KR101835020B1 - Electron transport material and organic electroluminescence element using same - Google Patents

Abstract

식 (1)에 있어서, Py는 독립적으로 식 (2), (3) 또는 (4)로 표시되는 기이며；

m 및 n은 0 또는 1이지만, m＋n=1이며；그리고, 식 (1) 중의 벤젠환, 나프탈렌환 및 피리딘환의 수소 중 적어도 하나는 탄소수 1∼6의 알킬 또는 탄소수 3∼6의 시클로알킬로 치환되어 있다.The compound represented by the formula (1) of the present invention is useful as an electron transporting material of an organic EL device, and the use of the electron transporting material contributes to the longevity and the like of the organic EL device.

In the formula (1), Py is independently a group represented by the formula (2), (3) or (4);

m and n are 0 or 1, and m + n = 1; and at least one of the benzene ring, naphthalene ring and pyridine ring hydrogen in formula (1) is substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms .

Description

TECHNICAL FIELD [0001] The present invention relates to an electron transporting material and an organic electroluminescent device using the same. BACKGROUND ART [0002]

The present invention relates to a novel electron transporting material having a pyridyl group, an organic electroluminescent device using the electron transporting material (hereinafter sometimes abbreviated as an organic EL element or an element), and the like.

BACKGROUND ART [0002] In recent years, organic EL devices have attracted attention as a next-generation full-color flat panel display, and active research is underway. In order to promote the practical use of the organic EL device, reduction of the driving voltage of the device and long-term longevity are indispensable factors. To achieve these, a new electron transporting material has been developed. In particular, it is essential to lower the driving voltage of the blue element and to prolong the life span of the blue element. Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-123983) discloses an organic EL device which can be driven at a low voltage by using a phenanthroline derivative or a 2,2'-bipyridyl compound as a substituent in an electron transporting material . However, the device characteristics (drive voltage, luminous efficiency, etc.) reported in the embodiments of this document are only relative values based on the comparative example, and actual values that can be judged as practical values are not described. In addition, examples in which 2,2'-bipyridyl compounds are used as electron transport materials are disclosed in Non-Patent Document 1 (Proceedings of the 10th International Workshop on Inorganic and Organic Electroluminescence), Patent Document 2 (Japanese Patent Application Publication No. 2002-158093 And Patent Document 3 (International Publication 2007/86552 pamphlet). The compound described in Non-Patent Document 1 had a low Tg and was not practical. The compounds described in Patent Documents 2 and 3 can drive the organic EL device at a comparatively low voltage, but in order to put the compound into practical use, longer life is required.

Japanese Patent Application Laid-Open No. 2003-123983 Japanese Patent Application Laid-Open No. 2002-158093 International publication 2007/86552 Brochure

Proceedings of the 10th International Workshop on Inorganic and Organic Electroluminescence (2000)

The present invention has been made in view of the problems of the prior art. An object of the present invention is to provide an electron transporting material contributing to long-term longevity and the like of an organic EL device. It is another object of the present invention to provide an organic EL device using the electron transporting material.

As a result of extensive investigations, the inventors of the present invention have found that when naphthyl or phenyl of 9- (2-naphthyl) -10-phenylanthracene has pyridyl, bipyridyl or pyridylphenyl, By using a compound in which at least one of naphthalene ring and hydrogen of pyridine ring is substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms in the electron transporting layer of the organic EL device, an organic EL device capable of driving with a long life is obtained The present invention has been completed based on this finding. The above problems are solved by the following respective items.

[1] A compound represented by the following formula (1).

In the formula (1)

Py is independently a group represented by formula (2), (3) or (4);

m and n are 0 or 1, but m + n = 1;

At least one of the benzene ring, the naphthalene ring and the hydrogen of the pyridine ring in the formula (1) is substituted with an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 6 carbon atoms.

[2] The compound according to the above item [1], which is represented by the following formula (1-1) or (1-2)

In the formulas (1-1) and (1-2)

Py is a group represented by the formula (2), (3) or (4);

At least one of the benzene ring, naphthalene ring and hydrogen of the pyridine ring in the formulas (1-1) and (1-2) is substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms.

[3] The compound according to the above item [1], which is represented by the following formula (1-3), (1-4), (1-5) or (1-6)

In the formulas (1-3) to (1-6)

Py is a group represented by the formula (2), (3) or (4);

At least one of the benzene ring, naphthalene ring and hydrogen of the pyridine ring in the formulas (1-3) to (1-6) is substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms.

[4] The compound according to the above-mentioned [1], which is represented by the following formula (1-7) or (1-8).

In formulas (1-7) and (1-8), Py is a group represented by formula (2), (3) or (4);

R is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms; and p is an integer of 1 to 5.

[5] The compound according to the above-mentioned [1], which is represented by the following formula (1-9) or (1-10).

In the formulas (1-9) and (1-10)

Py is a group represented by the formula (2), (3) or (4);

R is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms;

q is an integer of 1 to 5;

[6] The compound according to the above-mentioned [1], which is represented by the following formula (1-11) or (1-12).

In the formulas (1-11) and (1-12)

Py ¹ is a group represented by the formula (2 '), (3') or (4 ');

In the formulas (2 '), (3') and (4 '), R is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms; and s is an integer of 1 to 4.

[7] The compound according to the above-mentioned [1], which is represented by the following formula (1-13) or (1-14).

In the formulas (1-13) and (1-14)

Py ¹ is a group represented by the formula (2 '), (3') or (4 ');

In formula (2 '), (3') or (4 '), R is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms; and s is an integer of 1 to 4.

[8] A compound according to the above item [1], which is represented by the following formula (1-15) or (1-16).

In the formulas (1-15) and (1-16)

Py is a group represented by the formula (2), (3) or (4);

R is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms; and t is an integer of 1 to 4.

[9] The compound according to the above-mentioned [1], which is represented by the following formula (1-7-26).

[10] The compound according to the above-mentioned [1], which is represented by the following formula (1-7-74).

[11] The compound according to the above-mentioned [1], which is represented by the following formula (1-7-98).

[12] The compound according to the above-mentioned [1], which is represented by the following formula (1-7-96).

[13] The compound according to the above item [1], which is represented by the following formula (1-14-14).

[14] A compound represented by any one of the following formulas (1-11-1), (1-11-2), (1-11-3), (1-11-4), (1-11-5) (1-11-8), (1-11-18), (1-11-39), (1-14-2), (1-14-3), (1-14-11) , (1-14-12), (1-14-13), (1-14-15), (1-14-16), (1-14-17), (1-14-18), and The compound according to the above-mentioned [1], wherein the compound is represented by any one of (1-14-20).

[15] An electron transporting material containing the compound according to any one of [1] to [14].

A pair of electrodes made of a positive electrode and a negative electrode; A light emitting layer disposed between the pair of electrodes; And an electron transport layer and / or an electron injection layer disposed between the cathode and the light emitting layer and containing the electron transporting material according to the item [15].

At least one of the electron transporting layer and the electron injection layer may further comprise at least one selected from the group consisting of a quinolinol-based metal complex, a bipyridine derivative, a phenanthroline derivative, and a borane derivative. Lt; / RTI >

At least one of the electron transporting layer and the electron injecting layer may be at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metal oxides, alkaline earth metal halides, rare earth metals Of the above [16] or [17], further comprising at least one selected from the group consisting of oxides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals. Lt; / RTI >

The compound of the present invention is stable even when a voltage is applied in a thin film state, and has a high charge transport ability. The compound of the present invention is suitable as a charge transporting material in an organic EL device. By using the compound of the present invention for the electron transporting layer and / or the electron injecting layer of the organic EL device, an organic EL device having a long lifetime can be obtained. By using the organic EL device of the present invention, a high-performance display device such as a full color display can be manufactured.

Hereinafter, the present invention will be described in more detail. In the present specification, for example, the "compound represented by the formula (1-7-26)" may be referred to as "the compound (1-7-26)". The compound represented by the formula (1-7-74) may be referred to as the compound (1-7-74). Other expression symbols and expression numbers are handled in the same manner.

<Description of compound>

The first invention of the present application is a compound having pyridyl, bipyridyl or pyridylphenyl represented by the following formula (1).

In the formula (1), Py is independently a group represented by the formula (2), (3) or (4), and m and n are 0 or 1, but m + n = 1. It is a feature of the present invention that at least one of the benzene ring, naphthalene ring and pyridine ring in the formula (1) is substituted with an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 3 to 6 carbon atoms.

The pyridyl represented by the formula (2) is specifically 2-pyridyl, 3-pyridyl or 4-pyridyl.

Specific examples of the bipyridyl represented by the formula (3) include 2,2'-bipyridin-5-yl, 2,2'-bipyridin-6-yl, , 2,3'-bipyridin-5-yl, 2,3'-bipyridin-6-yl, , 4'-bipyridin-6-yl, 2,4'-bipyridin-4-yl, 3,2'-bipyridin-6-yl, Bipyridin-6-yl, 3,3'-bipyridin-5-yl, 3,4'-bipyridin-6-yl, 3,4'- Bipyridin-3-yl, 4,3'-bipyridin-3-yl, or 4,4'-bipyridin-3-yl.

Specific examples of the pyridylphenyl represented by the formula (4) include 4- (2-pyridyl) phenyl, 4- (3-pyridyl) phenyl, 4- 2- (3-pyridyl) phenyl, 3- (3-pyridyl) phenyl, 2- -Pyridyl) phenyl. &Lt; / RTI &gt;

In the formula (1), the linking of Py may be at any position in the phenyl or in the 2-naphthyl, but preferably at the 4-position and the 3-position in the phenyl, and in the 2-naphthyl is preferably 6 Position and the seventh position. Particularly, the position 3 of the phenyl is preferable in terms of not expanding the conjugated system and not lowering the level of the LUMO. Further, the 6-position of 2-naphthyl is particularly preferable in view of the availability of raw materials.

Examples of the alkyl having 1 to 6 carbon atoms substituted with a benzene ring, a naphthalene ring and a pyridine ring in the formula (1) include methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, Pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, and isohexyl. Among these, preferable alkyl is methyl, ethyl, isopropyl, and tert-butyl, and methyl and tert-butyl are more preferable. Examples of the cycloalkyl having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Among them, preferable cycloalkyl is cyclohexyl, considering ease of raw material availability and ease of synthesis.

The compound represented by the formula (1) is specifically a compound represented by the following formula (1-1) or (1-2).

The definition of Py in the formulas (1-1) and (1-2) is as described above.

More specifically, the compound represented by the formula (1) is a compound represented by any one of the following formulas (1-3) to (1-6).

The definition of Py in the formulas (1-3) to (1-6) is as described above.

More specifically, the compound represented by the formula (1) is a compound represented by any one of the following formulas (1-7) to (1-10).

The definitions of Py and R in the formulas (1-7) to (1-10) are as described above.

P in the formulas (1-7) and (1-8) is an integer of 1 to 5, preferably an integer of 1 to 2, more preferably 1. There is no restriction on the position of the phenyl substituted by R, but it is preferably the position 3 or 4. Q in the formulas (1-9) and (1-10) is an integer of 1 to 5, preferably an integer of 1 to 2, more preferably 1. There is no restriction on the position of the naphthyl substituted by R, but it is preferably a position 6 or 7.

More specifically, the compound represented by the formula (1) is a compound represented by any one of the following formulas (1-11) to (1-14).

The definition of Py ^{1 in} the formulas (1-11) to (1-14) is as described above. The definition of R in the above-mentioned formula (2 '), (3') or (4 ') is as described above. s is an integer of 1 to 4, preferably 1 or 2, more preferably 1. The position of the pyridyl substituted by R is not particularly limited.

More specifically, the compound represented by the formula (1) is a compound represented by the following formula (1-15) or (1-16).

The definitions of Py and R in the formulas (1-15) and (1-16) are as described above. t is an integer of 1 to 4, preferably 1 or 2, more preferably 1. There is no restriction on the position of phenylene in which R is substituted, but in consideration of easiness of synthesis, in the case of 1,4-phenylene, it is preferable that the position is 3 times with respect to carbon connected to anthracene. In the case of 1,3-phenylene, it is preferably the 4-position based on the carbon connected to the anthracene.

As described above, the compounds represented by the formula (1) are specifically classified into the compounds represented by the formulas (1-7) to (1-16). Among them, preferred structures are the formulas (1-7), (1-9) to (1-11) and (1-13) to (1-16) to be.

<Specific Example of Compound>

Specific examples of the compound of the present invention are shown below in the formulas listed below, but the present invention is not limited by the disclosure of these specific structures.

Specific examples of the compound represented by the formula (1-7)

Specific examples of the compound represented by the formula (1-7) are represented by the following formulas (1-7-1) to (1-7-144). Among these compounds, preferable compounds are the compounds represented by formulas (1-7-1) to (1-7-6), (1-7-10) to (1-7-12), (1-7-16) (1-7-34) to (1-7-36), (1-7-40) to (1-7-48), (1-7-73) to 1-7-78), equations 1-7-82 to 1-7-84, equations 1-7-88 to 1-7-102, equations 1-7-106- (1-7-108) and equations (1-7-112) to (1-7-120).

Specific examples of the compound represented by the formula (1-8)

Specific examples of the compound represented by the formula (1-8) are represented by the following formulas (1-8-1) to (1-8-105).

<Specific examples of the compound represented by formula (1-9)

Specific examples of the compound represented by the formula (1-9) are represented by the following formulas (1-9-1) to (1-9-48). Among them, preferred compounds are the compounds represented by formulas (1-9-10) to (1-9-12), (1-9-16) to (1-9-18), (1-9-34) 9-36) and (1-9-40) to (1-9-42).

<Specific examples of the compound represented by formula (1-10)

Specific examples of the compound represented by the formula (1-10) are represented by the following formulas (1-10-1) to (1-10-48). Among them, preferable compounds are compounds represented by formulas (1-10-1) to (1-10-6), (1-10-10) to (1-10-12) and (1-10-16) -21).

Specific examples of the compound represented by the formula (1-11)

Specific examples of the compound represented by the formula (1-11) are represented by the following formulas (1-11-1) to (1-11-60). Among them, preferred compounds are the compounds represented by formulas (1-11-3) to (1-11-10), (1-11-25) to (1-11-28), (1-11-51) -60).

<Specific examples of the compound represented by formula (1-12)

Specific examples of the compound represented by the formula (1-12) are represented by the following formulas (1-12-1) to (1-12-60).

<Specific examples of the compound represented by formula (1-13)

Specific examples of the compound represented by the formula (1-13) are represented by the following formulas (1-13-1) to (1-13-60). Among them, preferable compounds are the formulas (1-13-21) to (1-13-28) and the formulas (1-13-31) to (1-31-40).

Specific examples of the compound represented by the formula (1-14)

Specific examples of the compound represented by the formula (1-14) are represented by the following formulas (1-14-1) to (1-14-60). Among them, preferable compounds are the formulas (1-14-1) to (1-14-18).

Specific examples of the compound represented by the formula (1-15)

Specific examples of the compound represented by the formula (1-15) are represented by the following formulas (1-15-1) to (1-15-48). Among them, preferred compounds are the compounds represented by formulas (1-15-10) to (1-15-12), (1-15-16) to (1-15-18), (1-15-34) 15-36) and (1-15-40) to (1-15-42).

Specific examples of the compound represented by the formula (1-16)

Specific examples of the compound represented by the formula (1-16) are represented by the following formulas (1-16-1) to (1-16-24). Among them, preferred compounds are the formulas (1-16-1) to (1-16-5).

&Lt; Synthesis method of compound &

Hereinafter, the synthesis method of the compound of the present invention will be described. The compounds of the present invention can be synthesized by appropriately combining conventional synthetic methods which are generally used.

<Synthesis method of the compound represented by formula (1-7-1) to formula (1-7-144)> [

R is an alkyl having 1 to 6 carbon atoms or a cycloalkyl having 1 to 6 carbon atoms

m: integer of 1 to 5

First, 9-phenylanthracene in which phenyl is substituted with an alkyl group (cycloalkyl group) in Reaction 1 is synthesized. Alkyl substituted bromobenzene is reacted with metal magnesium in THF to give a Grignard reagent which is then reacted with 9-bromoanthracene in the presence of a catalyst to give 9-phenylanthracene in which the phenyl is substituted with an alkyl group (cycloalkyl group) . The coupling of the benzene ring and the anthracene ring is not limited to the above method. For example, a coupling reaction using a zinc complex, a Suzuki coupling reaction using a boronic acid or a boronic acid ester, and the like can be used. Conventional methods can be suitably used.

In reaction 2, N-bromosuccinimide is used to brominate the 10-position of 9-phenylanthracene in which phenyl is substituted with an alkyl group (cycloalkyl group). Here, conventionally used brominating agents other than N-bromosuccinimide can also be used.

In reaction 3, anthracene ring and naphthalene ring are coupled. First, 2-bromo-6-methoxynaphthalene is converted into Grignard reagent according to a conventional method, and 9-bromoanthracene derivative synthesized in Reaction 2 is reacted with 9- (6-methoxy Naphthalen-2-yl) -10-phenylanthracene derivative is synthesized. In the same manner as in Reaction 1, coupling of a benzene ring and an anthracene ring is not limited to the above method. For example, a Negishi coupling reaction using a zinc complex, a Suzuki coupling reaction using a boronic acid or a boronic ester , These conventional methods can be suitably used depending on the situation.

In reaction 4, the methoxy group of the 9- (6-methoxynaphthalen-2-yl) -10-phenylanthracene derivative is demethylated to naphthol. Here too, reagents conventionally used for the demethylation reaction can be suitably used.

In reaction 5, -OH of naphthol is referred to as trifluoromethylsulfonate (triflate). -OTf in the reaction scheme is - an abbreviation of OSO ₂ CF _3.

In the reaction 6, a pyridine ring is bonded to the naphthalene ring by a negative coupling reaction. First, 4-bromopyridine is made into a Grignard reagent. In this case, since stable 4-bromopyridine hydrochloride is used as a raw material, isopropylmagnesium chloride is used at a ratio of 2 times, but it may be used as a molar for a raw material which does not need to use a hydrochloride. A zinc chloride complex of pyridine is synthesized by adding zinc chloride tetramethylethylenediamine complex to a Grignard reagent, and the triflate obtained in the reaction 5 is reacted in the presence of a palladium catalyst to synthesize a target product.

In Reaction 6, besides the Negishi coupling reaction, a commonly used coupling reaction such as a Suzuki coupling reaction can be suitably used. When a Suzuki coupling reaction is used, an optimum boronic acid or boric acid ester may be prepared according to the target product. For example, a target compound can be obtained using a boronic acid ester as shown in the following reaction 7.

Specific examples of the palladium catalyst used in the coupling reaction include Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) ₂ , tris (dibenzylideneacetone) 2 palladium (Dibenzylideneacetone) palladium (0), bis (tri tert-butylphosphino) palladium (0), or (1,1'-bis (diphenylphosphino) ) Ferrocene) dichloropalladium (II).

In order to promote the reaction, a phosphine compound may be added to these palladium compounds, as the case may be. Specific examples of such phosphine compounds include tri (tert-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (ditert- butylphosphino) N, N-dibutylaminomethyl) -2- (ditert-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (ditert- butylphosphino) ferrocene, 1,1'- (ditert-butylphosphino) -1,1'-binaphthyl, 2-methoxy-2 '- (ditert-butylphosphino) , 1'-binaphthyl, or 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl.

Specific examples of the base used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium tert-butoxide, sodium acetate, And potassium fluoride.

Specific examples of the solvent used in the reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N, N-dimethylformamide, tetrahydrofuran, diethylether, tert- 4-dioxane, methanol, ethanol, cyclopentyl methyl ether or isopropyl alcohol. These solvents may be appropriately selected and used singly or as a mixed solvent.

&Lt; Synthesis method of compound represented by formulas (1-8-1) to (1-8-105) &gt;

In the above-described reaction 3, 2-bromo-7-methoxynaphthalene may be used in place of 2-bromo-6-methoxynaphthalene to similarly synthesize.

<Synthesis of Compound Represented by Formula (1-9-1) to Formula (1-9-48) and Formula (1-10-1) to Formula (1-10-48)

Instead of the raw materials used in the above-described reactions 1 to 3, the benzene skeleton and the naphthalene skeleton can be substituted and the raw materials can be used to synthesize them as described above. That is, coupling of Grignard reagent of 2-bromoanthracene with 9-bromoanthracene, bromination of position 10 of anthracene according to Reaction 2, and subsequent bromination of this bromide with paramethoxybenzene or metamethoxybenzene (4- or 3-methoxyphenyl) -10- (2-naphthyl) anthracene is obtained by reacting with Grignard reagent of benzyl benzene. The step after the demethylation of the methoxy group with respect to this compound may be carried out in the same manner as described above. It goes without saying that, besides the specifically exemplified compounds, the compounds can also be synthesized in accordance with the above-described synthesis method by appropriately using the starting materials in accordance with the desired products.

Expressions (1-11-1) to (1-11-60), Expressions (1-12-1) to (1-12-60), Expressions (1-13-1) to (1- 13-60) and the synthesis methods of the compounds represented by the formulas (1-14-1) to (1-14-60)

The pyridine derivative substituted with an alkyl group or a cycloalkyl group can be used instead of the pyridine derivative of the raw material used in the reaction 6 or 7 described above to prepare a raw material.

Pyridine derivatives substituted with an alkyl group or a cycloalkyl group can be synthesized as shown in the following reactions 8 to 9. Here, the synthesis method of the pyridine moiety in the compound represented by the formula (1-11-11), the formula (1-12-11), the formula (1-13-11) and the formula (1-14-11) , A pyridine derivative substituted with various alkyl groups or cycloalkyl groups can be synthesized by appropriately changing the raw materials.

<Synthesis of Compound Represented by Formula (1-15-1) to Formula (1-15-48) and Formula (1-16-1) to Formula (1-16-24)

In the synthesis method of the compound represented by the above-mentioned "Formulas (1-9-1) to (1-9-48) and Formulas (1-10-1) to (1-10-48)" At the introduction step, a phenyl group substituted with an alkyl group or a cycloalkyl group may be used. For example, a synthesis method represented by the following reaction 10 can be used.

The definition of R in the formula is as described above. o is an integer of 1 to 4; R may be linked to any desired position of the benzene ring depending on the desired compound, as many as desired.

When the compound of the present invention is used for an electron injection layer or an electron transporting layer in an organic EL device, it becomes stable when an electric field is applied. This indicates that the compound of the present invention is excellent as an electron injecting material or an electron transporting material of an electroluminescent device. The electron injecting layer referred to herein is a layer for receiving electrons from the cathode to the organic layer, and the electron transporting layer is for transporting injected electrons to the light emitting layer. Further, the electron transporting layer may also serve as an electron injecting layer. The materials used for each layer are referred to as an electron injecting material and an electron transporting material.

<Description of Organic EL Device>

The second invention of the present application is an organic EL device containing the compound represented by the formula (1) of the present invention in the electron injection layer or electron transport layer. The organic EL device of the present invention has low driving voltage and high durability during driving.

Although the structure of the organic EL device of the present invention is various, it is basically a multilayer structure sandwiching at least a hole transporting layer, a light emitting layer and an electron transporting layer between the anode and the cathode. Examples of specific configurations of the device include (1) anode / hole transporting layer / light emitting layer / electron transporting layer / cathode, (2) anode / hole injecting layer / hole transporting layer / light emitting layer / electron transporting layer / cathode, (3) anode / / Hole transporting layer / light emitting layer / electron transporting layer / electron injecting layer / cathode.

Since the compound of the present invention has a high electron injecting property and an electron transporting property, it can be used alone or in combination with other materials for an electron injecting layer or an electron transporting layer. In the organic EL device of the present invention, light emission of blue, green, red or white may be obtained by combining a hole injection layer, a hole transporting layer, a light emitting layer, or the like using another material for the electron transporting material of the present invention.

The light emitting material or luminescent dopant usable in the organic EL device of the present invention is a light emitting material or a light emitting dopant which can be used in daylight as described in Polymer Functional Materials Series, &quot; Functional Materials &quot;, Kyodo Publications (1991) Emitting materials such as fluorescent materials, fluorescent whitening agents, laser pigments, organic scintillators, and various fluorescence analysis reagents, supervised by Junji Kuno, "Organic EL materials and displays", published by Siemens Publishing Co. (2001) P155 to 156 A luminescent material of a triplet material as described in P170 to 172, and the like.

The compound which can be used as a light emitting material or a luminescent dopant includes a polycyclic aromatic compound, a heteroaromatic compound, an organic metal complex, a dye, a polymer light emitting material, a styryl derivative, an aromatic amine derivative, a coumarin derivative, a borane derivative, Compounds having a ring, oxadiazole derivatives, and fluorene derivatives. Examples of the polycyclic aromatic compound include anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, pyrene derivatives, chrysene derivatives, perylene derivatives, coronene derivatives, and rubrene derivatives. Examples of the heteroaromatic compound include oxadiazole derivatives having a dialkylamino group or diarylamino group, pyrazoloquinoline derivatives, pyridine derivatives, pyran derivatives, phenanthroline derivatives, siroo derivatives, thiophene derivatives having triphenylamino groups, And the like. Examples of the organometallic complexes include metal complexes such as zinc, aluminum, beryllium, europium, terbium, dysprosium, iridium, platinum, osmium, gold and the like, quinolinol derivatives, benzoxazole derivatives, benzothiazole derivatives, oxadiazole derivatives, A benzoimidazole derivative, a pyrrole derivative, a pyridine derivative, a phenanthroline derivative and the like. Examples of the coloring matter are oxetane derivatives, polymethine derivatives, porphyrin derivatives, coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, oxobenzanthracene derivatives, carbostyryl derivatives, perylene derivatives, benzoxazole derivatives , Benzothiazole derivatives, benzoimidazole derivatives, and the like. Examples of the polymer light emitting material include polyparaphenylenevinylene derivatives, polythiophene derivatives, polyvinylcarbazole derivatives, polysilane derivatives, polyfluorene derivatives, and polyparaphenylene derivatives. Examples of the styryl derivatives include amine-containing styryl derivatives, styrylarylene derivatives and the like.

Other electron transporting materials used in the organic EL device of the present invention can be arbitrarily selected from compounds usable as an electron transporting compound in a photoconductive material, an electron transporting layer of an organic EL device, and a compound usable in an electron injecting layer have.

Specific examples of such electron transporting materials include quinolinol-based metal complexes, 2,2'-bipyridyl derivatives, phenanthroline derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives, thiophene derivatives, A thiadiazole derivative, a metal complex of an oxine derivative, a quinoxaline derivative, a polymer of a quinoxaline derivative, a benzazole compound, a gallium complex, a pyrazole derivative, a perfluorinated phenylene derivative, a triazine derivative, a pyrazine derivative, Benzoquinoline derivatives, imidazopyridine derivatives, borane derivatives, and the like.

As for the hole injecting material and the hole transporting material used in the organic EL device of the present invention, it is preferable to use a compound conventionally used as a charge transporting material of a hole in a photoconductive material, a hole injecting layer and a hole transporting layer of an organic EL device Any of the well-known known ones may be selected and used. Specific examples thereof include carbazole derivatives, trilaurylamine derivatives, phthalocyanine derivatives and the like.

Each layer constituting the organic EL device of the present invention can be formed by thinning a material constituting each layer by a vapor deposition method, a spin coating method, a casting method, or the like. The film thickness of each layer thus formed is not particularly limited and may be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The thin film forming method of the light emitting material is preferably a vapor deposition method in that a homogeneous film is easily obtained and pinholes are difficult to be generated. In the case of thinning using a vapor deposition method, the deposition conditions differ depending on the kind of the light emitting material of the present invention. The deposition conditions are generally in the range of boat heating temperature 50 to 400 占 폚, vacuum degree ^10-6 to ^10-3 Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature 150 to 300 占 폚 and film thickness 5 nm to 5 占 퐉 As shown in Fig.

The organic EL device of the present invention is preferably supported on the substrate in any of the above-described structures. The substrate is not particularly limited as long as it has mechanical strength, thermal stability and transparency, and glass, transparent plastic film and the like can be used. The anode material may be a metal, alloy, electrically conductive compound and mixtures thereof having a work function greater than 4 eV. Specific examples thereof include metals such as Au, CuI, indium tin oxide (hereinafter abbreviated as ITO), SnO ₂ , and ZnO.

The cathode material may use a work function metal, alloy, electroconductive compound, and mixtures thereof less than 4 eV. Specific examples thereof include aluminum, calcium, magnesium, lithium, a magnesium alloy, an aluminum alloy, and the like. Specific examples of the alloy include aluminum / lithium fluoride, aluminum / lithium, magnesium / silver, magnesium / indium and the like. In order to efficiently obtain luminescence of the organic EL device, it is preferable that at least one of the electrodes has a light transmittance of 10% or more. It is preferable that the sheet resistance as the electrode is several hundreds? /? Or less. The film thickness varies depending on the properties of the electrode material, but is usually set in the range of 10 nm to 1 占 퐉, preferably 10 to 400 nm. Such an electrode can be produced by forming a thin film by a method such as vapor deposition or sputtering using the electrode material described above.

Next, as an example of a method for producing an organic EL device using the light emitting material of the present invention, a method for producing an organic EL device comprising the anode / hole injection layer / hole transporting layer / light emitting layer / electron transporting material / cathode of the present invention Will be described. A thin film of a cathode material is formed on a suitable substrate by a vapor deposition method to produce a cathode, and a thin film of a hole injection layer and a hole transport layer is formed on the anode. And a thin film of the light emitting layer is formed thereon. The electron transporting material of the present invention is vacuum-deposited on the light-emitting layer to form a thin film to form an electron transporting layer. Further, a target organic EL device can be obtained by forming a thin film made of a material for a negative electrode by vapor deposition to form a negative electrode. In the above-described production of the organic EL device, the cathode, the electron transporting layer, the light emitting layer, the hole transporting layer, the hole injecting layer, and the anode may be prepared in this order.

When a direct current voltage is applied to the organic EL device thus obtained, the positive electrode may be applied with the polarity of + or -. When a voltage of about 2 to 40 V is applied, the transparent or semitransparent electrode side , And both) can be observed. Further, this organic EL element emits light even when an AC voltage is applied. The waveform of the applied alternating current can be arbitrarily set.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples. First, synthesis examples of the compounds used in the examples will be described below.

[Synthesis Example 1] Synthesis of Compound (1-7-74)

&Lt; Synthesis of 9- (4-tert-butylphenyl) anthracene &gt;

Under nitrogen atmosphere, 9-bromo-anthracene 31 g, 4-tert- butyl-phenyl boronic acid _{25 g, Pd (PPh 3)} 4 1.3 g, potassium phosphate, and 51 g of 1,2,4-trimethyl benzene, 150 ml flask containing a Were stirred at reflux temperature for 21 hours. After the reaction solution was cooled to room temperature, water and toluene were added thereto to separate the solution. The solvent was distilled off under reduced pressure, and the precipitated solid was collected by suction filtration, washed with methanol and then with ethyl acetate to obtain 28 g of 9- (4-tert-butylphenyl) anthracene.

<Synthesis of 9-bromo-10- (4-tert-butylphenyl) anthracene>

In a flask containing 27 g of 9- (4-tert-butylphenyl) anthracene, 0.1 g of oxo and 300 ml of THF, 19 g of N-bromosuccinimide was added under nitrogen atmosphere. The mixture was stirred at room temperature for 18 hours, and an aqueous solution of sodium thiosulfate was added to terminate the reaction. The solution was transferred to a separatory funnel and extracted with chloroform. The solvent was distilled off under reduced pressure to precipitate a solid. The solid was collected by suction filtration and then recrystallized from chlorobenzene to obtain 29 g of 9-bromo-10- (4-tert-butylphenyl) anthracene.

<Synthesis of 3- (6-bromonaphthalen-2-yl) pyridine>

10 g of 3-bromopyridine and 60 ml of THF was cooled in an ice bath and 35 ml of a 2 M solution of isopropylmagnesium chloride in THF was added dropwise with stirring under a nitrogen atmosphere. After completion of the dropwise addition, the temperature was once increased to room temperature, then cooled with ice water, and 17 g of zinc tetramethylethylenediamine chloride complex was added with stirring. Thereafter, the mixture was stirred at room temperature for 1 hour, 18 g of 6-bromonaphthalene-2-yl trifluoromethanesulfonate and 1.6 g of PdCl ₂ (dppp) were added, and the mixture was stirred at reflux temperature for 3 hours. After cooling the reaction solution to room temperature, a solution in which an ethylenediamine tetraacetic acid · tetrasodium salt dihydrate equivalent to approximately 3 times the molar amount of the aimed compound is dissolved in an appropriate amount of water (hereinafter referred to as &quot; , Abbreviated as EDTA · 4 Na aqueous solution) and toluene were added to the solution. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography [toluene / ethyl acetate = 7/3 (volume ratio)] to obtain 12 g of 3- (6-bromonaphthalen-2-yl) pyridine.

&Lt; Synthesis of Compound (1-7-74) &gt;

6.2 g of 3- (6-bromonaphthalen-2-yl) pyridine, 5.9 g of bispinolol acetone, 0.4 g of bis (dibenzylideneacetone) palladium (0), 0.5 g of tricyclohexylphosphine, g and 50 ml of dimethoxyethane was stirred in a nitrogen atmosphere at a reflux temperature for 4 hours. 8.6 g of 9-bromo-10- (4-tert-butylphenyl) anthracene, 9.3 g of potassium phosphate and 50 ml of 1,2,4-trimethylbenzene were added to this solution, and dimethoxyethane was added dropwise to a solution of Dean- ) Tube, and the mixture was heated and distilled off at room temperature. 5 ml of tert-butyl alcohol, 5 ml of water, 0.4 g of bis (dibenzylideneacetone) palladium (0) and 0.5 g of tricyclohexylphosphine were added, and the mixture was further stirred at a reflux temperature for 5 hours. The reaction solution was cooled to room temperature, washed with water to dissolve the salt, and then the solid was collected by suction filtration. The resulting solid was washed with methanol followed by ethyl acetate and then purified by silica gel column chromatography [toluene / ethyl acetate = 9/1 (volume ratio)] to obtain the compound (1-7-74) - (4-tert-butyl) phenyl) anthracene-9-yl) naphthalen-2-yl) pyridine. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 9.07 (m, 1H), 8.68 (dd, 1H), 8.23 (m, 1H), 8.15 (d, 1H), 8.08 (m, 1H), 8.03 (m, (M, 3H), 7.30 (d, 2H), 7.83 (d, (m, 4 H), 1.49 (s, 9 H).

Synthesis Example 2 Synthesis of Compound (1-7-26)

&Lt; Synthesis of 9- (3-tolyl) anthracene &gt;

Under nitrogen atmosphere, 9-bromo-anthracene 36 g, 3- methylphenyl boronic acid _{21 g, Pd (PPh 3)} 4 1.4 g, potassium phosphate, and 59 g of 1,2,4-trimethyl benzene, 150 ml is into a reflux flask Lt; / RTI &gt; for 2.5 hours. After the reaction solution was cooled to room temperature, water and toluene were added thereto to separate the solution. The obtained toluene solution was purified by a silica gel short column, and then the solvent was distilled off under reduced pressure. Heptane was added to the obtained oil, and the precipitated solid was collected by suction filtration to obtain 31 g of 9- (3-tolyl) anthracene.

<Synthesis of 9-bromo-10- (3-tolyl) anthracene>

30 g of 9- (3-tolyl) anthracene and 200 ml of THF was cooled in an ice bath under a nitrogen atmosphere, 20 g of N-bromosuccinimide and 0.1 g of oxo were added. The mixture was stirred at room temperature for 15 hours, and an aqueous solution of sodium thiosulfate was added to stop the reaction. The solution was transferred to a separatory funnel, extracted with toluene, and then purified with a silica gel short column. The solvent was distilled off under reduced pressure, heptane was added to the resulting solution, and the precipitated solid was collected by suction filtration to obtain 30 g of 9-bromo-10- (3-tolyl) anthracene.

Synthesis of <4,4,5,5-tetramethyl-2- (10- (3-tolyl) anthracen-9-yl) -1,3,2-dioxaborolane>

30 g of 9-bromo-10- (3-tolyl) anthracene, 26 g of bispinolacetodiboron, 1.5 g of bis (dibenzylideneacetone) palladium (0), 1.4 g of tricyclohexylphosphine, , 12 g of potassium carbonate and 100 ml of cyclopentyl methyl ether was stirred in a nitrogen atmosphere at a reflux temperature for 16 hours. After the reaction solution was cooled to room temperature, water and toluene were added thereto for liquid separation, and the resulting toluene solution was purified by a silica gel short column. The solvent was distilled off under reduced pressure, heptane was added to the obtained oil, and the precipitated solid was collected by suction filtration to obtain 4,4,5,5-tetramethyl-2- (10- (3-tolyl) anthracene- ) -1,3,2-dioxaborolane (24 g).

&Lt; Synthesis of Compound (1-7-26) &gt;

12 g of 4,4,5,5-tetramethyl-2- (10- (3-tolyl) anthracene-9-yl) -1,3,2-dioxaborolane, 3- (6-bromonaphthalene- 2- yl) pyridine _{10 g, Pd (PPh 3)} 4 1.0 g, potassium phosphate, 13 g, 1,2,4- trimethyl benzene, 50 ml, tert- butyl alcohol and 10 ml of water containing 10 ml of the flask at reflux And stirred for 1 hour. After the reaction solution was cooled to room temperature, water and toluene were added thereto for liquid separation, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography [toluene / ethyl acetate = 20/1 (volume ratio)] and then recrystallized from toluene / heptane mixed solution to obtain the compound (1-7-26) (3-tolyl) anthracen-9-yl) naphthalen-2-yl) pyridine. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 9.06 (m, 1H), 8.67 (dd, 1H), 8.22 (m, 1H), 8.14 (d, 1H), 8.06 (m, 1H), 8.02 (m, 1H), 7.45 (m, 1H), 7.27-7.39 (m, 2H), 7.81 (d, , &Lt; / RTI &gt; 7H), 2.50 (s, 3H).

[Synthesis Example 3] Synthesis of Compound (1-7-98)

<Synthesis of 9- (3-tert-butylphenyl) anthracene>

In a nitrogen atmosphere, 23 g of 9-bromoanthracene, 25 g of 2- (3-tert-butylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, ₃ ) ₄ , 37 g of potassium phosphate, 250 ml of 1,2,4-trimethylbenzene, 50 ml of tert-butyl alcohol and 30 ml of water were stirred at a reflux temperature for 21 hours. After the reaction solution was cooled to room temperature, water and toluene were added thereto to separate the solution. The obtained toluene solution was purified by silica gel short column, and the solvent was distilled off under reduced pressure. The solid precipitated by adding methanol was collected by suction filtration to obtain 24 g of 9- (3-tert-butylphenyl) anthracene.

Synthesis of <9-bromo-10- (3-tert-butylphenyl) anthracene>

13 g of N-bromosuccinimide was added to a flask containing 23 g of 9- (3-tert-butylphenyl) anthracene, 0.1 g of oxo and 100 ml of THF in a nitrogen atmosphere. The mixture was stirred at room temperature for 1 hour, and an aqueous solution of sodium thiosulfate was added to stop the reaction. The solution was transferred to a separatory funnel and extracted with toluene. The obtained toluene solution was purified by silica gel short column, and the solvent was distilled off under reduced pressure, followed by re-precipitation with toluene / methanol to obtain 23 g of 9-bromo-10- (3-tert-butylphenyl) anthracene.

&Lt; Synthesis of Compound (1-7-98) &gt;

6.2 g of 3- (6-bromonaphthalen-2-yl) pyridine, 5.9 g of bispinolol acetone, 0.4 g of bis (dibenzylideneacetone) palladium (0), 0.5 g of tricyclohexylphosphine, g and 50 ml of dimethoxyethane was stirred in a nitrogen atmosphere at a reflux temperature for 4 hours. To this solution, 8.6 g of 9-bromo-10- (3-tert-butylphenyl) anthracene, 9.3 g of potassium phosphate and 50 ml of 1,2,4-trimethylbenzene were added and dimethoxyethane was added , And the mixture was heated and distilled off at room temperature. 5 ml of tert-butyl alcohol, 5 ml of water, 0.4 g of bis (dibenzylideneacetone) palladium (0) and 0.5 g of tricyclohexylphosphine were added, and the mixture was further stirred at a reflux temperature for 2 hours. The reaction solution was cooled to room temperature, washed with water to dissolve the salt, and then the solid was collected by suction filtration. The resulting solid was purified by silica gel column chromatography [toluene / ethyl acetate = 9/1 (volume ratio)] and then recrystallized from toluene to obtain 3- (6- (10- (3- 9-yl) naphthalen-2-yl) pyridine (1.5 g) was obtained. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 9.07 (m, 1H), 8.68 (dd, 1H), 8.23 (s, 1H), 8.16 (d, 1H), 8.08 (m, 1H), 8.03 (m, (M, 2H), 7.83 (m, 1H), 7.75 (d, 2H), 7.72 (m, 5 H), 1.41 (s, 9 H).

[Synthesis Example 4] Synthesis of Compound (1-7-96)

Synthesis of 2- (10- (4-tert-butylphenyl) anthracen-9-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane [

7.8 g of 9-bromo-10- (4-tert-butylphenyl) anthracene, 6.1 g of bispinolate diboron, 0.3 g of bis (dibenzylideneacetone) palladium (0), 0.3 g of tricyclohexylphosphine, 3.9 g of potassium, 2.8 g of potassium carbonate, and 40 ml of cyclopentyl methyl ether was stirred in a nitrogen atmosphere at a reflux temperature for 6 hours and a half. After the reaction solution was cooled to room temperature, water and toluene were added thereto for liquid separation, and the solvent was distilled off under reduced pressure. Heptane was added to the obtained oil, and the precipitated solid was collected by suction filtration to obtain 2- (10- (4-tert-butylphenyl) anthracen-9-yl) -4,4,5,5- To obtain 6.9 g of 3,2-dioxaborolane.

<Synthesis of 4- (3- (6-bromonaphthalen-2-yl) phenyl) pyridine>

9.8 g of 4- (3-bromophenyl) pyridine and 20 ml of THF were cooled in a dry ice / methanol bath to -70 ° C or lower, and 17 ml of 2.6 M normal butyl lithium was slowly dropped in a nitrogen atmosphere. After completion of the dropwise addition, the mixture was stirred at the same temperature for 0.5 hours, and 12 g of zinc chloride tetramethylethylenediamine complex was added. Thereafter, the mixture was stirred at room temperature for 0.5 hours, 15 g of 6-bromonaphthalene-2-yl trifluoromethanesulfonate, 5 g of bis (dibenzylideneacetone) palladium (0) and 1,2- Propano) was added, and the mixture was stirred at a reflux temperature for 1 hour. After completion of the reaction, an aqueous EDTA · 4 Na solution and ethyl acetate were added and the liquid was separated. The solvent was distilled off under reduced pressure, and the residue was purified by activated alumina column chromatography [toluene / ethyl acetate = 9/1 (volume ratio)]. Subsequently, this was washed with methanol and recrystallized from an ethyl acetate / methanol mixed solvent to obtain 5.3 g of 4- (3- (6-bromonaphthalen-2-yl) phenyl) pyridine.

&Lt; Synthesis of Compound (1-7-96) &gt;

6.1 g of 4- (3- ((4-tert-butylphenyl) anthracene-9-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 6-bromo-naphthalene-2-yl) phenyl) pyridine _{5.0 g, Pd (PPh 3)} 4 0.5 g, potassium phosphate 3.0 g, 1,2,4- trimethyl benzene, 25 ml, tert- butyl alcohol and 5 ml water 5 ml was stirred at reflux temperature for 6 hours. After the reaction solution was cooled to room temperature, an aqueous EDTA · 4Na solution and toluene were added to the reaction solution, and the solvent was distilled off under reduced pressure. The resulting crude product was purified by activated alumina column chromatography [toluene / ethyl acetate = 9/1 (volume ratio)]. The solvent was distilled off under reduced pressure and the obtained solid was washed with ethyl acetate and then recrystallized from toluene to obtain the compound (1-7-96): 4 (3- (6- (10- (4-tert- butylphenyl) anthracene- Yl) naphthalen-2-yl) phenyl) pyridine (3.3 g). The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : 8.73 (dd, 2H), 8.27 (m, 1H), 8.15 (d, 1H), 8.03 (m, 3H), 7.99 (m, 2H), 7.78 (d, 2H) , 7.73 (d, 2H), 7.61-7.70 (m, 7H), 7.44 (m, 2H), 7.30-7.38 (m, 4H), 1.49 (s, 9H).

[Synthesis Example 5] Synthesis of the compound (1-14-14)

Synthesis of <9- (3-ethoxyphenyl) -10- (naphthalen-2-yl) anthracene>

For 1-bromo-3-ethoxy benzene in a flask 72.4 g, (10- (naphthalene-2-yl) anthracene-9-yl) boronic acid _{104.5 g, Pd (PPh 3)} 4 10.4 g, 127.4 g potassium phosphate, 600 ml of 1,2,4-trimethylbenzene, 120 ml of 2-propanol and 120 ml of water were placed, and the mixture was stirred at a reflux temperature for 6 hours under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, the solid in the liquid was collected by suction filtration and washed with methanol to obtain 82 g of 9- (3-ethoxyphenyl) -10- (naphthalene-2-yl) anthracene.

Synthesis of <3- (10- (naphthalen-2-yl) anthracene-9-yl) phenol>

82 g of 9- (3-ethoxyphenyl) -10- (naphthalen-2-yl) anthracene and 446.0 g of pyridine hydrochloride were placed in a flask and stirred at a reflux temperature for 8 hours. The reaction solution was cooled to room temperature and then water was added thereto. The precipitated solid was collected by suction filtration, washed with methanol and then with toluene to obtain 3- (10- (naphthalen-2-yl) anthracene- 76.0 g was obtained.

Synthesis of <3- (10- (naphthalen-2-yl) anthracene-9-yl) phenyltrifluoromethanesulfonate>

A flask containing 3- (10- (naphthalen-2-yl) anthracene-9-yl) phenol (76.0 g) and pyridine (1 L) was cooled in an ice bath and trifluoromethanesulfonic anhydride 65.0 g was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 15 hours, and water was added thereto, and the precipitated solid was collected by suction filtration. This solid was washed with methanol to obtain 90.3 g of 3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyltrifluoromethanesulfonate.

Synthesis of 4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane [

The flask was charged with 90.3 g of 3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyltrifluoromethanesulfonate, 52.1 g of bispinolate diboron, 7.4 g of bis (dibenzylideneacetone) palladium 7.2 g of tricyclohexylphosphine, 33.6 g of potassium acetate, 23.6 g of potassium carbonate and 500 ml of anisole were placed and stirred at a reflux temperature for 5 hours. After the reaction solution was cooled to room temperature, the celite was suction filtered through a Kiriyama-rhoto funnel to remove insolubles, and the filtrate was washed with an aqueous EDTA · 4Na solution. The solvent of the filtrate was distilled off under reduced pressure, and the resulting solid was washed with heptane to obtain 4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracene- ) -1,3,2-dioxaborolane (52.0 g).

&Lt; Synthesis of compound (1-14-14) &gt;

8.6 g of 4,4,5,5-tetramethyl-2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane, Japanese Patent Application a 5'-bromo synthesized by the method described in Publication No. 2009-124114 Mo-3-methyl-2,2'-bipyridine _{5.1 g, Pd (PPh 3)} 4 0.6 g, potassium phosphate 7.2 g, 25 ml of 1,2,4-trimethylbenzene, 5 ml of tert-butyl alcohol, and 1 ml of water, and the mixture was stirred at a reflux temperature for 2.5 hours. After the reaction solution was cooled to room temperature, water was added, and the solid in the solution was collected by suction filtration and washed with methanol. This solid was purified by silica gel column chromatography [toluene / ethyl acetate = 9/1 (volume ratio)] and then further purified by activated carbon column chromatography. The solution was concentrated and recrystallized from chlorobenzene to obtain the compound (1-14-14): 3-Methyl-5'- (3- (10- (naphthalen- And 2.3 g of 2'-bipyridine. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 9.05 (m, 1H), 8.55 (d, 1H), 8.11 (dd, 1H), 8.09 (d, 1H), 8.02 (m, 1H), 8.00 (s, 1H), 7.73-7.95 (m, 9H), 7.60 (m, 5H), 7.30-7.40 (m, 4H), 7.23 (m,

[Synthesis Example 6] Synthesis of the compound (1-11-1)

Synthesis of 2-methyl-4- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl)

(2.0 g), 4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) bromo-2-methylpyridine (0.8 g), Pd (PPh 3) 4 (0.3 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene (20 ml), tert- butyl alcohol (5 ml ) And water (1 ml) were placed in a flask, and stirred at reflux temperature for 7 hours and 30 minutes under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 95/5). Next, the obtained eluate was passed through an activated carbon short column to remove the colored component. The precipitated crystals were collected while distilling off the filtrate under reduced pressure to obtain the compound 2-methyl-4- (6- (10-phenylanthracene-9-yl) naphthalene-2 Yl) pyridine (0.7 g). The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 8.66 (d, 1H), 8.30 (s, 1H), 8.17 (d, 1H), 8.03 (m, 2H), 7.87 (d, 1H), 7.72-7.78 ( (m, 4H), 7.70 (d, 1H), 7.65 (m, 2H), 7.58 (m, 2H), 7.56 (m, 3H), 7.31-7.

[Synthesis Example 7] Synthesis of compound (1-11-2)

Synthesis of 3-methyl-4- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl)

(2.0 g), 4,4,5,5-tetramethyl-2- (6- (10-phenylanthracen-9-yl) bromo-3-methyl-pyridine hydrochloride (1.0 g), Pd (PPh 3) 4 (0.3 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene (20 ml), tert- butyl alcohol (5 ml) and water (1 ml) were placed in a flask, and stirred at a reflux temperature for 24 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 95/5). Next, the obtained eluate was passed through an activated carbon short column to remove the colored component. The precipitated crystals were collected while distilling off the filtrate under reduced pressure and recrystallized from toluene to obtain the compound 3-methyl-4- (6- (10-phenylanthracene-9 Yl) naphthalen-2-yl) pyridine (0.5 g). The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 8.62 (s, 1H), 8.58 (d, 1H), 8.13 (d, 1H), 8.06 (s, 1H), 8.02 (d, 1H), 7.99 (s, 2H), 7.53 (m, 2H), 7.33-7.39 (m, 5H), 2.44 (s, 2H) , 3H).

[Synthesis Example 8] Synthesis of the compound (1-11-3)

Synthesis of 2-methyl-5- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl)

2-yl) -1,3,2-dioxaborolane (2.0 g), 5- (4-fluorophenyl) Pd (PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml) and tert-butanol (5 ml) And water (1 ml) were placed in a flask, and stirred at reflux temperature for 5 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 95/5). The solvent was distilled off under reduced pressure, and the resulting solid was recrystallized from toluene to obtain the compound 2-methyl-5- (6- (10-phenylanthracene-9-yl) naphthalen- Pyridine (1.2 g). The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 8.95 (m, 1H), 8.20 (s, 1H), 8.14 (d, 1H), 8.01 (m, 2H), 7.96 (dd, 1H), 7.81 (dd, 2H), 7.57 (m, 2H), 7.30-7.37 (m, 5H), 2.67 (s, , 3H).

[Synthesis Example 9] Synthesis of the compound (1-11-4)

Synthesis of 3-methyl-5- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl)

2-yl) -1,3,2-dioxaborolane (2.0 g), 3- (4-fluoropyrimidin- Pd (PPh ₃ ) ₄ (0.3 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml) and tert-butanol (5 ml) And water (1 ml) were put in a flask, and stirred at a reflux temperature for 7 hours and a half under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 95/5). Next, the obtained eluate was passed through an activated carbon short column to remove the colored component. The solvent was distilled off under reduced pressure, and heptane was added to re-precipitate to obtain the compound 3-methyl-5- (6- (10-phenylanthracene-9-yl) naphthalen- Pyridine (1.3 g). The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} :

2H), 7.89 (m, IH), 7.83 (dd, IH), 8.13 (d, , 7.73 (m, 4H), 7.67 (d, 1H), 7.63 (m, 2H), 7.57 (m, 2H) ).

[Synthesis Example 10] Synthesis of the compound (1-11-5)

Synthesis of 4-methyl-3- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl)

2-yl) -1,3,2-dioxaborolane (2.0 g), 3- (4-fluoropyrimidin- bromo-4-methyl-pyridine hydrochloride (1.0 g), Pd (PPh 3) 4 (0.3 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene (20 ml), tert- butyl alcohol (5 ml) and water (1 ml) were placed in a flask, and the mixture was stirred at a reflux temperature for 7 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 95/5). Next, the obtained eluate was passed through an activated carbon short column to remove the colored component. The solvent was distilled off under reduced pressure, and the resulting solid was recrystallized from toluene to obtain the compound 4-methyl-3- (6- (10-phenylanthracene-9-yl) naphthalen- ) Pyridine (0.6 g) was obtained. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 8.64 (s, 1H), 8.55 (d, 1H), 8.14 (d, 1H), 8.06 (s, 1H), 8.02 (d, 1H), 7.99 (s, 2H), 7.53 (m, 2H), 7.32-7.39 (m, 4H), 7.30 (d, , &Lt; / RTI &gt; 1H), 2.45 (s, 3H).

[Synthesis Example 11] Synthesis of Compound (1-11-6)

Synthesis of 2-methyl-3- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl)

2-yl) -1,3,2-dioxaborolane (2.0 g), 3- (4-fluoropyrimidin- bromo-2-methylpyridine (0.8 g), Pd (PPh 3) 4 (0.15 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene (20 ml), tert- butyl alcohol (5 ml ) And water (1 ml) were placed in a flask, and stirred at a reflux temperature for 4 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 95/5). Next, the obtained eluate was passed through an activated carbon short column to remove the colored component. The solvent was distilled off under reduced pressure, and heptane was added to re-precipitate to obtain the compound 2-methyl-3- (6- (10-phenylanthracene-9-yl) naphthalen- Pyridine (1.1 g). The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 8.60 (m, 1H), 8.11 (d, 1H), 8.05 (s, 1H), 8.00 (d, 1H), 7.96 (s, 1H), 7.74 (m, 2H), 7.56 (m, 2H), 7.30-7.37 (m, 4H), 7.28 (m, 1H), 2.66 , 3H).

Synthesis Example 12 Synthesis of Compound (1-11-8)

Synthesis of 5-methyl-2- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl)

2-yl) -1,3,2-dioxaborolane (2.5 g), 3- (4-fluorophenyl) bromo-2-methylpyridine (1.0 g), Pd (PPh 3) 4 (0.15 g), potassium phosphate (2.1 g), 1,2,4- trimethyl benzene (20 ml), tert- butyl alcohol (5 ml ) And water (1 ml) were placed in a flask, and stirred at a reflux temperature for 18 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and the precipitated solid was collected by suction filtration. The resulting solid was purified by silica gel column chromatography (eluent: toluene). Next, the obtained eluate was passed through an activated carbon short column to remove the colored component. The solvent was distilled off under reduced pressure, and ethyl acetate was added to re-precipitate to obtain the compound 5-methyl-2- (6- (10-phenylanthracene-9-yl) naphthalen- ) Pyridine (1.5 g). The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 8.63 (m, 2H), 8.23 (dd, 1H), 8.16 (d, 1H), 8.00 (m, 2H), 7.86 (d, 1H), 7.73 (m, (M, 4H), 7.60-7.67 (m, 4H), 7.56 (t, 1H), 7.51 (m, 2H), 7.30-7.36 (m, 4H), 2.44

[Synthesis Example 13] Synthesis of the compound (1-11-39)

Synthesis of <5-bromo-2'-methyl-3,4'-bipyridine>

A flask containing 4-bromo-2-methylpyridine (13.8 g) and toluene (150 ml) was cooled in an acetone / dry ice bath. A 1.6 M normal butyl lithium hexane solution (55 ml) was added dropwise to this solution. After completion of the dropwise addition, the mixture was stirred for 1 hour while cooling in an acetone / dry ice bath, zinc chloride tetramethylethylenediamine (29.3 g) and THF (45 ml) were added, and the acetone / dry ice bath was removed and the temperature was raised. After the temperature was raised to room temperature, toluene (20 ml), 3,5-dibromopyridine (19.0 g) and Pd (PPh ₃ ) ₄ (2.8 g) were added and the mixture was stirred at reflux temperature for 2 hours. After the reaction solution was cooled to room temperature, an aqueous solution of EDTA · 4Na and toluene were added to separate the solution. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate). At this time, referring to the method described in "Organic Chemistry Experiment Guide (1) -Material Handling Method and Separation and Refinement Method" published by Kagaku Dojin Publishing Co., Ltd., page 94, the ratio of ethyl acetate in the developing solution was gradually increased, Lt; / RTI &gt; Subsequently, the solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from heptane to obtain 5-bromo-2'-methyl-3,4'-bipyridine (5.3 g).

Synthesis of 2'-methyl-5- (6- (10-phenylanthracene-9-yl) naphthalen-2-yl)

2-yl) -1,3,2-dioxaborolane (2.5 g), 5- (4-fluoropyridin- bromo-2'-methyl-3,4'-bipyridine (1.1 g), Pd (PPh 3) 4 (0.15 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene (20 ml) , tert-butyl alcohol (5 ml) and water (1 ml) were put in a flask and stirred at a reflux temperature for 3 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 1/1). The solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from toluene to obtain the compound 2'-methyl-5- (6- (10-phenylanthracene-9-yl) naphthalene- Yl) 3,4'-bipyridine (0.3 g) was obtained. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 9.11 (m, 1H), 8.92 (m, 1H), 8.65 (d, 1H), 8.28 (m, 2H), 8.17 (d, 1H), 8.05 (m, 2H), 7.87 (d, 1H), 7.68-7.75 (m, 5H), 7.61 (m, 2H), 7.56 (t, (m, 4 H), 2.70 (s, 3 H).

[Synthesis Example 14] Synthesis of compound (1-14-2)

Synthesis of 3-methyl-4- (3- (10- (naphthalen-2-yl) anthracen-9-yl)

Yl) phenyl) -1,3,2-dioxaborolane (2.5 g), 4,4,5,5-tetramethyl-2- (3- (10- (naphthalen- 4-bromo-3-methyl-pyridine hydrochloride (1.3 g), Pd (PPh 3) 4 (0.35 g), potassium phosphate (3.2 g), 1,2,4- trimethyl benzene, 20 ml, tert- butyl alcohol, 5 ml , And water (1 ml), and the mixture was stirred at a reflux temperature for 11 hours and a half. After the reaction solution was cooled to room temperature, toluene and water were added to the solution, and the solution was separated. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 95/5). Next, the obtained eluate was passed through an activated carbon short column to remove the colored component. The solvent was distilled off under reduced pressure, and heptane was added to re-precipitate to obtain the compound 3-methyl-4- (3- (10- (naphthalen-2-yl) anthracene- Phenyl) pyridine (1.4 g) was obtained. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} :

1H), 7.70-7.78 (m, 1H), 8.02 (d, 1H), 8.02 (d, 5H), 7.48-7.63 (m, 6H), 7.35-7.39 (m, 2H), 7.29-7.34 (m, 3H), 2.41 (s, 3H).

[Synthesis Example 15] Synthesis of the compound (1-14-3)

Synthesis of 2-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl)

Yl) phenyl) -1,3,2-dioxaborolane (2.5 g), 4,4,5,5-tetramethyl-2- (3- (10- (naphthalen- 5-bromo-2-methylpyridine (1.0 g), Pd (PPh 3) 4 (0.35 g), potassium phosphate (3.2 g), 20 ml 1,2,4- trimethylbenzene, tert- butyl alcohol, 5 ml, And 1 ml of water, and the mixture was stirred at a reflux temperature for 8 hours and a half. The reaction solution was cooled to room temperature, and the precipitated solid was collected by suction filtration. The resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 95/5). Next, the obtained eluate was passed through an activated carbon short column to remove the colored component. The solvent was distilled off under reduced pressure, and the resulting solid was washed with ethyl acetate to obtain the compound 2-methyl-5- (3- (10- (naphthalen-2-yl) anthracene- Yl) phenyl) pyridine (1.5 g) was obtained. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 8.45 (m, 1H), 8.08 (d, 1H), 8.03 (m, 1H), 7.99 (s, 1H), 7.93 (m, 1H), 7.87 (dd, (S, 3H), 7.30-7.40 (m, 4H), 7.30-7.81 (m, 7H), 7.57-7.63 .

[Synthesis Example 16] Synthesis of the compound (1-14-11)

Synthesis of <5-bromo-6'-methyl-2,2'-bipyridine>

A flask containing 2-bromo-6-methylpyridine (5.2 g) and cyclopentyl methyl ether (30 ml) was cooled in a methanol / dry ice bath. To this solution was added dropwise a 1.6 M normal butyl lithium hexane solution (22 ml). After completion of the dropwise addition, the mixture was stirred for 2 hours while cooling in a methanol / dry ice bath, zinc tetramethylethylenediamine chloride (8.3 g) was added, the methanol / dry ice bath was removed and the temperature was raised. After the temperature was raised to room temperature, 2,5-dibromopyridine (7.1 g) and Pd (PPh ₃ ) ₄ (1.0 g) were added and stirred at reflux temperature for 3 hours and a half. The reaction solution was cooled to room temperature, and then an aqueous EDTA · 4 Na solution and toluene were added to the reaction mixture. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. Subsequently, the solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from heptane to obtain 5-bromo-6'-methyl-2,2'-bipyridine (1.4 g).

Synthesis of 6'-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,2'-

2-yl) anthracene-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 4,4,5,5-tetramethyl- 5-bromo-6'-methyl-2,2'-bipyridine (1.0 g), Pd (PPh 3) 4 (0.15 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene, 20 ml , 5 ml of tert-butyl alcohol and 1 ml of water, and the mixture was stirred at a reflux temperature for 7 hours and a half. The reaction solution was cooled to room temperature, and the precipitated solid was collected by suction filtration. The obtained solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 95/5), and the obtained eluate was directly subjected to suction filtration using an activated charcoal using a Kankiriamarut funnel to remove the colored component. The solvent was distilled off under reduced pressure, and ethyl acetate was added to re-precipitate to obtain the compound 6'-methyl-5- (3- (10- (naphthalen-2-yl) anthracene- Yl) phenyl) -2,2'-bipyridine (1.2 g) was obtained. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 9.03 (m, 1H), 8.49 (dd, 1H), 8.22 (d, 1H), 8.09 (m, 2H), 8.03 (m, 1H), 8.00 (s, 1H), 7.93 (m, 1H), 7.87 (d, 1H), 7.68-7.83 (m, 7H), 7.55-7.64 (m, 4H), 7.30-7.40 , &Lt; / RTI &gt; 2.65 (s, 3H).

[Synthesis Example 17] Synthesis of the compound (1-14-12)

Synthesis of <5-bromo-5'-methyl-2,2'-bipyridine>

A flask containing 2-bromo-5-methylpyridine (1.7 g) and THF (5 ml) was cooled in an ice bath and 2 M isopropyl magnesium chloride THF solution (5.5 ml) was added dropwise to this solution. After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 3 hours and 30 minutes, cooled again in an ice bath, and zinc tetramethylethylenediamine chloride (2.8 g) was added thereto. After the ice bath was removed and the temperature was raised to room temperature, 2,5-dibromopyridine (2.4 g) and Pd (PPh ₃ ) ₄ (0.35 g) were added and stirred at a reflux temperature for 1 hour and a half. The reaction solution was cooled to room temperature, and then an aqueous EDTA · 4 Na solution and toluene were added to the reaction mixture. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 9/1). The solvent was distilled off under reduced pressure, and heptane was added to re-precipitate to obtain 5-bromo-5'-methyl-2,2'-bipyridine (1.5 g).

Synthesis of 5-methyl-5 '- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,2'-

2-yl) anthracene-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 4,4,5,5-tetramethyl- 5-bromo-5'-methyl-2,2'-bipyridine (1.2 g), Pd (PPh 3) 4 (0.15 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene, 20 ml , 5 ml of tert-butyl alcohol, and 1 ml of water were placed, and the mixture was stirred at reflux temperature for 6 hours. After the reaction solution was cooled to room temperature, toluene and water were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 95/5) and the obtained eluate was passed through an activated carbon short column to remove the colored component. The solvent was distilled off under reduced pressure, ethyl acetate was added to re-precipitate the product, and the obtained solid was recrystallized from toluene to obtain the compound 5-methyl-5'- (3- (10- (naphthalene Yl) anthracene-9-yl) phenyl) -2,2'-bipyridine (1.2 g). The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 9.03 (m, 1H), 8.52 (s, 1H), 8.44 (dd, 1H), 8.33 (d, 1H), 8.09 (m, 1H), 8.03 (m, 2H), 7.93 (m, 1H), 7.87-7.83 (m, 6H), 7.56-7.66 (m, 5H), 7.31-7.39 , &Lt; / RTI &gt; 2.41 (s, 3H).

[Synthesis Example 18] Synthesis of the compound (1-14-13)

Synthesis of <5'-bromo-4-methyl-2,2'-bipyridine>

A flask containing 2-bromo-4-methylpyridine (6.9 g) and THF (20 ml) was cooled in an ice bath and 2 M isopropyl magnesium chloride THF solution (24 ml) was added dropwise to this solution. After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 1 hour, then cooled in an ice bath, and zinc tetramethylethylenediamine chloride (12.1 g) was added. After the ice bath was removed and the temperature was raised to room temperature, 2,5-dibromopyridine (9.5 g) and Pd (PPh ₃ ) ₄ (1.4 g) were added and stirred at a reflux temperature for 2 hours and a half. The reaction solution was cooled to room temperature, and then an aqueous EDTA · 4 Na solution and toluene were added to the reaction mixture. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 9/1). The solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from heptane to obtain 5'-bromo-4-methyl-2,2'-bipyridine (5.5 g).

Synthesis of 4-methyl-5 '- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,2'-

2-yl) anthracene-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 4,4,5,5-tetramethyl- 5'-bromo-4-methyl-2,2'-bipyridine (1.2 g), Pd (PPh 3) 4 (0.15 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene, 20 ml , 5 ml of tert-butyl alcohol, and 1 ml of water, and the mixture was stirred at a reflux temperature for 16 hours. After the reaction solution was cooled to room temperature, toluene and water were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 95/5) and the obtained eluate was passed through an activated carbon short column to remove the colored component. The solvent was distilled off under reduced pressure and the residue was washed with heptane to obtain the compound 4-methyl-5'- (3- (10- (naphthalen-2-yl) anthracene- ) -2,2'-bipyridine (1.4 g) was obtained. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} :

1H), 8.03 (d, IH), 8.05 (d, IH), 8.05 (d, (M, 4H), 7.30-7.40 (m, 4H), 7.14 (m, IH) (d, 1 H), 2.45 (s, 3 H).

[Synthesis Example 19] Synthesis of Compound (1-14-15)

Synthesis of <5-bromo-6'-methyl-2,3'-bipyridine>

A flask containing 5-bromo-2-methylpyridine (3.4 g) and THF (10 ml) was cooled in an ice bath, and a 2 M solution of isopropylmagnesium chloride in THF (11 ml) was added dropwise. After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 3 hours, cooled again in an ice bath, and zinc tetramethylethylenediamine chloride (5.5 g) was added. After the ice bath was removed and the temperature was raised to room temperature, 2,5-dibromopyridine (4.7 g) and Pd (PPh ₃ ) ₄ (0.7 g) were added and the mixture was stirred at reflux temperature for 5 hours. After the reaction solution was cooled to room temperature, an aqueous solution of EDTA · 4Na and toluene were added to separate the solution. The solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 7/3) to obtain 5-bromo- g).

Synthesis of 6'-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,3'-

2-yl) anthracene-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 4,4,5,5-tetramethyl- 5-bromo-6'-methyl -2,3'- bipyridine (1.2 g), Pd (PPh 3) 4 (0.15 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene, 25 ml , 5 ml of tert-butyl alcohol and 1 ml of water, and the mixture was stirred at reflux temperature for 5 hours. After the reaction solution was cooled to room temperature, the precipitated solid was collected by suction filtration, washed with methanol and then with ethyl acetate. Then, the solution was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 4/1), and the obtained eluate was passed through an activated carbon short column to remove the colored component. The solvent was distilled off under reduced pressure, and the obtained solid was further recrystallized from chlorobenzene to obtain the compound 6'-methyl-5- (3- (10- (naphthalen-2-yl) anthracene Yl) phenyl) -2,3'-bipyridine (1.3 g) was obtained. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} :

1H), 7.93 (m, 1H), 7.86 (m, 1H), 8.07 (m, 1H), 7.73-7.83 (m, 7H), 7.57-7.64 (m, 4H), 7.31-7.39 (m, 4H), 7.28 (d,

[Synthesis Example 20] Synthesis of compound (1-14-16)

Synthesis of <5-bromo-5'-methyl-2,3'-bipyridine>

A flask containing 3-bromo-5-methylpyridine (3.4 g) and THF (10 ml) was cooled in an ice bath, and a 2 M solution of isopropylmagnesium chloride in THF (11 ml) was added dropwise. After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 1 hour and a half, then cooled in an ice bath, and zinc tetramethylethylenediamine chloride (5.5 g) was added thereto. After the ice bath was removed and the temperature was raised to room temperature, 2,5-dibromopyridine (4.7 g) and Pd (PPh ₃ ) ₄ (0.7 g) were added and the mixture was stirred at reflux temperature for 5 hours. The reaction solution was cooled to room temperature, and then an aqueous EDTA · 4 Na solution and toluene were added to the reaction mixture. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 7/3) to obtain 5-bromo-5'-methyl-2,3'-bipyridine g).

Synthesis of 5'-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,3'-

2-yl) anthracene-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 4,4,5,5-tetramethyl- 5-bromo-6'-methyl -2,3'- bipyridine (1.2 g), Pd (PPh 3) 4 (0.15 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene, 25 ml , 5 ml of tert-butyl alcohol and 1 ml of water, and the mixture was stirred at reflux temperature for 5 hours. After the reaction solution was cooled to room temperature, the precipitated solid was collected by suction filtration, washed with methanol and then with ethyl acetate. Subsequently, the solution was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 4/1), and the eluted solution obtained was passed through an activated carbon short column to remove the colored component. The solvent was distilled off under reduced pressure, and the resulting solid was recrystallized from chlorobenzene to obtain the compound 5'-methyl-5- (3- (10- (naphthalen-2-yl) anthracene- Yl) phenyl) -2,3'-bipyridine (1.3 g) was obtained. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 9.08 (m, 1H), 9.04 (s, 1H), 8.50 (s, 1H), 8.21 (s, 1H), 8.09 (m, 2H), 8.04 (m, 1H), 8.00 (s, 1H), 7.93 (m, 1H), 7.73-7.88 (m, 8H), 7.62 (m, 4H), 7.31-7.40 (m, 4H), 2.45 (s,

[Synthesis Example 21] Synthesis of compound (1-14-17)

Synthesis of <5-bromo-4'-methyl-2,3'-bipyridine>

A flask containing 3-bromo-4-methylpyridine (5.2 g) and THF (10 ml) was cooled in an ice bath, and a 2 M solution of isopropylmagnesium chloride in THF (17 ml) was added dropwise. After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 9 hours, cooled again in an ice bath, and zinc chloride tetramethylethylenediamine (8.3 g) was added thereto. After the ice bath was removed and the temperature was raised to room temperature, 2.5 g of dibromopyridine (7.1 g), Pd-137 (Johnson Matthias) (0.4 g) and NMP (25 ml) Lt; / RTI &gt; The reaction solution was cooled to room temperature, and then an aqueous EDTA · 4 Na solution and toluene were added to the reaction mixture. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 7/3). The solvent was distilled off under reduced pressure, and the resulting solid was washed with heptane to obtain 5-bromo-4'-methyl-2,3'-bipyridine (2.4 g).

Synthesis of 4'-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,3'-

2-yl) anthracene-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 4,4,5,5-tetramethyl- 5-bromo-6'-methyl -2,3'- bipyridine (1.2 g), Pd (PPh 3) 4 (0.15 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene, 25 ml , 5 ml of tert-butyl alcohol and 1 ml of water, and the mixture was stirred at reflux temperature for 5 hours. After the reaction solution was cooled to room temperature, toluene and water were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 7/3) and the obtained eluate was passed through an activated carbon short column to remove the colored component. The solvent was distilled off under reduced pressure, and the resulting solid was recrystallized from toluene to obtain the compound 4'-methyl-5- (3- (10- (naphthalen-2-yl) anthracene-9 Yl) phenyl) -2,3'-bipyridine (0.7 g) was obtained. The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 9.09 (s, 1H), 8.67 (s, 1H), 8.51 (d, 1H), 8.09 (m, 2H), 8.03 (m, 1H), 8.00 (m, 1H), 7.93 (m, 4H), 7.93 (m, 1H) (d, 1 H), 2.46 (s, 3 H).

[Synthesis Example 22] Synthesis of the compound (1-14-18)

Synthesis of <5-bromo-2'-methyl-2,3'-bipyridine>

A flask containing 3-bromo-2-methylpyridine (5.2 g) and THF (10 ml) was cooled in an ice bath, and a 2 M solution of isopropylmagnesium chloride in THF (17 ml) was added dropwise. After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 2 hours, then cooled in an ice bath and zinc chloride tetramethylethylenediamine (8.3 g) was added. After the ice bath was removed and warmed to room temperature, was added 2,5-dibromo-pyridine (7.1 g), Pd (PPh 3) 4 (1.0 g) and xylene (10 ml), and the mixture was stirred for 7 hours at reflux temperature. The reaction solution was cooled to room temperature, and then an aqueous EDTA · 4 Na solution and toluene were added to the reaction mixture. After the solvent was distilled off under reduced pressure, the resulting solid was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate = 4/1) to obtain 5-bromo-2'-methyl-2,3'-bipyridine g).

Synthesis of 2'-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,3'-

2-yl) anthracene-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 4,4,5,5-tetramethyl- 5-bromo-6'-methyl -2,3'- bipyridine (1.2 g), Pd (PPh 3) 4 (0.15 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene, 25 ml , 5 ml of tert-butyl alcohol, and 1 ml of water, and the mixture was stirred at a reflux temperature for 12 hours. After the reaction solution was cooled to room temperature, toluene and water were added to separate the layers. The solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 4/1), and the obtained eluate was passed through an activated carbon short column to remove the colored component. The solvent was distilled off under reduced pressure, and the precipitated solid was collected by suction filtration to obtain the compound 2'-methyl-5- (3- (10- (naphthalen-2-yl) anthracene Yl) phenyl) -2,3'-bipyridine (0.8 g) was obtained. The structure of the compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ ):? = 9.08 (m, 1H), 8.57 (m, 1H), 7.99-8.10 (m, 4H), 7.92 (D, 1H), 7.30-7.40 (m, 4H), 7.25 (m, 1H), 2.66 (s, 3H).

[Synthesis Example 23] Synthesis of the compound (1-14-20)

Synthesis of <5-bromo-3'-methyl-2,4'-bipyridine>

A flask containing 4-bromo-3-methylpyridine (5.0 g) and THF (30 ml) was cooled in a dry ice / methanol bath, and a 2 M solution of isopropylmagnesium chloride in THF (16 ml) . After completion of the dropwise addition, the cooling bath was removed, and the mixture was stirred at room temperature for 2 hours and a half, then cooled in an ice bath, and zinc tetramethylethylenediamine chloride (8.0 g) was added thereto. After the ice bath was removed and the temperature was raised to room temperature, 2,5-dibromopyridine (7.6 g) and Pd (PPh ₃ ) ₄ (1.0 g) were added and the mixture was stirred at reflux temperature for 2 hours. After the reaction solution was cooled to room temperature, an aqueous EDTA · 4 Na solution and ethyl acetate were added to the reaction mixture, and the mixture was separated. After the solvent was distilled off under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 5/1) to obtain 5-bromo-3'-methyl-2,4'-bipyridine g).

Synthesis of 3'-methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,4'-

2-yl) anthracene-9-yl) phenyl) -1,3,2-dioxaborolane (2.0 g), 4,4,5,5-tetramethyl- 5-bromo-3'-methyl -2,4'- bipyridine (1.2 g), Pd (PPh 3) 4 (0.15 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene 1 ml 1 ml of tert-butyl alcohol, and 1 ml of water were placed, and the mixture was stirred at a reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, water was added, and the precipitate was collected by suction filtration. The obtained solid was washed with water and methanol, and then purified by column chromatography (eluent: toluene) with NH-modified silica gel (DM1020, manufactured by Fuji Silysia) to obtain the compound 3'- Methyl-5- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2,4'-bipyridine (1.7 g). The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 9.09 (m, 1H), 8.56 (s, 1H), 8.55 (d, 1H), 8.10 (m, 2H), 8.03 (m, 1H), 8.00 (d, 1H), 7.93 (d, 1H), 7.88 (d, 1H), 7.73-7.83 (m, 6H), 7.61 (m, 4H), 7.53 (s, 3 H).

[Synthesis Example 24] Synthesis of the compound (1-11-18)

Synthesis of 2'-methyl-5- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl)

2-yl) -1,3,2-dioxaborolane (2.0 g), 5- (4-fluorophenyl) bromo-2'-methyl -2,3'- bipyridine (1.2 g), Pd (PPh 3) 4 (0.15 g), potassium phosphate (1.7 g), 1,2,4- trimethyl benzene (20 ml) , tert-butyl alcohol (5 ml) and water (1 ml) were placed in a flask, and the mixture was stirred at a reflux temperature for 8 hours under a nitrogen atmosphere. After the completion of the heating, the reaction solution was cooled to room temperature, and the precipitated solid was collected by suction filtration, washed with methanol and then with ethyl acetate. Subsequently, purification was carried out by silica gel column chromatography (developing solution: toluene / ethyl acetate = 7/3), and the eluted solution obtained was passed through an activated carbon short column to remove coloring components. The solvent was distilled off under reduced pressure, and the precipitated solid was collected by suction filtration to obtain the compound 2'-methyl-5- (6- (10-phenylanthracene-9-yl) naphthalene -2-yl) 2,3'-bipyridine (1.1 g). The structure of the compound was confirmed by NMR measurement.

_{^{1 H-NMR (CDCl 3)}} : δ = 9.17 (m, 1H), 8.60 (dd, 1H), 8.230 (s, 1H), 8.19 (m, 2H), 8.06 (m, 2H), 7.87 (dd, 2H), 7.26-7.37 (m, 5H), 2.73 (m, 2H), 7.85 (d, (s, 3 H).

Other derivative compounds of the present invention can be synthesized by the method according to the above-mentioned synthesis example by suitably changing the compound of the starting material.

Hereinafter, to describe the present invention in more detail, examples of the organic EL device using the compound of the present invention are shown, but the present invention is not limited thereto.

The devices according to Examples 1 to 4 and Comparative Examples 1 and 2 were manufactured and the driving start voltage (V) in the constant current driving test and the time (hr) in which the luminance was maintained at 90% or more of the initial value were measured . Examples and Comparative Examples are described below in detail.

In the devices according to Examples 1 to 4 and Comparative Examples 1 and 2, the material composition of each layer is shown in Table 1 below.

[Table 1]

In Table 1, "HI" refers to N ⁴ , N ^{4 '} -diphenyl -N ⁴ , N ^4' -bis (9-phenyl-9H-carbazol- ] -4,4'-diamine, "NPD" is N ^4, N ^{4 '-} di (naphthalene-1-yl) -N ^4, N ^4' - diphenyl - [1,1'-biphenyl] -4 , 4'-diamine, the compound (A) is 9-phenyl-10- (4-phenyl-1-yl) anthracene, the compound (B) is ^{N 5, N 5, N 9} , N 9 -7, 7- ([2,2'-bipyridine] -5-yl) anthracene, the compound (D) is a compound represented by the formula 9,10-bis (4- (pyridin-3-yl) naphthalen-1-yl) anthracene. Liq "used in the layer formed between the electron transporting layer and the cathode shows a chemical structure in the following.

[Example 1]

&Lt; Device using Compound (1-7-74) as electron transport layer &gt;

A glass substrate of 26 mm x 28 mm x 0.7 mm (manufactured by Optoscience Co., Ltd.), in which ITO formed to a thickness of 180 nm by polishing was polished to 150 nm by sputtering was used as a transparent support substrate. This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and molybdenum-containing boats containing HI, molybdenum-containing boats containing NPD, molybdenum containing compound (A) Molybdenum boats with compounds (B), molybdenum boats with compounds (1-7-74), molybdenum boats with Liq, molybdenum boats with magnesium, and silver The tungsten boat was installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum tank was evacuated to 5 x 10 &lt; ^-4 &gt; Pa. First, an evacuation boat containing HI was heated to form a hole injection layer to a film thickness of 40 nm. Next, Followed by evaporation to a thickness of 30 nm by heating to form a hole transport layer. Next, an evaporation boat containing the compound (A) and an evaporation booth containing the compound (B) were simultaneously heated to deposit a film having a film thickness of 35 nm to form a light emitting layer. The deposition rate was controlled so that the weight ratio of compound (A) to compound (B) was approximately 95: 5. Next, an evaporation boat containing the compound (1-7-74) was heated and evaporated to a film thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / sec.

Thereafter, the deposition boats containing Liq were heated to deposit at a deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm. Subsequently, a boat containing magnesium and a boat containing silver were heated at the same time to deposit a film having a thickness of 100 nm to form a negative electrode. At this time, the deposition rate was controlled so that the ratio of atomic ratio of magnesium and silver was 10: 1, and a cathode was formed so as to have a deposition rate of 0.1 to 10 nm / sec to obtain an organic electroluminescent device.

When a DC voltage was applied to the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode, blue light emission with a wavelength of about 460 nm was obtained. When the constant current driving test was carried out by the current density for obtaining the initial luminance of 2000 cd / m ² , the driving test starting voltage was 7.33 V, and the luminance was maintained at 90% (1800 cd / m ² ) or more of the initial value The time was 45 hours.

[Example 2]

&Lt; Device using Compound (1-7-26) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-7-74) was changed to the compound (1-7-26). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 6.36 V, and the time for maintaining the luminance of 90% or more of the initial value was 151 hours.

[Example 3]

&Lt; Device using Compound (1-7-98) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-7-74) was changed to the compound (1-7-98). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 7.34 V, and the time for maintaining the luminance of 90% or more of the initial value was 265 hours.

[Example 4]

&Lt; Device using compound (1-7-96) in electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-7-74) was changed to the compound (1-7-96). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 5.33 V, and the time for maintaining the luminance of 90% or more of the initial value was 103 hours.

[Comparative Example 1]

An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-7-74) was changed to the compound (C). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the driving test starting voltage was 5.06 V, and the time for maintaining the luminance of 90% or more of the initial value was 6 hours.

[Comparative Example 2]

An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-7-74) was changed to the compound (D). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the driving test starting voltage was 5.05 V, and the time for maintaining the luminance of 90% or more of the initial value was 10 hours.

Table 2 summarizes the above results.

[Table 2]

The devices according to Examples 5 to 20 and Comparative Examples 3 to 5 were manufactured and the driving start voltage (V) in the constant current driving test and the time (hr) for maintaining the luminance of 90% or more of the initial value were measured . Hereinafter, examples and comparative examples will be described in detail.

In the devices according to the produced Examples 5 to 20 and Comparative Examples 3 to 5, the material composition of each layer is shown in Table 3 below.

[Table 3]

In Table 3, HT is a mixture of N - ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9- Phenyl) -9H-fluorene-2-amine, compound (E) is 9- (4- (naphthalen- (4- (10- (naphthalene-2-yl) phenyl) amino) dibenzonitrile, compound (G) (10-phenylanthracene-9-yl) phenyl) -2,2 ': 6', 2 "-terpyridine and compound (H) ) Pyridine, and the compound (I) is 6- (4- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl) -2,4'-bipyridine.

[Example 5]

&Lt; Device using Compound (1-11-1) as an electron transport layer &gt;

A glass substrate of 26 mm x 28 mm x 0.7 mm (manufactured by Optoscience Co., Ltd.), in which ITO formed to a thickness of 180 nm by polishing was polished to 150 nm by sputtering was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and molybdenum-containing boats containing HI, molybdenum-containing boats containing HT, molybdenum containing compound (E) Molybdenum boats with compound (F), molybdenum boats with compound (1-11-1), molybdenum boats with Liq, magnesium molybdenum boats and silver The tungsten boat was installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum tank was evacuated to 5 x 10 &lt; ^-4 &gt; Pa. First, an evacuation boat containing HI was heated to form a hole injection layer to a film thickness of 40 nm. Next, And the film was heated to a thickness of 30 nm to form a hole transport layer. Next, the evaporation boats containing the compound (E) and the evaporation boats containing the compound (F) were heated at the same time to deposit a film having a film thickness of 35 nm to form a light emitting layer. The deposition rate was controlled so that the weight ratio of compound (E) and compound (F) was approximately 95: 5. Next, an evaporation boat containing compound (1-11-1) and an evaporation booth containing Liq were simultaneously heated to deposit a film having a film thickness of 25 nm to form an electron transport layer. The deposition rate was controlled so that the weight ratio of the compound (1-11-1) and Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / sec.

Thereafter, the deposition boats containing Liq were heated to deposit at a deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm. Subsequently, a boat containing magnesium and a boat containing silver were heated at the same time to deposit a film having a thickness of 100 nm to form a negative electrode. At this time, the deposition rate was controlled so that the atomic ratio between magnesium and silver was 10: 1, and the cathode was formed so that the deposition rate was 0.1 to 10 nm / sec to obtain an organic electroluminescent device.

When a direct current voltage was applied to the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode, blue light emission with a wavelength of about 450 nm was obtained. Further, when the constant current driving test was performed by the current density for obtaining the initial luminance of 2000 cd / m ² , the driving test starting voltage was 4.00 V, and the luminance was maintained at 90% (1800 cd / m ² ) or more of the initial value The time was 87 hours.

[Example 6]

&Lt; Device using Compound (1-11-2) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-11-2). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 4.12 V, and the time for maintaining the luminance of 90% or more of the initial value was 85 hours.

[Example 7]

&Lt; Device using Compound (1-11-3) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-11-3). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 3.78 V, and the time for maintaining the luminance of 90% or more of the initial value was 97 hours.

[Example 8]

&Lt; Device using Compound (1-11-4) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-11-4). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 3.95 V, and the time for maintaining the luminance of 90% or more of the initial value was 83 hours.

[Example 9]

&Lt; Device using Compound (1-11-5) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-11-5). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 3.88 V, and the time for maintaining the luminance of 90% or more of the initial value was 93 hours.

[Example 10]

&Lt; Device using Compound (1-11-39) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-11-39). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 4.16 V, and the time for maintaining the luminance of 90% or more of the initial value was 74 hours.

[Example 11]

&Lt; Device using Compound (1-14-2) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-14-2). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 3.61 V, and the time to maintain the luminance of 90% or more of the initial value was 76 hours.

[Example 12]

&Lt; Device using Compound (1-14-3) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-14-3). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 3.85 V, and the time for maintaining the luminance of 90% or more of the initial value was 141 hours.

[Example 13]

&Lt; Device using Compound (1-14-11) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-14-11). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 4.16 V, and the time for maintaining the luminance of 90% or more of the initial value was 162 hours.

[Example 14]

&Lt; Device using Compound (1-14-12) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-14-12). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 3.87 V, and the time for maintaining the luminance of 90% or more of the initial value was 75 hours.

[Example 15]

&Lt; Device using Compound (1-14-14) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-14-14). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test start voltage was 3.82 V, and the time for maintaining the luminance of 90% or more of the initial value was 227 hours.

[Example 16]

&Lt; Device using Compound (1-14-15) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-14-15). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 3.98 V, and the time for maintaining the luminance of 90% or more of the initial value was 101 hours.

[Example 17]

&Lt; Device using Compound (1-14-16) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-14-16). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 4.25 V, and the time for maintaining the luminance of 90% or more of the initial value was 70 hours.

[Example 18]

&Lt; Device using Compound (1-14-18) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-14-18). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 3.75 V, and the time for maintaining the luminance of 90% or more of the initial value was 125 hours.

[Example 19]

&Lt; Device using Compound (1-14-20) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-14-20). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 4.19 V, and the time for maintaining the luminance of 90% or more of the initial value was 63 hours.

[Example 20]

&Lt; Device using Compound (1-11-18) as electron transport layer &gt;

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (1-11-18). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . The driving test starting voltage was 4.29 V, and the time for maintaining the luminance of 90% or more of the initial value was 60 hours.

[Comparative Example 3]

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (G). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the driving test starting voltage was 5.36 V, and the time for maintaining the luminance of 90% or more of the initial value was 2 hours.

[Comparative Example 4]

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (H). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the driving test starting voltage was 4.12 V, and the time for maintaining the luminance of 90% or more of the initial value was 26 hours.

[Comparative Example 5]

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-11-1) was changed to the compound (I). A constant current driving test was carried out by using the ITO electrode as a positive electrode and the magnesium / silver electrode as a negative electrode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the driving test starting voltage was 4.15 V, and the time for maintaining the luminance of 90% or more of the initial value was 30 hours.

Table 4 summarizes the above results.

[Table 4]

[Industrial Availability]

According to a preferred embodiment of the present invention, it is possible to provide an organic electroluminescent device which improves the lifetime of the light emitting device, and which is excellent in balance with the driving voltage, a display device including the organic electroluminescent device, and a lighting device including the same.

Claims (18)

A compound represented by the following formula (1-7) or (1-8):

In the above formulas (1-7) and (1-8)
Py is a group represented by the following formula (2), (3) or (4);

R is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms; and p is an integer of 1 to 5. A compound represented by the following formula (1-9) or (1-10):

In the above formulas (1-9) and (1-10)
Py is a group represented by the following formula (2), (3) or (4);

R is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms; and q is an integer of 1 to 5. A compound represented by the following formula (1-11) or (1-12):

In the above formulas (1-11) and (1-12)
Py ¹ is a group represented by the following formula (2 '), (3') or (4 ');

In the above formulas (2 '), (3') and (4 '), R is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms; and s is an integer of 1 to 4. A compound represented by the following formula (1-13) or (1-14):

In the above formulas (1-13) and (1-14)
Py ¹ is a group represented by the following formula (2 '), (3') or (4 ');

In the formula (2 '), (3') or (4 '), R is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms; and s is an integer of 1 to 4. A compound represented by the following formula (1-15) or (1-16):

In the above formulas (1-15) and (1-16)
Py is a group represented by the following formula (2), (3) or (4);

R is alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms; and t is an integer of 1 to 4. A compound represented by the following formula (1-7-26):

. A compound represented by the following formula (1-7-74):

. A compound represented by the following formula (1-7-98):

. A compound represented by the following formula (1-7-96):

. A compound represented by the following formula (1-14-14):

. (1-11-1), (1-11-2), (1-11-3), (1-11-4), (1-11-5), (1-11-6), (1-11-8), (1-11-18), (1-11-39), (1-14-2), (1-14-3), (1-14-11), (1-14-13), (1-14-15), (1-14-16), (1-14-17), (1-14-18), and (1- 14-20).

. An electron transporting material containing the compound according to any one of claims 1 to 11. A pair of electrodes made of a positive electrode and a negative electrode;
A light emitting layer disposed between the pair of electrodes; And
An electron transport layer disposed between the cathode and the light emitting layer and containing an electron transporting material according to claim 12 and /
Lt; / RTI &gt; 14. The method of claim 13,
Wherein at least one of the electron transporting layer and the electron injecting layer further contains at least one selected from the group consisting of a quinolinol-based metal complex, a bipyridine derivative, a phenanthroline derivative, and a borane derivative. 14. The method of claim 13,
Wherein at least one of the electron transporting layer and the electron injection layer is formed of an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, an alkali metal halide, an oxide of an alkaline earth metal, a halide of an alkaline earth metal, , At least one selected from the group consisting of a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. 15. The method of claim 14,
Wherein at least one of the electron transporting layer and the electron injection layer is formed of an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, an alkali metal halide, an oxide of an alkaline earth metal, a halide of an alkaline earth metal, , At least one selected from the group consisting of a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. delete delete