KR102438617B1 - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention is an organic light emitting compound represented by the following [Formula I], and when it is employed in the light emitting layer, it is possible to realize an organic light emitting device having very excellent light emitting properties such as light emitting efficiency.
[Formula Ⅰ]

Description

An electroluminescent compound and an electroluminescent device comprising the same

The present invention relates to an organic light emitting compound, and more particularly, to an organic light emitting compound employed in an organic material layer in an organic light emitting device, and an organic light emitting device having significantly improved light emitting characteristics such as luminous efficiency by employing the same.

Organic electroluminescent devices can be formed on transparent substrates as well as low voltage driving of 10 V or less compared to plasma display panels or inorganic electroluminescent (EL) displays, and power consumption is relatively low. It has the advantage of excellent color and can display three colors of green, blue, and red.

However, in order for such an organic light emitting device to exhibit the above characteristics, a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, and an electron blocking material, which are materials constituting the organic layer in the device, are stable and efficient. Supported by materials should be preceded, but the development of stable and efficient organic layer materials for organic light emitting devices has not yet been sufficiently developed. Therefore, the development of a new material capable of improving light-emitting characteristics and the development of an organic material layer structure in a device are continuously required.

Accordingly, an object of the present invention is to provide a novel organic light emitting compound that is employed as a light emitting layer compound in an organic light emitting device to significantly improve light emitting characteristics such as luminous efficiency, and an organic light emitting device including the same.

In order to solve the above problems, the present invention provides an organic light emitting compound represented by the following [Formula I] and an organic electroluminescent device comprising the same.

[Formula Ⅰ]

The specific structure and substituents of the [Formula I] will be described later.

The organic light emitting device employing the organic light emitting compound according to the present invention in the light emitting layer has significantly superior light emitting characteristics such as luminous efficiency compared to conventional devices, and thus can be usefully used in various display devices.

1 is a representative view showing the structure of an organic light emitting compound according to the present invention.

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

The present invention is an organic light emitting compound represented by the following [Formula I], and when employed in the light emitting layer in the organic light emitting device, it is possible to realize an organic light emitting device with significantly improved light emitting characteristics such as luminous efficiency.

[Formula Ⅰ]

In the above [Formula I],

X is any one selected from O, S, NR ₃ , BR ₄ , R ₅ -CR ₆ , R ₇ -Si-R ₈ , R ₉ -Ge-R ₁₀ and R ₁₁ -Se-R ₁₂ , wherein R ₃ to R ₁₂ are each independently selected from hydrogen, a substituted or unsubstituted C 1 to C 6 alkyl group, and a substituted or unsubstituted C 6 to C 20 aryl group.

R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 1 to C 24 alkoxy group A substituted or unsubstituted C 3 to C 30 of a cycloalkyl group, a substituted or unsubstituted C1-C24 alkylsilyl group, a substituted or unsubstituted C1-C24 arylsilyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted A heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms in which one or more substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms is fused, a substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms Among a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, and a heteroarylamino group having 6 to 24 carbon atoms in which one or more alkyl is fused is chosen

According to a specific embodiment, the organic light-emitting compound according to the present invention is characterized in that X is O, wherein R ₁ and R ₂ are the same as or different from each other, and each of the following [Structural Formula 1] to [Structural Formula 2] It may be any one selected.

[Structural Formula 1]

[Structural Formula 2]

In the [Structural Formula 1] to [Structural Formula 3],

L is a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted carbazolylene group, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms A substitution in which one or more substituted or unsubstituted arylene groups having 6 to 50 carbon atoms and substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms are fused to one or more ene groups, substituted or unsubstituted cycloalkyls having 3 to 30 carbon atoms are fused or an unsubstituted heteroarylene group having 2 to 50 carbon atoms (n is an integer of 1 to 3).

Ar ₁ to Ar ₃ are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 An aryl group, a substituted or unsubstituted C 2 to C 50 heteroaryl group, a substituted or unsubstituted substituted or unsubstituted C 6 to C 50 aryl group fused with one or more substituted or unsubstituted C 3 to C 30 cycloalkyl, and a substituted or unsubstituted It is selected from a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms in which at least one cyclic cycloalkyl having 3 to 30 carbon atoms is fused.

Wherein Ar ₁ To Ar ₂ Are bonded to each other or connected to adjacent substituents to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, S And it may be substituted with any one or more heteroatoms selected from O.

The organic light emitting compound according to the present invention has excellent light emitting characteristics such as long lifespan and luminous efficiency in the organic light emitting device employing it in the organic material layer due to the structure of the skeleton and the characteristics of the introduced substituents as described above.

On the other hand, in the definition of R ₁ to R ₁₂ , L and Ar ₁ to Ar ₃ , substituted or unsubstituted means R ₁ to R ₁₄ , L and Ar ₁ to Ar ₃ are deuterium, cyano group, halogen group, hydroxyl group, Nitro group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C1-C24 alkenyl group, C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group , C6-C24 arylalkyl group, C2-C24 heteroaryl group, or C2-C24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 aryl It is selected from the group consisting of an amino group, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 1 to 24 carbon atoms, and an aryloxy group having 1 to 24 carbon atoms, and selected from one or two or more substituents. It means that it is substituted, or is substituted with a substituent to which two or more of the substituents are connected, or does not have any substituents.

For specific examples, the substituted aryl group means that a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, etc. are substituted with other substituents do.

The substituted heteroaryl group includes a pyridyl group, a thiophenyl group, a triazine group, a quinoline group, a phenanthroline group, an imidazole group, a thiazole group, an oxazole group, a carbazole group and a condensed heterocyclic group thereof, such as a benzquinoline group, a benz It means that an imidazole group, a benzoxazole group, a benzthiazole group, a benzcarbazole group, a dibenzothiophenyl group, a dibenzofuran group, etc. are substituted with other substituents.

In the present invention, examples of the substituents will be described in detail below, but the present invention is not limited thereto.

In the present invention, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, and the like, but is not limited thereto.

Specific examples of the aryloxy group used in the present invention include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, indenyloxy, and the like, and at least one hydrogen atom contained in the aryloxy group. is further substitutable.

Specific examples of the silyl group used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl and the like.

In the present invention, the aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 30. Examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and a stilbene group, and examples of the polycyclic aryl group include a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, tetracenyl group. , chrysenyl group, fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthrene group, etc., but the scope of the present invention is not limited to these examples.

In addition, the aryl group may also be further substituted with one or more substituents, and more specifically, at least one hydrogen atom of the aryl group is a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH(R), -N(R')(R"), R' and R" are each independently an alkyl group having 1 to 10 carbon atoms, in this case referred to as an "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C1-C24 alkenyl group, C1-C24 alkynyl group, C1-C24 hetero It may be substituted with an alkyl group, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, a heteroarylalkyl group having 2 to 24 carbon atoms, or the like.

In the present invention, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 20. Specific examples include a vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1 -Butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but are not limited thereto.

In the present invention, the heteroaryl group is a heterocyclic group containing O, N, or S as a heteroatom, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 30 carbon atoms. Examples include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole group, an acridyl group , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuranyl group, phenanthroline group, thiazolyl group, iso An oxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and the like, but are not limited thereto.

In the present invention, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohex Sil group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclo There is an octyl group, and the like, but is not limited thereto.

등이 있다.In the present invention, the fluorenyl group is a structure in which two ring organic compounds are connected through one atom, for example,

etc.

등이 있다.In the present invention, the fluorenyl group includes a structure of an open fluorenyl group, wherein the open fluorenyl group is a structure in which one ring compound is disconnected in a structure in which two ring organic compounds are connected through one atom. , for example

etc.

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

Specific examples of the arylamine group include a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 3-methyl-phenylamine group, a 4-methyl-naphthylamine group, and a 2-methyl-biphenyl group. an amine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenyl naphthylamine group, a ditolylamine group, a phenyltolylamine group, a carbazole group, and a triphenylamine group, but is not limited thereto.

In the present invention, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heterocyclic group described above.

In the present invention, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In addition, various specific examples of the substituent according to the present invention can be clearly identified through the specific compounds described below.

The organic light emitting compound according to the present invention represented by the above [Formula I] can be used as an organic material layer of an organic light emitting device due to its structural specificity as described above, and more specifically, the characteristics of various substituents introduced into the characteristic skeleton. Accordingly, it may be used as a host compound or a dopant compound in the emission layer.

Preferred specific examples of the compound represented by [Formula I] according to the present invention include [Compound 1] to [Compound 178], and the scope of the present invention is not limited thereto.

By introducing various substituents into the core structure of the structure as described above, an organic light emitting compound having intrinsic properties of the introduced substituents can be synthesized. For example, by introducing a substituent used for the hole injection layer material, the hole transport layer material, the light emitting layer material, the electron transport layer material and the electron blocking layer material used in the manufacture of the organic light emitting device into the structure, the conditions required for each organic material layer are satisfied. A material can be prepared, and in particular, when the compound of [Formula I] according to the present invention is employed as the light emitting layer material, light emitting properties such as light emitting efficiency of the device can be further improved.

The organic light emitting compound according to the present invention can be applied to an organic light emitting device according to a conventional manufacturing method.

The organic electroluminescent device according to an embodiment of the present invention may have a structure including a first electrode and a second electrode and an organic material layer disposed therebetween, and the organic light emitting compound according to the present invention is used in the organic material layer of the device It may be manufactured using conventional device manufacturing methods and materials, except that

The organic material layer of the organic electroluminescent device according to the present invention may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, and the like. However, the present invention is not limited thereto and may include a smaller number or a larger number of organic material layers.

Accordingly, in the organic electroluminescent device according to the present invention, the organic material layer may include at least one of a hole transport layer, an electron blocking layer, and a light emitting layer, and at least one of the layers is organic light emitting represented by the [Formula I] compounds may be included.

In addition, the organic light emitting device according to the present invention uses a PVD (physical vapor deposition) method, such as sputtering or e-beam evaporation, to form a metal or a conductive metal oxide or an alloy thereof on a substrate. It can be prepared by depositing an anode to form an anode, forming an organic material layer including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic layer is formed using a variety of polymer materials by a solvent process rather than a vapor deposition method, for example, spin coating, dip coating, doctor blading, screen printing, inkjet printing, or a thermal transfer method using a smaller number of methods. It can be made in layers.

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc. Metal oxides, combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT) , a conductive polymer such as polypyrrole and polyaniline, but is not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof, and multilayers such as LiF/Al or LiO ₂ /Al Structural materials and the like, but are not limited thereto.

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is suitable, and a material having high hole mobility is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The light-emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole and There are benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, rubrene, and the like, but is not limited thereto.

As the electron transport material, a material capable of well injecting electrons from the cathode and transferring them to the light emitting layer, and a material having high electron mobility is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline, a complex including Alq ₃ , an organic radical compound, and a hydroxyflavone-metal complex.

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

In addition, the organic light emitting compound according to the present invention can act on a principle similar to that applied to the organic light emitting device in an organic electronic device including an organic solar cell, an organic photoreceptor, an organic transistor, and the like.

Hereinafter, synthesis examples and device examples of preferred compounds are provided to help the understanding of the present invention. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereby.

Synthesis example 1: Synthesis of compound 2

(One) production example 1: Synthesis of Intermediate 2-1

1,1'-binaphthyl-2,2'-diol (10 g, 0.035 mol, sigma aldrich), p-TsOH (6.01 g, 0.035 mmol, sigma aldrich), 250 mL of Tol were added and stirred at 100 °C for 12 hours. and reacted. After completion of the reaction, extraction was performed using an aqueous calcium carbonate solution and EA, followed by column purification (N-HEXANE: EA) to obtain 6.6 g (yield 70.4%) of <Intermediate 2-1>.

(2) production example 2: Synthesis of intermediate 2-2

Intermediate 2-1 (10 g, 0.037 mol), 200 mL of chloroform was added, and after cooling to 0 °C, bromine (12.51 g, 0.078 mol, sigma aldrich) was slowly added dropwise, and the reaction was stirred at room temperature for 12 hours. After completion of the reaction, bromine was removed using 2M aqueous NaOH solution, and the resulting solid was filtered to obtain 13.8 g (yield 86.9%) of <Intermediate 2-2>.

(3) production example 3: Synthesis of intermediate 2-3

Methyl 2-iodobenzoate (10 g, 0.038 mol, sigma aldrich), Bis(pinacolato)diboron (11.63 g, 0.046 mol, sigma aldrich), potassium acetate (7.49 g, 0.076 mol, sigma aldrich), PdCl ₂ (dppf) ( 0.84 g, 0.0011 mol, sigma aldrich) and 1,4-Dioxane (200 mL) were added, and the reaction was stirred at 95 °C for 12 hours. After completion of the reaction, H ₂ 0 was added, the layers were separated, and column purification (N-HEXANE: MC) was performed to obtain 7.4 g (yield 74%) of <Intermediate 2-3>.

(4) production example 4: Synthesis of Intermediate 2-4

Intermediate 2-2 (10 g, 0.0235 mol), Intermediate 2-3 (13.53 g, 0.052 mol), potassium carbonate (12.97 g, 0.094 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (1.36 g, 0.0012 mol, sigma aldrich), THF 200 mL, H ₂ O 40 mL, and reacted by stirring under reflux for 6 hours. After completion of the reaction, extraction was performed using H ₂ 0: EA, followed by column purification (N-HEXANE: EA) to obtain 9.9 g (yield 78.6%) of <Intermediate 2-4>.

(5) production example 5: Synthesis of intermediate 2-5

Intermediate 2-4 (10 g, 0.0186 mol), 200 mL of THF were added, methylmagnesium chloride solution was slowly added dropwise at 0 °C, stirred for 1 hour, and then slowly raised to room temperature and stirred for 10 hours to react. The reaction was terminated using 1N HCl, and after extraction with EA, the organic layer was purified by column (N-HEXANE: EA) to obtain 7.8 g (yield 78%) of <Intermediate 2-5>.

(6) production example 6: Synthesis of intermediate 2-6

Intermediate 2-5 (10 g, 0.0186 mol) and 250 mL of AcOH were stirred at 0° C. for 10 minutes, and 400 mL of phosphoric acid was added, followed by stirring at room temperature for 2 hours. After completion of the reaction, the reaction was neutralized with NaOH, extracted using H ₂ O:EA, and purified by column (N-HEXANE:EA) to obtain 7.2 g of <Intermediate 2-6> (yield 77.2%).

(7) production example 7: Synthesis of intermediate 2-7

Intermediate 2-6 (10 g, 0.020 mol), 200 mL of chloroform was added, and after cooling to 0 ° C, Bromine (6.70 g, 0.042 mol, sigma aldrich) was slowly added dropwise, and the reaction was stirred at room temperature for 12 hours. After completion of the reaction, bromine was removed using 2M aqueous NaOH solution, and the resulting solid was filtered to obtain 11 g (yield 83.6%) of <Intermediate 2-7>.

(8) production example 8: Synthesis of compound 2

Intermediate 2-7 (10 g, 0.0152 mol), phenylboronic acid (4.07 g, 0.0334 mol, sigma aldrich), potassium carbonate (8.40 g, 0.061 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (0.88 g, 0.0008 mol) , sigma aldrich), Tol 200 mL, EtOH 40 mL, H ₂ O 20 mL, and reacted by stirring under reflux for 6 hours. After completion of the reaction, layer separation was performed using H20:EA and column purification (N-HEXANE:EA) was performed to obtain 8 g of Compound 2 (yield 80.7%).

H-NMR (200 MHz, CDCl3): δ ppm, 2H (8.15/d, 7.83/s, 7.69/d, 7.41/m) 4H (8.55/d, 7.55/m, 7.52/d, 7.51/m) 12H ( 1.78/s)

LC/MS: m/z=652 [(M+1) ⁺ ]

Synthesis example 2: Synthesis of compound 40

(One) production example 1: Synthesis of intermediate 40-1

Intermediate 2-7 (10 g, 0.0152 mol), phenylboronic acid (2.22 g, 0.018 mol, sigma aldrich), potassium carbonate (5.25 g, 0.038 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (0.88 g, 0.0008 mol) , sigma aldrich), Tol 200 mL, EtOH 40 mL, H ₂ O 20 mL, and reacted by stirring under reflux for 6 hours. After completion of the reaction, layer separation was performed using H ₂ 0: EA, followed by column purification (N-HEXANE: EA) to obtain 8 g (yield 80.3%) of <Intermediate 40-1>.

(2) production example 2: Synthesis of compound 40

Intermediate 40-1 (10 g, 0.015 mol), dibenzo[b,d]furan-2-ylboronic acid (3.88 g, 0.018 mol, Yurui), potassium carbonate (5.27 g, 0.038 mol, sigma aldrich), Pd(PPh) ₃ ) ₄ (0.88 g, 0.0008 mol, sigma aldrich), 200 mL of Tol, 40 mL of EtOH, and 20 mL of H ₂ O were put, and the reaction was stirred under reflux for 6 hours. After completion of the reaction, layer separation was performed using H ₂ 0: EA, followed by column purification (N-HEXANE: EA) to obtain 9.3 g of compound 40 (yield 82%).

H-NMR (200 MHz, CDCl3): δ ppm, 1 (7.89/d, 7.81/d, 7.72/d, 7.71/s, 7.66/d, 7.41/m, 7.38/m, 7.32/m) 2H (8.15/m) d, 7.83/s, 7.69/d, 7.52/d, 7.51/m) 4H (8.55/d, 7.55/m) 12H (1.78/s)

LC/MS: m/z=742 [(M+1) ⁺ ]

Synthesis example 3: Synthesis of compound 76

(One) production example 1: Synthesis of Intermediate 76-1

Intermediate 2-6 (10 g, 0.020 mol), 200 mL of chloroform was added, and after cooling to 0 °C, Bromine (3.51 g, 0.022 mol, sigma aldrich) was slowly added dropwise and reacted by stirring at room temperature for 12 hours. After completion of the reaction, bromine was removed using 2M aqueous NaOH solution, and the resulting solid was filtered to obtain 9.6 g (yield 82.9%) of <Intermediate 76-1>.

(2) production example 2: Synthesis of intermediate 76-2

3-bromo-9-phenyl-9H-carbazole (10 g, 0.031 mol, TCI), Bis(pinacolato)diboron (10.25 g, 0.040 mol, sigma aldrich), potassium acetate (6.09 g, 0.062 mol, sigma aldrich), PdCl ₂ (dppf) (0.68 g, 0.0009 mol, sigma aldrich), 200 mL of 1,4-Dioxane was added, and the reaction was stirred at 95 °C for 12 hours. After completion of the reaction, H ₂ 0 was added, the layers were separated, and column purification was performed (N-HEXANE: MC) to obtain 9 g (yield 78.5%) of <Intermediate 76-2>.

(3) production example 3: Synthesis of compound 76

Intermediate 76-1 (10 g, 0.017 mol), Intermediate 76-2 (7.65 g, 0.021 mol), potassium carbonate (7.15 g, 0.052 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (1.00 g, 0.0009 mol, sigma aldrich), toluene 150 mL, EtOH 30 mL, H ₂ O 15 mL, and reacted by stirring under reflux for 8 hours. After completion of the reaction, layer separation was performed using H ₂ 0: EA, followed by column purification (N-HEXANE: EA) to obtain 10.4 g of compound 76 (yield 81.24%).

H-NMR (200 MHz, CDCl3): δ ppm, 1H (8.15/d, 8.09/d, 7.94/d, 7.87/d, 7.83/s, 7.77/s, 7.61/d, 7.45/m, 7.44/m, 7.33/m, 7.25/m, 7.24/m) 2H (7.69/d, 7.58/m, 7.50/d) 4H (7.55/m) 5H (8.55/d) 12H (1.78/s)

LC/MS: m/z=741 [(M+1) ⁺ ]

Synthesis example 4: Synthesis of compound 83

(One) production example 1: Synthesis of Intermediate 83-1

1-bromo-4-tert-butylbenzene (10 g, 0.031 mol, sigma aldrich), 4-tert-butylaniline (7.60 g, 0.037 mol, sigma aldrich), Sodium tert-butoxide (9.02 g, 0.094 mol, sigma aldrich) , 150 mL of toluene was added to the catalyst Pd(dba) ₂ (1.35 g, 0.0023 mol, sigma aldrich), tri-tert-Bu-phosphine (0.95 g, 0.0047 mol, sigma aldrich), and stirred at 100 °C for 1 hour to react did it After completion of the reaction, the layers were separated in H ₂ 0: MC and then column purified (N-HEXANE: EA) to obtain 10.3 g (yield 78%) of <Intermediate 83-1>.

(2) production example 2: Synthesis of compound 83

Intermediate 2-7 (10 g, 0.015 mol), Intermediate 83-1 (7.33 g, 0.033 mol), Sodium tert-butoxide (4.38 g, 0.046 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.44 g, 0.0008) mol, sigma aldrich), tri-tert-Bu-phosphine (0.31 g, 0.0015 mol, sigma aldrich) was added with 200 mL of toluene and stirred at 100 °C for 1 hour to react. After completion of the reaction, 11.6 g (yield 81.67%) of compound 83 was obtained by performing column purification (N-HEXANE: EA) after layer separation in H ₂ 0:MC.

H-NMR (200 MHz, CDCl3): δ ppm, 2H (7.84/d, 6.81/s, 6.64/d) 4H (8.55/d, 7.55/m) 8H (7.01/d, 6.55/d) 12H (1.78/d) s) 36H (1.35/s)

LC/MS: m/z=1058[(M+1) ⁺ ]

Synthesis example 5: Synthesis of compound 103

(One) production example 1: Synthesis of Intermediate 103-1

2-bromonaphthalene (10 g, 0.048 mol, sigma aldrich), aniline (6.3 g, 0.0676 mol, sigma aldrich), sodium tert-butoxide (9.28 g, 0.096 mol, sigma aldrich), catalyst Pd(dba) ₂ (1.39 g) , 0.0024 mol, sigma aldrich), tri-tert-Bu-phosphine (0.98 g, 0.0048 mol, sigma aldrich) was added with 150 mL of toluene, followed by stirring at 100 °C for 1 hour. After completion of the reaction, layer separation was performed on H ₂ 0: MC, followed by column purification (N-HEXANE: EA) to obtain 8.4 g (yield 79.3%) of <Intermediate 103-1>.

(2) production example 2: Synthesis of compound 103

Intermediate 2-7 (10 g, 0.015 mol), Intermediate 103-1 (7.33 g, 0.033 mol), Sodium tert-butoxide (4.38 g, 0.046 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.44 g, 0.0008) mol, sigma aldrich), tri-tert-Bu-phosphine (0.31 g, 0.0015 mol, sigma aldrich) was added with 200 mL of toluene and stirred at 100 °C for 1 hour to react. After completion of the reaction, 11.3 g (yield 79.56%) of compound 103 was obtained by performing column purification (N-HEXANE: EA) after layer separation in H ₂ 0:MC.

H-NMR (200 MHz, CDCl3): δ ppm, 2H (8.07/d, 8.02/d, 7.84/d, 7.57/d, 7.54/m, 7.53/m, 7.38/m, 6.98/d, 6.64/d) 4H (8.55/d, 7.55/m, 7.20/m, 6.81/m, 6.63/d) 12H (1.78/s)

LC/MS: m/z=934 [(M+1) ⁺ ]

Synthesis example 6: Synthesis of compound 131

(One) production example 1: Synthesis of intermediate 131-1

4-bromodibenzo[b,d]furan (10 g, 0.040 mol, sigma aldrich), 3,5-dimethylaniline (5.89 g, 0.0486 mol, sigma aldrich), Sodium tert-butoxide (7.78 g, 0.081 mol, sigma aldrich) , Toluene 200 mL was added to the catalyst Pd(dba) ₂ (1.16 g, 0.0020 mol, sigma aldrich), tri-tert-Bu-phosphine (0.82 g, 0.004 mol, sigma aldrich) and stirred at 100 °C for 1 hour to react did it After completion of the reaction, layer separation was carried out in H ₂ 0: MC, followed by column purification (N-HEXANE: EA) to obtain 9.4 g (yield 80.8%) of <Intermediate 131-1>.

(2) production example 2: Synthesis of compound 131

Intermediate 2-7 (10 g, 0.015 mol), Intermediate 131-1 (9.60 g, 0.033 mol), Sodium tert-butoxide (4.38 g, 0.046 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.44 g, 0.0008) mol, sigma aldrich), tri-tert-Bu-phosphine (0.31 g, 0.0015 mol, sigma aldrich) was added with 200 mL of toluene and stirred at 100 °C for 1 hour to react. After completion of the reaction, H ₂ 0: After layer separation in MC, column purification (N-HEXANE: EA) was performed to obtain 13 g of Compound 131 (yield 79.9%).

H-NMR (200 MHz, CDCl3): δ ppm, 2H (7.89/d, 7.84/d, 7.66/d, 7.38/m, 7.32/m, 7.25/d, 7.07/m, 6.81/s, 6.71/s, 6.64/d, 6.39/d) 4H (8.55/d, 7.55/m, 6.36/d) 12H (2.34/s, 1.78/s)

LC/MS: m/z=1070[(M+1) ⁺ ]

Synthesis example 7: Synthesis of compound 153

(One) production example 1: Synthesis of intermediate 153-1

4-bromo-2-methylbiphenyl (10 g, 0.040 mol, Alfa), p-toluidine (5.20 g, 0.0486 mol, sigma aldrich), Sodium tert-butoxide (7.78 g, 0.081 mol, sigma aldrich), catalyst Pd (dba ) ₂ (1.16 g, 0.0020 mol, sigma aldrich), tri-tert-Bu-phosphine (0.82 g, 0.004 mol, sigma aldrich) was added with 200 mL of toluene, followed by stirring at 100 °C for 1 hour. After completion of the reaction, H ₂ 0: After layer separation in MC, column purification (N-HEXANE: EA) was performed to obtain 9 g (yield 81.36%) of <Intermediate 153-1>.

(2) production example 2: Synthesis of compound 153

Intermediate 2-7 (10 g, 0.015 mol), Intermediate 153-1 (9.13 g, 0.033 mol), Sodium tert-butoxide (4.38 g, 0.046 mol, sigma aldrich), Catalyst Pd(dba) ₂ (0.44 g, 0.0008) mol, sigma aldrich), tri-tert-Bu-phosphine (0.31 g, 0.0015 mol, sigma aldrich) was added with 200 mL of toluene and stirred at 100 °C for 1 hour to react. After completion of the reaction, 12.7 g (yield 80.15%) of compound 153 was obtained by performing column purification (N-HEXANE: EA) after layer separation in H ₂ 0:MC.

H-NMR (200 MHz, CDCl3): δ ppm, 2H (7.84/d, 7.42/d, 7.41/m, 6.81/s, 6.64/d, 6.61/s, 6.50/d) 4H (8.55/d, 7.55/d) m, 7.52/d, 7.51/m, 6.98/d, 6.51/m) 6H (2.59/s, 2.34/s) 12H (1.78/s)

LC/MS: m/z=1070[(M+1) ⁺ ]

device embodiment

In an embodiment according to the present invention, the ITO transparent electrode is patterned so that the light emitting area is 2 mm × 2 mm on a glass substrate of 25 mm × 25 mm × 0.7 mm, using an ITO glass substrate to which an ITO transparent electrode is attached. and then washed. After the substrate was mounted in a vacuum chamber, the base pressure was set to 1 × 10 ^-6 torr, and the organic material and the metal were deposited on the ITO in the following structure.

Device Examples 1 to 10

By using the compound implemented according to the present invention as a compound of the light emitting layer, a blue light emitting organic light emitting device having the following device structure was manufactured, and light emitting properties including light emitting efficiency were measured.

ITO / hole injection layer (HAT_CN 5 nm) / hole transport layer (α-NPB 100 nm) / electron blocking layer (TCTA 10 nm) / light emitting layer (20 nm) / electron transport layer (201:Liq 30 nm) / LiF (1 nm) / Al (100 nm)

In order to form a hole injection layer on the ITO transparent electrode, the thickness of the hole injection layer was formed by vacuum thermal evaporation to 5 nm using HAT_CN, and then the hole transport layer was formed using α-NPB. The electron blocking layer was formed of TCTA with a thickness of 10 nm. In addition, as the host compound in the light emitting layer, Chemical Formulas 2, 6, 11, 24, 32, 40, 60, 65, 74, 76 according to the present invention are used, and the dopant compound is [BD1] and has a thickness of 20 nm. 30 nm of an electron transport layer (50% doping of the compound Liq below), 1 nm of LiF, and 100 nm of aluminum were further deposited by vapor deposition to prepare an organic electroluminescent device.

Device Comparative Example 1

An organic electroluminescent device for Device Comparative Example 1 was manufactured in the same manner as in Example 1, except that BH1 was used instead of the compound according to the present invention as a light emitting layer compound in the device structure of Example 1.

Experimental Example 1: Light emitting properties of Device Examples 1 to 10

For the organic electroluminescent device manufactured according to the above example, voltage, current and luminous efficiency were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and a current density of 10 mA/ The voltage in cm 2 was defined as “driving voltage” and compared, and the results are shown in [Table 1] below.

Example light emitting layer V cd/A QE (%) CIEx CIEy One Formula 2 4.20 7.42 5.86 0.144 0.154 2 Formula 6 4.18 7.50 5.93 0.145 0.155 3 Formula 11 4.18 7.45 5.88 0.144 0.155 4 Formula 24 4.21 7.52 5.94 0.145 0.154 5 Formula 32 4.24 7.44 5.88 0.145 0.155 6 Formula 40 4.20 7.41 5.85 0.144 0.155 7 Formula 60 4.24 7.36 5.81 0.145 0.154 8 Formula 65 4.20 7.43 5.87 0.144 0.154 9 Formula 74 4.25 7.38 5.82 0.145 0.155 10 Formula 76 4.23 7.46 5.89 0.145 0.154 Comparative Example 1 BH1 4.24 5.2 4.54 0.147 0.156

Looking at the results shown in [Table 1], first, when the compound according to the present invention is employed as a host compound in the light emitting layer of the device, the light emitting properties such as luminous efficiency and quantum efficiency are significantly superior to those of the conventional device (Comparative Example 1). can confirm.

[HAT_CN] [α-NPB] [BH1] [BD1] [201]

[TCTA]

Device Examples 11 to 20

Using the compound according to the present invention as the compound of the light emitting layer, a blue light emitting organic light emitting device having the following device structure was manufactured, and light emitting properties including light emitting efficiency were measured.

ITO / hole injection layer (HAT_CN 5 nm) / hole transport layer (α-NPB 100 nm) / electron blocking layer (TCTA 10 nm) / light emitting layer (20 nm) / electron transport layer (201:Liq 30 nm) / LiF (1 nm) ) / Al (100 nm)

In order to form a hole injection layer on the ITO transparent electrode, the thickness of the hole injection layer was formed by vacuum thermal evaporation to 5 nm using HAT_CN, and then the hole transport layer was formed using α-NPB. The electron blocking layer was formed of TCTA with a thickness of 10 nm. In addition, [BH1] is used as the host compound in the light emitting layer, and the dopant compound has a thickness of 20 nm using Chemical Formulas 83, 88, 98, 103, 116, 131, 147, 153, 164, and 176 according to the present invention. 30 nm of an electron transport layer (50% doping of the compound Liq below), 1 nm of LiF, and 100 nm of aluminum were further deposited by vapor deposition to prepare an organic electroluminescent device.

Device Comparative Example 2

An organic electroluminescent device for Device Comparative Example 2 was manufactured in the same manner as in Example 11, except that BD1 was used instead of the compound according to the present invention as a light emitting layer compound in the device structure of Example 11.

Experimental Example 2: Light emitting properties of device Examples 11 to 20

For the organic electroluminescent device manufactured according to the above example, voltage, current and luminous efficiency were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and a current density of 10 mA/ The voltage in cm 2 was defined as “driving voltage” and compared, and the results are shown in [Table 2] below.

Example Emissive layer dopant V cd/A lm/w luminous color One Formula 83 4.20 8.11 6.06 blue 2 Formula 88 4.23 7.88 5.85 blue 3 Formula 98 4.21 7.93 5.91 blue 4 Formula 103 4.19 7.91 5.93 blue 5 Formula 116 4.22 7.98 5.94 blue 6 Formula 131 4.26 7.80 5.75 blue 7 chemical formula 147 4.23 7.84 5.82 blue 8 Formula 153 4.19 8.01 6.00 blue 9 Formula 164 4.22 7.92 5.89 blue 10 Formula 176 4.24 7.86 5.82 blue Comparative Example 2 BD1 4.25 5.20 3.84 blue

Looking at the results shown in [Table 2], first, when the compound according to the present invention is employed as a dopant compound in the light emitting layer of the device, the light emitting properties such as luminous efficiency and quantum efficiency are significantly higher than that of the conventional device (Comparative Example 2). excellence can be seen.

Claims (8)

An organic light emitting compound represented by the following [Formula I]:
[Formula Ⅰ]

In the [Formula I],
X is any one selected from O, S, NR ₃ , BR ₄ , R ₅ -CR ₆ , R ₇ -Si-R ₈ , R ₉ -Ge-R ₁₀ and R ₁₁ -Se-R ₁₂ , wherein R ₃ to R ₁₂ are each independently selected from hydrogen, a substituted or unsubstituted C 1 to C 6 alkyl group and a substituted or unsubstituted C 6 to C 20 aryl group,
R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 1 to C 24 alkoxy group A substituted or unsubstituted C 3 to C 30 of a cycloalkyl group, a substituted or unsubstituted C1-C24 alkylsilyl group, a substituted or unsubstituted C1-C24 arylsilyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted A heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms in which one or more substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms is fused, a substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms Among a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, and a heteroarylamino group having 6 to 24 carbon atoms in which one or more alkyl is fused is chosen The method of claim 1,
Wherein R ₁ And R ₂ Are the same as or different from each other, and each organic light emitting compound, characterized in that any one selected from the following [Structural Formula 1] to [Structural Formula 2]:
[Structural Formula 1]

[Structural Formula 2]

In the [Structural Formula 1] to [Structural Formula 3],
L is a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted carbazolylene group, or a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms A substitution in which one or more substituted or unsubstituted arylene groups having 6 to 50 carbon atoms and substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms are fused to one or more ene groups, substituted or unsubstituted cycloalkyls having 3 to 30 carbon atoms or an unsubstituted heteroarylene group having 2 to 50 carbon atoms (n is an integer of 1 to 3),
Ar ₁ to Ar ₃ are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 An aryl group, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms in which one or more substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms is fused, and a substituted or unsubstituted It is selected from a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms in which one or more cyclic cycloalkyl having 3 to 30 carbon atoms is fused,
Wherein Ar ₁ To Ar ₂ Are bonded to each other or connected to adjacent substituents to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, S And it may be substituted with any one or more heteroatoms selected from O. According to claim 1,
The X is an organic light emitting compound, characterized in that O. 3. The method of claim 1 or 2,
In the definition of R ₁ to R ₁₂ , L and Ar ₁ to Ar ₃ , substituted or unsubstituted means R ₁ to R ₁₂ , L and Ar ₁ to Ar ₂ are deuterium, cyano group, halogen group, hydroxyl group, nitro group , C1-C24 alkyl group, C1-C24 halogenated alkyl group, C1-C24 alkenyl group, C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, carbon number An arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, or a heteroarylalkyl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, It is selected from the group consisting of a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 1 to 24 carbon atoms and an aryloxy group having 1 to 24 carbon atoms, and is substituted with one or more selected substituents; , An organic light emitting compound which means that two or more of the substituents are substituted with a connected substituent, or do not have any substituents. According to claim 1,
The organic light emitting compound represented by the [Formula I] is an organic light emitting compound, characterized in that any one selected from the following [Formula 1] to [Formula 178]:

An organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic material layers disposed between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic light emitting device, characterized in that it comprises at least one organic light emitting compound represented by [Formula I] according to claim 1. 7. The method of claim 6,
The organic layer includes at least one of an electron injection layer, an electron transport layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, and a light emitting layer,
At least one of the layers comprises an organic light emitting compound represented by the [Formula I]. 8. The method of claim 7,
The organic light emitting compound represented by the [Formula I] is an organic electroluminescent device, characterized in that included in the light emitting layer.

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