TWI508949B - Electron transport material and organic electroluminescent device using the same - Google Patents

Description

Electron transport material and organic electroluminescent element using same

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 simply referred to as an organic EL device, or simply an element).

In recent years, organic EL elements have attracted attention as next-generation full color flat panel displays, and the industry is actively studying them. In order to promote the practical use of organic EL devices, reduction in device driving voltage and life extension are indispensable factors, and in order to realize these factors, the industry has been developing new electron transport materials. In particular, it is necessary to reduce the driving voltage of the blue element and extend the life. In the case of using a 2,2'-bipyridine compound as a phenanthroline derivative or an analog thereof, an electron transporting material is described in Patent Document 1 (Japanese Laid-Open Patent Publication No. 2003-123983). The organic EL element can be driven at a low voltage. However, the element characteristics (driving voltage, luminous efficiency, and the like) reported by the examples of this document are only relative values based on the comparative example, and the actual measured values which can be judged to be practical values are not described. Further, the compounds 2,2'-bipyridine Examples of electron transport materials for Non-Patent Document ^{1 (Proceedings of the 10 th International} Workshop on Inorganic and Organic Electroluminescence, tenth inorganic and organic electroluminescent light Proceedings International Symposium It is disclosed in Patent Document 2 (Japanese Patent Laid-Open Publication No. 2002-158093) and Patent Document 3 (International Publication No. 2007/86552). The compound described in Non-Patent Document 1 has a low Tg and is not practical. Although the compound described in Patent Document 2 and Patent Document 3 can drive the organic EL element at a relatively low voltage, it is expected to further extend the life in practical use.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-123983

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-158093

[Patent Document 3] International Publication 2007/86552 Manual

[Non-patent literature]

[Patent Document ^{1] Proceedings of the 10 th International} Workshop on Inorganic and Organic Electroluminescence (2000) ( the tenth inorganic and organic light International Symposium (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 which contributes to prolonging the life of an organic EL device. Further, an object of the present invention is to provide an organic EL device using the electron transport material.

As a result of intensive studies, the present inventors have found that an organic EL device capable of driving with a long lifetime can be obtained by using the following compound for an electron transport layer of an organic EL device, which is 9-(2-naphthyl). Any one of a naphthyl group or a phenyl group of -10-phenylindole having a pyridyl group, a bipyridyl group, or a pyridylphenyl group, and at least one hydrogen on the benzene ring, the naphthalene ring, and the pyridine ring is substituted with carbon a combination of an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms The present invention was completed based on this finding.

The above problems are solved by the items shown below.

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

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

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

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

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

Further, at least one hydrogen on the benzene ring, the naphthalene ring and the pyridine ring in the formulae (1-1) and (1-2) is substituted with an alkyl group having 1 to 6 carbon atoms or a ring having 3 to 6 carbon atoms. alkyl.

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

In the formulae (1-3) to (1-6), Py is a group represented by the formula (2), (3) or (4);

Further, at least one hydrogen on the benzene ring, the naphthalene ring and the pyridine ring in the formulae (1-3) to (1-6) is substituted with an alkyl group having 1 to 6 carbon atoms or a ring having 3 to 6 carbon atoms. alkyl.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[14] The compound according to the above [1], which is represented by the following formulas (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), (1-14-12), (1-14-13), (1-14-15), (1-14-16), (1-14 Any one of -17), (1-14-18), and (1-14-20)

[15] An electron transporting material comprising any of the above [1] to [14] a compound as described.

[16] An organic electroluminescence device comprising: a pair of electrodes including an anode and a cathode; a light-emitting layer disposed between the pair of electrodes; and disposed between the cathode and the light-emitting layer and containing the above The electron transport layer and/or the electron injection layer of the electron transport material of item 15].

[17] The organic electroluminescent device according to the above [16], wherein at least one of the electron transport layer and the electron injecting layer further comprises a hydroxyquinoline-based metal complex, a bipyridine derivative, and a morphine. At least one of a group consisting of a morphine derivative and a borane derivative.

[18] The organic electroluminescent device of the above-mentioned [16] or [17], wherein at least one of the electron transport layer and the electron injecting layer further comprises an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal Oxides, alkali metal halides, alkaline earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earths At least one of the group consisting of organic complexes of metals.

The compound of the present invention is stable even when a voltage is applied in a thin film state, and has a feature that the charge transporting ability is high. The compound of the present invention is suitably used as a charge transport material in an organic EL element. By using the compound of the present invention in an electron transport layer and/or an electron injection layer of an organic EL device, an organic EL device having a long life can be obtained. By using the organic EL element of the present invention, a high-performance display device such as a full-color display can be produced.

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 "compound (1-7-26)". The compound represented by the formula (1-7-74) is sometimes referred to as "compound (1-7-74)". The symbols and formulas of other formulas are also the same.

<Description of Compound>

The first invention of the present invention is a compound having a pyridyl group, a bipyridyl group or a pyridylphenyl group 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, and m + n = 1. Further, the substitution of at least one hydrogen on the benzene ring, the naphthalene ring and the pyridine ring in the formula (1) to an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms is a feature of the present compound.

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

The bipyridyl group represented by the formula (3) is specifically 2,2'-bipyridin-5-yl, 2,2'-bipyridyl-6-yl, 2,2'-bipyridin-4-yl, 2, 3'-bipyridyl-5-yl, 2,3'-bipyridyl-6-yl, 2,3'-bipyridin-4-yl, 2,4'-bipyridyl-5-yl, 2,4' -Link Pyridine-6-yl, 2,4'-bipyridin-4-yl, 3,2'-bipyridyl-6-yl, 3,2'-bipyridin-5-yl, 3,3'-bipyridine- 6-yl, 3,3'-bipyridyl-5-yl, 3,4'-bipyridyl-6-yl, 3,4'-bipyridin-5-yl, 4,2'-bipyridine-3- Base, 4,3'-bipyridin-3-yl, or 4,4'-bipyridin-3-yl.

The pyridylphenyl group represented by the formula (4) is specifically 4-(2-pyridyl)phenyl, 4-(3-pyridyl)phenyl, 4-(4-pyridyl)phenyl, 3-(2 -pyridyl)phenyl, 3-(3-pyridyl)phenyl, 3-(4-pyridyl)phenyl, 2-(2-pyridyl)phenyl, 2-(3-pyridyl)phenyl Or 2-(4-pyridyl)phenyl.

In the formula (1), the position at which Py is bonded may be any position on the phenyl group or the 2-naphthyl group, preferably 4 positions and 3 positions on the phenyl group, and preferably 6 positions on the 2-naphthyl group. And 7 digits. In terms of not expanding the conjugated system and not lowering the energy level of LUMO (lowest unoccupied molecular orbital), it is particularly preferable to be the 3-position of the phenyl group. Further, in terms of easy availability of the raw material, it is particularly preferably a 6-position of 2-naphthyl group.

Examples of the alkyl group having 1 to 6 carbon atoms substituted in the benzene ring, the naphthalene ring, and the pyridine ring in the formula (1) are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and the like. Isobutyl, tert-butyl, n-pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, and isohexyl. Among the preferred alkyl groups are methyl, ethyl, isopropyl, and tert-butyl, more preferably methyl and tert-butyl. Examples of the cycloalkyl group having 3 to 6 carbon atoms are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Among them, a preferred cycloalkyl group is a cyclohexyl group in consideration of availability of a raw material 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 definitions of Py in the formulae (1-1) and (1-2) are the same 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 formulae (1-3) to (1-6) is the same as described above.

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

The definitions of Py and R in the formulae (1-7) to (1-10) are the same as described above. p in the formulae (1-7) and (1-8) is an integer of 1 to 5, preferably an integer of 1 to 2, more preferably 1. The position of the phenyl group substituted by R is not limited, and is preferably 3 or 4 positions. q in the formulae (1-9) and (1-10) is an integer of 1 to 5, preferably an integer of 1 to 2, more preferably 1. The position of the naphthyl group substituted by R is not limited, and is preferably 6 or 7 positions.

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

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

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

The definitions of Py and R in the formulae (1-15) and (1-16) are the same as described above. t is an integer of 1 to 4, preferably 1 or 2, more preferably 1. The position of the phenyl group substituted by R is not limited, and in view of the ease of synthesis, in the case of a 1,4-phenylene group, the position is preferably 3 positions based on the carbon bonded to ruthenium. In the case of a 1,3-phenylene group, it is preferably 4 positions based on the carbon bonded to the hydrazine.

Specifically, the compound represented by the above formula (1) is roughly classified into the compounds represented by the formulae (1-7) to (1-16). Among these, the preferred structures are the formula (1-7), the formula (1-9) to (1-11), and the formula (1-13) to (1-16), and the more preferable structure is the formula (1). -7).

<Specific Example of Compound>

Specific examples of the compound of the present invention can be disclosed as the following formulas, but the present invention is not limited to the disclosure of these specific structures.

<Specific Example of Compound represented by Formula (1-7)>

Specific examples of the compound represented by the formula (1-7) are shown by the following formulas (1-7-1) to (1-7-144). Among these, preferred compounds are of the formula (1-7-1) to (1-7-6), the formula (1-7-10) to (1-7-12), and the formula (1-7-16). )~(1-7-30), formula (1-7-34)~(1-7-36), formula (1-7-40)~(1-7-48), formula (1-7- 73)~(1-7-78), formula (1-7-82)~(1-7-84), formula (1-7-88)~(1-7-102), formula (1-7 -106)~(1-7-108) and formula (1-7-112)~(1-7-120).

<Specific Example of Compound represented by Formula (1-8)>

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

<Specific Example of Compound represented by Formula (1-9)>

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

<Specific Example of Compound represented by Formula (1-10)>

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

<Specific Example of Compound represented by Formula (1-11)>

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

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

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

<Specific Example of Compound represented by Formula (1-13)>

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

<Specific Example of Compound represented by Formula (1-14)>

Specific examples of the compound represented by the formula (1-14) are shown by the following formulas (1-14-1) to (1-14-60). Among these, preferred compounds are the formulae (1-14-1) to (1-14-18).

<Specific Example of Compound represented by Formula (1-15)>

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

<Specific example of the compound represented by the formula (1-16)>

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

<Synthesis method of compound>

Hereinafter, a method for synthesizing the compound of the present invention will be described. The compounds of the present invention can be synthesized by a suitable combination using a general known synthetic method.

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

First, 9-phenylindole substituted by an alkyl group (cycloalkyl group) is synthesized by the reaction 1. The alkyl-substituted bromobenzene is reacted with magnesium metal in THF to form a Grignard reagent, which is reacted with 9-bromoindole in the presence of a catalyst to form a phenyl group via an alkyl group (ring). Alkyl) substituted 9-phenylindole. The combination of the benzene ring and the anthracene ring is not limited to the above method, and for example, a root-shore coupling reaction using a zinc complex or a Suzuki coupling reaction using boric acid or a boric acid ester may be employed, and these conventional methods may be suitably used depending on the situation.

Reaction 2 is the bromination of the 10-position of 9-phenylindole substituted with an alkyl group (cycloalkyl group) using N-bromosuccinimide. Here, a conventional brominating agent other than N-bromosuccinimide may also be used.

Reaction 3 is the coupling of an anthracene ring to a naphthalene ring. First, 2-bromo-6-methoxynaphthalene is prepared into a Grignard reagent according to a conventional method, and reacted with a 9-bromoindole derivative synthesized in the reaction 2 in the presence of a catalyst to synthesize 9-(6-A). Oxynaphthalen-2-yl)-10-phenylindole derivatives. In the same manner as in the reaction 1, the benzene ring and the anthracene ring are not limited to the above method, and for example, a root-shore coupling reaction using a zinc complex or a Suzuki coupling reaction using boric acid or a boric acid ester may be employed, and may be suitably used depending on the situation. Use these conventional methods.

Reaction 4 is a demethylation of a methoxy group of a 9-(6-methoxynaphthalen-2-yl)-10-phenylindole derivative to form a naphthol. Here, a reagent which is commonly used for the demethylation reaction can also be suitably used.

Reaction 5 is the conversion of the -OH of naphthol to triflate. -OTf in the reaction formula is an abbreviation for -OSO ₂ CF ₃ .

Reaction 6 is a pyridine by a Negishi coupling reaction. The ring is bonded to the naphthalene ring. First, 4-bromopyridine was made into a Grignard reagent. Here, since 4-bromopyridine hydrochloride which is stable to a raw material is used, 2-fold molar isopropyl magnesium chloride is used, but it is also possible to use a salt which is not necessary to use a hydrochloride. Adding zinc chloride tetramethylethylenediamine complex to the Grignard reagent, synthesizing zinc chloride complex of pyridine, and reacting it with trifluoromethanesulfonate obtained in reaction 5 in the presence of a palladium catalyst The reaction is combined to synthesize the target.

In addition to the root-coupling reaction, the reaction 6 may suitably employ a conventional coupling reaction such as a Suzuki coupling reaction. In the case of using the Suzuki coupling reaction, the most suitable boric acid or boric acid ester may be prepared depending on the target. For example, a boric acid ester represented by the following reaction 7 can be used to obtain a target product.

Specific examples of the palladium catalyst used for the coupling reaction include Pd(PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd(OAc) ₂ , and tris(dibenzylideneacetone)dipalladium (0). , tris(dibenzylideneacetone)dipalladium(0)chloroform complex, bis(dibenzylideneacetone)palladium(0), bis(tri-t-butylphosphino)palladium(0), or (1 , 1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II).

Further, in order to promote the reaction, a phosphine compound may be added to the palladium compounds as the case may be. Specific examples of the phosphine compound include tris(t-butyl)phosphine, tricyclohexylphosphine, and 1-(N,N-dimethylaminomethyl)-2-(di-t-butylphosphine). Ferrocenyl, 1-(N,N-dibutylaminomethyl)-2-(di-t-butylphosphino)ferrocene, 1-(methoxymethyl)-2-( Di-tert-butylphosphino)ferrocene, 1,1'-bis(di-t-butylphosphino)ferrocene, 2,2'-bis(di-t-butylphosphino)-1,1 '-binaphthyl, 2-methoxy-2'-(di-t-butylphosphino)-1,1'-binaphthyl, or 2-dicyclohexylphosphino-2',6'-dimethoxy Base benzene.

Specific examples of the base to be used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium butoxide, sodium acetate, and the like. Tripotassium phosphate, or potassium fluoride.

Further, specific examples of the solvent used for the reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N,N-dimethylformamide, tetrahydrofuran, and diethyl ether. , tert-butyl methyl ether, 1,4-dioxane, methanol, ethanol, cyclopentyl methyl ether or isopropanol. These solvents may be appropriately selected and used singly or as a mixed solvent.

<Synthesis method of compound represented by formula (1-8-1)~ formula (1-8-105)>

In the above reaction 3, when 2-bromo-7-methoxynaphthalene is used instead of 2-bromo-6-methoxynaphthalene, the synthesis can be carried out in the same manner.

<Formula (1-9-1)~Formula (1-9-48) and Formula (1-10-1)~Formula (1-10-48) Method for synthesizing the indicated compounds >

The raw materials used in the above Reactions 1 to 3 can be used in the same manner as described above by using the raw materials substituted with the benzene skeleton and the naphthalene skeleton instead of the raw materials used in the above Reactions 1 to 3. That is, the 2-bromoindrene Grenner reagent is coupled with 9-bromoindole, and the 10 position of the indole is brominated according to the reaction 2, followed by the bromide with p-methoxybromobenzene or m-methoxybromobenzene. The reagent is reacted to obtain 9-(4- or 3-methoxyphenyl)-10-(2-naphthyl)anthracene. With respect to this compound, the order after the demethylation reaction of the methoxy group may be carried out in accordance with the above. Further, in addition to the specifically exemplified compound, it is of course possible to carry out the synthesis according to the above synthesis method by suitably using a raw material according to the target.

<Formula (1-11-1)~Formula (1-11-60), Formula (1-12-1)~Formula (1-12-60), Formula (1-13-1)~Formula (1- Synthesis method of compound represented by formula (1-14-1) to formula (1-14-60)>

The pyridine derivative of the starting material used in the above reaction 6 or reaction 7 can be used as a raw material by using a pyridine derivative substituted with an alkyl group or a cycloalkyl group, and the synthesis can be carried out in the same manner as above.

The pyridine derivative substituted with an alkyl group or a cycloalkyl group can be synthesized as shown in the following Reaction 8 to Reaction 9. Here, although 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) is exemplified The synthesis method, but by appropriately changing the starting materials, various alkyl or cycloalkyl-substituted pyridine derivatives can be synthesized.

<Synthesis method of the compound represented by the formula (1-15-1) to the formula (1-15-48) and the formula (1-16-1) to the formula (1-16-24)>

Phenyl group in the above "Formula (1-9-1) to formula (1-9-48) and formula (1-10-1) to formula (1-10-48)" In the introduction step, a phenyl group substituted with an alkyl group or a cycloalkyl group may be used. For example, the synthesis method shown in the following reaction 10 can be used.

The definition of R in the formula is the same as described above. o is an integer from 1 to 4. Only the desired amount of R may be linked at any position of the benzene ring depending on the target compound.

In the case where the compound of the present invention is used for an electron injecting layer or an electron transporting layer in an organic EL device, it is relatively stable when an electric field is applied. This case indicates that the compound of the present invention is used as an electron injecting material for an electroluminescence type element. Excellent in materials or electron transport materials. Here, the electron injecting layer refers to a layer that receives electrons from the cathode and injects the organic layer; the so-called electron transporting layer refers to a layer for transporting the injected electrons to the light emitting layer. Further, the electron transport layer may also serve as an electron injection layer. The materials used for each layer are referred to as electron injecting materials and electron transporting materials.

<Description of Organic EL Element>

The second invention of the present invention is an organic EL device comprising a compound represented by the formula (1) of the present invention in an electron injecting layer or an electron transporting layer. The organic EL device of the present invention has a low driving voltage and high durability at the time of driving.

The organic EL device of the present invention has various types of structures, and is basically a multilayer structure in which at least a hole transport layer, a light-emitting layer, and an electron transport layer are sandwiched between an anode and a cathode. Examples of specific configurations of components are: (1) anode/hole transport layer/light-emitting layer/electron transport layer/cathode, (2) anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/cathode (3) anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode, and the like.

Since the compound of the present invention has high electron injectability and electron transportability, it can be used alone or in combination with other materials for the electron injecting layer or the electron transporting layer. The organic EL device of the present invention can also obtain blue, green, red or white light by using a hole injection layer, a hole transport layer, a light-emitting layer or the like of another material in combination with the electron transport material of the present invention.

The luminescent material or the luminescent dopant which can be used in the organic EL device of the present invention is a luminescent material such as a polymer functional material, a polymer functional material series "optical functional material", and a co-published (1991) and P236 , fluorescent brightener, laser pigment, scintillator, various kinds of firefly A luminescent material such as a photoanalytical reagent; a masterbatch edited by Cheng Yuji, "Organic EL Materials and Displays", CMC Publications (2001), a dopant material described in P155-156, and a luminescent material of a triplet material described in P170-172.

Compounds which can be used as luminescent materials or luminescent dopants are: polycyclic aromatic compounds, heterocyclic aromatic compounds, organometallic complexes, pigments, polymeric luminescent materials, styryl derivatives, aromatic amines A derivative, a coumarin derivative, a borane derivative, an oxazine derivative, a compound having a spiro ring, an oxadiazole derivative, an anthracene derivative, and the like. Examples of the polycyclic aromatic compound are an anthracene derivative, a phenanthrene derivative, a condensed tetraphenyl derivative, an anthracene derivative, a condensed naphthalene derivative, an anthracene derivative, an anthracene derivative, a red fluorene derivative, and the like. Examples of the heterocyclic aromatic compound are: an oxadiazole derivative having a dialkylamino group or a diarylamine group, a pyrazoloquinoline derivative, a pyridine derivative, a pyran derivative, a phenanthroline derivative, A fluorene heterocyclic pentadiene derivative, a thiophene derivative having a triphenylamine group, a quinacridone derivative or the like. Examples of organometallic complexes are: zinc, aluminum, ruthenium, osmium, iridium, osmium, iridium, platinum, rhodium, gold, etc. with hydroxyquinoline derivatives, benzoxazole derivatives, benzothiazole derivatives, evil A complex of an oxadiazole derivative, a thiadiazole derivative, a benzimidazole derivative, a pyrrole derivative, a pyridine derivative, a phenanthroline derivative, or the like. Examples of the coloring matter are: xanthene derivatives, polymethine derivatives, porphyrin derivatives, coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylene groups A pigment such as a thiopyran derivative, a pendant oxybenzoxanthene derivative, a quinolinone derivative, an anthracene derivative, a benzoxazole derivative, a benzothiazole derivative, or a benzimidazole derivative. Examples of the polymer light-emitting material are: a polyparaphenylene derivative, a polythiophene derivative, a polyvinylcarbazole derivative, and a polyfluorene. An alkane derivative, a polyfluorene derivative, a polyparaphenylene derivative or the like. Examples of the styryl derivative are an amine-containing styryl derivative, a styryl extended aryl derivative, and the like.

The other electron transporting material used in the organic EL device of the present invention can be arbitrarily selected from the compounds which can be used as an electron transporting compound in the photoconductive material, and the compound which can be used for the electron transporting layer and the electron injecting layer of the organic EL device.

Specific examples of such an electron transporting material are: a quinolinol metal complex, a 2,2'-bipyridine derivative, a phenanthroline derivative, a biphenyl hydrazine derivative, an anthracene derivative, an oxadiazole derivative, Thiophene derivative, triazole derivative, thiadiazole derivative, metal complex of 8-hydroxyquinoline derivative, quinoxaline derivative, polymer of quinoxaline derivative, terpenoid, gallium maltal a compound, a pyrazole derivative, a perfluorophenylene derivative, a triazine derivative, a pyrazine derivative, a benzoquinoline derivative, an imidazopyridine derivative, a borane derivative or the like.

The hole injecting material and the hole transporting material used in the organic EL device of the present invention can be a compound which is conventionally used as a charge transporting material of a hole in a photoconductive material, or a hole injecting layer of an organic EL element, and The well-known materials used in the hole transport layer are arbitrarily selected for use. Specific examples of these are: carbazole derivatives, triarylamine derivatives, phthalocyanine derivatives, and the like.

Each layer constituting the organic EL device of the present invention can be formed by forming a film of a material to be formed into each layer by a vapor deposition method, a spin coating method, or a casting method. The film thickness of each layer formed in this manner is not particularly limited, and may be appropriately set depending on the properties of the material, and is usually in the range of 2 nm to 5000 nm. Further, the method of thinning the luminescent material is preferably a vapor deposition method because it is easy to obtain a homogeneous film and it is difficult to form pinholes or the like. In the case of thin film formation by a vapor deposition method, the vapor deposition conditions vary depending on the kind of the light-emitting material of the present invention. The evaporation condition is usually preferably set within the following range: the heating boat temperature is 50 ° C to 400 ° C, the vacuum degree is 10 ^-6 Pa to 10 ^-3 Pa, and the evaporation rate is 0.01 nm / sec to 50 nm / sec. The substrate temperature is -150 ° C to +300 ° C, and the film thickness is 5 nm to 5 μm.

The organic EL device of the present invention is preferably supported by a substrate regardless of any of the above structures. As long as the substrate has mechanical strength, thermal stability, and transparency, a glass, a transparent plastic film, or the like can be used. The anode material may use a metal having a work function greater than 4 eV, an alloy, a conductive compound, and mixtures thereof. Specific examples thereof include a metal such as Au, CuI, indium tin oxide (hereinafter abbreviated as ITO), SnO ₂ , ZnO, or the like.

As the cathode material, a metal, an alloy, a conductive compound, and a mixture of these having a work function of less than 4 eV can be used. Specific examples thereof include aluminum, calcium, magnesium, lithium, magnesium alloys, and aluminum alloys. Specific examples of the alloy are: aluminum/lithium fluoride, aluminum/lithium, magnesium/silver, magnesium/indium, and the like. In order to efficiently extract the light emission of the organic EL element, it is preferable that the light transmittance of at least one of the electrodes is 10% or more. The sheet resistance as the electrode is preferably several hundred Ω/□ or less. Further, although the film thickness is also dependent on the properties of the electrode material, it is usually set in the range of 10 nm to 1 μm, preferably 10 nm 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 above electrode material.

Next, as an example of a method of producing an organic EL element using the luminescent material of the present invention, the above-described anode/hole injection layer/hole transmission is included. A method of producing an organic EL device of a layer/light-emitting layer/electron transport material/cathode of the present invention will be described. A thin film of an anode material is formed on a suitable substrate by a vapor deposition method to form an anode, and then a film of a hole injection layer and a hole transport layer is formed on the anode. A film on which a light-emitting layer is formed. The electron transporting material of the present invention was vacuum-deposited on the light-emitting layer to form a thin film, thereby forming an electron transporting layer. Next, a film containing a substance for a cathode was formed by a vapor deposition method to form a cathode, whereby a target organic EL element was obtained. Further, in the production of the above-described organic EL device, the order of fabrication may be reversed, and the cathode, the electron transport layer, the light-emitting layer, the hole transport layer, the hole injection layer, and the anode may be sequentially formed.

When a DC voltage is applied to the organic EL element obtained in this way, a voltage may be applied to the polarity in which the anode is + and the cathode is -, and when a voltage of about 2 V to 40 V is applied, it may be transparent or translucent. Luminescence was observed on the electrode side (anode or cathode, and both sides). Further, the organic EL element emits light even when an alternating voltage is applied. Further, the waveform of the applied alternating current may be arbitrary.

[Example]

Hereinafter, the present invention will be described in more detail based on examples. First, a synthesis example of the compound used in the examples will be described below.

[Synthesis Example 1] Synthesis of Compound (1-7-74) Synthesis of <9-(4-t-butylphenyl)anthracene>

Under nitrogen atmosphere, 31 g of 9-bromoindole, 25 g of 4-t-butylphenylboronic acid, 1.3 g of Pd(PPh ₃ ) ₄ , 51 g of potassium phosphate and 150 ml of 1,2,4-trimethylbenzene were added. The flask was stirred at reflux temperature for 21 hours. After cooling the reaction liquid to room temperature, water and toluene were added for liquid separation. The solid which precipitated by solvent distillation under reduced pressure was collected by suction filtration, washed with methanol, and washed with ethyl acetate to obtain 28 g of 9-(4-t-butylphenyl)fluorene.

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

To a flask to which 27 g of 9-(4-t-butylphenyl)anthracene, 0.1 g of iodine and 300 ml of THF were added, 19 g of N-bromosuccinimide was added under a nitrogen atmosphere. After stirring at room temperature for 18 hours, an aqueous sodium thiosulfate solution was added to stop the reaction. The solution was transferred to a liquid separation funnel and extracted with chloroform. The solid precipitated by distillation under reduced pressure was collected by suction filtration, followed by recrystallization from chlorobenzene to obtain 29 g of 9-bromo-10-(4-t-butylphenyl)phosphonium.

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

A flask containing 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 while stirring under a nitrogen atmosphere. After the completion of the dropwise addition, the temperature was raised to room temperature, and then cooled in ice water, and 17 g of zinc chloride tetramethylethylenediamine complex was added while stirring. Thereafter, the mixture was stirred at room temperature for 1 hour, and then 18 g of 6-bromo naphthalene-2-carboxylate 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, in order to remove the metal ions of the catalyst, ethylenediaminetetraacetic acid tetrasodium salt dihydrate which is equivalent to about 3 times the molar amount of the target compound is added and dissolved in an appropriate amount of water. The resulting solution (hereinafter, abbreviated as EDTA‧4Na aqueous solution) and toluene were subjected to liquid separation. After distilling off the solvent under reduced pressure, 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.

<Synthesis of Compound (1-7-74)>

6.2 g of 3-(6-bromonaphthalen-2-yl)pyridine, 5.9 g of pinacol borate, bis (dibenzylideneacetone)palladium (0) 0.4 g, and tricyclohexylphosphine 0.5 g were added. A flask of 3.9 g of potassium acetate and 50 ml of dimethoxyethane was stirred at reflux temperature for 4 hours under a nitrogen atmosphere. To the solution, 8.6 g of 9-bromo-10-(4-t-butylphenyl)phosphonium, 9.3 g of potassium phosphate and 50 ml of 1,2,4-trimethylbenzene were added, using a Dean-Stark tube. Dimethoxyethane was removed by heating and distillation at normal temperature. 5 ml of tributanol, 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 reflux temperature for 5 hours. The reaction solution was cooled to room temperature, washed with water to dissolve the salt, and then a solid was collected by suction filtration. The obtained solid was washed with methanol, washed with ethyl acetate, and purified by silica gel column chromatography (toluene / ethyl acetate = 9 / 1 (volume ratio)) to obtain compound (1-7- 74): 3-(6-(10-(4-T-butyl)phenyl)fluoren-9-yl)naphthalen-2-yl)pyridine 1.0 g. 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, 2H), 7.83 (dd, 1H), 7.78 (d, 2H), 7.72 (d, 2H), 7.68 (dd, 1H), 7.63 (d, 2H), 7.42-7.48 (m, 3H), 7.30-7.38 (m, 4H), 1.49 (s, 9H).

[Synthesis Example 2] Synthesis of Compound (1-7-26) Synthesis of <9-(3-tolyl)indole>

Under a nitrogen atmosphere, a flask containing 36 g of 9-bromoindole, 21 g of 3-methylphenylboronic acid, 1.4 g of Pd(PPh ₃ ) ₄ , 59 g of potassium phosphate and 150 ml of 1,2,4-trimethylbenzene was added. Stir at reflux temperature for 2.5 hours. After cooling the reaction liquid to room temperature, water and toluene were added to carry out liquid separation. After the obtained toluene solution was purified by a short-twist hose column, the solvent was evaporated under reduced pressure. Heptane was added to the obtained oil, and the precipitated solid was collected by suction filtration to obtain 9-(3-tolyl)indole 31 g.

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

To a flask to which 30 g of 9-(3-methylphenyl)indole and 200 ml of THF were added, the mixture was cooled in an ice bath under a nitrogen atmosphere, and 20 g of N-bromosuccinimide and 0.1 g of iodine were added. After stirring at room temperature for 15 hours, an aqueous sodium thiosulfate solution was added to stop the reaction. The solution was transferred to a liquid separation funnel, extracted with toluene, and purified using a short-twist hose column. The solvent was distilled off under reduced pressure, and heptane was added to the obtained solution, and the precipitated solid was collected by suction filtration to obtain 30 g of 9-bromo-10-(3-methylphenyl)indole.

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

30 g of 9-bromo-10-(3-tolyl)fluorene, 26 g of pinacol borate, 26 g of bis(dibenzylideneacetone)palladium(0), 1.4 g of tricyclohexylphosphine, and potassium acetate were added. A flask of 15 g, 12 g of potassium carbonate and 100 ml of cyclopentylmethyl ether was stirred at reflux temperature for 16 hours under a nitrogen atmosphere. After cooling the reaction liquid to room temperature, water and toluene were added for liquid separation, and the obtained toluene solution was purified by a short-twist hose column. The solvent was distilled off under reduced pressure, and 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-methyl)indol-9-yl)-1,3,2-dioxaborolane 24g.

<Synthesis of Compound (1-7-26)>

4,4,5,5-tetramethyl-2-(10-(3-methylphenyl)fluoren-9-yl)-1,3,2-dioxaborolane 12g, 3-( 6-bromonaphthalen-2-yl)pyridine 10 g, Pd(PPh ₃ ) ₄ 1.0 g, potassium phosphate 13 g, 1,2,4-trimethylbenzene 50 ml, third butanol 10 ml, and water 10 ml flask at reflux temperature Stir under 1 hour. After cooling the reaction liquid to room temperature, water and toluene were added to carry out liquid separation, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by a ruthenium column chromatography (toluene/ethyl acetate = 20/1 (volume ratio)), and then recrystallized from a toluene/heptane mixed solution to obtain a compound (1-7- 26): 7.1 g of 3-(6-(10-(3-methylphenyl)fluoren-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, 2H), 7.81 (m, 1H), 7.75 (d, 2H), 7.72 (d, 2H), 7.66 (dd, 1H), 7.50 (t, 1H), 7.45 (m, 1H), 7.27-7.39 (m) , 7H), 2.50 (s, 3H).

[Synthesis Example 3] Synthesis of Compound (1-7-98) Synthesis of <9-(3-t-butylphenyl)anthracene>

Under nitrogen, 23 g of 2-bromoindole, 2-(3-t-butylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborate will be added. A flask of 25 g of a ring, Pd(PPh ₃ ) ₄ 3.1 g, 37 g of potassium phosphate, 250 ml of 1,2,4-trimethylbenzene, 50 ml of a third butanol, and 30 ml of water were stirred at reflux temperature for 21 hours. After cooling the reaction liquid to room temperature, water and toluene were added to carry out liquid separation. The obtained toluene solution was purified by a short-twist hose column, and the solvent was evaporated under reduced pressure, and a solid precipitated by the addition of methanol was collected by suction filtration to obtain 24 g of 9-(3-t-butylphenyl)fluorene.

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

To a flask to which 23 g of 9-(3-t-butylphenyl)fluorene, 0.1 g of iodine, and 100 ml of THF were added, 13 g of N-bromosuccinimide was added under a nitrogen atmosphere. After stirring at room temperature for 1 hour, an aqueous sodium thiosulfate solution was added to stop the reaction. The solution was transferred to a liquid separation funnel and extracted with toluene. The obtained toluene solution was purified by a short-twist hose column, and the solvent was distilled off under reduced pressure, and then toluene/methanol was re-precipitated to obtain 23 g of 9-bromo-10-(3-t-butylphenyl)fluorene.

<Synthesis of Compound (1-7-98)>

6.2 g of 3-(6-bromonaphthalen-2-yl)pyridine, 5.9 g of pinacol borate, bis (dibenzylideneacetone)palladium (0) 0.4 g, and tricyclohexylphosphine 0.5 g were added. A flask of 3.9 g of potassium acetate and 50 ml of dimethoxyethane was stirred at reflux temperature for 4 hours under a nitrogen atmosphere. To the solution, 8.6 g of 9-bromo-10-(3-tert-butylphenyl)phosphonium, 9.3 g of potassium phosphate, and 50 ml of 1,2,4-trimethylbenzene were added, using a Dean-Stark tube. The dimethoxyethane was removed by heating and distillation at normal temperature. 5 ml of a third butanol, 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 reflux temperature for 2 hours. The reaction solution was cooled to room temperature, washed with water to dissolve the salt, and then a solid was collected by suction filtration. The obtained solid was purified by ruthenium column chromatography (toluene / ethyl acetate = 9 / 1 (volume ratio)), and then recrystallized from toluene to obtain compound (1-7-98): 3-( 6-(10-(3-tert-butylphenyl) 蒽-9-yl)naphthalen-2-yl)pyridine 1.5 g. 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, 2H), 7.83 (m, 1H), 7.75 (d, 2H), 7.72 (d, 2H), 7.68 (m, 1H), 7.52-7.61 (m, 3H), 7.46 (m, 1H), 7.30-7.38 (m, 5H), 1.41 (s, 9H).

[Synthesis Example 4] Synthesis of Compound (1-7-96) Synthesis of <2-(10-(4-t-butylphenyl)fluoren-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane >

7.8 g of 9-bromo-10-(4-t-butylphenyl)phosphonium, 6.1 g of pinacol borate, bis(dibenzylideneacetone)palladium(0) 0.3 g, tricyclohexyl group were added. A flask of 0.3 g of phosphine, 3.9 g of potassium acetate, 2.8 g of potassium carbonate, and 40 ml of cyclopentylmethyl ether was stirred at reflux temperature for 6.5 hours under a nitrogen atmosphere. After cooling the reaction liquid to room temperature, water and toluene were added to carry out 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-t-butylphenyl)fluoren-9-yl)-4,4,5,5- Tetramethyl-1,3,2-dioxaborolane 6.9 g.

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

A flask to which 9.8 g of 4-(3-bromophenyl)pyridine and 20 ml of THF were added was cooled to -70 ° C or less in a dry ice/methanol bath under nitrogen atmosphere, and 17 ml of 2.6 M n-butyllithium was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at the same temperature for 0.5 hour, and 12 g of zinc chloride tetramethylethylenediamine complex was added. Thereafter, after stirring at room temperature for 0.5 hour, 6-bromonaphthalene-2-ester trifluoromethanesulfonate 15 was added. g, bis(dibenzylideneacetone)palladium(0) and 1,2-bis(diphenylphosphino)propane 0.5 g, and stirred at reflux temperature for 1 hour. After completion of the reaction, an aqueous solution of EDTA‧4Na and ethyl acetate were added to carry out liquid separation, and the solvent was distilled off under reduced pressure, followed by active alumina column chromatography (toluene / ethyl acetate = 9 / 1 (volume ratio)) Purification was carried out. Subsequently, it was washed with methanol and recrystallized from a mixed solvent of ethyl acetate/methanol to obtain 5.3 g of 4-(3-(6-bromonaphthalen-2-yl)phenyl)pyridine.

<Synthesis of Compound (1-7-96)>

2-(10-(4-Tertibutylphenyl)fluoren-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 6.1 will be added. g, 4-(3-(6-bromonaphthalen-2-yl)phenyl)pyridine 5.0 g, Pd(PPh ₃ ) ₄ 0.5 g, potassium phosphate 3.0 g, 1,2,4-trimethylbenzene 25 ml, A flask of 5 ml of butanol and 5 ml of water was stirred at reflux temperature for 6 hours. After cooling the reaction liquid to room temperature, an aqueous solution of EDTA‧4Na and toluene were added to carry out liquid separation, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by activated alumina column chromatography (toluene / ethyl acetate = 9 / 1 (volume ratio)). The solid obtained by distilling off the solvent under reduced pressure with ethyl acetate was washed, and then recrystallized from toluene to obtain compound (1-7-96): 4 (3-(6-(10-(4-) Phenylphenyl)fluoren-9-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 to 7.70 (m, 7H), 7.44 (m, 2H), 7.30 to 7.38 (m, 4H), 1.49 (s, 9H).

[Synthesis Example 5] Synthesis of Compound (1-14-14) Synthesis of <9-(3-ethoxyphenyl)-10-(naphthalen-2-yl)anthracene>

72.4 g of 1-bromo-3-ethoxybenzene, 104.5 g of (10-(naphthalen-2-yl)fluoren-9-yl)boronic acid, 10.4 g of Pd(PPh ₃ ) ₄ , and 127.4 g of potassium phosphate were added to the flask. 600 ml of 1,2,4-trimethylbenzene, 120 ml of 2-propanol, and 120 ml of water were stirred under a nitrogen atmosphere at reflux temperature for 6 hours. After cooling the reaction liquid 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-(naphthalen-2-yl)anthracene.

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

82 g of 9-(3-ethoxyphenyl)-10-(naphthalen-2-yl)indole and 446.0 g of pyridine hydrochloride were added to the flask, and the mixture was stirred at reflux temperature for 8 hours under a nitrogen atmosphere. After cooling the reaction liquid to room temperature, water was added, and the precipitated solid was collected by suction filtration, washed with methanol, and washed with toluene to obtain 3-(10-(naphthalen-2-yl)fluoren-9-yl) Phenol 76.0 g.

Synthesis of <3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl trifluoromethanesulfonate>

The flask to which 3-(10-(naphthalen-2-yl)fluoren-9-yl)phenol (76.0 g) and pyridine (1 L) were added was cooled in an ice bath, and trifluorogen was added dropwise thereto under a nitrogen atmosphere. Methanesulfonic anhydride 65.0 g. After completion of the dropwise addition, the mixture was further stirred at room temperature for 15 hours, water was added, and the precipitated solid was collected by suction filtration. The solid was washed with methanol to obtain 90.3 g of 3-(10-(naphthalen-2-yl)indol-9-yl)phenyl trifluoromethanesulfonate.

<4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-1,3,2-dioxaborolan Synthesis>

Add 3-(10-(naphthalen-2-yl)fluoren-9-yl trifluoromethanesulfonate to the flask 90.3 g of phenyl ester, 52.1 g of pinacol borate, 7.4 g of bis(dibenzylideneacetone)palladium (0), 7.2 g of tricyclohexylphosphine, 33.6 g of potassium acetate, 23.6 g of potassium carbonate, and anisole 500 ml, stirred at reflux temperature for 5 hours. After cooling the reaction solution to room temperature, the insoluble matter was removed by suction filtration using a Kiriyama funnel coated with diatomaceous earth, and the filtrate was washed with an aqueous solution of EDTA‧4Na. The solid obtained by distilling off the solvent of the filtrate under reduced pressure was washed with heptane to obtain 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)fluoren-9-yl) Phenyl)-1,3,2-dioxaborolane (52.0 g).

<Synthesis of Compound (1-14-14)>

Add 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-1,3,2-dioxa to the flask 8.5 g of boron pentane ring, 5.1 g of 5'-bromo-3-methyl-2,2'-bipyridine synthesized by the method described in JP-A-2009-124114, Pd(PPh ₃ ) ₄ 0.6 g 7.2 g of potassium phosphate, 25 ml of 1,2,4-trimethylbenzene, 5 ml of third butanol, and 1 ml of water were stirred at reflux temperature for 2.5 hours. After cooling the reaction liquid to room temperature, water was added, and the solid in the liquid was collected by suction filtration, and washed with methanol. The solid was purified by oxime column chromatography (toluene / ethyl acetate = 9 / 1 (volume ratio)) and then purified further by activated carbon column chromatography. The solution is concentrated and recrystallized from chlorobenzene to give compound (1-14-14): 3-methyl-5'-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl 2,2'-bipyridyl 2.3 g. 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, 1H), 2.56 (s, 3H).

[Synthesis Example 6] Synthesis of Compound (1-11-1) Synthesis of <2-methyl-4-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)pyridine>

4,4,5,5-tetramethyl-2-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)-1,3,2-dioxaborolan (2.0 g), 4-bromo-2-methylpyridine (0.8 g), Pd(PPh ₃ ) ₄ (0.3 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), Tributyl alcohol (5 ml) and water (1 ml) were added to the flask, and stirred at reflux temperature for 7.5 hours under a nitrogen atmosphere. After the completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (developing solvent: toluene/ethyl acetate = 95/5). Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The crystals precipitated during the distillation of the obtained filtrate were distilled off under reduced pressure to obtain the compound 2-methyl-4-(6-(10-phenylfluoren-9-yl)naphthalene represented by (1-11-1). 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), 7.31-7.39 (m, 4H), 2.73 (s, 3H).

[Synthesis Example 7] Synthesis of Compound (1-11-2) Synthesis of <3-methyl-4-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)pyridine>

4,4,5,5-tetramethyl-2-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)-1,3,2-dioxaborolan (2.0 g), 4-bromo-3-methylpyridine hydrochloride (1.0 g), Pd(PPh ₃ ) ₄ (0.3 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml) The third butanol (5 ml) and water (1 ml) were added to the flask, and the mixture was stirred at reflux temperature for 24.5 hours under a nitrogen atmosphere. After the completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was evaporated under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 95/5). Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The crystals precipitated in the process of removing the obtained filtrate by distillation under reduced pressure were further subjected to recrystallization in toluene to obtain the compound represented by (1-11-2) 3-methyl-4-(6-(10-benzene). Based on 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, 1H), 7.75 (d, 4H), 7.70 (dd, 1H), 7.65 (t, 2H), 7.59 (t, 2H), 7.53 (m, 2H), 7.33 - 7.39 (m, 5H), 2.44 (s , 3H).

[Synthesis Example 8] Synthesis of Compound (1-11-3) Synthesis of <2-methyl-5-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)pyridine>

4,4,5,5-tetramethyl-2-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)-1,3,2-dioxaborolan (2.0 g), 5-bromo-2-methylpyridine (0.8 g), Pd(PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), Tributyl alcohol (5 ml) and water (1 ml) were added to the flask, and the mixture was stirred at reflux temperature for 5 hours under a nitrogen atmosphere. After the completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was evaporated under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 95/5). The solid obtained by distilling off the solvent under reduced pressure was recrystallized from toluene to obtain the compound 2-methyl-5-(6-(10-phenylfluoren-9-yl) represented by (1-11-3). Naphthalen-2-yl)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, 1H), 7.74 (m, 4H), 7.67 (dd, 1H), 7.63 (t, 2H), 7.57 (t, 1H), 7.52 (m, 2H), 7.30-7.37 (m, 5H), 2.67 (s) , 3H).

[Synthesis Example 9] Synthesis of Compound (1-11-4) Synthesis of <3-methyl-5-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)pyridine>

4,4,5,5-tetramethyl-2-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)-1,3,2-dioxaborolan (2.0 g), 3-bromo-5-methylpyridine (0.8 g), Pd(PPh ₃ ) ₄ (0.3 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), Tributyl alcohol (5 ml) and water (1 ml) were added to the flask, and the mixture was stirred at reflux temperature for 7.5 hours under a nitrogen atmosphere. After the completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was evaporated under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 95/5). Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The solvent was distilled off under reduced pressure, and heptane was added for reprecipitation to obtain the compound represented by (1-11-4) 3-methyl-5-(6-(10-phenylfluoren-9-yl)naphthalene-2- Pyridine (1.3 g).

The structure of the compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=8.87 (m, 1H), 8.51 (m, 1H), 8.22 (s, 1H), 8.15 (d, 1H), 8.03 (m, 2H), 7.89 (m, 1H), 7.83 (dd, 1H), 7.73 (m, 4H), 7.67 (dd, 1H), 7.63 (m, 2H), 7.57 (t, 1H), 7.52 (m, 2H), 7.30-7.37 (m) , 4H), 2.49 (s, 3H).

[Synthesis Example 10] Synthesis of Compound (1-11-5) Synthesis of <4-methyl-3-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)pyridine>

4,4,5,5-tetramethyl-2-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)-1,3,2-dioxaborolan (2.0 g), 3-bromo-4-methylpyridine hydrochloride (1.0 g), Pd(PPh ₃ ) ₄ (0.3 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml) ), tert-butanol (5 ml) and water (1 ml) were added to the flask, and the mixture was stirred at reflux temperature for 7 hours under a nitrogen atmosphere. After the completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was evaporated under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 95/5). Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from toluene to obtain the compound (1-11-5) represented by (1-11-5) 4-methyl-3-(6-(10-phenylfluoren-9-yl) Naphthyl-2-yl)pyridine (0.6 g).

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, 1H), 7.76 (m, 4H), 7.70 (dd, 1H), 7.63 (m, 2H), 7.59 (t, 2H), 7.53 (m, 2H), 7.32 - 7.39 (m, 4H), 7.30 (d) , 1H), 2.45 (s, 3H).

[Synthesis Example 11] Synthesis of Compound (1-11-6) Synthesis of <2-methyl-3-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)pyridine>

4,4,5,5-tetramethyl-2-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)-1,3,2-dioxaborolan (2.0 g), 3-bromo-2-methylpyridine (0.8 g), Pd(PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), Tributyl alcohol (5 ml) and water (1 ml) were added to the flask, and the mixture was stirred at reflux temperature for 4 hours under a nitrogen atmosphere. After the completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was evaporated under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 95/5). Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The solvent was distilled off under reduced pressure, and heptane was added for reprecipitation to obtain a compound represented by (1-11-6) 2-methyl-3-(6-(10-phenylfluoren-9-yl)naphthalene-2- 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, 4H), 7.69 (m, 2H), 7.63 (m, 2H), 7.57 (m, 2H), 7.52 (m, 2H), 7.30-7.37 (m, 4H), 7.28 (m, 1H), 2.66 (s) , 3H).

[Synthesis Example 12] Synthesis of Compound (1-11-8) Synthesis of <5-Methyl-2-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)pyridine>

4,4,5,5-tetramethyl-2-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)-1,3,2-dioxaborolan (2.5 g), 3-bromo-2-methylpyridine (1.0 g), Pd(PPh ₃ ) ₄ (0.15 g), potassium phosphate (2.1 g), 1,2,4-trimethylbenzene (20 ml), Tributyl alcohol (5 ml) and water (1 ml) were added to the flask, and the mixture was stirred at reflux temperature for 18 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. The obtained solid was purified by oxime column chromatography (developing solution: toluene). Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The solvent was distilled off under reduced pressure, and ethyl acetate was added to reprecipitate to obtain the compound 5-methyl-2-(6-(10-phenylfluoren-9-yl)naphthalene-2 represented by (1-11-8). -yl)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, 4H), 7.60-7.67 (m, 4H), 7.56 (t, 1H), 7.51 (m, 2H), 7.30-7.36 (m, 4H), 2.44 (s, 3H).

[Synthesis Example 13] Synthesis of Compound (1-11-39) Synthesis of <5-bromo-2'-methyl-3,4'-bipyridyl>

A flask to which 4-bromo-2-methylpyridine (13.8 g) and toluene (150 ml) were added was cooled in an acetone/dry ice bath. To the solution was added dropwise a 1.6 M solution of n-butyllithium in hexane (55 ml). After completion of the dropwise addition, the mixture was stirred for 1 hour while cooling in an acetone/dry ice bath, and zinc chloride tetramethylethylenediamine (29.3 g) and THF (45 ml) were added thereto, and the acetone/dry ice bath was removed and the temperature was raised. After warming 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 cooling the reaction solution to room temperature, the EDTA‧4Na aqueous solution and toluene were separated by liquid. After the solvent was distilled off under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate). At this time, refer to the method described in "Introduction to Organic Chemistry (1) - Substance Treatment and Separation and Purification -" Chemicals, Inc., page 94, to slowly increase the ratio of ethyl acetate in the developing solution. The target is dissolved. Then, 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-phenylfluoren-9-yl)naphthalen-2-yl)-3,4'-bipyridine

4,4,5,5-tetramethyl-2-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)-1,3,2-dioxaborolan (2.5 g), 5-bromo-2'-methyl-3,4'-bipyridine (1.1 g), Pd(PPh ₃ ) ₄ (0.15 g), potassium phosphate (1.7 g), 1,2,4-three Methylbenzene (20 ml), tert-butanol (5 ml) and water (1 ml) were added to the flask, and stirred at reflux temperature for 3 hours under a nitrogen atmosphere. After the completion of the heating, the reaction solution was cooled to room temperature, and water and toluene were added for liquid separation. The solvent was evaporated under reduced pressure, and the obtained 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-phenylindole-9-) represented by (1-11-39). Naphthyl-2-yl)-3,4'-bipyridine (0.3 g).

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, 1H), 7.51 (m, 3H), 7.45 (m, 1H), 7.30-7.37 (m, 4H), 2.70 (s, 3H).

[Synthesis Example 14] Synthesis of Compound (1-14-2) Synthesis of <3-methyl-4-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)pyridine>

Add 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)indol-9-yl)phenyl)-1,3,2-dioxaborolan (2.5g), 4-bromo-3-methylpyridine hydrochloride (1.3g), Pd(PPh ₃ ) ₄ (0.35g), potassium phosphate (3.2g), 1,2,4-trimethylbenzene 20 ml, 5 ml of third butanol, and 1 ml of water were stirred at reflux temperature for 11.5 hours. After cooling the reaction solution to room temperature, toluene and water were added to carry out liquid separation. The solvent was evaporated under reduced pressure, and the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 95/5). Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The solvent was distilled off under reduced pressure, and heptane was added for reprecipitation to obtain the compound 3-methyl-4-(3-(10-(naphthalen-2-yl)fluoren-9-yl) represented by (1-14-2). Phenyl)pyridine (1.4 g).

The structure of the compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=8.53 (s, 1H), 8.50 (d, 1H), 8.08 (dd, 1H), 8.02 (m, 1H), 7.97 (d, 1H), 7.92 (m, 1H), 7.70-7.78 (m, 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 Compound (1-14-3) Synthesis of <2-methyl-5-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)pyridine>

Add 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)indol-9-yl)phenyl)-1,3,2-dioxaborolan (2.5 g), 5-bromo-2-methylpyridine (1.0 g), Pd(PPh ₃ ) ₄ (0.35 g), potassium phosphate (3.2 g), 1,2,4-trimethylbenzene 20 ml, 5 ml of tributyl alcohol and 1 ml of water were stirred at reflux temperature for 8.5 hours. After the reaction solution was cooled to room temperature, the precipitated solid was collected by suction filtration. The obtained solid was purified by hydrazine column chromatography (developing solvent: toluene / ethyl acetate = 95/5). Next, the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The solvent was distilled off under reduced pressure, and the obtained solid was washed with ethyl acetate to give the compound 2-methyl-5-(3-(10-(naphthalen-2-yl)) represented by (1-14-3). -9-yl)phenyl)pyridine (1.5 g).

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), 7.78 (dd, 1H), 7.70-7.81 (m, 7H), 7.57-7.63 (m, 3H), 7.54 (m, 1H), 7.30-7.40 (m, 4H), 7.23 (d, 1H), 2.61 (s, 3H) .

[Synthesis Example 16] Synthesis of Compound (1-14-11) Synthesis of <5-bromo-6'-methyl-2,2'-bipyridyl>

A flask to which 2-bromo-6-methylpyridine (5.2 g) and cyclopentylmethyl ether (30 ml) were added was cooled in a methanol/dry ice bath. To the solution was added dropwise a 1.6 M solution of n-butyllithium in hexane (22 ml). After completion of the dropwise addition, the mixture was stirred for 2 hours while cooling in a methanol/dry ice bath, and zinc chloride tetramethylethylenediamine (8.3 g) was added thereto, and the methanol/dry ice bath was removed and the temperature was raised. After warming to room temperature, 2,5-dibromopyridine (7.1 g) and Pd(PPh ₃ ) ₄ (1.0 g) were added, and the mixture was stirred at reflux temperature for 3.5 hours. After cooling the reaction solution to room temperature, an aqueous solution of EDTA‧4Na and toluene were added to carry out liquid separation. After the solvent was distilled off under reduced pressure, the obtained 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. Then, 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)indol-9-yl)phenyl)-2,2'-bipyridine

Add 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)indol-9-yl)phenyl)-1,3,2-dioxaborolan (2.0 g), 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 20 ml of trimethylbenzene, 5 ml of third butanol, and 1 ml of water were stirred at reflux temperature for 7.5 hours. After the reaction solution was cooled to room temperature, the precipitated solid was collected by suction filtration. The obtained solid was purified by a silica gel column chromatography (developing solution: toluene/ethyl acetate = 95/5), and the obtained eluate was directly subjected to suction filtration using a Kiriyama funnel coated with activated carbon to remove the coloring. ingredient. The solvent was distilled off under reduced pressure, and ethyl acetate was added to reprecipitate to obtain the compound 6'-methyl-5-(3-(10-(naphthalen-2-yl)indole-9) represented by (1-14-11). -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), 8.49 (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 (m, 4H), 7.17 (d, 1H) , 2.65 (s, 3H).

[Synthesis Example 17] Synthesis of Compound (1-14-12) Synthesis of <5-bromo-5'-methyl-2,2'-bipyridyl>

The flask to which 2-bromo-5-methylpyridine (1.7 g) and THF (5 ml) were added was cooled in an ice bath, and a 2 M solution of isopropylmagnesium chloride in THF (5.5 ml) was added dropwise. After completion of the dropwise addition, the ice bath was removed and stirred at room temperature for 3.5 hours, and then cooled again in an ice bath, and zinc chloride tetramethylethylenediamine (2.8 g) was added. After removing the ice bath and warming to room temperature, 2,5-dibromopyridine (2.4 g) and Pd(PPh ₃ ) ₄ (0.35 g) were added, and the mixture was stirred at reflux temperature for 1.5 hours. After cooling the reaction solution to room temperature, an aqueous solution of EDTA‧4Na and toluene were added to carry out liquid separation. After distilling off the solvent under reduced pressure, the obtained 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 and reprecipitated to obtain 5-bromo-5'-methyl-2,2'-bipyridine (1.5 g).

Synthesis of <5-Methyl-5'-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-2,2'-bipyridine

Add 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)indol-9-yl)phenyl)-1,3,2-dioxaborolan (2.0 g), 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 20 ml of trimethylbenzene, 5 ml of third butanol, and 1 ml of water were stirred at reflux temperature for 6 hours. After cooling the reaction solution to room temperature, toluene and water were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (developing solvent: toluene/ethyl acetate = 95/5), and the obtained solvent was passed through a short activated carbon tube column to remove the coloring. ingredient. The solvent was distilled off under reduced pressure, and ethyl acetate was added to reprecipitate, and the obtained solid was further recrystallized from toluene to obtain a compound represented by (1-14-12) 5-methyl-5'-(3- (10-(Naphthalen-2-yl)fluoren-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, 1H), 8.00 (s, 2H), 7.93 (m, 1H), 7.87 (m, 1H), 7.73-7.83 (m, 6H), 7.56-7.66 (m, 5H), 7.31-7.39 (m, 4H) , 2.41 (s, 3H).

[Synthesis Example 18] Synthesis of Compound (1-14-13) Synthesis of <5'-bromo-4-methyl-2,2'-bipyridyl>

A flask to which 2-bromo-4-methylpyridine (6.9 g) and THF (20 ml) were added was cooled in an ice bath, and a 2 M solution of isopropylmagnesium chloride in THF (24 ml) was added dropwise. After completion of the dropwise addition, the ice bath was removed and stirred at room temperature for 1 hour, and then cooled again in an ice bath, and zinc chloride tetramethylethylenediamine (12.1 g) was added. After removing the ice bath and warming to room temperature, 2,5-dibromopyridine (9.5 g) and Pd(PPh ₃ ) ₄ (1.4 g) were added, and the mixture was stirred at reflux temperature for 2.5 hours. After cooling the reaction solution to room temperature, an aqueous solution of EDTA‧4Na and toluene were added to carry out liquid separation. After distilling off the solvent under reduced pressure, the obtained 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)fluoren-9-yl)phenyl)-2,2'-bipyridine

Add 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)indol-9-yl)phenyl)-1,3,2-dioxaborolan (2.0g), 5'-bromo-4-methyl-2,2'-bipyridine (1.2g), Pd(PPh ₃ ) ₄ (0.15g), potassium phosphate (1.7g), 1,2,4 20 ml of trimethylbenzene, 5 ml of third butanol, and 1 ml of water were stirred at reflux temperature for 16 hours. After cooling the reaction solution to room temperature, toluene and water were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (developing solvent: toluene/ethyl acetate = 95/5), and the obtained solvent was passed through a short activated carbon tube column to remove the coloring. ingredient. The solvent was distilled off under reduced pressure and washed with heptane to give the compound 4-methyl-5'-(3-(10-(naphthalen-2-yl)indole-9- represented by (1-14-13). Phenyl)-2,2'-bipyridyl (1.4 g).

The structure of the compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=9.04 (m, 1H), 8.55 (d, 1H), 8.47 (dd, 1H), 8.28 (s, 1H), 8.11 (dd, 1H), 8.09 (d, 1H), 8.03 (m, 1H), 8.00 (s, 1H), 7.93 (m, 1H), 7.88 (d, 1H), 7.73-7.83 (m, 6H), 7.57-7.63 (m, 4H), 7.30 - 7.40 (m, 4H), 7.14 (d, 1H), 2.45 (s, 3H).

[Synthesis Example 19] Synthesis of Compound (1-14-15) Synthesis of <5-bromo-6'-methyl-2,3'-bipyridyl>

The flask to which 5-bromo-2-methylpyridine (3.4 g) and THF (10 ml) were added 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 stirred at room temperature for 3 hours, and then cooled again in an ice bath, and zinc chloride tetramethylethylenediamine (5.5 g) was added. After removing the ice bath and warming 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 cooling the reaction solution to room temperature, an aqueous solution of EDTA‧4Na and toluene were added to carry out liquid separation. After distilling off the solvent under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 7/3) to give 5-bromo-6'-methyl-2,3. '-Bipyridine (1.5 g).

Synthesis of <6'-Methyl-5-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-2,3'-bipyridine

Add 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)indol-9-yl)phenyl)-1,3,2-dioxaborolan (2.0 g), 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 25 ml of trimethylbenzene, 5 ml of third butanol, and 1 ml of water were stirred at reflux temperature for 5 hours. After cooling the reaction liquid to room temperature, the precipitated solid was collected by suction filtration, washed with methanol, and washed with ethyl acetate. Subsequently, the mixture was purified by a silica gel column chromatography (developing solution: toluene/ethyl acetate = 4/1), and the obtained eluate was passed through a short activated carbon tube column to remove the coloring 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-(naphthalene-2) represented by (1-14-15). -yl)fluoren-9-yl)phenyl)-2,3'-bipyridine (1.3 g).

The structure of the compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=9.13 (m, 1H), 9.07 (m, 1H), 8.28 (dd, 1H), 8.01 to 8.11 (m, 3H), 8.00 (s, 1H), 7.93 ( m,1H), 7.86 (m, 1H), 7.73-7.83 (m, 7H), 7.57-7.64 (m, 4H), 7.31-7.39 (m, 4H), 7.28 (d, 1H), 2.63 (s, 3H).

[Synthesis Example 20] Synthesis of Compound (1-14-16) Synthesis of <5-bromo-5'-methyl-2,3'-bipyridyl>

A flask to which 3-bromo-5-methylpyridine (3.4 g) and THF (10 ml) were added 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 stirred at room temperature for 1.5 hours, and then cooled again in an ice bath, and zinc chloride tetramethylethylenediamine (5.5 g) was added. After removing the ice bath and warming 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 cooling the reaction solution to room temperature, an aqueous solution of EDTA‧4Na and toluene were added to carry out liquid separation. After distilling off the solvent under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 7/3) to give 5-bromo-5'-methyl-2,3. '-Bipyridine (1.4 g).

Synthesis of <5'-Methyl-5-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-2,3'-bipyridine

Add 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)indol-9-yl)phenyl)-1,3,2-dioxaborolan (2.0 g), 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 25 ml of trimethylbenzene, 5 ml of third butanol, and 1 ml of water were stirred at reflux temperature for 5 hours. After cooling the reaction liquid to room temperature, the precipitated solid was collected by suction filtration, washed with methanol, and washed with ethyl acetate. Subsequently, the mixture was purified by ruthenium column chromatography (developing solution: toluene/ethyl acetate = 4/1), and the obtained eluate was passed through a short activated carbon tube column to remove the coloring component. The solvent was distilled off under reduced pressure, and the obtained solid was further recrystallized from chlorobenzene to obtain the compound 5'-methyl-5-(3-(10-(naphthalene-2)) represented by (1-14-16). -yl)fluoren-9-yl)phenyl)-2,3'-bipyridine (1.3 g).

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, 3H).

[Synthesis Example 21] Synthesis of Compound (1-14-17) Synthesis of <5-bromo-4'-methyl-2,3'-bipyridyl>

A flask to which 3-bromo-4-methylpyridine (5.2 g) and THF (10 ml) were added 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 stirred at room temperature for 9 hours, and then cooled again in an ice bath, and zinc chloride tetramethylethylenediamine (8.3 g) was added. After removing the ice bath and warming to room temperature, 2,5-dibromopyridine (7.1 g), Pd-137 (British Johnson Matthey) (0.4 g) and NMP (25 ml) were added, and the mixture was stirred at reflux temperature. hour. After cooling the reaction solution to room temperature, an aqueous solution of EDTA‧4Na and toluene were added to carry out liquid separation. After the solvent was distilled off under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 7 / 3). The solvent was distilled off under reduced pressure, and the obtained solid was washed with heptane to give 5-bromo-4'-methyl-2,3'-bipyridine (2.4 g).

Synthesis of <4'-Methyl-5-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-2,3'-bipyridine

Add 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)indol-9-yl)phenyl)-1,3,2-dioxaborolan (2.0 g), 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 25 ml of trimethylbenzene, 5 ml of third butanol, and 1 ml of water were stirred at reflux temperature for 5 hours. After cooling the reaction solution to room temperature, toluene and water were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (developing solvent: toluene/ethyl acetate = 7/3), and the obtained solvent was passed through a short activated carbon column to remove Coloring ingredients. The solvent was distilled off under reduced pressure, and the obtained solid was further recrystallized from toluene to obtain the compound 4'-methyl-5-(3-(10-(naphthalene-2-)) represented by (1-14-17). )-9-yl)phenyl)-2,3'-bipyridyl (0.7 g).

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, 1H), 7.88 (d, 1H), 7.73-7.84 (m, 6H), 7.61 (m, 4H), 7.52 (d, 1H), 7.31-7.40 (m, 4H), 7.23 (d, 1H), 2.46 (s, 3H).

[Synthesis Example 22] Synthesis of Compound (1-14-18) Synthesis of <5-bromo-2'-methyl-2,3'-bipyridyl>

The flask to which 3-bromo-2-methylpyridine (5.2 g) and THF (10 ml) were added 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 stirred at room temperature for 2 hours, and then cooled again in an ice bath, and zinc chloride tetramethylethylenediamine (8.3 g) was added. After removing the ice bath and warming to room temperature, 2,5-dibromopyridine (7.1 g), Pd(PPh ₃ ) ₄ (1.0 g) and xylene (10 ml) were added, and the mixture was stirred at reflux temperature for 7 hours. After cooling the reaction solution to room temperature, an aqueous solution of EDTA‧4Na and toluene were added to carry out liquid separation. After distilling off the solvent under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 4/1) to give 5-bromo-2'-methyl-2,3. '-Bipyridine (1.3 g).

Synthesis of <2'-Methyl-5-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-2,3'-bipyridine

Add 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)indol-9-yl)phenyl)-1,3,2-dioxaborolan (2.0 g), 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 25 ml of trimethylbenzene, 5 ml of third butanol, and 1 ml of water were stirred at reflux temperature for 12 hours. After cooling the reaction solution to room temperature, toluene and water were added to carry out liquid separation. The solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (developing solvent: toluene/ethyl acetate = 4/1), and the obtained eluate was passed through a short activated carbon column to remove Coloring ingredients. 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)indole) represented by (1-14-18). 9-yl)phenyl)-2,3'-bipyridine (0.8 g).

The structure of the compound was confirmed by NMR measurement.

¹ H-NMR (CDCl ₃ ): δ=9.08 (m, 1H), 8.57 (m, 1H), 7.99-8.10 (m, 4H), 7.92 (m, 1H), 7.88 (d, 1H), 7.73 7.83 (m, 7H), 7.61 (m, 4H), 7.51 (dd, 1H), 7.30-7.40 (m, 4H), 7.25 (m, 1H), 2.66 (s, 3H).

[Synthesis Example 23] Synthesis of Compound (1-14-20) Synthesis of <5-bromo-3'-methyl-2,4'-bipyridyl>

The flask to which 4-bromo-3-methylpyridine (5.0 g) and THF (30 ml) were added was cooled in a dry ice/methanol bath, and 2M isopropylmagnesium chloride in THF (16 ml) was added dropwise. After completion of the dropwise addition, the cooling bath was removed, and the mixture was stirred at room temperature for 2.5 hours, and then cooled in an ice bath to add zinc chloride tetramethylethylenediamine (8.0 g). After removing the ice bath and warming 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 cooling the reaction mixture to room temperature, an aqueous solution of EDTA‧4Na and ethyl acetate were added to carry out liquid separation. After distilling off the solvent under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: toluene/ethyl acetate = 5/1) to give 5-bromo-3'-methyl-2,4. '-Bipyridine (5.6 g).

Synthesis of <3'-Methyl-5-(3-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-2,4'-bipyridine

Add 4,4,5,5-tetramethyl-2-(3-(10-(naphthalen-2-yl)indol-9-yl)phenyl)-1,3,2-dioxaborolan (2.0 g), 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 1 ml of trimethylbenzene, 1 ml of tributanol, and 1 ml of water were stirred at reflux temperature for 4 hours. After cooling the reaction liquid 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 an NH-based modified silicone (DM1020: manufactured by Fuji Chemical Co., Ltd.) column chromatography (developing solution: toluene) to obtain (1-14-20) The compound represented by 3'-methyl-5-(3-(10-(naphthalen-2-yl)indol-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 (d, 1H), 7.31-7.41 (m, 5H), 2.44 (s, 3H).

[Synthesis Example 24] Synthesis of Compound (1-11-18) Synthesis of <2'-Methyl-5-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)2,3'-bipyridine

4,4,5,5-tetramethyl-2-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)-1,3,2-dioxaborolan (2.0 g), 5-bromo-2'-methyl-2,3'-bipyridine (1.2g), Pd(PPh ₃ ) ₄ (0.15g), potassium phosphate (1.7g), 1,2,4-three Methylbenzene (20 ml), third butanol (5 ml) and water (1 ml) were added to the flask, and the mixture was stirred at reflux temperature for 8 hours under a nitrogen atmosphere. After the completion of the heating, the reaction liquid was cooled to room temperature, and the precipitated solid was collected by suction filtration, washed with methanol, and then washed with ethyl acetate. Subsequently, purification was carried out by silica gel column chromatography (developing solution: toluene/ethyl acetate = 7/3), and the obtained eluate was passed through a short activated carbon tube column to remove the coloring 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-(6-(10-phenylfluoren-9-yl)naphthalene represented by (1-11-18). 2-yl) 2,3'-bipyridyl (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), 7.78 (dd, 1H), 7.85 (dd, 1H), 7.73 (m, 4H), 7.69 (dd, 1H), 7.55-7.65 (m, 4H), 7.51 (m, 2H), 7.26-7.37 (m, 5H), 2.73 (s, 3H).

The other derivative compound of the present invention can be synthesized by a method suitable for changing the starting material and by a method according to the above synthesis example.

Hereinafter, in order to explain the present invention in further detail, an example of an organic EL device using the compound of the present invention is disclosed, but the present invention is not limited thereto.

The elements of Examples 1 to 4 and Comparative Examples 1 to 2 were produced, and the driving start voltage (V) in the constant current driving test and the time (hour) at which the luminance of 90% or more of the initial value was maintained were measured. Hereinafter, examples and comparative examples will be described in detail.

The material compositions of the respective layers of the produced Examples 1 to 4 and Comparative Examples 1 to 2 are shown in Table 1 below.

In Table 1, "HI" is N ⁴ , N ^{4 '} -diphenyl-N ⁴ , N ^{4 '} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1'- Biphenyl]-4,4'-diamine, "NPD" is N ⁴ , N ^{4 '} -di(naphthalen-1-yl)-N ⁴ , N ^{4 '} -diphenyl-[1,1'-linked Benzene]-4,4'-diamine, compound (A) is 9-phenyl-10-(4-phenylnaphthalen-1-yl)anthracene, and compound (B) is N ⁵ , N ⁵ , N ⁹ , N ⁹ -7,7-hexaphenyl-7H-benzo[c]indole-5,9-diamine, compound (C) is 9,10-di([2,2'-bipyridine]-5- The compound (D) is 9,10-bis(4-(pyridin-3-yl)naphthalen-1-yl)anthracene. The chemical structure of "Liq" used for the compound and the layer formed between the electron transport layer and the cathode is disclosed as follows.

[Example 1] <Component for using compound (1-7-74) for electron transport layer>

A glass substrate (manufactured by Opto Science Co., Ltd.) of 26 mm × 28 mm × 0.7 mm polished to 150 nm by ITO having a film having a thickness of 180 nm by sputtering was used as a transparent supporting substrate. The transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum boat for vapor deposition to which HI is added, a molybdenum boat for vapor deposition to which NPD is added, and a Molybdenum boat for vapor deposition of compound (A), added Molybdenum boat for vapor deposition of compound (B), molybdenum boat for vapor deposition to which compound (1-7-74) is added, molybdenum boat for vapor deposition to which Liq is added, molybdenum boat to which magnesium is added, and silver added with silver A tungsten boat for vapor deposition.

The following layers were sequentially formed on the ITO film of the transparent supporting substrate. The vacuum chamber was depressurized to 5 × 10 ^-4 Pa. First, the boat for vapor deposition to which HI was added was heated, and vapor deposition was performed so as to have a film thickness of 40 nm to form a hole injection layer, followed by heating the steam to which NPD was added. The plating boat was vapor-deposited so that the film thickness became 30 nm, and the hole transport layer was formed. Then, the vapor deposition boat to which the compound (A) was added and the vapor deposition boat to which the compound (B) was added were heated, and vapor deposition was performed so that the film thickness became 35 nm, and the light-emitting layer was formed. The vapor deposition rate was adjusted so that the weight ratio of the compound (A) to the compound (B) became about 95:5. Next, the boat for vapor deposition to which the compound (1-7-74) was added was heated, and vapor deposition was performed so that the film thickness became 15 nm, and the electron transport layer was formed. The vapor deposition rate of each layer is from 0.01 nm/sec to 1 nm/sec.

Thereafter, the boat for vapor deposition to which Liq was added was heated, and vapor deposition was performed at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec so that the film thickness became 1 nm. Next, the boat to which magnesium was added and the boat to which silver was added were simultaneously heated, and vapor deposition was performed so that the film thickness became 100 nm, and a cathode was formed. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver became 10:1, and the cathode was formed so that the vapor deposition rate became 0.1 nm/sec to 10 nm/sec, and the organic electroluminescent device was obtained.

When a direct current voltage is applied using an ITO electrode as an anode and a magnesium/silver electrode as a cathode, blue light emission having a wavelength of about 460 nm is obtained. Further, for obtaining the initial luminance by 2000cd / m ² and a current density of the constant current driving test, driving test initiation voltage of 7.33V, holding time 90% of the initial value of the luminance (1800cd / m ²⁾ or more of 45 hours.

[Example 2] <Components for using compound (1-7-26) for electron transport layer>

An organic EL element was obtained by the method according to Example 1, except that the compound (1-7-74) was replaced with the compound (1-7-26). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 6.36 V, and the time for maintaining the brightness of 90% or more of the initial value was 151 hours.

[Example 3] <Component for using compound (1-7-98) for electron transport layer>

An organic EL element was obtained by the method according to Example 1, except that the compound (1-7-74) was replaced with the compound (1-7-98). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 7.34 V, and the time for maintaining the brightness of 90% or more of the initial value was 265 hours.

[Example 4] <Component for using compound (1-7-96) for electron transport layer>

An organic EL element was obtained by the method according to Example 1, except that the compound (1-7-74) was replaced with the compound (1-7-96). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test start voltage was 5.33 V, and the time for maintaining the brightness of 90% or more of the initial value was 103 hours.

[Comparative Example 1]

An organic EL element was obtained by the method according to Example 1, except that the compound (1-7-74) was replaced with the compound (C). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of 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 brightness of 90% or more of the initial value was 6 hours.

[Comparative Example 2]

An organic EL element was obtained by the method according to Example 1, except that the compound (1-7-74) was replaced with the compound (D). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . As a result, the driving test start voltage was 5.05 V, and the time for maintaining the brightness of 90% or more of the initial value was 10 hours.

The above results are summarized in Table 2.

The elements of Examples 5 to 20 and Comparative Examples 3 to 5 were produced, and the driving start voltage (V) in the constant current driving test and the time (hour) at which the luminance of 90% or more of the initial value was maintained were measured. Hereinafter, examples and comparative examples will be described in detail.

The material constitution of each of the elements of Examples 5 to 20 and Comparative Examples 3 to 5 produced was shown in Table 3 below.

In Table 3, HT is N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl -N-(4-(9-phenyl-9H-indazol-3-yl)phenyl)-9H-indol-2-amine, compound (E) is 9-(4-(naphthalen-1-yl) Phenyl)-10-phenylindole, compound (F) is 4,4'-((7,7-diphenyl-7H-benzo[c]indole-5,9-diyl)bis((phenyl) Amino))dibenzonitrile, compound (G) is 4'-(4-(10-(naphthalen-2-yl)fluoren-9-yl)phenyl)-2,2':6',2 "-terpyridine, compound (H) is 3-(6-(10-phenylfluoren-9-yl)naphthalen-2-yl)pyridine, and compound (I) is 6-(4-(10-(naphthalene)- 1-yl)fluoren-9-yl)phenyl)-2,4'-bipyridine.

[Example 5] <Component for using compound (1-11-1) for electron transport layer>

A glass substrate (manufactured by Opto Science Co., Ltd.) of 26 mm × 28 mm × 0.7 mm polished to 150 nm by ITO having a film having a thickness of 180 nm by sputtering was used as a transparent supporting substrate. The transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum boat for vapor deposition to which HI is added and a molybdenum boat for vapor deposition to which HT is added are added. Molybdenum boat for vapor deposition of compound (E), molybdenum boat for vapor deposition to which compound (F) is added, molybdenum boat for vapor deposition to which compound (1-11-1) is added, and molybdenum boat for vapor deposition to which Liq is added A molybdenum boat to which magnesium is added and a tungsten boat for vapor deposition to which silver is added.

The following layers were sequentially formed on the ITO film of the transparent supporting substrate. The vacuum chamber was depressurized to 5 × 10 ^-4 Pa. First, the boat for vapor deposition to which HI was added was heated, and vapor deposition was performed so as to have a film thickness of 40 nm to form a hole injection layer, followed by heating and evaporation of HT. The hole transport layer was formed by vapor deposition so that the film thickness became 30 nm. Next, the boat for vapor deposition to which the compound (E) was added and the boat for vapor deposition to which the compound (F) was added were simultaneously heated to form a light-emitting layer so as to have a film thickness of 35 nm. The vapor deposition rate was adjusted so that the weight ratio of the compound (E) to the compound (F) became about 95:5. Then, the vapor deposition boat to which the compound (1-11-1) was added and the boat for vapor deposition to which Liq was added were heated, and vapor deposition was performed so that the film thickness became 25 nm, and the electron transport layer was formed. The vapor deposition rate was adjusted so that the weight ratio of the compound (1-11-1) to Liq became about 1:1. The vapor deposition rate of each layer is from 0.01 nm/sec to 1 nm/sec.

Thereafter, the boat for vapor deposition to which Liq was added was heated to have a film thickness of 1 nm. The method was carried out at a vapor deposition rate of 0.01 nm/sec to 0.1 nm/sec. Next, the boat to which magnesium was added and the boat to which silver was added were simultaneously heated, and vapor deposition was performed so that the film thickness became 100 nm, and a cathode was formed. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver became 10:1, and the cathode was formed so that the vapor deposition rate became 0.1 nm/sec to 10 nm/sec, and the organic electroluminescent device was obtained.

When a direct current voltage is applied using an ITO electrode as an anode and a magnesium/silver electrode as a cathode, blue light emission having a wavelength of about 450 nm is obtained. Further, for obtaining the initial luminance by 2000cd / m ² and a current density of the constant current driving test, driving test initiation voltage of 4.00V, holding time 90% of the initial value of the luminance (1800cd / m ²⁾ or more of 87 hours.

[Example 6] <Component for using compound (1-11-2) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-11-2). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The drive test start voltage was 4.12 V, and the time to maintain the brightness of 90% or more of the initial value was 85 hours.

[Example 7] <Component for using compound (1-11-3) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-11-3). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 3.78 V, and the time for maintaining the brightness of 90% or more of the initial value was 97 hours.

[Example 8] <Component for using compound (1-11-4) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-11-4). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 3.95 V, and the time for maintaining the brightness of 90% or more of the initial value was 83 hours.

[Example 9] <Component for using compound (1-11-5) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-11-5). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 3.88 V, and the time for maintaining the brightness of 90% or more of the initial value was 93 hours.

[Example 10] <Components for using compound (1-11-39) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-11-39). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 4.16 V, and the time for maintaining the brightness of 90% or more of the initial value was 74 hours.

[Example 11] <Component for using compound (1-14-2) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-14-2). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The drive test start voltage was 3.61 V, and the time for maintaining the brightness of 90% or more of the initial value was 76 hours.

[Example 12] <Component for using compound (1-14-3) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-14-3). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 3.85 V, and the time for maintaining the brightness of 90% or more of the initial value was 141 hours.

[Example 13] <Component for using compound (1-14-11) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-14-11). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The drive test start voltage was 4.16 V, and the time to maintain the brightness of 90% or more of the initial value was 162 hours.

[Example 14] <Component for using compound (1-14-12) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-14-12). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 3.87 V, and the time for maintaining the brightness of 90% or more of the initial value was 75 hours.

[Example 15] <Component for using compound (1-14-14) for electron transport layer>

An organic EL element was obtained by the method according to Example 5 except that the compound (1-11-1) was replaced with the compound (1-14-14). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test start voltage was 3.82 V, and the time for maintaining the brightness of 90% or more of the initial value was 227 hours.

[Example 16] <Component for using compound (1-14-15) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-14-15). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The drive test start voltage was 3.98 V, and the time for maintaining the brightness of 90% or more of the initial value was 101 hours.

[Example 17] <Component for using compound (1-14-16) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-14-16). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The drive test start voltage was 4.25 V, and the time for maintaining the brightness of 90% or more of the initial value was 70 hours.

[Example 18] <Component for using compound (1-14-18) for electron transport layer>

An organic EL element was obtained by the method according to Example 5 except that the compound (1-11-1) was replaced with the compound (1-14-18). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 3.75 V, and the time for maintaining the brightness of 90% or more of the initial value was 125 hours.

[Example 19] <Component for using compound (1-14-20) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-14-20). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The drive test start voltage was 4.19 V, and the time to maintain the brightness of 90% or more of the initial value was 63 hours.

[Example 20] <Components for using compound (1-11-18) for electron transport layer>

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (1-11-18). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . The driving test starting voltage was 4.29 V, and the time for maintaining the brightness of 90% or more of the initial value was 60 hours.

[Comparative Example 3]

An organic EL element was obtained by the method according to Example 5, except that the compound (1-11-1) was replaced with the compound (G). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . As a result, the driving test start voltage was 5.36 V, and the time for maintaining the brightness of 90% or more of the initial value was 2 hours.

[Comparative Example 4]

An organic EL element was obtained by the method according to Example 5 except that the compound (1-11-1) was replaced with the compound (H). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . As a result, the driving test start voltage was 4.12 V, and the time for maintaining the brightness of 90% or more of the initial value was 26 hours.

[Comparative Example 5]

An organic EL element was obtained by the method according to Example 5 except that the compound (1-11-1) was replaced with the compound (I). A constant current driving test was carried out by using an ITO electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m ² . As a result, the driving test start voltage was 4.15 V, and the time for maintaining the brightness of 90% or more of the initial value was 30 hours.

The above results are summarized in Table 4.

[Industrial availability]

According to a preferred embodiment of the present invention, it is possible to provide an organic electroluminescence device which is excellent in balance between the driving voltage and the display device, and an illumination device including the same, which is excellent in the balance between the driving voltage and the driving voltage.

Claims (18)

a compound represented by the following formula (1), In the formula (1), Py is independently a group represented by the formula (2), (3) or (4); m and n are 0 or 1, m+n=1; and at least one hydrogen on the benzene ring, the naphthalene ring and the pyridine ring in the formula (1) is substituted with an alkyl group having 1 to 6 carbon atoms or a carbon number It is a 3 to 6 cycloalkyl group. The compound according to claim 1, which is represented by the following formula (1-1) or (1-2), In the formulae (1-1) and (1-2), Py is a group represented by the formula (2), (3) or (4); Further, at least one hydrogen on the benzene ring, the naphthalene ring and the pyridine ring in the formulae (1-1) and (1-2) is substituted with an alkyl group having 1 to 6 carbon atoms or a ring having 3 to 6 carbon atoms. alkyl. A compound according to claim 1, which is represented by the following formula (1-3), (1-4), (1-5), or (1-6). In the formulae (1-3) to (1-6), Py is a group represented by the formula (2), (3) or (4); Further, at least one hydrogen on the benzene ring, the naphthalene ring and the pyridine ring in the formulae (1-3) to (1-6) is substituted with an alkyl group having 1 to 6 carbon atoms or a ring having 3 to 6 carbon atoms. alkyl. A compound according to claim 1, which is represented by the following formula (1-7) or (1-8), In the formulae (1-7) and (1-8), Py is a group represented by the formula (2), (3) or (4); R is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms; and p is an integer of 1 to 5. A compound according to claim 1, which is represented by the following formula (1-9) or (1-10). In the formulae (1-9) and (1-10), Py is a group represented by the formula (2), (3) or (4); R is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms; and q is an integer of 1 to 5. A compound according to claim 1, which is represented by the following formula (1-11) or (1-12), In the formulae (1-11) and (1-12), Py ¹ is a group represented by the formula (2'), (3') or (4'); In the formulae (2'), (3') and (4'), R is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms; and s is an integer of 1 to 4. A compound according to claim 1, which is represented by the following formula (1-13) or (1-14), In the formulae (1-13) and (1-14), Py ¹ is a group represented by the formula (2'), (3') or (4'); In the formula (2'), (3') or (4'), R is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms; and s is an integer of 1 to 4. A compound according to claim 1, which is represented by the following formula (1-15) or (1-16), In the formulae (1-15) and (1-16), Py is a group represented by the formula (2), (3) or (4); R is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms; and t is an integer of 1 to 4. A compound according to claim 1, which is represented by the following formula (1-7-26) A compound according to claim 1, which is represented by the following formula (1-7-74) A compound according to claim 1, which is represented by the following formula (1-7-98) A compound according to claim 1, which is represented by the following formula (1-7-96) A compound according to claim 1, which is represented by the following formula (1-14-14) The compound according to claim 1, which is represented by the following formulas (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), (1-14-12), (1-14-13), (1-14-15), (1-14-16), (1-14-17 Any one of (1-14-18), and (1-14-20) means: An electron transporting material comprising the compound according to any one of claims 1 to 14. An organic electroluminescent device comprising: a pair of electrodes including an anode and a cathode; a light-emitting layer disposed between the pair of electrodes; and disposed between the cathode and the light-emitting layer and containing item 15 of the patent application scope The electron transport layer and/or the electron injection layer of the electron transport material. The organic electroluminescent device of claim 16, wherein at least one of the electron transport layer and the electron injecting layer further comprises a hydroxyquinoline metal complex, a bipyridine derivative, At least one of the group consisting of a phenanthroline derivative and a borane derivative. The organic electroluminescent device of claim 16 or 17, wherein at least one of the electron transport layer and the electron injecting layer further comprises an alkali metal, an alkaline earth metal, a rare earth metal, or a base. Metal oxides, alkali metal halides, alkaline earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes And at least one of the group consisting of organic complexes of rare earth metals.