KR20180063709A - 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 1. When the compound is used as an electron transporting material in an electron transporting layer, it is possible to produce organic electroluminescent devices with outstanding quantum efficiency and luminous efficiency.

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.

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

(I)

The specific structure and substituent of the above-mentioned formula (I) 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) and having excellent quantum efficiency and luminous efficiency when used as an electron transporting material in an organic layer in an organic electroluminescent device.

(I)

In the above formula (I)

X ₁ is CR ₁ R ₂ , X ₂ to X ₄ are the same as or different from each other, and each independently CR ₃ or N;

Wherein R ₁ to R ₂ are the same or different and each is independently selected from an aryl group of hydrogen, substituted or unsubstituted C 1 -C 7 alkyl group and a substituted or unsubstituted C6 to C30 of the ring to each other, the R ₁ to R ₂ may be connected to each other or adjacent substituents to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle.

Accordingly, the formula [I] may be as follows.

[Formula (I-1)

R ₃ 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 cycloalkyl having 3 to 20 carbon atoms, A substituted or unsubstituted C 3 -C 30 heteroaryl group having at least one fused substituted or unsubstituted C 6 -C 30 aryl group and a substituted or unsubstituted C 3 -C 20 cycloalkyl.

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 ₂ 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 C 6 -C 30 aryl group and a substituted or unsubstituted C 3 -C 20 cycloalkyl wherein at least one of the substituted or unsubstituted C3 to C20 cycloalkyl is fused, Lt; RTI ID = 0.0 >

In the present invention, the substituted or unsubstituted alkyl group may be substituted with at least one substituent selected from the group consisting of hydrogen, a halogen group, a nitro group, a hydroxy group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group and a heterocyclic group Means that at least two of the substituents in the substituent are substituted with a substituent to which they are linked, or have no 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,

,

.

The organic luminescent 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 diode due to its structural specificity, and more specifically, as an electron transport layer material of an organic material layer.

Preferred examples of the compound represented by the formula (I) 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 Particularly, when the compound of the formula (I) according to the present invention is used alone as an electron transporting layer material or after designing a plurality of electron transporting layers as a plurality of electron transporting layers together with a conventional electron transporting layer material, The luminous efficiency and the life characteristic can be further improved.

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).

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 such a structure, the compound represented by Formula (I) 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) (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).

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 this structure, the compound represented by the formula (I) may be contained in the hole injection layer (3), the hole transport layer (4) or the electron transport layer (6) 1 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).

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 this structure, the compound represented by Formula (I) may be included in the hole transport layer (4), the light emitting layer (5), or the electron transport layer (6) 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).

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) may be included in the light emitting layer (5) or the electron transport layer (6). Particularly, the electron transport layer (6) 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).

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) may be included in the light emitting layer (5).

According to a preferred embodiment of the present invention, the compound represented by the formula (I) may be contained 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, it may be an organic light-emitting compound represented by Formula (I) according to the present invention, or may be an Al complex of 8-hydroxyquinoline, a complex containing Alq ₃ , an organic radical compound, a hydroxyflavone-metal complex, . According to a preferred embodiment of the present invention, a plurality of layers comprising a first electron transporting layer comprising the above-mentioned conventional electron transporting material and an organic light emitting compound represented by the following formula 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 1

(1) Synthesis of intermediate 1-1

Bis (pinacolato) diboron (23.26 g, 0.09 mol, Sigma Aldrich), Pd (dppf) Cl ₂ (2.79 g, 0.003 mol), 4-bromo-9,9-dimethyl-9H- 500 mL of 1,4-dioxane was added to potassium acetate (22.47 g, 0.23 mol, Sigma aldrich), and the mixture was refluxed for 3 hours and stirred. After completion of the reaction, the reaction mixture was cooled, and then the reaction product was washed with distilled water and extracted with methylene chloride, and the organic layer was collected. The combined organic layer was dried over anhydrous magnesium sulfate and the solvent was removed by distillation under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 20 g (yield: 82%) of Intermediate 1-1.

LC / MS: m / z = 320 [(M + 1) ^< ^{+ &}

(2) Synthesis of intermediate 1-2

Intermediate 1-1 (19.7 g, 0.044 mol) , 9,10-dibromoanthracene (11 g, 0.044 mol, sigma aldrich), Pd (PPh 3) 4 (2.564 g, 0.002 mol, sigma aldrich) in THF 300 mL and 2M 100 mL of potassium carbonate was added, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was cooled, and then the reaction product was washed with distilled water and extracted with ethyl acetate to collect an organic layer. The combined organic layer was dried over anhydrous magnesium sulfate and the solvent was removed by distillation under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 15 g (yield 75.3%) of intermediate 1-2.

LC / MS: m / z = 496 [(M + 1) ^< ^{+ &}

(3) Synthesis of intermediate 1-3

Intermediate 1-3 was obtained in an amount of 15 g (yield: 87%) using the same method as the synthesis of Intermediate 1-1.

LC / MS: m / z = 448 [(M + 1) ^< ^{+ &}

(4) Synthesis of Compound 1

(15 g, 0.069 mol), intermediate 1-3 (13.2 g, 0.083 mol), Pd (PPh ₃ ), 2- (biphenyl-4-yl) -4-chloro- _{4 (tetrakis (triphenylphosphine) palladium (} 0)) (4.01 g, 0.0034 mol, sigma aldrich), XPhos (3.31 g, 0.007 mol, sigma aldrich) were placed in a reaction flask was charged with nitrogen gas and then vacuum dried. 200 mL of toluene was added to the reaction flask to dissolve the compounds, and then 50 mL of ethanol and 50 mL of a 2.0 M K ₂ CO ₃ aqueous solution were added thereto, followed by refluxing and stirring for 3 hours. After completion of the reaction, the reaction mixture was cooled, and then the reaction product was washed with distilled water and extracted with methylene chloride, and the organic layer was collected. The combined organic layer was dried over anhydrous magnesium sulfate and the solvent was removed by distillation under reduced pressure. The resultant residue was subjected to silica gel column chromatography to obtain 28 g (yield 60%) of Compound 1.

^{1 H-NMR (400 MHz,} CDCl 3): δ ppm, 8.28 (d, 2H), 7.91 (d, 4H), 7.87 (d, 1H), 7.85 (d, 2H), 7.63 (d, 1H), 2H), 7.51 (d, 2H), 7.51 (m, 2H), 7.51 (d, (s, 6 H)

LC / MS: m / z = 677 [(M + 1) ^< ^{+ &}

Synthesis Example 2: Synthesis of Compound 66

(1) Synthesis of Intermediate 66-1

Intermediate 66-1 (25 g, yield: 77%) was obtained in the same manner as in the synthesis of Intermediate 1-1.

LC / MS: m / z = 320 [(M + 1) ^< ^{+ &}

(2) Synthesis of intermediate 66-2

Intermediate 66-2 (15 g, yield: 82%) was obtained in the same manner as in the synthesis of Intermediate 1-2.

LC / MS: m / z = 448 [(M + 1) ^< ^{+ &}

(3) Synthesis of intermediate 66-3

Intermediate 66-3 (15 g, yield: 87%) was obtained in the same manner as in the synthesis of intermediate 1-3.

LC / MS: m / z = 496 [(M + 1) ^< ^{+ &}

(4) Synthesis of intermediate 66-4

Using the same method as the synthesis of the compound 1-4, 20 g (yield: 60%) of Intermediate 66-4 was obtained.

LC / MS: m / z = 458 [(M + 1) ^< ^{+ &}

(5) Synthesis of Compound 66

Compound (66) (27 g, yield: 62%) was obtained in the same manner as in the synthesis of Compound (1).

^{1 H-NMR (400 MHz,} CDCl 3): δ ppm, 8.30 (d, 2H), 8.23 (s, 1H), 7.93 (d, 2H), 7.91 (d, 4H), 7.87 (d, 2H), 2H), 7.51 (d, 2H), 7.51 (d, 2H), 7.77 (d, 2H) (m, 6H), 7.28 (t, 2H), 1.72 (s, 12H)

LC / MS: m / z = 792 [(M + 1) ^< ^{+ &}

Synthesis Example 3: Synthesis of Compound 99

(1) Synthesis of intermediate 99-1

Intermediate 99-1 (20 g, yield: 61%) was obtained in the same manner as in the synthesis of Intermediate 1-1.

LC / MS: m / z = 320 [(M + 1) ^< ^{+ &}

(2) Synthesis of intermediate 99-2

Intermediate 99-2 (14.2 g, yield: 65.3%) was obtained in the same manner as in the synthesis of Intermediate 1-2.

LC / MS: m / z = 448 [(M + 1) ^< ^{+ &}

(3) Synthesis of intermediate 99-3

Intermediate 99-3 (12.3 g, yield: 77%) was obtained in the same manner as in the synthesis of intermediate 1-3.

LC / MS: m / z = 496 [(M + 1) ^< ^{+ &}

(4) Synthesis of compound 99

19.2 g (yield: 65%) of compound 99 was obtained using the same method as the synthesis of compound 1 above.

^{1 H-NMR (400 MHz,} CDCl 3): δ ppm, 8.28 (d, 2H), 7.91 (d, 4H), 7.87 (d, 1H), 7.85 (d, 2H), 7.83 (d, 1H), 2H), 7.55 (d, 2H), 7.52 (d, 2H), 7.51 (t, 4H), 7.44 (m, 3H), 7.39 (s, 6 H)

LC / MS: m / z = 677 [(M + 1) ^< ^{+ &}

Synthesis Example 4: Synthesis of Compound 127

(1) Synthesis of intermediate 127-1

2-bromo-4'-chlorobiphenyl (30 g, 0.112 mol, Yurui) was placed in a reaction flask, vacuum-dried and then purged with nitrogen gas. 300 mL of THF was added to the reaction flask to dissolve the compounds, and then -78 Lt; 0 > C. 2.5 M n-BuLi (7.9 g, 0.123 mol, Sigma aldrich) was slowly added to the flask and stirred for 1 hour at the same temperature. 9H-fluoren-9-one (20.2 g, 0.112 mol, Sigma aldrich) dissolved in THF was slowly added to the above reaction flask, and -78 Lt; 0 > C for 1 hour and then at room temperature for 3 hours. After completion of the reaction, the reaction product was treated with distilled water and stirred for 30 minutes, followed by extraction with ethyl acetate to collect an organic layer. The combined organic layer was dried over anhydrous magnesium sulfate and the solvent was removed by distillation under reduced pressure. The obtained residue was washed with methanol and then recrystallized with toluene to obtain Intermediate 127-1 (35 g, yield 76%).

LC / MS: m / z = 368 [(M + 1) ^< ^{+ &}

(2) Synthesis of intermediate 127-2

Acetic acid (500 mL) and HCl (40 mL) were added to Intermediate 127-1 (35 g, 0.094 mol) and refluxed for 2 hours. After completion of the reaction, the reaction mixture was cooled, and then the reaction product was washed with distilled water and filtered. The obtained residue was washed with methanol and hexane to obtain 31 g (yield: 93%) of Intermediate 127-2.

LC / MS: m / z = 350 [(M + 1) ^< ^{+ &}

(3) Synthesis of intermediate 127-3

Pd (dppf) Cl ₂ (2.62 g, 0.003 mol, Sigma Aldrich), XPhos (3.424 g, 0.085 mol), Bis (pinacolato) diboron (26.05 g, 0.1 mol, Sigma Aldrich) 600 mL of 1,4-dioxane was added to potassium acetate (25.17 g, 0.26 mol, Sigma aldrich), and the mixture was refluxed for 3 hours and stirred. After completion of the reaction, the reaction mixture was cooled, and then the reaction product was washed with distilled water and extracted with methylene chloride, and the organic layer was collected. The combined organic layer was dried over anhydrous magnesium sulfate and the solvent was removed by distillation under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 32 g (yield: 85%) of Intermediate 127-3.

LC / MS: m / z = 442 [(M + 1) ^< ^{+ &}

(4) Synthesis of intermediate 127-4

Intermediate 127-4 (30 g, yield: 76.6%) was obtained in the same manner as in the synthesis of Intermediate 1-1.

LC / MS: m / z = 571 [(M + 1) ^< ^{+ &}

(5) Synthesis of intermediate 127-5

28.5 g (yield: 88%) of Intermediate 127-5 was obtained using the same method as the synthesis of intermediate 1-3 above.

LC / MS: m / z = 618 [(M + 1) ^< ^{+ &}

(6) Synthesis of Compound 127

Compound 127 (16.8 g, yield: 65.1%) was obtained in the same manner as in the synthesis of compound 1 above.

^{1 H-NMR (400 MHz,} CDCl 3): δ ppm, 8.28 (d, 2H), 7.93 (d, 1H), 7.91 (d, 4H), 7.87 (d, 1H), 7.85 (d, 2H), 2H), 7.41 (d, 2H), 7.75 (d, 2H), 7.75 (d, 2H), 7.16 (d, 2H), 7.16 (d, 2H), 7.35 (m,

LC / MS: m / z = 799 [(M + 1) ^< ^{+ &}

Synthesis Example 5: Synthesis of Compound 143

Intermediates 66-4 and 127-5 were used to obtain compound 143 (12.3 g, yield: 61.7%) in the same manner as in the synthesis of compound 1 above.

^{1 H-NMR (400 MHz,} CDCl 3): δ ppm, 8.30 (d, 2H), 8.23 (s, 1H), 7.93 (d, 2H), 7.91 (d, 4H), 7.87 (d, 2H), 2H), 7.75 (d, 2H), 7.75 (d, 2H), 7.75 (d, 2H) 2H), 7.16 (t, 2H), 7.16 (t, 2H), 1.72 (s, 6H)

LC / MS: m / z = 914 [(M + 1) ^< ^{+ &}

Synthesis Example 6: Synthesis of Compound 160

(1) Synthesis of intermediate 160-1

29.8 g (yield: 81%) of intermediate 160-1 was obtained using the same method as the synthesis of Intermediate 1-1.

LC / MS: m / z = 254 [(M + 1) ^< ^{+ &}

(2) Synthesis of intermediate 160-2

Using the same method as the synthesis of Intermediate 1-2, 34.4g (yield: 86.6%) of Intermediate 160-2 was obtained.

LC / MS: m / z = 282 [(M + 1) ^< ^{+ &}

(3) Synthesis of Compound 160

Compound 160 (15.4 g, yield: 78.7%) was obtained in the same manner as in the synthesis of intermediate 1-2 above.

^{1 H-NMR (400 MHz,} CDCl 3): δ ppm, 8.0 (d, 2H), 7.93 (d, 2H), 7.91 (d, 4H), 7.77 (d, 2H), 7.75 (d, 2H), 2H), 7.55 (d, 2H), 7.39 (t, 4H), 7.35 (m, 3H), 7.28 (m, 4H)

LC / MS: m / z = 694 [(M + 1) ^< ^{+ &}

Synthesis Example 7: Synthesis of Compound 168

(1) Synthesis of intermediate 168-1

Intermediate 168-1 (22.3 g, yield: 85%) was obtained in the same manner as in the synthesis of Intermediate 1-1.

LC / MS: m / z = 412 [(M + 1) ^< ^{+ &}

(2) Synthesis of intermediate 168-2

17.7 g (yield: 93%) of intermediate 168-2 was obtained using the same method as the synthesis of Intermediate 127-2.

LC / MS: m / z = 394 [(M + 1) ^< ^{+ &}

(3) Synthesis of intermediate 168-3

Intermediate 168-3 (14.6 g, yield: 87%) was obtained in the same manner as in the synthesis of Intermediate 127-3.

LC / MS: m / z = 442 [(M + 1) ^< ^{+ &}

(4) Synthesis of intermediate 168-4

12.6 g (yield: 68.3%) of Intermediate 168-4 was obtained in the same manner as in the synthesis of Intermediate 1-2.

LC / MS: m / z = 570 [(M + 1) ^< ^{+ &}

(5) Synthesis of intermediate 168-5

Intermediate 168-5 (8.7 g, yield: 80%) was obtained in the same manner as in the synthesis of intermediate 1-3 above.

LC / MS: m / z = 618 [(M + 1) ^< ^{+ &}

(6) Synthesis of Compound 168

Compound 168 (13.9 g, yield: 63%) was obtained in the same manner as in the synthesis of compound 1 above.

^{1 H-NMR (400 MHz,} CDCl 3): δ ppm, 8.28 (d, 2H), 7.91 (d, 4H), 7.85 (d, 3H), 7.75 (d, 2H), 7.55 (d, 2H), 2H), 7.51 (d, 2H), 7.51 (d, 2H), 7.41 (t, 2H), 7.39 (t, 4H) (m, 4H)

LC / MS: m / z = 799 [(M + 1) ^< ^{+ &}

Synthesis Example 8: Synthesis of Compound 191

(1) Synthesis of intermediate 191-1

28.7 g (yield: 78%) of intermediate 191-1 was obtained in the same manner as in the synthesis of Intermediate 1-1.

LC / MS: m / z = 254 [(M + 1) ^< ^{+ &}

(2) Synthesis of intermediate 191-2

Intermediate 191-2 (30.9 g, yield: 64.8%) was obtained in the same manner as in the synthesis of Intermediate 1-2.

LC / MS: m / z = 282 [(M + 1) ^< ^{+ &}

(3) Synthesis of Compound 191

Compound 191 (17.4 g, yield: 70.7%) was obtained in the same manner as in the synthesis of Intermediate 1-2.

^{1 H-NMR (400 MHz,} CDCl 3): δ ppm, 8.42 (d, 2H), 8.04 (d, 2H), 7.91 (d, 4H), 7.75 (d, 3H), 7.61 (m, 2H), 2H), 7.25 (d, 4H), 7.16 (m, 4H), 7.35 (m, 2H)

LC / MS: m / z = 694 [(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 through 12

A blue light emitting organic electroluminescent device having the following device structure was prepared by using the compound represented by formula (I) according to the present invention as a compound of the first electron transporting layer, and the luminescent characteristics including the luminous efficiency were measured.

(20 nm) / first electron transporting layer (10 nm) / second electron transporting layer (201: Liq 20 nm) / LiF (20 nm) / ITO / hole injection layer (HAT_CN 5 nm) / hole transport layer 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, 16, 31, 66 and 80, which are implemented by the present invention, were formed by using [BH1] as a compound and [BD1] as a dopant compound and having a thickness of about 20 nm. , 99, 114, 127, 143, 160, 168, and 191, respectively. Further, a second electron transport layer (doped with Liq 50% of compound [201] below) was deposited to a thickness of 20 nm, LiF 1 nm and aluminum of 100 nm 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 electron transport layer 1 was not used in the device structure of Example 1 above.

EXPERIMENTAL EXAMPLE 1: Luminescent characteristics of element embodiments 1 to 12

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 Formula 1 4.34 7.21 5.34 0.144 0.154 2 Formula 16 4.42 7.09 5.30 0.145 0.155 3 31 4.44 7.20 5.39 0.145 0.154 4 66 4.40 7.0 5.26 0.145 0.155 5 80 4.45 7.16 5.42 0.144 0.155 6 Formula 99 4.41 7.11 5.55 0.145 0.154 7 114 4.40 7.13 5.57 0.146 0.155 8 127 4.44 7.25 5.62 0.144 0.154 9 143 4.37 7.33 5.58 0.145 0.155 10 Formula 160 4.33 7.51 5.72 0.145 0.155 11 168 4.46 7.11 5.52 0.146 0.154 12 191 4.51 7.12 5.51 0.142 0.155 Comparative Example not used 4.45 5.2 4.51 0.147 0.156

When the compounds according to the present invention were applied to a device using the compound according to the present invention as a first electron transport layer, the luminescent properties such as luminous efficiency and quantum efficiency were remarkably superior to those of the conventional device (comparative example) can confirm.

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

Claims (6)

An organic light-emitting compound represented by the following formula (I):
(I)

In the above formula (I)
X ₁ is CR ₁ R ₂ , X ₂ to X ₄ are the same or different and are each independently CR ₃ or N,
Wherein R ₁ to R ₂ are the same or different and each is independently selected from an aryl group of hydrogen, substituted or unsubstituted C 1 -C 7 alkyl group and a substituted or unsubstituted C6 to C30 of the ring to each other, the R ₁ to R ₂ may form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle by being connected to each other or adjacent substituents,
R ₃ is selected from the group consisting of 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 cycloalkyl having 3 to 20 carbon atoms, A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms in which one or more substituted or unsubstituted C3 to C20 cycloalkyl is fused,
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 ₂ 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 C 6 -C 30 aryl group and a substituted or unsubstituted C 3 -C 20 cycloalkyl wherein at least one of the substituted or unsubstituted C3 to C20 cycloalkyl is fused, Lt; RTI ID = 0.0 >
The substituted or unsubstituted heterocyclic group is substituted with one or two or more substituents selected from the group consisting of hydrogen, halogen, nitro, hydroxy, alkyl, cycloalkyl, alkoxy, alkenyl, aryl and heterocyclic groups, Quot; means that the above substituents are substituted with a connected substituent, or have no substituent. The method according to claim 1,
The organic luminescent compound according to claim 1, wherein the compound represented by Formula (I) is selected from the following [compounds 1] to [194]:

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 comprises at least one organic light emitting compound represented by Formula (I) 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). 5. The method of claim 4,
Wherein the electron transporting layer comprises an organic light emitting compound represented by the above formula (I). 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).

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