WO2019098695A1 - Organic compound and organic electroluminescent device using same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device comprising the same. A compound according to the present invention is employed in an organic layer of an organic electroluminescent device, preferably in a light-emitting layer, an emission auxiliary layer, an electron transport auxiliary layer or an electron transport layer, thus improving emission efficiency, driving voltage, lifespan, etc. in the organic electroluminescent device.

Description

Organic compounds and organic electroluminescent devices using the same

The present invention relates to a novel organic compound and an organic electroluminescent device using the same and more preferably to a compound having excellent electron transporting ability and light emitting ability and by incorporating it into one or more organic layers to improve characteristics such as luminous efficiency, And an organic electroluminescent device.

A study on organic electroluminescent devices which resulted in blue electroluminescence using anthracene single crystals in 1965 based on observation of organic thin film emission of Bernanose in the 1950s was carried out by Tang in 1987 by the function of hole layer and luminescent layer An organic electroluminescent device having a laminated structure divided into layers has been proposed. Thereafter, in order to form a high efficiency and high number of organic electroluminescent devices, each organic material layer has been developed into a form in which each organic material layer has been introduced into the device, leading to the development of specialized materials used therefor.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic layer in the anode, and electrons are injected into the organic layer in the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. At this time, the material used as the organic material layer can be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material and the like depending on its function.

The light emitting layer forming material of the organic electroluminescent device can be classified into blue, green and red light emitting materials according to the luminescent color. In addition, yellow and orange light emitting materials are also used as light emitting materials for realizing better color. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material.

The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. The development of such a phosphorescent material can theoretically improve luminescence efficiency up to four times as compared with that of fluorescence, and attention is focused on phosphorescent host materials as well as phosphorescent dopants.

Up to now, hole injecting layer, hole transporting layer. NPB, BCP, Alq ₃ and the like are widely known as materials used in the hole blocking layer and the electron transporting layer, and anthracene derivatives are reported as luminescent materials. Particularly, a metal complex compound containing Ir such as Firpic, Ir (ppy) ₃ , (acac) Ir (btp) ₂ and the like having advantages in terms of efficiency improvement as a light emitting material has a blue, green, 4,4-dicarbazolybiphenyl (CBP) is used as a phosphorescent dopant material for red phosphorescent dopants.

However, conventional organic material layers have advantages in terms of light emission characteristics, but their glass transition temperature is low and their thermal stability is not very good, so that they are not satisfactory in terms of lifetime in an organic electroluminescent device. Therefore, development of an organic material layer having excellent performance is required.

* Prior Art Document 1: Korean Patent Laid-Open Publication No. 2016-0150184

The present invention relates to a novel compound capable of being used for an organic material layer material of an organic electroluminescence device, specifically a light emitting layer material, a life improving layer material, a light emitting auxiliary layer material, or an electron transporting layer material, And to provide the above objects.

Another object of the present invention is to provide an organic electroluminescent device including the novel compound, which has low driving voltage, high luminous efficiency, and improved lifetime.

In order to accomplish the above object, an example of the present invention provides a compound represented by the following formula:

In Formula 1,

X ₁ to X ₃ are each nitrogen or CR ₄ , and contain at least two or more nitrogen atoms,

One of Y ₁ to Y ₄ is nitrogen and the other is CR ₅ , and when there are plural R _{5 s} , they are the same or different,

n is an integer of 1 to 3,

L is selected from the group consisting of a single bond, an arylene group having ₆ to ₁₈ carbon atoms and a heteroarylene group having 5 to 18 nuclear atoms,

R ₁ is in combination with a selected from hydrogen, deuterium, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, and the group consisting of an aryl group of C ₆ ~ C ₆₀ of or, or adjacent groups (e.g., adjacent the other R _1, etc.) To form a fused ring, wherein the plurality of R < ₁ > are the same or different from each other;

a is an integer of 0 to 4,

A is a substituent represented by the following formula (2) or (3)

In the above Chemical Formulas 2 to 3,

Z ₁ to Z ₃ are each nitrogen or CR ₆ , and contain at least two or more nitrogen atoms,

Z ₄ to Z ₆ are each nitrogen or CR ₇ , and contain at least two or more nitrogen atoms,

Ar ₁ to Ar ₄ are the same or different and each independently represents hydrogen, deuterium, halogen, cyano, C ₂ to C ₄₀ alkenyl, C ₂ to C ₄₀ alkynyl, C ₃ to C ₄₀ cyclo An alkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group , A C ₆ to C ₆₀ aryloxy group, a C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group , is selected from the group consisting of a C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl group of an amine of,

R ₂ to R ₇ are the same or different and are each independently hydrogen, deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ alkenyl group of the C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C ₂ ~ C ₄₀ A cycloalkyl group having ₃ to ₄₀ carbon atoms, a heterocycloalkyl group having 3 to 40 nuclear atoms, an aryl group having ₆ to ₆₀ carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkynyl group, C ₆ -C ₆₀ aryloxy groups, C ₁ -C ₄₀ alkylsilyl groups, C ₆ -C ₆₀ arylsilyl groups, C ₁ -C ₄₀ alkylboron groups, C ₆ -C ₆₀ the arylboronic group, C ₆ ~ C ₆₀ aryl phosphine group, and selected from the group consisting of C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl group of an amine of,

* Represents a moiety bonded to Formula 1,

The alkyl group and aryl group of R _{1 and} the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxyl group and the like of Ar ₁ to Ar ₄ and R ₂ to R ₇ The aryl group and the heteroarylene group of L each independently represent a group selected from the group consisting of deuterium, a halogen group, a cyano group, an alkyl group, an alkoxy group, an aryloxy group, An amino group, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, a C ₃ to C ₄₀ cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms A cycloalkyl group, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C ₁ to C ₄₀ alkyl silyl group, C ₆ ~ C ₆₀ aryl silyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₁ ~ C ₄₀ of the phosphine group, C ₁ ~ C ₄₀ phosphine of Ox Group and a C ₆ ~ is unsubstituted or substituted by one or more substituents selected from the group consisting of an aryl amine of the C _60, when the substituent is a plurality a plurality of substituents are the same or different from each other.

In addition, the present invention provides an organic electroluminescent device comprising a cathode, a cathode, and at least one organic layer sandwiched between the anode and the cathode, wherein at least one of the organic layers includes a compound represented by Formula 1 A light emitting device is provided. The organic material layer containing the compound represented by Formula 1 may be selected from the group consisting of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting auxiliary layer, an electron transporting layer, and an electron injecting layer. At this time, the compound represented by Formula 1 may be used as an electron transporting material for the electron transporting layer and the electron transporting layer.

The compound represented by the formula (1) according to an example of the present invention is excellent in heat resistance, carrier transport ability, and light emitting ability, and can be used as an organic material layer material of an organic electroluminescent device

In addition, the organic electroluminescent device including the compound according to an example of the present invention can significantly improve aspects such as light emitting performance, driving voltage, lifetime, and efficiency, and thus can be effectively applied to a full color display panel and the like.

Hereinafter, the present invention will be described in detail.

1. Organic compounds

A novel organic compound according to the present invention includes an electron-withdrawing group (EWG) in which two or more nitrogen (N) is contained in an electron-withdrawing group (EWG) in which pyridine compound is bonded to triazine or pyrimidine, and a linker to form an asymmetrically connected structure. In this case, electron-donating groups containing two or more nitrogen atoms are triazine, pyrimidine, and triazolopyridine. Compounds having various substituents introduced into these basic skeletons are represented by the above formula (1).

The compound represented by the formula (1) has a higher electron transporting ability than the conventional organic EL device materials and can exhibit a relatively high luminous efficiency. The compound represented by the formula (1) has a high glass transition temperature and thus is excellent in thermal stability, It is excellent. Therefore, when the compound of Formula 1 is included in the organic electroluminescent device, the driving voltage, efficiency, lifetime, etc. of the device can be improved.

In addition, the compound is not only excellent in electron mobility but also excellent in high glass transition temperature and thermal stability. Accordingly, the compound represented by the general formula (1) of the present invention is excellent in electron transporting ability and light emitting property, and therefore, it is preferable that the compound represented by the general formula (1) It can be used as a material. Preferably an electron transporting auxiliary layer laminated on the light emitting layer of green phosphorescence, the electron transporting layer and the electron transporting layer. In addition, since the electron transporting layer has high triplet energy, it can exhibit excellent efficiency due to the triplet-triplet fusion (TTF) effect. Further, it is possible to prevent the excitons generated in the light emitting layer from diffusing into the electron transporting layer or the hole transporting layer adjacent to the light emitting layer. The number of the excitons contributing to light emission in the light emitting layer can be increased to improve the light emitting efficiency of the device and the durability and stability of the device can be improved and the lifetime of the device can be efficiently increased. Most of the developed materials exhibit physical characteristics that can be driven at low voltage, thereby improving lifetime.

Accordingly, when the compound represented by Formula 1 is used in an organic electroluminescent device, excellent thermal stability, carrier transport ability (in particular, electron transportation ability) and light emission performance can be expected, and a driving voltage, Can be improved.

Further, the compound represented by the above formula (1) is not only very advantageous for electron transport, but also exhibits long life characteristics. The excellent electron transporting ability of such a compound can have high efficiency and fast mobility in an organic electroluminescent device, and it is easy to control HOMO and LUMO energy levels according to the direction or position of a substituent. Therefore, high electron transportability can be exhibited in the organic electroluminescent device using such a compound.

Specifically, the compound represented by the formula (1) according to the present invention can be represented by any one of the following formulas (4) to (8).

X ₁ to X ₃ , Y ₁ to Y ₄ , L, A and n are as defined in formula (1).

Preferably, L in the formula (1) may be a single bond or a structure represented by the following formulas L-1 to L-5.

Preferably, A in the formula (1) may be selected from the group consisting of the structures represented by the following A-1 to A-12.

Preferably, A in the formula (1) may be selected from the group consisting of the structures represented by the following A-13 to A-26.

Preferably, Ar ₁ to Ar ₄ may each independently be an aryl group selected from the following structures.

The compound represented by formula (1) according to the present invention may be further represented by any of compounds 1 to 160 shown below. However, the compounds represented by formula (1) of the present invention are not limited by the following examples.

In the present invention, "alkyl" means a monovalent functional group obtained by removing a hydrogen atom from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl , Pentyl, iso-amyl, hexyl, and the like.

In the present invention, "alkenyl" means a monovalent substituent derived from a straight-chain or branched-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples of such alkenyl include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

In the present invention, " alkynyl " means a monovalent substituent derived from a straight-chain or branched-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples of such alkynyls include, but are not limited to, ethynyl, 2-propynyl, and the like.

&Quot; Aryl " in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined. Also, a form in which two or more rings are pendant or condensed with each other may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.

&Quot; Heteroaryl " in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. Wherein at least one of the carbons, preferably one to three carbons, is replaced by a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are pendant or condensed with each other may be included, and further, a condensed form with an aryl group may be included. Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl indolyl), purinyl, quinolyl, benzothiazole, carbazolyl, and heterocyclic rings such as 2-furanyl, N-imidazolyl, 2- , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

In the present invention, "aryloxy" means a monovalent functional group represented by R "O-, and R" is aryl having 6 to 60 carbon atoms. Non-limiting examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy, and the like.

In the present invention, " alkyloxy " means a monovalent functional group represented by R'O-, and R 'is alkyl having 1 to 40 carbon atoms, which may be linear, branched or cyclic . ≪ / RTI > Non-limiting examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

"Cycloalkyl" in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms (saturated cyclic hydrocarbon). Non-limiting examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

In the present invention, "heterocycloalkyl" means a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 nuclear atoms, and includes at least one carbon atom in the ring, preferably 1 Lt; RTI ID = 0.0 > N, < / RTI > O or S. Non-limiting examples thereof include morpholine, piperazine, and the like.

&Quot; Alkylsilyl " means silyl substituted with alkyl having 1 to 40 carbon atoms, " arylsilyl " means silyl substituted with aryl having 6 to 60 carbon atoms, Quot; means a boron group substituted with aryl having 6 to 60 carbon atoms, " arylphosphine group " means a phosphine group substituted with aryl having 1 to 60 carbon atoms, &Quot; arylamine " means an amine substituted with aryl having 6 to 60 carbon atoms.

In the present invention, the term "condensed rings" means condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings, condensed heteroaromatic rings, or a combination thereof.

The compound represented by formula (1) according to the present invention can be synthesized in various ways by referring to the synthesis process of the following examples. Detailed synthesis of the compound of the present invention will be described in detail in Synthesis Examples to be described later.

2. Organic Field  Light emitting element

The present invention provides an organic electroluminescent device comprising a compound represented by the above formula (1).

More specifically, the organic electroluminescent device according to the present invention includes at least one anode, an anode, and at least one organic layer sandwiched between the anode and the cathode, and at least one of the one or more organic layers Include the compounds represented by the above formula (1). At this time, the compounds may be used alone or in combination of two or more.

The at least one organic material layer may be at least one of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting auxiliary layer, an electron transporting layer and an electron injecting layer. ≪ / RTI > compounds. Specifically, it is preferable that the organic material layer containing the compound of Formula 1 is a light emitting layer, an electron transporting auxiliary layer and an electron transporting layer.

The light emitting layer of the organic electroluminescence device of the present invention may include a host material (preferably, a phosphorescent host material). The light emitting layer of the organic electroluminescent device of the present invention may contain a compound other than the compound of Formula 1 as a host.

The structure of the organic electroluminescent device of the present invention is not particularly limited, but may be a structure in which a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting layer and a cathode are sequentially stacked . At least one of the hole injecting layer, the hole transporting layer, the light-emitting auxiliary layer, the light emitting layer, and the electron transporting layer may include the compound represented by the formula (1), and preferably the light emitting layer or the electron transporting layer comprises the compound represented by the formula . ≪ / RTI > Here, an electron injection layer may be further stacked on the electron transport layer. Further, the structure of the organic electroluminescent device of the present invention may be a structure in which an electrode and an electron transporting auxiliary layer are added together with the organic material layer described above. At this time, at least one of the hole injecting layer, the hole transporting layer, the light emitting auxiliary layer, the light emitting layer, the electron transporting supporting layer and the electron transporting layer may include the compound represented by the above formula (1) The transport layer may contain a compound represented by the above formula (1).

Meanwhile, the organic electroluminescent device of the present invention can be manufactured by forming an organic material layer and an electrode by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by the above formula have.

The organic material layer may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

The substrate used in the fabrication of the organic electroluminescent device of the present invention is not particularly limited, but silicon wafer, quartz, glass plate, metal plate, plastic film and sheet can be used.

Examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole or polyaniline; And carbon black, but are not limited thereto.

Examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; And multi-layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting layer, the hole transporting layer, and the light emitting auxiliary layer are not particularly limited, and ordinary materials known in the art can be used.

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

[ Preparation Example  One] PPY Synthesis of -1

<Step 1> PPY Synthesis of -1

4,6-Dichloro-2-phenyl-pyrimidine and 45.0 g (4- (pyridin-3-yl) phenyl) Boro acid 40.0 g, tetrakis (triphenylphosphine) palladium _{(0) 6.0 g, K 2} CO 3 42 g was added to 800 ml of toluene, 200 ml of ethanol and 200 ml of water and the mixture was refluxed with stirring for 2 hours. After completion of the reaction, the reaction solution was deactivated with a sufficient amount of water. Then, the solution was transferred to a separatory funnel and extracted with methylene chloride. The organic layer was dried with magnesium sulfate, concentrated and purified by column chromatography to obtain 39.8 g of PPY- &Lt; / RTI &gt;

1H), 7.25 (d, 2H) 7.03 (s, IH), 7.70 (d, IH)

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 344

[ Preparation Example  2] PPY Synthesis of -2-3

<Step 1> Synthesis of (E) -1- (4- Bromophenyl ) -3- (4-pyridin-3-yl) phenyl) prop-2-en-

50.0 g of 4- (pyridin-3-yl) benzaldehyde, 49.1 g of 1- (4-bromophenyl) ethan-1-one and 18.2 g of sodium methoxide were placed in 800 ml of ethanol and stirred for 8 hours. After completion of the reaction, the mixture was stirred at room temperature for 1 hour, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated and purified by column chromatography to obtain (E) -1- (4-bromophenyl) - (4-pyridin-3-yl) phenyl) prop-2-en-1-one 36.4 g (yield 72%).

(D, 2H), 7.60-7.45 (m, 6H), 8.08-8.01 (m, 3H)

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 364

<Step 2> PPY Synthesis of -2

(4-bromophenyl) -3- (4-pyridin-3-yl) phenyl) prop-2-en-1-one and 24.1 g of benzimidamide hydrochloride, 14.2 g of the side was placed in 500 ml of ethanol, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to a volume of 250 ml and then deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel and extracted with methylene chloride. The organic layer was dried over magnesium sulfate, concentrated and purified by column chromatography to obtain PPY -2 36.2 g (yield 79%).

2H), 7.59-7.55 (m, 6H), 7.25 (d, 2H), 7.76 (d, 2H)

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 464

<Step 3> PPY Synthesis of -3

PPY-2 15.0 g, and (3-chlorophenyl) Boro acid 6.1 g, tetrakis (triphenylphosphine) palladium (0), 0.9 g, K ₂ CO ₃ 7.0 g 300 ㎖ a toluene, ethanol ㎖ 60, water 60 ㎖ And the mixture was refluxed with stirring for 2 hours. After completion of the reaction, the reaction mixture was deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel and extracted with methylene chloride. The organic layer was dried over magnesium sulfate, concentrated and purified by column chromatography to obtain 10.9 g (yield: 68%) of PPY- &Lt; / RTI &gt;

(M, 6H), 7.97 (s, IH), 7.76 (d, 2H), 7.59-7. 55 (m, 6H) , 7.48 (m, 2 H), 7.39 (d, 1 H), 7.25 (d, 2 H)

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 496

[ Preparation Example  3] PPY Synthesis of -4 to 6

<Step 1> Synthesis of (E) -1- (3- Bromophenyl ) -3- (4-pyridin-3-yl) phenyl) prop-2-en-

50.0 g of 4- (pyridin-3-yl) benzaldehyde and 49.1 g of 1- (3-bromophenyl) ethan-1-one and 18.2 g of sodium methoxide were placed in 800 ml of ethanol and stirred for 8 hours. After completion of the reaction, the reaction mixture was stirred at room temperature for 1 hour and then extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, concentrated and purified by column chromatography to obtain (E) -1- (3- - (4-pyridin-3-yl) phenyl) prop-2-en-1-one 38.2 g (yield 74%).

(D, IH), 8.08-8.01 (m, 3H), 7.82 (d, IH), 7.60-7. 45 (m, 7H)

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 364

<Step 2> PPY Synthesis of -4

38.2 g of (E) -1- (3-bromophenyl) -3- (4-pyridin-3- yl) phenyl) 14.8 g of the side was placed in 500 ml of ethanol, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to a volume of 250 ml and then deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel and extracted with methylene chloride. The organic layer was dried over magnesium sulfate, concentrated and purified by column chromatography to obtain PPY -4 (34.2 g, yield 75%).

(D, IH), 7.67 (d, IH), 7.50-7.43 (m, 6H) 7.25 (d, 2 H)

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 464

<Step 3> PPY Synthesis of -5

PPY-4 15.0 g, and (3-chlorophenyl) Boro acid 6.1 g, tetrakis (triphenylphosphine) palladium (0), 0.9 g, K ₂ CO ₃ 7.0 g 300 ㎖ a toluene, ethanol ㎖ 60, water 60 ㎖ And the mixture was refluxed with stirring for 2 hours. After completion of the reaction, the reaction mixture was deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel and extracted with methylene chloride. The organic layer was dried over magnesium sulfate, concentrated and purified by column chromatography to obtain 10.1 g of PPY- &Lt; / RTI &gt;

1H), 7.67 (d, 1H), 7.67 (d, 1H), 7.50-7.30 (m, 7.43 (m, 8 H), 7.35 (d, 1 H), 7.25 (d, 2 H)

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 496

<Step 4> PPY Synthesis of -6

PPY-5 10.0 g, and (3-chlorophenyl) Boro acid _{4.1 g, Pd (OAc) 2} 0.1 g, XPhos 0.4 g, Cs 2 CO 3 4.5 g, placed in a 200 ㎖ toluene, ethanol 40 ㎖, water 40 ㎖ 2 And the mixture was refluxed with stirring for a time. After completion of the reaction, the reaction solution was deactivated with sufficient water. The solution was transferred to a separatory funnel and extracted with methylene chloride. The organic layer was dried with magnesium sulfate, concentrated and purified by column chromatography to obtain 6.7 g (yield 66%) of PPY- &Lt; / RTI &gt;

(D, IH), 7.67 (d, IH), 7.70 (d, IH) (d, IH), 7.50-7.40 (m, IH), 7.35 (d, 2H), 7.25

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 572

[ Preparation Example  4] PTZ Synthesis of -1 to 2

<Step 1> PTZ Synthesis of -1

45.0 g of 2,4-dichloro-6-phenyl-1,3,5-triazine and 39.2 g of (4- (pyridin-3-yl) phenyl) boronic acid, tetrakis (triphenylphosphine) palladium 6.0 g and K ₂ CO _{3 (} 42 g) were added to toluene (800 ml), ethanol (200 ml) and water (200 ml), and the mixture was refluxed with stirring for 2 hours. After completion of the reaction, the reaction mixture was deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel and extracted with methylene chloride. The organic layer was dried over magnesium sulfate, concentrated and purified by column chromatography to obtain 36.2 g of PTZ- &Lt; / RTI &gt;

2H), 7.57-7.50 (m, 4H), 7.25 (d, 2H), 7.96 (d,

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 345

<Step 2> PTZ Synthesis of -2

(Tetrakis (triphenylphosphine) palladium (0) 0.6 g and K ₂ CO ₃ 4.7 g) were dissolved in toluene (200 ml), ethanol (40 ml) and water (40 ml) And the mixture was refluxed with stirring for 2 hours. After completion of the reaction, the reaction mixture was deactivated with a sufficient amount of water. The solution was transferred to a separatory funnel and extracted with methylene chloride. The organic layer was dried over magnesium sulfate, concentrated and purified by column chromatography to obtain 8.7 g (71% &Lt; / RTI &gt;

(S, 1H), 7.96-7.95 (m, 3H), 7.50-7.43 (m, 3H), 8.42-8.30 6H), &lt; / RTI &gt; 7.25 (d, 2H)

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 421

[ Preparation Example  5] Synthesis of ID-1

&Lt; Step 1 > [(2- Pyridinylamino ) Thioxomethyl ] -, ethyl ester ( 9CI ) Synthesis of

To 100 g of 2-aminopyridine was added 500 ml of dichloromethane (DCM). 0 and 139.3 g ethoxycarbonylisothiocyanate was slowly added dropwise over 15 minutes. The reaction solution was warmed to room temperature and stirred for 20 hours. The solvent was appropriately removed by distillation under reduced pressure and the mixture was filtered. After drying with warm air, [(2-pyridinylamino) thioxomethyl] -, ethyl ester (215 g, yield 90%) was obtained.

<Step 2> [1,2,4] triazolo [1,5-a] pyridine -2- Amine  synthesis

A mixed solvent of ethanol / methanol (1: 1, 2.15 L) was added to 298 g of hydroxylamine hydrochloride. 399 ml of triethylamine was added to the reaction solution and stirred for 1 hour. 215 g of [(2-pyridinylamino) thioxomethyl] -, ethyl ester synthesized above was added and the temperature was gradually raised, and the mixture was heated to reflux for 3 hours. The temperature was cooled to room temperature and the resulting solid was filtered. The obtained solid products were combined and washed with purified water, an ethanol / methanol mixed solvent and n-hexane, and dried under a warm air stream to obtain [l, 2,4] triazolo [l, 5- a] pyridin- ).

(D, 1H), 6.97 (s, 2H), 7.90 (d, 1H)

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 134

<Step 3> 2- Bromo - [1,2,4] triazolo [1,5-a] pyridine  Synthesis of

To 115 g of the [1,2,4] triazolo [1,5-a] pyridin-2-amine synthesized above was added 57.5 g of CuBr 2 and 1.2 L of tetrahydrofuran (THF). The reaction solution was cooled to 0, 1.2 L of HBr was slowly added, and 177 g of sodium hydroxide was dissolved in 600 ml of purified water and slowly added dropwise. The reaction solution was stirred at room temperature for 12 hours. To the reaction mixture was added 500 ml of an aqueous solution of sodium hydroxide. After stirring for 1 hour, the mixture was extracted with 2 L of ethyl acetate (EA) and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure and purified by silica gel column chromatography to obtain 2-bromo- [1,2,4] triazolo [1,5-a] pyridine (102 g, yield 60% &Lt; / RTI &gt;

(Dd, 1H), 7.72 (td, 1H), 7.23 (td, 1H)

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 198

<Step 4> Synthesis of ID-1

102 g of the 2-bromo- [1,2,4] triazolo [1,5-a] pyridine synthesized above, 4 g of 4,4,4 ', 4', 5,5,5 ' To 58.8 g of methyl-2,2'-bi (1,3,2-dioxaborolane) was added 1.5 L of 1,4-dioxane. 7.8 g of Pd (dppf) Cl _{2 and} 57.1 g of potassium acetate were added to the reaction solution. The mixture was heated to reflux at 130 for 12 hours. The reaction solution was cooled to room temperature and the reaction was terminated with 1.5 L of aqueous ammonium chloride solution. The mixture was extracted with 2.5 L of EA and washed with distilled water. The obtained organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure, and purified by silica gel column chromatography to obtain ID-1 (31.1 g, yield 25%).

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 246

[ Synthetic example  1] Synthesis of Compound 1

3.0 g of PPY-1 and 3.4 g of (4- (4,6-diphenyl-1,3,5-triazine-2-yl) phenyl) boronic acid, tetrakis (triphenylphosphine) palladium mg of 2M potassium carbonate aqueous solution (15 ml) were added to toluene (60 ml), ethanol (12 ml) and water (12 ml), and the mixture was refluxed with stirring for 2 hours. After the temperature was lowered to room temperature and the reaction was terminated, the potassium phosphate solution was removed, the layers were separated, vacuum distilled, and purified by silica gel column chromatography (using methylene chloride alone) to give Compound 1 (2.3 g, yield 55%).

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 617

[ Synthetic example  2] Synthesis of Compound 3

Compound 3 (2.7 g, yield 53%) was prepared in the same manner as in Synthesis Example 1, except that PTZ-1 was used instead of PPY-1.

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 618

[ Synthetic example  3] Synthesis of Compound 6

PPY-2 was used instead of PPY-1 in Synthesis Example 1 and ID-1 was used instead of (4- (4,6-diphenyl-1,3,5-triazin- Compound 6 (2.9 g, yield 56%) was prepared in the same manner except that

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 503

[ Synthetic example  4] Synthesis of Compound 11

(3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenylboronic acid was used in place of (4- -Triazin-2-yl) phenyl) boronic acid, the compound 11 (2.3 g, yield 51%) was prepared.

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 617

[ Synthetic example  5] Synthesis of Compound 13

Compound 13 (2.3 g, yield 50%) was prepared in the same manner as in Synthesis Example 4, except that PTZ-1 was used instead of PPY-1.

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 618

[ Synthetic example  6] Synthesis of Compound 16

Compound 16 (3.1 g, yield 59%) was prepared in the same manner as in Synthesis Example 3, except that PPY-4 was used instead of PPY-2.

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 503

[ Synthetic example  7] Synthesis of Compound 21

Compound 21 (2.6 g, yield: 54%) was prepared in the same manner as in Synthesis Example 2, except that PPY-2 was used instead of PTZ-1.

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 693

[ Synthetic example  8] Synthesis of Compound 31

Compound 31 (2.3 g, yield 52%) was prepared in the same manner as in Synthesis Example 4, except that PPY-2 was used instead of PPY-1.

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 693

[ Synthetic example  9] Synthesis of Compound 36

2.0 g of PPY-3, 2.1 g of ID-1, 3.0 g of Cs ₂ CO _3, 60 ml of toluene, 12 ml of ethanol and 12 ml of water were added, and then 55 mg of Pd (OAc) ₂ and 250 mg of Xphos Lt; / RTI &gt; for 1 hour. After completion of the reaction, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water and extracted with chloroform, dried the organic layer with MgSO _4. The mixture was concentrated under reduced pressure and then subjected to column chromatography with THF: Hex = 1: 3 to prepare Compound 36 (2.4 g, yield 58%).

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 579

[ Synthetic example  10] Synthesis of Compound 41

Compound 41 (1.9 g, yield 45%) was prepared in the same manner as in Synthesis Example 4, except that PPY-4 was used instead of PPY-1.

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 693

[ Synthetic example  11] Synthesis of Compound 43

PTZ-2 was used instead of PPY-3 in Synthesis Example 9, and (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) boronic acid Compound 43 (3.2 g, yield 61%) was prepared in the same manner except for using the compound obtained in Preparation Example 1.

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 694

[ Synthetic example  12] Synthesis of Compound 46

Compound 46 (1.3 g, yield 36%) was prepared in the same manner as in Synthesis Example 9, except that PPY-5 was used instead of PPY-3.

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 579

[ Synthetic example  13] Synthesis of Compound 71

Compound 71 (1.8 g, yield 33%) was prepared in the same manner as in Synthesis Example 11, except that PPY-5 was used instead of PTZ-2.

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 769

[ Synthetic example  14] Synthesis of Compound 76

Compound 76 (2.1 g, yield 41%) was prepared in the same manner as in Synthesis Example 9, except that PPY-6 was used instead of PPY-3.

Mass: [(M + H) &lt; ⁺ & gt ^; ]: 655

[ Example  1 to 14] blue organic Field  Fabrication of light emitting device

Compounds 1, 3, 6, 11, 13, 16, 21, 31, 36, 41, 43, 46, 71 and 76 synthesized in Synthesis Examples were subjected to high purity sublimation purification by a conventionally known method, Thereby preparing an organic electroluminescent device.

First, glass substrate coated with ITO (Indium tin oxide) thin film of 1500 Å thickness was cleaned with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, and methanol, and dried. Then, the substrate was transferred to a UV OZONE cleaner (Power sonic 405, Hoshin Tech) The substrate was transferred to a vacuum evaporator.

(15 nm) / ADN + 5% DS-405 (Doosan Electronics, 30 nm) / electron transport layer material (Table 1) on the ITO transparent electrode prepared above 30 nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to fabricate an organic electroluminescent device.

[ Comparative Example  1] Blue organic Field  Fabrication of light emitting device

A blue organic electroluminescent device was fabricated in the same manner as in Example 1 except that Alq ₃ was used instead of Compound 1 as the electron transport layer material.

[ Comparative Example  2] Blue organic Field  Fabrication of light emitting device

A blue organic electroluminescent device was fabricated in the same manner as in Example 1 except that Compound 1 was not used as an electron transport layer material.

The structures of NPB, ADN and Alq3 used in Examples 1 to 14 and Comparative Examples 1 and 2 are as follows.

[Evaluation Example 1]

Each of the blue organic electroluminescent devices fabricated in Examples 1 to 14 and Comparative Examples 1 and 2 was measured for driving voltage, current efficiency, and emission wavelength at a current density of 10 mA / cm 2, Respectively.

Sample	Electron transport layer	The driving voltage (V)	Emission peak (nm)	Current efficiency (cd / A)
Example 1	Compound 1	3.5	455	8.1
Example 2	Compound 3	3.3	455	8.3
Example 3	Compound 6	3.4	456	7.9
Example 4	Compound 11	3.6	453	8.3
Example 5	Compound 13	3.2	454	8.1
Example 6	Compound 16	3.4	456	8.3
Example 7	Compound 21	3.5	455	8.7
Example 8	Compound 31	3.9	456	8.2
Example 9	Compound 36	3.7	454	8.3
Example 10	Compound 41	3.5	453	8.1
Example 11	Compound 43	3.3	455	8.3
Example 12	Compound 46	3.7	455	8.1
Example 13	Compound 71	3.8	454	8.8
Example 14	Compound 76	4.3	454	7.3
Comparative Example 1	Alq 3	4.8	457	5.6
Comparative Example 2	-	4.7	459	6.1

As shown in the above Table 1, the blue organic electric field of Compound 1, 3, 6, 11, 13, 16, 21, 31, 36, 41, 43, 46, 71, Compared to the blue organic electroluminescent device using the conventional Alq ₃ as the electron transporting layer (Comparative Example 1) and the blue organic electroluminescent device without the electron transporting layer (Comparative Example 2) using the conventional Alq ₃ , the light emitting devices (Examples 1 to 14) Peak and current efficiency.

Claims (10)

1. A compound represented by the following formula (1):

   [Chemical Formula 1]

   

   In Formula 1,

   X ₁ to X ₃ are each nitrogen or CR ₄ , and contain at least two or more nitrogen atoms,

   One of Y ₁ to Y ₄ is nitrogen and the other is CR ₅ , and when a plurality of R _{5 s} are the same,

   n is an integer of 1 to 3,

   L is selected from the group consisting of a single bond, an arylene group having ₆ to ₁₈ carbon atoms and a heteroarylene group having 5 to 18 nuclear atoms,

   R ₁ is selected from the group consisting of hydrogen, deuterium, halogen, cyano, C ₁ to C ₄₀ alkyl, and C ₆ to C ₆₀ aryl, or combines with adjacent groups to form a condensed ring;

   a is an integer of 0 to 4,

   A is a substituent represented by the following formula (2) or (3)

   (2)

   

   (3)

   

   In the above Chemical Formulas 2 to 3,

   Z ₁ to Z ₃ are each nitrogen or CR ₆ , and contain at least two or more nitrogen atoms,

   Z ₄ to Z ₆ are each nitrogen or CR ₇ , and contain at least two or more nitrogen atoms,

   Ar ₁ to Ar ₄ are the same or different and each independently represents hydrogen, deuterium, halogen, cyano, C ₂ to C ₄₀ alkenyl, C ₂ to C ₄₀ alkynyl, C ₃ to C ₄₀ cyclo An alkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group , A C ₆ to C ₆₀ aryloxy group, a C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group , is selected from the group consisting of a C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl group of an amine of,

   R ₂ to R ₇ are the same or different and are each independently hydrogen, deuterium, a halogen, a cyano group, a nitro group, C ₁ ~ alkenyl group of the C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C ₂ ~ C ₄₀ A cycloalkyl group having ₃ to ₄₀ carbon atoms, a heterocycloalkyl group having 3 to 40 nuclear atoms, an aryl group having ₆ to ₆₀ carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkynyl group, C ₆ -C ₆₀ aryloxy groups, C ₁ -C ₄₀ alkylsilyl groups, C ₆ -C ₆₀ arylsilyl groups, C ₁ -C ₄₀ alkylboron groups, C ₆ -C ₆₀ the arylboronic group, C ₆ ~ C ₆₀ aryl phosphine group, and selected from the group consisting of C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl group of an amine of,

   * Represents a moiety bonded to Formula 1,

   The alkyl group and aryl group of R _{1 and} the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxyl group and the like of Ar ₁ to Ar ₄ and R ₂ to R ₇ The aryl group and the heteroarylene group of L each independently represent a group selected from the group consisting of deuterium, a halogen group, a cyano group, an alkyl group, an alkoxy group, an aryloxy group, An amino group, a C ₁ to C ₄₀ alkyl group, a C ₂ to C ₄₀ alkenyl group, a C ₂ to C ₄₀ alkynyl group, a C ₃ to C ₄₀ cycloalkyl group, a heteroaryl group having 3 to 40 nuclear atoms A cycloalkyl group, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ aryloxy group, a C ₁ to C ₄₀ alkyl silyl group, C ₆ ~ C ₆₀ aryl silyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₁ ~ C ₄₀ of the phosphine group, C ₁ ~ C ₄₀ phosphine of Ox Group and a C ₆ ~ is unsubstituted or substituted by one or more substituents selected from the group consisting of an aryl amine of the C _60, when the substituent is a plurality a plurality of substituents are the same or different from each other.
2. The method according to claim 1,

   Wherein the compound represented by the formula (1) is represented by any one of the following formulas (4) to (8)

   [Chemical Formula 4]

   

   [Chemical Formula 5]

   

   [Chemical Formula 6]

   

   (7)

   

   [Chemical Formula 8]

   

   In the above Chemical Formulas 4 to 8,

   X ₁ to X ₃ , Y ₁ to Y ₄ , L, A and n are as defined in claim 1.
3. The method according to claim 1,

   Wherein L in the general formula (1) is a single bond or a structure represented by the following formulas L-1 to L-5:

   

   

   

   

   

   .
4. The method according to claim 1,

   Wherein A in the above formula (1) is selected from the group consisting of the structures represented by the following A-1 to A-12:

   

   

   

   

   

   

   

   

   

   

   

   
5. The method according to claim 1,

   Wherein A in the above formula (1) is selected from the group consisting of the structures represented by the following A-13 to A-26.

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   .
6. The method according to claim 1,

   Wherein Ar ₁ to Ar ₄ are each independently an aryl group selected from the following structures:

   

   .
7. The method according to claim 1,

   Wherein the compound represented by Formula 1 is any one selected from the following Compounds 1 to 160:

   

   

   

   

   

   

   

   

   .
8. 1. An organic electroluminescent device comprising an anode, a cathode, and one or more organic layers sandwiched between the anode and the cathode,

   Wherein at least one of the one or more organic layers includes a compound according to any one of claims 1 to 7.
9. 9. The method of claim 8,

   Wherein the organic compound layer containing the compound is selected from the group consisting of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting layer, an electron transporting auxiliary layer and an electron injecting layer.
10. 9. The method of claim 8,

    Wherein the organic compound layer containing the compound is selected from the group consisting of an electron transporting layer and an electron transporting auxiliary layer.