KR20180063708A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound represented by chemical formula I or chemical formula II. When the organic light emitting compound is used as an electron transporting material of an electron transporting layer, an organic electroluminescent device having excellent quantum efficiency and light emitting efficiency can be realized.

Description

TECHNICAL FIELD The present invention relates to an organic electroluminescent compound and an electroluminescent device comprising the same,

TECHNICAL FIELD The present invention relates to an organic light emitting compound, and more particularly, to an organic light emitting device employing an organic light emitting compound employed in an electron transporting layer of an organic electroluminescent device, and an organic electroluminescent device using the same to remarkably improve light emitting properties such as luminous efficiency and quantum efficiency.

The organic electroluminescent device can not only form an element on a transparent substrate but also can operate at a low voltage of 10 V or less as compared with a plasma display panel (Plasma Display Panel) or an inorganic electroluminescence (EL) display, It has the advantage of excellent color and has three colors of green, blue, and red. It has recently become a subject of interest as a next generation display device.

However, in order for such an organic electroluminescent device to exhibit such characteristics, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material, which are materials forming an organic layer in a device, However, until now, stable and efficient development of an organic material layer material for an organic electroluminescence device has not been sufficiently achieved. Therefore, development of a new material capable of improving luminescence characteristics and development of an organic layer structure in a device are continuously required.

Accordingly, it is an object of the present invention to provide a novel organic light emitting compound and an organic electroluminescent device including the same, which can be used in an electron transporting layer in an organic electroluminescent device to significantly improve light emitting efficiency.

Further, it is an object of the present invention to provide an organic electroluminescent device in which quantum efficiency and luminous efficiency can be remarkably improved by employing a novel organic luminescent compound together with a conventional electron transporting material by using the electron transporting layer as a plurality of layers.

The present invention provides an organic electroluminescent compound represented by the following formula (I) or (II) and an organic electroluminescent device comprising the same, in order to solve the above problems.

(I)

[Formula II]

Specific structures and substituents of the above-mentioned formula (I) or (II) will be described later.

The organic electroluminescent device employing the organic luminescent compound according to the present invention in the electron transport layer can realize significantly improved luminescent efficiency as compared with the device employing the conventional electron transporting material and can be usefully used in various display devices.

1 to 5 are cross-sectional views illustrating the structure of an organic electroluminescent device according to an embodiment of the present invention.

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

The present invention relates to an organic electroluminescent device having an organic electroluminescent compound represented by the following formula [I] or [II] and having excellent quantum efficiency and luminous efficiency when used as an electron transporting material in an organic layer in an organic electroluminescent device It is possible.

(I)

[Formula II]

In the above formula (I) or formula (II)

X ₁ to X ₃ are the same or different from each other and each independently CR ₁ or N; R ₁ is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, A substituted or unsubstituted C6 to C30 aryl group and at least one substituted or unsubstituted C3 to C20 cycloalkyl substituted or unsubstituted C1 to C20 alkyl 3 to 30 heteroaryl groups.

L ₁ to L ₃ are each independently a direct bond, a substituted or unsubstituted arylene group and a substituted or unsubstituted heteroarylene group.

Ar ₁ to Ar ₅ are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, or a substituted or unsubstituted C3 to C20 cycloalkyl having 3 to 20 carbon atoms, A substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted carbazole group.

The substituted or unsubstituted alkyl group may have 1 or 2 substituents selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, silyl, alkyl, cycloalkyl, alkoxy, alkenyl, Substituted with at least two of the above substituents, or at least two of the substituents are substituted with a substituted or unsubstituted substituent.

Specific examples of the substituted arylene group include a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group and a tetracenyl group. Anthracenyl group and the like are substituted with other substituents.

The substituted heteroarylene 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 condensed heterocyclic groups thereof such as a benzquinoline group, A benzimidazole group, a benzimidazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzzcarbazole group, a dibenzothiophenyl group, a dibenzofurane group and the like are substituted with other substituents.

In the present invention, examples of the substituents will be specifically described 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, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, Ethyl, propyl, isopropyl, n-butyl, isobutyl, isobutyl, isobutyl, A tert-butyl group, a tert-butyl group, a 2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, 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 are not limited thereto.

In the present invention, the alkoxy group may be linear or branched. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably in the range of 1 to 20, which does not cause steric hindrance. Specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an i-propyloxy group, a n-butoxy group, an isobutoxy group, a tert- , Neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n- , A benzyloxy group, a p-methylbenzyloxy group, and the like, but are not limited thereto.

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, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2-yl group, But are not limited to, - (naphthyl-1-yl) vinyl-1-yl group, 2,2-bis (diphenyl-1-yl) vinyl-1-yl group, stilbenyl group, styrenyl group 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. Examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, , A chlorenyl group, a fluorenyl group, an acenaphthacenyl group, a triphenylene group, and a fluororanthrene group, but the scope of the present invention is not limited to these examples.

In the present invention, the heterocyclic group is a hetero ring group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane group, a furyl 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 pyridazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, , An indole group, a carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a dibenzofurancyl group, a phenanthroline group, An isothiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group and the like, but is not limited thereto.

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

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

,

등이 있다.In the present invention, a fluorenyl group is a structure in which two cyclic organic compounds are connected via one atom,

,

.

,

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

,

.

In the present invention, the silyl group is specifically exemplified by trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, But are not limited thereto.

The organic luminescent compound according to the present invention represented by the above formula (I) or (II) can be used as an organic material layer of an organic light emitting device due to its structural specificity, and more specifically, as an electron transport material material of an organic material layer.

Preferable specific examples of the compound represented by the formula (I) or (II) according to the present invention include, but are not limited to, the following compounds.

An organic luminescent compound having the intrinsic characteristics of the substituent introduced by introducing various substituents into the core structure having the above structure can be synthesized. For example, by introducing a substituent used in a hole injection layer material, a hole transport layer material, a light emitting layer material, and an electron transport layer material used in the production of an organic electroluminescent device into the structure, a material meeting the requirements of each organic layer can be manufactured In particular, after the compound of the formula (I) or (II) according to the present invention is used alone as an electron transporting layer material or the electron transporting layer is designed as a plurality of layers, a plurality of electron transporting layers It is possible to further improve the luminous efficiency and lifetime characteristics of the device.

The organic luminescent compound according to the present invention can be applied to an organic electroluminescent device according to a conventional production method.

The organic electroluminescent device according to one embodiment of the present invention may have a structure including a first electrode, a second electrode and an organic material layer disposed therebetween, and the organic electroluminescent compound according to the present invention may be used for an organic material layer And can be manufactured using conventional device manufacturing methods and materials.

The organic material layer of the organic electroluminescent device according to the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer. However, it is not so limited and may include fewer or greater numbers of organic layers.

Therefore, in the organic electroluminescent device according to the present invention, the organic material layer may include at least one of an electron injection layer, an electron transport layer, and layers simultaneously performing electron injection and electron transport, May include organic luminescent compounds represented by Formula (I) or (II).

For example, the structure of an organic electronic device according to the present invention is illustrated in Figs.

1 shows an organic electroluminescent device 1 in which an anode 2, a hole injecting layer 3, a hole transporting layer 4, a light emitting layer 5, an electron transporting layer 6 and a cathode 7 are sequentially laminated on a substrate 1 Are illustrated. In this structure, the compound represented by Formula (I) or (II) may be included in the hole injection layer (3), the hole transport layer (4), the light emitting layer (5), or the electron transport layer (6) Particularly, the electron transport layer 6 may be composed of a first electron transporting layer and a second electron transporting layer, the second electron transporting layer may be a conventional electron transporting compound, and the first electron transporting layer may be a compound represented by the formula (I) And the like.

2 shows the structure of an organic electroluminescent device in which an anode 2, a hole injecting layer 3, a hole transporting layer 4, a light emitting layer 5 and a cathode 7 are sequentially laminated on a substrate 1 . In such a structure, the compound represented by the formula (I) or the formula (II) may be contained in the hole injection layer (3), the hole transport layer (4) or the electron transport layer (6) (6) may be composed of a first electron transporting layer and a second electron transporting layer, the second electron transporting layer may be a conventional electron transporting compound, and the first electron transporting layer may include a compound represented by the above formula (I) or can do.

3 shows a structure of an organic electroluminescent device in which an anode 2, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6 and a cathode 7 are sequentially stacked on a substrate 1 have. In such a structure, the compound represented by the formula (I) or the formula (II) may be contained in the hole transport layer (4), the light emitting layer (5) or the electron transport layer (6) ) May comprise a first electron transporting layer and a second electron transporting layer, the second electron transporting layer may comprise a conventional electron transporting compound, and the first electron transporting layer may comprise a compound represented by the above formula (I) or (II) have.

4 shows a structure of an organic electroluminescent device in which an anode 2, a light emitting layer 5, an electron transport layer 6 and a cathode 7 are sequentially laminated on a substrate 1. In FIG. In this structure, the compound represented by the formula (I) or the formula (II) may be contained in the light emitting layer (5) or the electron transport layer (6). In particular, the electron transport layer (6) And a second electron transporting layer, the second electron transporting layer may comprise a conventional electron transporting compound, and the first electron transporting layer may comprise a compound represented by the above formula (I) or (II).

5 illustrates a structure of an organic electroluminescent device in which an anode 2, a light emitting layer 5, and a cathode 7 are sequentially laminated on a substrate 1. In FIG. In such a structure, the compound represented by Formula (I) or (II) may be included in the light emitting layer (5).

According to a preferred embodiment of the present invention, the compound represented by Formula (I) or (II) may be included in the electron transport layer (6).

For example, the organic electroluminescent device according to the present invention can be manufactured by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form a metal oxide or a conductive metal oxide on the substrate, An anode is formed by depositing an alloy on the anode, and an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer is formed on the anode, and then a substance usable as a cathode is deposited thereon.

In addition to such a method, an organic electroluminescent device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate. The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport 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 material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO) metal oxides, ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT) , Conductive polymers such as polypyrrole and polyaniline, but are not limited thereto.

The negative electrode 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 a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or an alloy thereof; a multilayer such as LiF / Al or LiO ₂ / Structural materials, and the like, but are not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, but are not limited thereto.

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

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having a high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazol-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole and A benzimidazole-based compound, a poly (p-phenylene vinylene) (PPV) -based polymer, a spiro compound, polyfluorene, rubrene, and the like.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is highly mobile, is suitable. Specifically, the compound may be an organic light-emitting compound represented by Formula (I) or Formula (II) according to the present invention, or may be an Al complex of 8-hydroxyquinoline, a complex containing Alq ₃ , an organic radical compound, Metal complexes and the like. According to a preferred embodiment of the present invention, the first electron transporting layer comprising the above-mentioned conventional electron transporting material and the organic electroluminescent compound represented by the formula (I) or (II) according to the present invention A plurality of layers can be designed.

The organic electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

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

Hereinafter, synthesis examples and device embodiments of preferred compounds are shown to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

Synthesis Example 1: Synthesis of Compound 2

(1) Synthesis of intermediate 2-3

To a round bottom flask was added starting material 2-1 (20 g, 81.27 mmol), compound 2-2 (10.9 g, 89.40 mmol, sigma aldrich), K ₂ CO ₃ (33.7 g, 243.83 mmol, sigma aldrich) and Pd ₃ ) ₄ (4.7 g, 4.07 mmol, Sigma aldrich), add 400 mL of toluene, 100 mL of ethanol and 100 mL of water. The reaction mixture is stirred at 100 < 0 > C for 5 hours. The reaction is cooled to room temperature and extracted twice with 300 mL of EtOAc. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 16.8 g (85%) of intermediate 2-3. (m / z = 243)

(2) Synthesis of intermediate 2-6

To a round bottom flask was added starting material 2-4 (20 g, 88.47 mmol, TCI), compound 2-5 (19.27 g, 97.31 mmol, sigma aldrich), K ₂ CO ₃ (36.7 g, 265.54 mmol, (PPh ₃ ) ₄ (5.1 g, 4.41 mmol, Sigma aldrich), add 440 mL of toluene, 110 mL of ethanol and 110 mL of water. The reaction mixture is stirred at 100 < 0 > C for 20 hours. The reaction is cooled to room temperature and extracted twice with 350 mL of EtOAc. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 24.9 g (81.9%) of intermediate 2-6. (m / z = 343)

(3) Synthesis of Compound 2

Add intermediate 2-3 (15 g, 61.65 mmol) to a round bottom flask and add 300 mL of DMF. The reaction mixture is cooled to 0 < 0 > C and 60% NaH (2.96 g, 74 mmol) is slowly added. After the addition, the reaction mixture is stirred for 30 minutes and then the intermediate 2-6 (23.3 g, 67.77 mmol) is added. The entire reaction mixture is stirred at room temperature for 5 hours. 200 mL of water is added dropwise to the reaction mixture to terminate the reaction, and then 250 mL of the DCM reaction mixture is extracted. The extraction process is carried out twice. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then subjected to column chromatography to obtain Compound (2) (25.4 g, 74.8%).

^{1 H-NMR (200MHz, CDCl3} ): δ ppm, 8.55 (1H, dd) 8.28 (2H, dd) 7.94 (1H, dd), 7.85-7.79 (5H, m) 7.61-7.22 (17H, m)

LC / MS: m / z = 551 [(M + 1) ^< ^{+ &}

Synthesis Example 2: Synthesis of Compound 58

(1) Synthesis of intermediate 58-2

To a round bottom flask was added starting material 2-1 (20 g, 81.27 mmol), compound 58-1 (21.3 g, 89.46 mmol, sigma aldrich), K ₂ CO ₃ (33.7 g, 243.83 mmol, sigma aldrich) and Pd ₃ ) ₄ (4.7 g, 4.07 mmol, Sigma aldrich), add 400 mL of toluene, 100 mL of ethanol and 100 mL of water. The reaction mixture is stirred at 100 < 0 > C for 5 hours. The reaction is cooled to room temperature and extracted twice with 300 mL of EtOAc. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 24.3 g (83.2%) of Intermediate 58-2. (m / z = 359)

(2) Synthesis of Compound 58

Add intermediate 58-2 (20 g, 55.64 mmol) to a round bottom flask and 280 mL of DMF. The reaction mixture is cooled to 0 < 0 > C and then 60% NaH (2.67 g, 66.75 mmol, sigma aldrich) is slowly added. After the addition, stir the reaction mixture for 30 minutes and then add intermediate 2-6 (21 g, 61.08 mmol). The entire reaction mixture is stirred at room temperature for 5 hours. 200 mL of water is added dropwise to the reaction mixture to terminate the reaction, and then 250 mL of the DCM reaction mixture is extracted. The extraction process is carried out twice. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 28.9 g (77.9%) of Compound 58.

^{1 H-NMR (200MHz, CDCl3} ): δ ppm, 8.55 (1H, dd) 8.28 (2H, dd) 7.94 (1H, dd), 7.93 (1H, dd), 7.87-7.77 (5H, m) 7.59-7.41 (12H, m), 7.38-7.25 (6H, m), 1.72 (6H, s)

LC / MS: m / z = 667 [(M + 1) ^< ^{+ &}

Synthesis Example 3: Synthesis of Compound 71

(1) Synthesis of intermediate 71-2

To a round bottom flask was added starting material 2-1 (20 g, 81.27 mmol), compound 71-1 (19.9 g, 89.62 mmol, sigma aldrich), K ₂ CO ₃ (33.7 g, 243.83 mmol, sigma aldrich) and Pd ₃ ) ₄ (4.7 g, 4.07 mmol, Sigma aldrich), add 400 mL of toluene, 100 mL of ethanol and 100 mL of water. The reaction mixture is stirred at 100 < 0 > C for 5 hours. The reaction is cooled to room temperature and extracted twice with 300 mL of EtOAc. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 23.8 g (85.3%) of Intermediate 71-2. (m / z = 343)

(2) Synthesis of Compound 71

Add the starting material 71-2 (20 g, 58.24 mmol) to a round bottom flask and add 300 mL of DMF. The reaction mixture is cooled to 0 < 0 > C and then 60% NaH (2.8 g, 70 mmol, Sigma aldrich) is slowly added. After the addition was complete, the reaction mixture was stirred for 30 minutes and then the intermediate 2-6 (22 g, 63.99 mmol) was added. The entire reaction mixture is stirred at room temperature for 5 hours. 200 mL of water is added dropwise to the reaction mixture to terminate the reaction, and then 250 mL of the DCM reaction mixture is extracted. The extraction process is carried out twice. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 30.2 g (79.7%) of Compound 71.

^{1 H-NMR (200MHz, CDCl3} ): δ ppm, 8.93 (2H, d), 8.55 (1H, dd) 8.28 (2H, dd) 8.12 (2H, d), 7.94-7.82 (9H, m) 7.59-7.41 (10H, m), 7.33-7.25 (4H, m)

LC / MS: m / z = 651 [(M + 1) ^< ^{+ &}

Synthesis Example 4: Synthesis of Compound 77

(1) Synthesis of intermediate 77-3

To a round bottom flask was added starting material 77-1 (22.6 g, 81.27 mmol, Yurui), compound 77-2 (17.7 g, 89.38 mmol, sigma aldrich), K ₂ CO ₃ (33.7 g, 243.83 mmol, (PPh ₃ ) ₄ (4.7 g, 4.07 mmol, Sigma aldrich), add 400 mL of toluene, 100 mL of ethanol and 100 mL of water. The reaction mixture is stirred at 100 < 0 > C for 5 hours. The reaction is cooled to room temperature and extracted twice with 300 mL of EtOAc. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 21.3 g (81.9%) of Intermediate 77-3. (m / z = 351)

(2) Synthesis of intermediate 77-4

Add intermediate 77-3 (21.3 g, 66.69 mmol) to a round bottom flask, add 150 mL of 1,2-dichlorobenzene and 150 mL of triethyl phosphite. The reaction mixture is refluxed for 20 hours. The reaction mixture is cooled to room temperature, and 150 mL of the remaining 1,2-dichlorobenzene and triethyl phosphite are removed by distillation under reduced pressure. The resulting solid was dissolved in chloroform and then separated by column chromatography to obtain 13.8 g (64.8%) of Intermediate 77-4. (m / z = 319)

(3) Synthesis of intermediate 77-7

Add the starting material 77-5 (20 g, 108.45 mmol, Sigma aldrich) to a round bottom flask and add 550 mL of THF. After cooling the reaction mixture to 0 < 0 > C, compound 77-6 (0.5 g, 478 mL) is slowly added dropwise. When dropwise addition is complete, the reaction temperature is raised to room temperature and stirred for 24 hours. The reaction is quenched with 350 mL of ice water and extracted twice with 500 mL of EtOAc. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 19.2 g (42.2%) of Intermediate 77-7. (m / z < / RTI > = 419)

(4) Synthesis of Compound 77

Add intermediate 77-4 (10 g, 31.31 mmol) to a round bottom flask and add 150 mL of DMF. The reaction mixture is cooled to 0 < 0 > C and then 60% NaH (1.5 g, 37.5 mmol, sigma aldrich) is slowly added. After the addition, stir the reaction mixture for 30 minutes and then add intermediate 77-7 (14.46 g, 34.44 mmol). The entire reaction mixture is stirred at room temperature for 5 hours. 100 mL of water is added dropwise to the reaction mixture to terminate the reaction, and 150 mL of the DCM reaction mixture is extracted. The extraction process is carried out twice. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 17.6 g (80%) of Compound 77.

¹ H-NMR (200 MHz, CDCl 3):? Ppm, 8.18 (1H, dd), 8.00 (1H, d) d) 7.52-7.41 (20 H, m), 7.25 (4 H, d)

LC / MS: m / z = 703 [(M + 1) ^< ^{+ &}

Synthesis Example 5: Synthesis of Compound 85

(1) Synthesis of intermediate 85-1

Add Intermediate 2-3 (55.4 g, 227.70 mmol) to a round bottom flask and add 1.2 L of DMF. The reaction mixture is cooled to 0 < 0 > C and then 60% NaH (10.9 g, 275.5 mmol, sigma aldrich) is slowly added. After the addition, the reaction mixture was stirred for 30 minutes and then Compound 77-5 (20 g, 108.45 mmol, Sigma aldrich) was added. The entire reaction mixture is stirred at room temperature for 5 hours. Add 1 L of water to the reaction to terminate the reaction, then extract the 1 M reaction mixture. The extraction process is carried out twice. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 38.2 g (58.9%) of Intermediate 85-1. (m / z = 598)

(2) Synthesis of Compound 85

Intermediate 85-1 (30 g, 50.16 mmol) in a round bottom flask, compound 58-1 (13.2 g, 55.44 mmol) , K 2 CO 3 (20.8 g, 150.5 mmol, sigma aldrich) and Pd (PPh _{3) 4} ( 2.9 g, 2.51 mmol, Sigma aldrich), add 240 mL of toluene, 60 mL of ethanol and 60 mL of water. The reaction mixture is stirred at 100 < 0 > C for 20 hours. After cooling to room temperature, the reaction mixture is separated into an organic layer and a water layer. The water layer is extracted twice with 200 mL of DCM. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 32.4 g (85.5%) of compound 85.

^{1 H-NMR (200MHz, CDCl3} ): δ ppm, 8.55 (2H, d), 7.94 (3H, dd), 7.87 (1H, dd), 7.79 (7H, m), 7.59-7.25 (18H / m), 1.72 (6H, s)

LC / MS: m / z = 756 [(M + 1) ^< ^{+ &}

Synthesis Example 6: Synthesis of Compound 112

(1) Synthesis of intermediate 112-2

(20 g, 193.78 mmol, sigma aldrich), potassium t- butoxide (76.1 g, 678.19 mmol, Sigma aldrich) and AcCN (23.9 g, 582.22 mmol, sigma aldrich) were placed in a round bottom flask, Add 600 mL. The reaction mixture is stirred at 20 < 0 > C for 12 hours. Ether and 2% NaHCO ₃ were added to the reaction. After separating into an organic layer and a water layer, the water layer is extracted twice with 200 mL of EtOAc. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 13.2 g (47.2%) of intermediate 112-2. (m / z = 144)

(2) Synthesis of intermediate 112-4

Add a mixture of Intermediate 112-2 (13.2 g, 91.56 mmol) and 112-3 (22.7 g, 100.76 mmol, Yurui) into a round bottom flask and add 200 mL of POCl ₃ . The reaction mixture is refluxed for 5 hours. The reaction mixture was added to ice water and then ammonium hydroxide (pH = 7) was added. After extraction with chloroform and water, the organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 20.7 g (65.9%) of intermediate 112-4. (m / z = 342)

(3) Synthesis of intermediate 112-6

The starting material 2-1 (20 g, 81.27 mmol) in a round bottom flask, compound 112-5 (21.3 g, 89.46 mmol, yurui), K 2 CO 3 (33.7 g, 243.83 mmol, sigma aldrich) and Pd (PPh ₃ ) ₄ (4.7 g, 4.07 mmol, Sigma aldrich), add 400 mL of toluene, 100 mL of ethanol and 100 mL of water. The reaction mixture is stirred at 100 < 0 > C for 5 hours. The reaction is cooled to room temperature and extracted twice with 300 mL of EtOAc. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 22.1 g (75.7%) of Intermediate 6-6. (m / z = 359)

(4) Synthesis of Compound 112

To a round bottom flask was added Intermediate 112-6 (10.5 g, 29.21 mmol) , Intermediate 112-4 (10.5 g, 30.63 mmol) , sodium t -butoxide (8.4 g, 87.41 mmol, sigma aldrich), Pd (dba) 2 (0.84 g, 1.46 mmol, Sigma aldrich) and ( t- Bu) ₃ P (50%, 1.2 g, 2.97 mmol, Sigma aldrich) and add 150 mL of xylene. The reaction mixture is refluxed for 20 hours. The reaction is cooled to room temperature and extracted twice with 100 mL of EtOAc. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then subjected to column chromatography to obtain Compound (112) (15.7 g, 80.7%).

^{1 H-NMR (200MHz, CDCl3} ): δ ppm, 8.55 (1H, d), 7.94 (1H, d), 7.87-7.79 (7H, m), 7.59-7.51 (9H, m), 7.44-7.25 (10H / m), 7.10 (1H, s), 1.72 (6H, s)

LC / MS: m / z = 756 [(M + 1) ^< ^{+ &}

Synthesis Example 7: Synthesis of Compound 137

(1) Synthesis of intermediate 137-2

(14.8 g, 81.12 mmol, sigma aldrich), compound 2-2 (10.9 g, 89.40 mmol, sigma aldrich), K ₂ CO ₃ (33.7 g, 243.83 mmol, sigma Aldrich) Pd (PPh ₃ ) ₄ (4.7 g, 4.07 mmol, Sigma aldrich), add 400 mL of toluene, 100 mL of ethanol and 100 mL of water. The reaction mixture is stirred at 100 < 0 > C for 5 hours. The reaction is cooled to room temperature and extracted twice with 300 mL of EtOAc. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 12.4 g (68.1%) of intermediate 137-2. (m / z = 224)

(2) Synthesis of intermediate 137-3

Intermediate 137-2 (12.4 g, 55.33 mmol) in a round bottom flask, compound 2-5 (12.1 g, 61.1 mmol, sigma aldrich), K 2 CO 3 (23 g, 166.41 mmol, sigma aldrich) and Pd (PPh ₃ ) ₄ (3.2 g, 2.77 mmol, Sigma aldrich), add 280 mL of toluene, 70 mL of ethanol and 70 mL of water. The reaction mixture is stirred at 100 < 0 > C for 5 hours. The reaction is cooled to room temperature and extracted twice with 300 mL of EtOAc. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain 16.7 g (88.4%) of intermediate 137-3. (m / z = 341)

(3) Synthesis of Compound 137

To a round bottom flask was added Intermediate 112-6 (10.5 g, 29.21 mmol) , Intermediate 137-3 (10.9 g, 31.88 mmol) , sodium t -butoxide (8.4 g, 87.41 mmol), Pd (dba) 2 (0.84 g, 1.46 mmol) and ( t- Bu) ₃ P (50%, 1.2 g, 2.97 mmol) and add 150 mL of xylene. The reaction mixture is refluxed for 20 hours. The reaction is cooled to room temperature and extracted twice with 100 mL of EtOAc. The extracted organic layer is treated with anhydrous MgSO ₄ and filtered. The filtered organic layer was concentrated under reduced pressure and then subjected to column chromatography to obtain Compound (137) (15.2 g, 80.3%).

^{1 H-NMR (200MHz, CDCl3} ): δ ppm, 8.81 (2H, d), 8.55 (1H, d), 8.30 (2H, d), 7.94 (1H, d), 7.88-7.79 (5H, m), 7.59-7.51 (9H, m), 7.44-7.25 (8H, m), 7.10 (2H, s), 1.72 (6H, s)

LC / MS: m / z = 665 [(M + 1) ^< ^{+ &}

Device Example

In the embodiment according to the present invention, the ITO transparent electrode is formed by patterning an ITO glass substrate having an ITO transparent electrode on a glass substrate of 25 mm x 25 mm x 0.7 mm so as to have a light emitting area of 2 mm x 2 mm And then washed. After the substrate was mounted in a vacuum chamber and the base pressure was adjusted to 1 × 10 ^-6 torr, organic matter and metal were deposited on the ITO by the following structure.

Device Embodiments 1 to 11

A blue light emitting organic electroluminescent device having the following device structure was prepared by using the compound represented by Formula (I) or (II) according to the present invention as a compound of the first electron transporting layer, Were measured.

A hole transporting layer (a-NPB 100 nm) / a light emitting layer (20 nm) / a first electron transporting layer (15 nm) / a second electron transporting layer (201: Liq 15 nm) / LiF 1 nm) / Al (100 nm)

In order to form a hole injection layer on the ITO transparent electrode, the hole injection layer was formed to a thickness of 5 nm by vacuum thermal deposition using [HAT_CN], and then the hole transport layer was formed using a-NPB, 17, 32, 58 and 71, which are implemented by the present invention, were formed by using [BH1] as a compound and [BD1] as a dopant compound to a thickness of about 20 nm. , 77, 85, 97, 112, 137, and 144, respectively. Further, 15 nm of a second electron transporting layer (doping with Liq 50% compound [201] below), 1 nm of LiF and 100 nm of aluminum were deposited by vapor deposition to produce an organic electroluminescent device.

Device Comparative Example 1

An organic electroluminescent device for Device Comparison Example 1 was fabricated in the same manner except that the first electron transporting layer was not used in the device structure of Example 1 above.

EXPERIMENTAL EXAMPLE 1: Luminescent characteristics of element examples 1 to 11

The voltage, current and luminous efficiency of the organic EL device were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research). The current density was 10 mA / Is defined as " driving voltage " The results are shown in Table 1 below.

Example Electron transport layer 1 V cd / A QE (%) CIEx CIEy One (2) 4.24 7.09 5.64 0.144 0.154 2 Formula 17 4.22 7.18 5.66 0.145 0.155 3 (32) 4.23 7.20 5.61 0.144 0.155 4 58 4.25 7.13 5.66 0.145 0.155 5 71 4.22 7.25 5.75 0.145 0.154 6 77 4.24 7.12 5.62 0.144 0.154 7 Formula 85 4.23 7.14 5.68 0.145 0.155 8 97 4.24 7.13 5.64 0.144 0.154 9 Formula 112 4.22 7.23 5.72 0.145 0.155 10 137 4.25 7.11 5.65 0.146 0.154 11 144 4.24 7.12 5.60 0.145 0.156 Comparative Example not used 4.24 5.2 4.6 0.147 0.156

When the organic electroluminescent compound according to the present invention is applied to a device using the first electron transport layer according to the present invention as shown in Table 1, the luminescent properties such as luminous efficiency and quantum efficiency are significantly It can be confirmed that it is excellent.

[HAT_CN] [? -NPB] [BH1] [BD1] [201]

Claims (6)

An organic luminescent compound represented by the following formula (I) or (II):
(I)

[Formula II]

In the above formula (I) or formula (II)
X ₁ to X ₃ are the same or different from each other, and each independently CR ₁ or N,
Wherein R ₁ is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, A substituted or unsubstituted aryl group having 6 to 30 carbon atoms and at least one substituted or unsubstituted C3 to C20 cycloalkyl wherein at least one of the substituted or unsubstituted C3 to C20 cycloalkyl is fused, Lt; / RTI > and < RTI ID = 0.0 >
L ₁ to L ₃ each independently represents a direct bond, a substituted or unsubstituted arylene group and a substituted or unsubstituted heteroarylene group,
Ar ₁ to Ar ₅ are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, or a substituted or unsubstituted C3 to C20 cycloalkyl having 3 to 20 carbon atoms, A substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted carbazole group,
Wherein said substituted or unsubstituted heterocyclic group is one or two or more substituents selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, silyl, alkyl, cycloalkyl, alkoxy, alkenyl, , Or two or more of the substituents of the substituents are substituted with a substituted or unsubstituted substituent. The method according to claim 1,
The organic electroluminescent compound according to any one of the above [1] to [242]

1. An organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode,
Wherein at least one of the organic material layers contains at least one organic light emitting compound represented by Formula (I) or (II) according to Claim 1. The method of claim 3,
Wherein the organic material 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,
Wherein at least one of the layers comprises an organic light emitting compound represented by the formula (I) or (II). 5. The method of claim 4,
Wherein the electron transporting layer comprises an organic light emitting compound represented by the formula (I) or (II). 5. The method of claim 4,
Wherein the electron transporting layer comprises a first electron transporting layer and a second electron transporting layer, and the first electron transporting layer comprises an organic light emitting compound represented by the formula (I) or (II) .

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