KR20110077871A - Organic light emitting compound and organic electroluminescent device comprising the same - Google Patents

Abstract

PURPOSE: An organic light-emitting compound is provided to improve luminous efficiency of an organic electroluminescent device, and to ensure high thermal stability and high glass transition temperature and to secure low power, high efficiency, high brightness, durability and lifetime. CONSTITUTION: An organic light-emitting compound is represented by chemical formula 1. In chemical formula 1, X is selected from the group consisting of CR13R14, NR15, O, S, S(=O), S(=O)2 and SiR16R17; R1-R17 are independently -[L]n-[Q]m; and n and m are an integer of 0-10. An organic electroluminescence device includes a positive electrode, a negative electrode, and a monolayered or multilayered organic layer interposed between the positive and negative electrodes.

Description

Organic light emitting compound and organic electroluminescent device including the same {ORGANIC LIGHT-EMITTING COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICES COMPRISING SAME}

The present invention is applied to an organic light emitting compound and the organic electroluminescent device, and preferably applied as a hole injection layer material, a hole transport layer material, a host material of the fluorescent layer or phosphorescent layer, electron transport and injection material, luminous efficiency, brightness, thermal The present invention relates to an organic EL device having improved stability, driving voltage, and lifespan.

Organic electroluminescent (EL) devices (hereafter simply referred to as 'organic EL devices') have several advantages such as low voltage driving, self-luminous, light weight, wide viewing angle, and fast response time. As one of the flat panel displays, research is being actively conducted in recent years.

In US Pat. No. 4,356,429, Tang discloses a two-layered organic EL device in which an organic light emitting medium comprises two organic layers sandwiched between an anode and a cathode. That is, in the organic EL device, the hole transporting layer adjacent to the anode contains a hole transporting material so that only holes are mainly transmitted to the light emitting layer in the organic EL device, and the electron transporting layer adjacent to the cathode is an electron transporting material. As a two-layer structure selected so as to mainly transmit electrons only in the organic EL device, the light emission efficiency was achieved to improve the technology of the organic EL device. Therefore, in terms of light emission efficiency, unless a multilayer system including a hole injection layer, a hole transport layer, and a hole blocking layer is used, it is difficult to expect high efficiency and high luminance emission characteristics. It is true.

Since low-voltage driving organic EL devices by stacked devices have been reported by CW Tang et al. (CW Tang and SA Vanslyke, "Applied Physics Letters, Vol. 51, p. 913, 1987"), organic materials There is an active research on an organic EL device having a constituent material.

Tang et al. Use tris (8-hydroxyquinolinol aluminum) as a light emitting layer and a triphenyldiamine derivative as a hole transporting layer.

Advantages of the laminated structure include increasing the injection efficiency of holes into the light emitting layer, blocking the electrons injected from the cathode to increase the generation efficiency of excitons generated by recombination, and confining excitons generated in the light emitting layer. Can be mentioned. As a structure of the organic EL element of such an example, the three-layer type of a hole transport (injection) layer, an electron transport light emitting layer, a hole transport (injection) layer, a light emitting layer, an electron transport (injection) layer, etc. are well known. In such a stacked structure device, in order to increase the recombination efficiency of the injected holes and electrons, the device structure and the formation method have been devised.

As light emitting materials, light emitting materials such as chelate complexes such as tris (8-quinolinolato) aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene derivatives and oxadiazole derivatives are known. From these, it has been reported that light emission in the visible region from blue to red can be obtained, and thus, the realization of color display elements is expected.

In practical use of organic electroluminescent element, drive stability, storage stability, etc. under high temperature environment in long-term drive stability, vehicle mounting, etc. are calculated | required. In particular, it is a serious problem that the constituent material crystallizes under these circumstances and the light emission uniformity of the device is impaired. In long-term driving, it is known that the constituent material of the element is subjected to a large thermal fluctuation due to the temperature rise due to the heat generation of the element itself or the heat caused by the external environmental change, and as a result, the organic compound is easily crystallized. Crystallization may cause short-circuits or defects in the device, impair the uniformity of the light emitting surface, and sometimes lead to light emission stop. For this reason, research on the technique which suppresses such crystallization is also made | formed.

A device using a phenylanthracene derivative as a light emitting material is disclosed in Japanese Patent Laid-Open No. 1996-012600. Although the anthracene derivative is used as a blue light emitting material, the stability of the thin film was required to increase the device life. However, conventional monoanthrasene derivatives are often crystallized and the thin films are often destroyed, and improvement is required. Further, Japanese Patent Laid-Open No. 2002-154993 discloses a light emitting device using a compound in which anthracene ring and fluorene ring are directly bonded, but does not provide improved light emission uniformity at high temperature.

A light emitting material in which spirofluorene is substituted at positions 9 and 10 of anthracene is disclosed (Japanese Patent Laid-Open No. 2002-121547). However, such a luminescent material is improved for crystallization, but since it has two spirofluorene skeletons having a large molecular weight, the deposition temperature is very high at 400 ° C. Eventually, it is reported that localization occurs and an inhomogeneous part exists, and the electric field concentrates on this part, leading to deterioration and destruction of the device.

Since the organic layer is usually used in an amorphous state, and the organic EL element is a current injection type element, if the material used has a low glass transition temperature (Tg), heat generated during use may cause deterioration of the organic EL element. It shortens the life of the device. Thus, materials having a high glass transition temperature are preferred.

Therefore, there is an urgent need for development of an excellent material having improved luminous efficiency of the organic EL device and having high thermal stability and high glass transition temperature.

Accordingly, an object of the present invention is to provide an organic light emitting compound which can be applied as an excellent hole injection layer material, a hole transport layer material, a host material of a fluorescent layer or a phosphorescent layer, an electron transport and injection material, and light emission efficiency, luminance, thermal stability, and driving thereof. It is to provide an organic EL device having improved characteristics such as voltage and lifetime.

In order to achieve the above object, the present invention provides a compound represented by the following formula (1).

Where

X is selected from the group consisting of CR ₁₃ R ₁₄ , NR ₁₅ , O, S, S (= 0), S (= 0) ₂ and SiR ₁₆ R ₁₇ ,

이되,R ₁ to R ₁₇ are each independently

This,

n and m are each independently an integer of 0 to 10, except that at the same time 0;

At least one L is each independently selected from the group consisting of CA ¹ A ² , NA ³ , O, S, S (= 0), S (= 0) ₂ and SiA ⁴ A ⁵ , wherein A ¹ to A ⁵ are each Independently hydrogen, deuterium, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted Or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C40 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C40 aryl Amine, substituted or unsubstituted C6-C40 diarylamine, substituted or unsubstituted C6-C40 aryloxy, substituted or unsubstituted C6-C40 aryl, or substituted or unsubstituted heteroatoms having 5 to 40 heteroatoms Aryl, A ¹ and A ² , A ⁴ and A ⁵ may combine with each other to form a cyclic ring;

At least one Q is independently hydrogen, deuterium, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3- C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C6-C60 diarylamine, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted nuclear atom 5 to 60 heteroaryl, substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted fused polycyclic aromatic hydrocarbon having 5 to 50 nuclear atoms, or Substituted or unsubstituted fused polycyclic 5 to 50 nuclear atoms Aromatic heterocycle;

R ₁ to R ₁₂ may combine with adjacent groups to form a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring;

R ₁₃ and R ₁₄ , R ₁₆ and R ₁₇ may combine with each other to form a cyclic ring.

In addition, the present invention, the anode; cathode; And an organic EL device comprising at least one organic layer interposed between the anode and the cathode, wherein at least one of the organic layers includes the compound described above.

The compound of formula 1 according to the present invention may have both fluorescence and phosphorescence properties and has excellent thermal stability, and thus, when adopted as a blue, green, or red fluorescence or phosphorescent host material, low power, high efficiency, high brightness and improved durability Life can be secured. In addition, by including both the electron and the hole substituents in the molecule, even as a hole injection layer, a hole transport layer, an electron injection layer and / or an electron transport layer material of an organic EL device comprising at least one organic layer between the anode and the cathode Can be applied. Therefore, the organic EL device including the compound of the present invention can be greatly improved in terms of light emitting performance and lifetime, and thus can be effectively applied to a full color display panel and the like.

The compound represented by Formula 1 according to the present invention is a compound having at least one phenanthrene derivative moiety, which is a phosphorescent host material, a fluorescent host material, a hole injection material, a hole transport material, an electron injection material and / or an electron transport material It can be used in an organic EL device as a material.

In the compound of formula 1 of the present invention, X is selected from the group consisting of CR ₁₃ R ₁₄ , NR ₁₅ , O, S, S (= 0), S (= 0) ₂ and SiR ₁₆ R ₁₇ .

이되, n 및 m은 각각 독립적으로 0 내지 10의 정수이며, 동시에 0인 경우는 제외되고; 하나 이상의 L은 각각 독립적으로 CA¹A², NA³, O, S, S(=O), S(=O)₂ 및 SiA⁴A⁵로 이루어진 군에서 선택되며, A¹ 내지 A⁵는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1-C40 알킬, 치환 또는 비치환된 C2-C40 알케닐, 치환 또는 비치환된 C2-C40 알키닐, 치환 또는 비치환된 C3-C40 사이클로알킬, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로사이클로알킬, (치환 또는 비치환된 C6-C40 아릴)C1-C40 알킬, 치환 또는 비치환된 C1-C40 알콕시, 치환 또는 비치환된 C6-C40 아릴아민, 치환 또는 비치환된 C6-C40 디아릴아민, 치환 또는 비치환된 C6-C40 아릴옥시, 치환 또는 비치환된 C6-C40 아릴, 또는 치환 또는 비치환된 핵원자수 5 내지 40의 헤테로아릴이고, A¹과 A², A⁴와 A⁵는 서로 결합하여 환상 고리를 형성할 수 있으며; 하나 이상의 Q는 각각 독립적으로 수소, 중수소, 치환 또는 비치환된 C1-C40 알킬, 치환 또는 비치환된 C2-C40 알케닐, 치환 또는 비치환된 C2-C40 알키닐, 치환 또는 비치환된 C3-C40 사이클로알킬, 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로사이클로알킬, (치환 또는 비치환된 C6-C60 아릴) C1-C40 알킬, 치환 또는 비치환된 C1-C40 알콕시, 치환 또는 비치환된 C6-C60 아릴아민, 치환 또는 비치환된 C6-C60 디아릴아민, 치환 또는 비치환된 C6-C60 아릴옥시, 치환 또는 비치환된 C6-C60 아릴, 치환 또는 비치환된 핵 원자수 5 내지 60의 헤테로아릴, 치환 또는 비치환된 C1-C30 알킬실릴, 치환 또는 비치환된 C6-C60 아릴실릴, 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 탄화수소, 또는 치환 또는 비치환된 핵원자수 5 내지 50의 축합(fused) 폴리사이클릭 방향족 헤테로환이다.R ₁ to R ₁₇ are each independently

Where n and m are each independently an integer from 0 to 10, except that at the same time 0; At least one L is each independently selected from the group consisting of CA ¹ A ² , NA ³ , O, S, S (= 0), S (= 0) ₂ and SiA ⁴ A ⁵ , wherein A ¹ to A ⁵ are each Independently hydrogen, deuterium, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted Or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C40 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C40 aryl Amines, substituted or unsubstituted C6-C40 diarylamines, substituted or unsubstituted C6-C40 aryloxy, substituted or unsubstituted C6-C40 aryl, or substituted or unsubstituted heteroaryl having 5 to 40 nuclear atoms And A ¹ and A ² , A ⁴ and A ⁵ may combine with each other to form a cyclic ring; At least one Q is independently hydrogen, deuterium, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3- C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C6-C60 diarylamine, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted 5 to 5 nuclear atoms. 60 heteroaryl, substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted fused polycyclic aromatic hydrocarbon having 5 to 50 nuclear atoms, or Substituted or unsubstituted fused polycycles having 5 to 50 nuclear atoms It is an aromatic heterocyclic ring.

Preferably, A ¹ to A ⁵ are each independently hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted Or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 20 nuclear atoms, (substituted or unsubstituted C6-C30 aryl) C1-C20 alkyl, substituted or unsubstituted C1-C20 Alkoxy, substituted or unsubstituted C6-C30 arylamine, substituted or unsubstituted C6-C30 diarylamine, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted Ring heteroaryl having 5 to 30 heteroaryl, A ¹ and A ² , A ⁴ and A ⁵ may be bonded to each other to form a ring having 5 to 8 nuclear atoms; At least one Q is independently hydrogen, deuterium, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3- C20 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 20 nuclear atoms, (substituted or unsubstituted C6-C30 aryl) C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 arylamine, substituted or unsubstituted C6-C30 diarylamine, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted nuclear atom 5 to 30 heteroaryl, substituted or unsubstituted C1-C20 alkylsilyl, substituted or unsubstituted C6-C30 arylsilyl, substituted or unsubstituted fused polycyclic aromatic hydrocarbon having 5 to 20 nuclear atoms, or Substituted or unsubstituted fused polycyclic 5 to 20 nuclear atoms Aromatic heterocycle.

R ₁ to R ₁₂ may combine with adjacent groups to form, for example, a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring of 5 to 50 nuclear atoms, and R ₁₃ and R ₁₄ , R ₁₆ and R ₁₇ may be bonded to each other to form a cyclic ring, for example, a cyclic ring having 5 to 8 nuclear atoms.

일 수 있다.R ₁ to R ₁₇ are each independently n is 0 and m is an integer of 1 to 10, preferably 1 to 5

Can be.

Alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, arylalkyl, alkoxy, arylamine, diarylamine, aryloxy, aryl, heteroaryl, alkylsilyl, arylsilyl, condensed poly of R ₁ to R ₁₇ The cyclic aromatic hydrocarbons and the condensed polycyclic aromatic heterocycles are each independently deuterium, halogen, nitrile, nitro, amine, C1-C20 alkyl, C1-C20 alkylamine, C1-C20 alkylsilyl, C6-C30 aryl, (C6 -C30 aryl) C1-C20 alkyl, C1-C20 alkoxy, C6-C30 aryloxy, C6-C30 arylthio, heteroaryl having 5 to 20 nuclear atoms, condensed polycyclic aromatic hydrocarbon having 5 to 20 nuclear atoms, And at least one substituent selected from the group consisting of condensed polycyclic aromatic heterocycles having 5 to 20 nuclear atoms. These substituents may be further substituted with C6-C30 aryl, heteroaryl having 5 to 20 nuclear atoms, and the like.

The following formulas are representative examples of the compound of formula 1 of the present invention, but the compounds of the present invention are not limited to those illustrated below.

As used herein, an "unsubstituted condensed polycyclic aromatic hydrocarbon" is an aromatic having 5 to 50, preferably 5 to 20, atoms formed by condensation of 5- to 8-membered aromatic rings with each other Moiety, non-limiting examples of which include fluorene, phenanthrene and the like.

"Unsubstituted condensed polycyclic aromatic heterocycle" refers to the condensation of 5- to 6-membered aromatic rings with each other to form an aromatic moiety of 5 to 50, preferably 5 to 20, atomic atoms. By at least one of the rings formed by condensation it is meant an aromatic moiety wherein at least one carbon, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O or S. Non-limiting examples thereof include carbazole and the like.

"Unsubstituted heterocycloalkyl" means a non-aromatic moiety having from 3 to 40, preferably from 3 to 30, atomic atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons is N, O or Substituted with a hetero atom such as S. Non-limiting examples thereof include morpholine, piperazine and the like.

“Unsubstituted heteroaryl” means a monoheterocyclic or polyheterocyclic aromatic moiety of 5 to 60, preferably 5 to 30, atoms of nuclear atoms, and at least one carbon, preferably 1 to 3 carbon atoms in the ring. Carbon is substituted with a heteroatom such as N, O or S. It is understood that two or more rings may be attached in a simple or fused form to each other and further include a condensed form with an aryl group. In the present invention, heteroaryl and aromatic heterocycle may be used in an overlapping sense.

Compounds of formula 1 of the present invention can be synthesized according to general synthetic methods (see J. Org. Chem. 73: 7369-7372 (2008) et al.). Detailed synthesis procedures for the compounds of the present invention will be described in detail in the synthesis examples described below.

An organic EL device according to the present invention comprises: an anode; Cathode; And at least one organic layer interposed between the anode and the cathode, wherein at least one of the at least one organic layer includes a compound represented by Chemical Formula 1.

The compound of Formula 1 may be included alone or in plurality.

The organic layer including the compound of Formula 1 of the present invention may be any one or more of a hole injection layer, a hole transport layer, an electron transport layer and a light emitting layer. In the present invention, the light emitting layer may include a phosphorescent dopant material or a fluorescent dopant material. Preferably, the compound of formula 1 of the present invention may be included in the organic EL device as a blue, green, and / or red phosphorescent host, a fluorescent host, a hole transport material, a hole injection material and / or an electron transport material. In addition, the compound of formula 1 of the present invention may be a phosphorescent guest material or a fluorescent guest material. More preferably, the compound of formula 1 of the present invention may be included in the organic EL device as a phosphorescent host or a fluorescent host, particularly preferably as a phosphorescent host.

Since the compound of the present invention has a high glass transition temperature of 150 ℃ or more, when the compound is used as an organic layer of the organic EL device, since the crystallization is minimized in the organic EL device, the driving voltage of the device can be lowered, luminous efficiency, luminance , Thermal stability, and lifetime characteristics can be improved.

For example, a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode may be sequentially stacked, wherein the light emitting layer, the hole injection layer, At least one of the hole transport layer and the electron transport layer may include a compound represented by Chemical Formula 1. An electron injection layer may be positioned on the electron transport layer.

In addition, as described above, the organic EL device according to the present invention may not only have a structure in which an anode, at least one organic layer, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at the interface between the electrode and the organic layer.

In the organic EL device of the present invention, the organic layer including the compound of Formula 1 may be formed by vacuum deposition or solution coating. Examples of the solution application include spin coating, dip coating, doctor blading, inkjet printing or thermal transfer method, but is not limited thereto.

The organic EL device of the present invention forms an organic layer and an electrode using materials and methods known in the art, except that at least one of the organic layers is formed to include the compound represented by the formula (1) of the present invention. can do.

For example, a silicon wafer, quartz, glass plate, metal plate, plastic film or sheet may be used as the substrate.

The anode material may be a metal such as vanadium, chromium, copper, zinc, gold or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but is not limited thereto.

Cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection layer, the hole transport layer, the electron transport layer and the electron injection layer are not particularly limited, and conventional materials known in the art may be used.

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.

< Synthetic example  1> Synthesis of Compound I-1

<Step 1> Compound 1 (9-o- tolylphenanthrene ) Synthesis

9-bromophenanthrene (20g, 76mmol), o-tolylboronic acid (10.2g, 76mmol), Palladium (II) acetate (0.34g, 0.152mmol), Patassium carbonate (52.4g, 380mmol) and Tertrabutylammonium bromide (48.4g, 150 mmol ) Was placed in a flask and dried in vacuo and charged with nitrogen. Distilled water was added thereto, heated to 70 ℃ and vigorously stirred for two hours.

After the reaction was completed, the mixture was cooled to room temperature, diluted with distilled water, and extracted with toluene. Magnesium sulfate was used to remove moisture and then dried. The obtained crude product was purified by column chromatography (Hexane) to give compound 1 (15.7g, yield: 76%).

GC-Mass (Theoretical value: 268.35 g / mol, Measured value: 268 g / mol)

<Step 2> Synthesis of Compound 2

Compound 1 (15.6 g, 58.1 mmol) obtained in <Step 1> was placed in a flask, and Pyridine (300 ml) was added to dissolve Compound 1. Thereafter, a solution of Potassium Permanganate (45 g) in 35 ml distilled water was added, followed by stirring under reflux for 2 hours. At this time, a solution in which Potassium Permanganate (9 g) was dissolved in 45 ml of distilled water was added every 30 minutes. After refluxing for another 5 hours, 300 ml of distilled water was added and refluxed for 12 hours.

After the reaction was completed, the resulting precipitate was filtered off and the product remaining in the precipitate was washed with boiling distilled water. The filtrate was collected and hydrochloric acid was added little by little until the solution became acidic. The precipitate formed was filtered and dried in an oven at 110 ° C. for 3 days to afford compound 2 (12.3 g, yield: 70%).

GC-Mass (Theoretical value: 298.33 g / mol, Measured value: 298 g / mol)

<Step 3> Compound 3 of  synthesis

Compound 2 (13.6 g, 45.55 mmol) synthesized in <Step 2> was slowly added to an Erlenmeyer flask containing 600 ml of concentrated sulfuric acid, stirred at 25 ° C. for 2 hours, and then ice was added to the flask.

Once a precipitate formed it was filtered and washed with distilled water. The obtained solid was put into potassium carbonate solution, stirred and filtered. Finally, washed with distilled water and dried in 110 ℃ oven to give compound 3 (8.5g, yield: 67%).

GC-Mass (Theoretical value: 280.32 g / mol, Measured value: 280 g / mol)

<Step 4> Compound 4 of  synthesis

Potassium hydroxide (34.7 g, 61.9 mmol) and diethylene glycol 300 ml were added to the flask and stirred. Here, Compound 3 (6.9g, 24.79mmol) and Hydrazine monohydrate (25.4g, 0.5mol) synthesized in <Step 3> were added thereto and stirred for 24 hours while heating to 185 ° C.

After the reaction was completed, the reaction solution was poured into ice acidified with hydrochloric acid and stirred. The precipitate formed was filtered off and dried and recrystallized with Acetic acid to give compound 4 (4.2 g, yield: 63%).

GC-Mass (Theoretical value: 266.34 g / mol, Measured value: 266 g / mol)

Step 5 Synthesis of Compound 5

Compound 4 (5 g, 18.7 mmol) synthesized in <Step 4> was dissolved in 95 ml of Tetrahydrofuran and then cooled to -78 ° C under nitrogen atmosphere. 23.3 mL (37.5 mmol) of n-BuLi (1.6 M in hexane) was added and stirred at the same temperature for 1 hour. Thereafter, 1-Bromoethane (2g, 18.7mmol) was added thereto, followed by stirring at room temperature for 6 hours.

After the reaction was completed, ice water was added to the reaction solution, extracted with Ethylacetate and dried over Magnesium sulphate. The obtained solid was filtered, washed and the filtrate was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (n-Hexane / Ethylacetate (9: 1)), concentrated under reduced pressure and dried to give pure compound 5 (3 g, yield: 54%) as a solid.

GC-Mass (Theoretical value: 294.39 g / mol, Measured value: 294.2 g / mol)

Step 6 Synthesis of Compound 6

Under nitrogen atmosphere, Compound 5 (5 g, 16.9 mmol) and FeCl ₃ (0.5 g, 3.4 mmol) synthesized in <Step 5> were dissolved in 85 ml of Chloroform, lowered to 0 ° C., and bromine (1.3 g, 16.9 mmol) was dissolved. Slowly added dropwise. The temperature of the reaction solution was raised to room temperature and then heated to 60 ° C. and stirred for 12 hours.

After the reaction was completed, the reaction solution was cooled to room temperature, diluted with distilled water and extracted with dichloromethane. Water was removed using magnesium sulfate, followed by drying. The crude product obtained was purified by column chromatography (Hexane) to give compound 6 (3.1 g, yield: 49%).

GC-Mass (Theoretical value: 373.29 g / mol, Measured value: 373.1 g / mol)

<Step 7> Compound 7 of  synthesis

Compound 6 (5g, 13.4mmol), Naphthalen-2-ylboronic acid (2.3g, 13.4mmol) and Pd (PPh ₃ ) ₄ (0.3g, 0.268 mmol) synthesized in step <6> were placed in a flask and nitrogen atmosphere. Under dissolving in a mixed solvent of 80 ml of Toluene and 40 ml of Ethanol. Thereafter, 40 ml of an aqueous solution of sodium carbonate (2.1 g, 20.1 mmol) was added thereto, followed by stirring under reflux for 12 hours.

After completion of the reaction, the mixture was extracted with dichloromethane, dried over Magnesium sulphate and filtered. The filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (n-Hexane: Dichloromethane = 7: 3) to afford the title compound I-1 (4.3 g, yield: 76%).

GC-Mass (Theoretical value: 420.54 g / mol, Measured value: 420.1 g / mol)

¹ H-NMR (THF-d ₈ , 500 MHz) d (ppm) 7.41 (m, 1H), 7.58 (m, 2H), 7.61 (m, 2H), 7.80 (m, 3H), 7.84 (m, 2H) , 8.01 (t, 3H), 8.12 (t, 1H), 8.27 (m, 2H), 8.85 (m, 2H), 8.93 (m, 2H), 1.67 (S, 6H).

< Synthetic example  2> Synthesis of Compound I-2

Except for using Phenylboronic acid in place of Naphthalen-2-ylboronic acid in <Step 7> of Synthesis Example 1 and the desired title compound I-2 (4.0 g, 72% yield) Obtained.

GC-Mass (Theoretical value: 420.54 g / mol, Measured value: 420.1 g / mol)

< Synthetic example  3> Synthesis of Compound I-5

Except for using Anthracen-2-ylboronic acid instead of Naphthalen-2-ylboronic acid in <Step 7> of Synthesis Example 1 and the desired title compound I-5 (5.1 g, Yield 77%).

GC-Mass (Theoretical value: 370.48g / mol, Measured value: 370.72g / mol)

< Synthetic example  4> Synthesis of Compound I-9

In <Step 7> of Synthesis Example 1, 4a ', 4b', 8a ', 9a'-tetrahydro-9,9'-spirobi [fluorene] -7-ylboronic acid is used instead of Naphthalen-2-ylboronic acid. Except for the same procedure as in Synthesis Example 1, to obtain the title compound I-9 (5.0 g, yield 68%).

GC-Mass (Theoretical value: 608.77 g / mol, Measured value: 608.52 g / mol)

< Synthetic example  5> Synthesis of Compound I-17

Except for using Fluoranthen-3-ylboronic acid in place of Naphthalen-2-ylboronic acid in <Step 7> of Synthesis Example 1 and the desired title compound I-17 (4.3g, Yield 61%).

GC-Mass (Theoretical value: 494.62 g / mol, Measured value: 494.3 g / mol)

< Example  1 to 5> organic EL  Manufacture of device

A glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol and the like was dried and then transferred to a plasma cleaner, and then the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum depositor.

Each compound synthesized in ITO / DS-205 (800nm) / NPB (150nm) / Synthesis Example 1-5 + 5% DS-405 (300nm) / Alq3 (250nm) / LiF (10nm) on the thus prepared ITO transparent electrode An organic EL device was manufactured in the order of / Al (2000 nm).

< Comparative example  1> organic EL  Manufacture of device

An organic EL device was manufactured in the same manner as in Example 1, except that 9,10-di- (2-naphthyl) anthracene (ADN) was used as a light emitting host material in place of the compound prepared in the synthesis example when forming the light emitting layer.

< Evaluation example  1>

For each organic EL device manufactured in Example 1-5 and Comparative Example 1, the driving voltage, current efficiency, color coordinates, and luminance were measured, and the results are shown in Table 1 below.

device Host Voltage (V) CIE (x, y) Efficiency (cd / A) color Example 1 I-1 5.2 0.153, 0.172 6.4 blue Example 2 I-2 5.0 0.153, 0.175 6.2 blue Example 3 I-5 5.1 0.155, 0.180 6.4 blue Example 4 I-9 5.3 0.159, 0.183 6.6 blue Example 5 I-17 4.9 0.158, 0.179 6.5 blue Comparative example ADN 5.7 0.162, 0.185 5.6 blue

As shown in Table 1, it can be seen that the organic EL device using the compound according to the present invention shows superior performance in terms of luminous efficiency and driving voltage than the organic EL device using the conventional ADN.

Claims (7)

 Compound represented by the following formula (1): <Formula 1>

Where X is selected from the group consisting of CR ₁₃ R ₁₄ , NR ₁₅ , O, S, S (= 0), S (= 0) ₂ and SiR ₁₆ R ₁₇ , R ₁ to R ₁₇ are each independently

This, n and m are each independently an integer of 0 to 10, except that at the same time 0; At least one L is each independently selected from the group consisting of CA ¹ A ² , NA ³ , O, S, S (= 0), S (= 0) ₂ and SiA ⁴ A ⁵ , wherein A ¹ to A ⁵ are each Independently hydrogen, deuterium, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted Or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C40 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C40 aryl Amines, substituted or unsubstituted C6-C40 diarylamines, substituted or unsubstituted C6-C40 aryloxy, substituted or unsubstituted C6-C40 aryl, or substituted or unsubstituted heteroaryl having 5 to 40 nuclear atoms And A ¹ and A ² , A ⁴ and A ⁵ may combine with each other to form a cyclic ring; At least one Q is independently hydrogen, deuterium, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3- C40 cycloalkyl, substituted or unsubstituted heterocycloalkyl having 3 to 40 nuclear atoms, (substituted or unsubstituted C6-C60 aryl) C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C6-C60 diarylamine, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted nuclear atom 5 to 60 heteroaryl, substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted fused polycyclic aromatic hydrocarbon having 5 to 50 nuclear atoms, or Substituted or unsubstituted fused polycyclic 5 to 50 nuclear atoms Aromatic heterocycle; R ₁ to R ₁₂ may combine with adjacent groups to form a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring; R ₁₃ and R ₁₄ , R ₁₆ and R ₁₇ may combine with each other to form a cyclic ring. The method of claim 1, R ₁ to R ₁₇ are each independently n is 0 and m is an integer of 1 to 10

The compound characterized by the above-mentioned. The method of claim 1, Alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, arylalkyl, alkoxy, arylamine, diarylamine, aryloxy, aryl, heteroaryl, alkylsilyl, arylsilyl, condensed poly of R ₁ to R ₁₇ Substituents of cyclic aromatic hydrocarbons and condensed polycyclic aromatic heterocycles are each independently deuterium, halogen, nitrile, nitro, amine, C1-C20 alkyl, C1-C20 alkylamine, C1-C20 alkylsilyl, C6-C30 aryl, (C6-C30 aryl) C1-C20 alkyl, C1-C20 alkoxy, C6-C30 aryloxy, C6-C30 arylthio, heteroaryl having 5 to 20 nuclear atoms, condensed polycyclic aromatic having 5 to 20 nuclear atoms At least one selected from the group consisting of hydrocarbons and condensed polycyclic aromatic heterocycles having 5 to 20 nuclear atoms. anode; cathode; And at least one organic layer interposed between the anode and the cathode, wherein the organic electroluminescent device comprises: At least one of the organic layers comprises an organic electroluminescent device comprising the compound according to any one of claims 1 to 3. The method of claim 4, wherein And the organic layer is selected from the group consisting of a light emitting layer, an electron transporting layer, an electron injection layer, a hole injection layer and a hole transporting layer. The method of claim 4, wherein The compound is an organic electroluminescent device, characterized in that the phosphorescent host material or a fluorescent host material. The method of claim 4, wherein The compound is an organic electroluminescent device, characterized in that the phosphorescent guest material or fluorescent guest material.