 1H imidazo [4,5f] [1,10] phenanthroline (2- (2 Synthesis of-(10H-phenoxazin-10-yl) phenyl) -1-phenyl 1Himidazo [4,5f] [1,10] phenanthroline)

0.39 g (1.0 eq, 1.74 mmol) of 1,10-phenanthroline-5,6-dione obtained in Example 1- (3), 2- (10H-) obtained in Example 3- (2) Phenoxazine-10-yl) benzaldehyde 0.5 g (1.0 eq, 1.74 mmol), aniline 0.81 g (5.0 eq, 8.70 mmol), and 1.66 g (12.4 eq, 21.58 mmol) of ammonium acetate were added to the reaction vessel and dried in vacuo. Filled with nitrogen gas. 13.0 ml of acetic acid was added to the reaction vessel to dissolve the compounds, and the mixture was stirred under reflux for 16 hours at a temperature of 130 ° C. After completion of the reaction, neutrality was adjusted using sodium carbonate, washed with distilled water, and the organic layer was extracted with dichloromethane. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Subsequently, after column chromatography, the compound 2- (2- (10H-phenoxazin-10-yl) phenyl) -1-phenyl 1H imidazo [4,5f] [1,10] phenan through recrystallization with isopropyl alcohol. 0.63 g of trolline (yield = 65.2%) were obtained. ( ¹ H NMR (500 MHz, CDCl 3) δ 9.13 (dd, J = 4.4, 1.8 Hz, 1H), 9.00 (dd, J = 4.3, 1.6 Hz, 1H), 8.70 (dd, J = 8.1, 1.8 Hz, 1H), 7.70-7.57 (m, 3H), 7.49-7.42 (m, 3H), 7.40-7.28 (m, 5H), 7.24-7.19 (m, 1H), 6.58 (dqd, J = 13.9, 7.2, 2.1 Hz, 6H), 5.99-5.84 (m, 2H) .APCI-MS (m / z): 553 [M + 1 ⁺ ])

Example 4: 10- (2 '-(1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthrolin-2-yl)-[1,1'-biphenyl]- 4-yl) -10H-phenoxazine (10- (2 '-(1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthrolin-2-yl)-[1,1'-biphenyl ] -4-yl) -10H-phenoxazine)

Example 4- (1): 10- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan 2-yl) phenyl) -10H-phenoxazine (10- Synthesis of (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-phenoxazine)

1.5 g (1.0 eq, 4.43 mmol) of 10- (4-bromophenyl) -10H-phenoxazine prepared in Example 1- (1) was placed in a reaction vessel and dried under vacuum, followed by filling with nitrogen gas. 8 ml of tetrahydrofuran was added to the reaction vessel to dissolve the compound, and the temperature of the reaction vessel was adjusted to -78 ° C using dry ice. While maintaining the temperature, 4.16 ml (1.5 eq, 6..65 mmol) of n-butyllithium at 1.6 M concentration was slowly added dropwise to the reaction vessel, followed by stirring for 90 minutes. 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-isopropoxy-4,4,5,5-tetramethyl-1,3) , 2-dioxaborolane) 0.90 ml (1.5 eq, 6.65 mmol) was added and stirred for 30 minutes, followed by stirring at room temperature for 2 hours. After completion of the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. 1.17 g of compound 10- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan 2-yl) phenyl) -10H-phenoxazine via column chromatography (Yield = 72.22%) was obtained. ( ¹ H NMR (500 MHz, CDCl 3) δ 8.03 (d, J = 8.2 Hz, 2H), 7.35 (d, J = 8.2 Hz, 2H), 6.68 (dd, J = 7.8, 1.6 Hz, 2H), 6.63 (t, J = 7.3 Hz, 2H), 6.56 (td, J = 7.8, 1.6 Hz, 2H), 5.91 (dd, J = 7.9, 1.0 Hz, 2H), 1.38 (s, 12H)

Example 4- (2): 4 '-(10H-phenoxazin-10-yl)-[1,1'-biphenyl] -2-carbaldehyde (4'-(10H-phenoxazin-10-yl) -[1,1'-biphenyl] -2-carbaldehyde)

Compound 10- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan 2-yl) phenyl) -10H-, obtained in step 4- (1) above. Phenoxazine 1.0 g (1.1 eq, 2.70 mmol), 2-bromobenzaldehyde 0.45 g (1.0 eq, 2.76 mmol), and tetrakis (triphenylphosphine) ) palladium (0)) 113 mg (0.04 eq, 0.098 mmol) was added to the reaction vessel and dried in vacuo and filled with nitrogen gas. 25 ml of toluene was added to the reaction vessel to dissolve the compound, followed by adding 3.36 g (10 eq, 24.6 mmol) of potassium carbonate at 2.0 M concentration and 0.11 ml (0.1 eq, 0.24 mmol) of Aliquat 336. It was stirred at reflux for hours. After completion of the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. 0.65 g of compound 4 '-(10H-phenoxazin-10-yl)-[1,1'-biphenyl] -2-carbaldehyde, dried over anhydrous magnesium sulfate, filtered through celite, and then purified by column chromatography. (Yield = 65.0%) was obtained. ( ¹ H NMR (500 MHz, CDCl 3) δ 10.09 (d, J = 0.7 Hz, 1H), 8.08 (dd, J = 7.8, 1.2 Hz, 1H), 7.70 (dt, J = 7.5, 3.8 Hz, 1H) , 7.64-7.59 (m, 2H), 7.55 (ddd, J = 10.5, 7.6, 0.8 Hz, 2H), 7.49-7.45 (m, 2H), 6.67 (dddd, J = 20.3, 15.0, 7.5, 1.8 Hz, 6H), 5.99 (dd, J = 7.8, 1.6 Hz, 2H))

Example 4- (3): 10- (2 '-(1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthrolin-2-yl)-[1,1'- Biphenyl] -4-yl) -10H-phenoxazine (10- (2 '-(1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthrolin-2-yl)-[1, 1'-biphenyl] -4-yl) -10H-phenoxazine)

0.33 g (1.0 eq, 1.57 mmol) of 1,10-phenanthroline-5,6-dione obtained in Example 1- (3), 4 ′-(10H) obtained in Example 4- (2) -Phenoxazin-10-yl)-[1,1'-biphenyl] -2-carbaldehyde 0.65 g (1.0 eq, 1.57 mmol), aniline 0.72 g (5.0 eq, 8.48 mmol), and 1.50 g ammonium acetate (12.4 eq, 19.51 mmol) was added to the reaction vessel, followed by vacuum drying and nitrogen gas. 15.0 ml of acetic acid was added to the reaction vessel to dissolve the compounds, and the mixture was stirred under reflux for 16 hours at a temperature of 120 ° C. After completion of the reaction, neutrality was adjusted using sodium carbonate, washed with distilled water, and the organic layer was extracted with methylene chloride. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Subsequently, after column chromatography, the compound 10- (2 '-(1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthrolin-2-yl is obtained by recrystallization with isopropyl alcohol. )-[1,1'-biphenyl] -4-yl) -10H-phenoxazine was obtained 0.49 g (yield = 49.49%). ( ¹ H NMR (500 MHz, CDCl 3) δ 9.21 (dd, J = 4.4, 1.8 Hz, 1H), 9.11 (dd, J = 8.1, 1.8 Hz, 1H), 9.06 (dd, J = 4.3, 1.6 Hz, 1H), 7.76 (dd, J = 8.1, 4.4 Hz, 1H), 7.74 (dd, J = 7.5, 1.3 Hz, 1H), 7.56-7.40 (m, 6H), 7.34 (t, J = 7.9 Hz, 2H ), 7.29-7.27 (m, 1H), 7.26-7.24 (m, 1H), 7.15-7.12 (m, 2H), 6.87 (d, J = 7.3 Hz, 2H), 6.62 (dd, J = 7.9, 1.5 Hz, 2H), 6.57 (td, J = 7.6, 1.4 Hz, 2H), 6.39 (td, J = 7.8, 1.5 Hz, 2H), 5.84 (dd, J = 8.0, 1.4 Hz, 2H) .APCI-MS (m / z): 629 [M ⁺ ])

Example 5: 2- (4- (9,9-dimethylacridin-10 (9H) -yl) phenyl) -1-phenyl-1H-imidazo [4,5-f] [1,10] phenan Synthesis of Troline (2- (4- (9,9-dimethylacridin-10 (9H) -yl) phenyl) -1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthroline)

Example 5- (1): Synthesis of methyl 2- (phenylamino) benzoate

1.0 g (1.0 eq, 46.9 mmol) of 2- (phenylamino) benzoic acid was placed in a reaction vessel, and then vacuum dried and charged with nitrogen. 60 ml of methanol was added to the reaction vessel, and the mixture was stirred under reflux at a temperature of 60 ° C. While maintaining the temperature, 6.1 ml (2.0 eq, 93.8 mmol) of SOCl ₂ was slowly added dropwise to the reaction vessel, and stirred at reflux for 12 hours at a temperature of 60 ° C. Subsequently, after cooling to room temperature, a saturated sodium bicarbonate solution was added to the reaction vessel to terminate the reaction, and the organic layer was extracted using ethyl acetate and distilled water. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Then column chromatography gave 8.5 g (yield = 80.2%) of compound methyl 2- (phenylamino) benzoate. ( ¹ H NMR (500 MHz, CDCl 3) δ 9.52 (s, 1H), 7.91 (d, J = 8.0 Hz, 1H), 7.26 (t, J = 7.8 Hz, 2H), 7.23-7.19 (m, 3H) , 7.18 (s, 1H), 7.01 (t, J = 7.3 Hz, 1H), 6.70-6.58 (m, 1H), 3.78 (s, 3H))

Example 5- (2): Synthesis of 9,10-dihydro9,9-dimethylacridine (9,10-dihydro-9,9-dimethylacridine)

8.5 g (1.0 eq, 37.4 mmol) of methyl 2- (phenylamino) benzoate prepared in Example 5- (1) were placed in a reaction vessel, vacuum dried, and charged with nitrogen gas. 400 ml of tetrahydrofuran was added to the reaction vessel, and 50 ml (4.0 eq, 149.6 mmol) of methylmagnesium bromide at a concentration of 3.0 M was slowly added dropwise to the reaction vessel, followed by stirring for 3 hours. After the reaction was terminated with an ammonium chloride solution, the organic layer was extracted with ethyl acetate and distilled water and dried. The dried reactant was put together with sulfuric acid in another reaction vessel and stirred at room temperature for 30 minutes. After completion of the reaction, neutralization was performed using an aqueous sodium hydroxide solution, and the organic layer was extracted using distilled water and ethyl acetate. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Thereafter, 4.93 g (yield = 63.0%) of compound 9,10-dihydro9,9-dimethylacridine was obtained through column chromatography. ( ¹ H NMR (500 MHz, CDCl 3) δ 7.38 (d, J = 7.7 Hz, 2H), 7.10 (t, J = 7.2 Hz, 2H), 6.92 (d, J = 6.8 Hz, 2H), 6.69 (d , J = 7.5 Hz, 2H), 6.13 (s, 1H), 1.58 (s, 3H))

Example 5- (3): 10- (4-bromophenyl) -9,10-dihydro-9,9-dimethylacridine (10- (4-bromophenyl) -9,10-dihydro-9, 9-dimethylacridine)

9,10-dihydro9,9-dimethylacridine 3.0 g (1.0 eq, 14.33 mmol) prepared in Example 5- (2), 5.27 g (1.3 eq, 18.63 mmol) of 4-bromoiodobenzene , 0.472 g (0.52 eq, 7.45 mmol) of Cu powder, 0.3 g (0.08 eq, 1.15 mmol) of 18-crown-6 and 7.92 g (4.0 eq, 57.34 mmol) of potassium carbonate were added to the reaction vessel and dried under vacuum. Filled. 20 ml of 1,2-dichlorobenzene was added to the reaction vessel to dissolve the compounds, and the mixture was stirred under reflux for 2 hours at a temperature of 190 ° C. After completion of the reaction, the organic layer was extracted with distilled water and ethyl acetate. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Then column chromatography gave 3.75 g (yield = 71.8%) of 10- (4-bromophenyl) -9,10-dihydro-9,9-dimethylacridine. ( ¹ H NMR (500 MHz, CDCl 3) δ 7.78-7.73 (m, 2H), 7.45 (dd, J = 7.6, 1.6 Hz, 2H), 7.24-7.20 (m, 2H), 7.00-6.91 (m, 4H ), 6.25 (dd, J = 8.1, 1.4 Hz, 2H), 1.70-1.66 (s, 6H))

Example 5- (4): Synthesis of 4- (9,9-dimethylacridin-10 (9H) -yl) benzaldehyde (4- (9,9-dimethylacridin-10 (9H) -yl) benzaldehyde)

3.75 g (1.0 eq, 5.16 mmol) of 10- (4-bromophenyl) -9,10-dihydro-9,9-dimethylacridine obtained in the Example 5- (3) was added to the reaction vessel. After vacuum drying, nitrogen gas was charged. 8 ml of tetrahydrofuran was added to the reaction vessel to dissolve the compound, and the temperature of the reaction vessel was adjusted to -78 ° C using dry ice. While maintaining the temperature, 6.2 ml (1.5 eq, 7.74 mmol) of 1.6 M concentration of n-butyllithium was slowly added dropwise to the reaction vessel, followed by stirring for 90 minutes. 1.2 ml (1.5 eq, 7.74 mmol) of dimethylformamide was added to the reaction vessel, followed by stirring at room temperature for 3 hours. After completion of the reaction, the organic layer was extracted with distilled water and ethyl acetate. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Thereafter, 2.4 g (yield = 74.2%) of compound 4- (9,9-dimethylacridin-10 (9H) -yl) benzaldehyde was obtained through recrystallization with hexane. ( ¹ H NMR (500 MHz, CDCl ₃ ) δ 10.12 (s, 1H), 8.17-8.10 (m, 2H), 7.56-7.52 (m, 2H), 7.51-7.47 (m, 2H), 7.02-6.96 ( m, 4H), 6.36-6.30 (m, 2H), 1.69 (s, 6H))

Example 5- (5): 2- (4- (9,9-dimethylacridin-10 (9H) -yl) phenyl) -1-phenyl-1H-imidazo [4,5-f] [1 , 10] phenanthroline (2- (4- (9,9-dimethylacridin-10 (9H) -yl) phenyl) -1-phenyl-1H-imidazo [4,5-f] [1,10] phenanthroline) Synthesis of

0.5 g (1.0 eq, 2.36 mmol) of 1,10-phenanthroline-5,6-dione obtained in Example 1- (3), 4- (9, 0.74 g (1.0 eq, 2.36 mmol) of 9-dimethylacridin-10 (9H) -yl) benzaldehyde, 1.08 ml (5.0 eq, 11.78 mmol) of aniline, and 2.13 g (12.4 eq, 29.22 mmol) of ammonium acetate Into the reaction vessel and dried under vacuum filled with nitrogen gas. 15.0 ml of acetic acid was added to the reaction vessel to dissolve the compounds, and the mixture was stirred under reflux for 16 hours at a temperature of 130 ° C. After completion of the reaction, neutrality was adjusted using sodium carbonate, washed with distilled water, and the organic layer was extracted with ethyl acetate. Dried over anhydrous magnesium sulfate, filtered through celite and evaporated the solvent. Subsequently, after column chromatography, the compound 2- (4- (9,9-dimethylacridin-10 (9H) -yl) phenyl) -1-phenyl-1H-imidazo [4, 0.5 g (yield = 36.8%) of 5-f] [1,10] phenanthroline were obtained. ( ¹ H-NMR: 9.21 (ddd, J = 9.8, 6.2, 1.8 Hz, 2H), 9.07 (dt, J = 23.2, 11.6 Hz, 1H), 7.91-7.83 (m, 2H), 7.79 (dd, J = 8.1, 4.4 Hz, 1H), 7.74-7.68 (m, 3H), 7.67-7.60 (m, 2H), 7.51 (dd, J = 8.4, 1.6 Hz, 1H), 7.48-7.43 (m, 2H), 7.32 (ddd, J = 8.5, 7.5, 3.1 Hz, 3H), 7.01-6.87 (m, 4H), 6.29-6.17 (m, 2H), 1.36 (dd, J = 17.1, 5.7 Hz, 6H). MS (m / z): 579 [M +])

Experimental Example 1 Measurement of Organic Electroluminescence Characteristics

A glass substrate coated with an indium tin oxide (ITO) thin film was used for OLED manufacturing, and the sheet resistance of the glass substrate was 10 Ω / square and the thickness was 180 nm. The ITO-coated glass was ultrasonically cleaned in an ultrasonic bath in the order of acetone, methyl alcohol, and distilled water, then left in isopropyl alcohol for 20 minutes, first dried using an N ₂ gas gun and then in a convection oven. Second drying was carried out for 10 minutes at a temperature of 110 ℃. The substrate was treated with O ₂ plasma in an Ar atmosphere to remove moisture or organic matter formation from the surface of the substrate. The ITO-coated glass was mounted on a substrate folder of a vacuum deposition apparatus, and (1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) -4, 4'-diamine (NPB) was added. After evacuating until the vacuum in the chamber reached 5.0 × 10 ⁻⁷ Torr, a current was applied to the cell to evaporate the organic layer to deposit a 50 nm thick hole injection layer on the ITO substrate. Then, tris (4-carbazoyl-9-ylphenyl) amine (TCTA) was evaporated under the same conditions to deposit a 10 nm thick hole transport layer. In addition, the organic light emitting compound (1-5) synthesized as in Example 1 was evaporated in the vacuum deposition equipment at a rate of 1.0 μs / sec to deposit a 20 nm thick light emitting layer on the hole transport layer. Later, under similar conditions, 2,2 ', 2''-(1,3,5-benzintril) -tris (1-phenyl-1-H-benzimidazole) (TPBi) and lithium quinolate (Liq) Evaporation was performed sequentially to deposit an electron transport layer and an electron injection layer having a thickness of 30 nm and 2 nm, respectively. All organic materials and metals is high ^vacuum was deposited under (5.0 × 10 ⁷ Torr). Then, an Al cathode was deposited to a thickness of 100 nm using another vacuum deposition equipment to manufacture an OLED.

OLEDs according to this Experimental Example were prepared in the following order: ITO (180 nm) / N, N′-di (1-naphthyl) -N, N′-diphenyl- (1,1′-biphenyl ) -4,4′-diamine (NPB, HIL) (50 nm) / tris (4-carbazoyl-9-ylphenyl) amine (TCTA, HTL) 10 nm / blue fluorescent material 1-5 (20 nm, EML ) / 2,2 ', 2 "-(1,3,5-benzintril) -tris (1-phenyl-1-H-benzimidazole) (TPBi, ETL) (30 nm) / lithium quinolate (Liq , EIL) (2 nm) / Al (100 nm).

The luminescence properties and electroluminescence (EL) spectra of the OLED were measured using a Keithley 2400 source measurement unit and a CS1000A spectrophotometer and the results are shown in Table 1.

The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application.

Claims (12)

An organic light emitting compound represented by Formula 1 below:
[Formula 1]

(In Formula 1,
R ₁ to R ₅ are each independently a single bond, a linear or branched C ₁ -C ₂₀ alkyl which may be substituted, an aryl, halogen, or cyano which may be substituted, C ₆ -C ₂₀ ,
A ₁ is a 5-membered unsaturated or aromatic ring which may be substituted, a 6-membered unsaturated or aromatic ring which may be substituted, a 5-membered unsaturated or aromatic heterocycle which may be substituted and a 6-membered unsaturated or aromatic which may be substituted At least one ring selected from the group consisting of hetero rings, or at least two rings selected from the group are fused polycyclic rings,
n is 0 or 1,
The hetero ring includes one or more selected from the group consisting of N, O and S,
Said substitution is by C ₁ -C ₆ alkyl or C ₆ -C ₂₀ aryl).
The method of claim 1,
R ₁ to R ₅ are each independently a single bond, methyl, phenyl which may be substituted, biphenyl, chrysene, phenanthrene, naphthyl, fluorenyl, quinoline, perylene, pyrene, halogen, cyano And combinations thereof.
Wherein said substitution is substituted by linear or branched C ₁ -C ₂₀ alkyl.
The method of claim 1,
A ₁ is phenoxazine, phenoxyazine, dimethylacridine, diphenylacridine, carbazole, phenyl, biphenyl, naphthalene, fluorene, anthracene, phenanthrene, pyrene, fluoranthene, Organic, comprising a substance selected from the group consisting of sen, benzofluoranthene, perylene, quinoline, indenoanthracene, indenophenanthrene, hydroanthracene, dibenzothiophene, dibenzofuran and combinations thereof Luminescent compounds.

The method of claim 1,
The organic light emitting compound is any one of the following compounds, an organic light emitting compound:

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A method for preparing an organic light emitting compound according to claim 1 comprising reacting a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, and a phenanthroline derivative in the presence of an ammonium salt:
[Formula 2]

[Formula 3]

(In Chemical Formulas 2 and 3,
R ₁ to R ₅ are each independently a single bond, a linear or branched C ₁ -C ₂₀ alkyl which may be substituted, an aryl, halogen, or cyano which may be substituted, C ₆ -C ₂₀ ,
A ₁ is a 5-membered unsaturated or aromatic ring which may be substituted, a 6-membered unsaturated or aromatic ring which may be substituted, a 5-membered unsaturated or aromatic heterocycle which may be substituted and a 6-membered unsaturated or aromatic which may be substituted At least one ring selected from the group consisting of hetero rings, or at least two rings selected from the group are fused polycyclic rings,
n is 0 or 1,
The hetero ring includes one or more selected from the group consisting of N, O and S,
Said substitution is by C ₁ -C ₆ alkyl or C ₆ -C ₂₀ aryl).
The method of claim 5, wherein
R ₁ to R ₅ are each independently a single bond, methyl, phenyl which may be substituted, biphenyl, chrysene, phenanthrene, naphthyl, fluorenyl, quinoline, perylene, pyrene, halogen, cyano And combinations thereof.
Wherein said substitution is substituted by linear or branched C ₁ -C ₂₀ alkyl.
The method of claim 5, wherein
A ₁ is phenoxazine, phenoxyazine, dimethylacridine, diphenylacridine, carbazole, phenyl, biphenyl, naphthalene, fluorene, anthracene, phenanthrene, pyrene, fluoranthene, Organic, comprising a material selected from the group consisting of sen, benzofluoranthene, perylene, quinoline, indenoanthracene, indenophenanthrene, hydroanthracene, dibenzothiophene, dibenzofuran and combinations thereof Method for producing a luminescent compound.
The method of claim 5, wherein
The phenanthroline derivative includes 1,10-phenanthroline-5,6-dione (1,20-phenanthroline-5,6-dione), a method for producing an organic light emitting compound.
The method of claim 5, wherein
The ammonium salt includes ammonium salt selected from the group consisting of ammonium acetate, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, ammonium cyanide, ammonium nitrate, ammonium sulfate, ammonium carbonate and combinations thereof , Manufacturing method of organic light emitting compound.
The method of claim 5, wherein
The reaction is carried out under a solvent, a method for producing an organic light emitting compound.
The method of claim 10,
The solvent may be acetic acid, water, ethanol, methanol, propanol, butanol, hexane, methylene chloride, ethyl acetate, propylene glycol, butylene glycol, dipropylene glycol, glycerin, ketone, acetone, dimethyl sulfoxide, dimethylformamide, toluene, A method for producing an organic light emitting compound, comprising a solvent consisting of tetrahydrofuran, dichloromethane, acetonitrile and combinations thereof.
An organic electroluminescent device comprising the organic light emitting compound according to any one of claims 1 to 4.

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