JP5281304B2 - Phosphorescent organic electroluminescent device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphorescent organic field light emitting element which contains a phenyl-group substituted 1,3,5-triazine compound as a constituent by manufacturing the compound. <P>SOLUTION: The phenyl-group substituted 1,3,5-triazine compound is manufactured which is expressed by a general formula (1) [where Ar<SP>1</SP>and Ar<SP>2</SP>are independently phenyl groups etc., R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are independently hydrogen atoms etc., X is identically or differently a phenylene group etc., (p) and (q) are identically or differently integers of 0 to 2, and Ar<SP>3</SP>and Ar<SP>4</SP>are identically or differently pyridyl groups etc.], and the phosphorescent organic field light emitting element containing it as a constituent is manufactured. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a phosphorescent organic electroluminescent device using a phenyl group-substituted 1,3,5-triazine compound. More specifically, the present invention relates to a phosphorescent organic electroluminescent device in which power consumption is reduced by using this phenyl group-substituted 1,3,5-triazine compound in at least one organic compound layer.

  An organic electroluminescent element is composed of a light emitting layer containing a compound that emits light, sandwiched between a hole transport layer and an electron transport layer, and an anode and a cathode attached to the outside, and holes and electrons are injected into the light emitting layer for recombination. It is an element that utilizes light emission (fluorescence or phosphorescence) when excitons generated when it is deactivated. In recent years, organic electroluminescence devices have been attracting attention as the next generation flat panel display, because they can be made thinner and lighter, they are self-luminous devices, have low power consumption, and have a simple device structure. Therefore, the manufacturing cost is low. The manufacturing method can be applied to various manufacturing techniques such as vacuum deposition, spin coating, ink jet, offset printing, thermal transfer, and the like. Currently, portable devices such as mobile phones, portable music devices, and PDAs (Personal Digital Assistants) have been put into practical use, but if larger size and higher definition are achieved, not only flat panel displays but also surface emitting light sources It is possible to expand to lighting, paper-like displays using flexible characteristics, wearable displays, see-through displays using transparency, and the market is expected to expand rapidly.

  However, there are still many technical issues that must be overcome, and in particular, the current situation is that the drive voltage is high and the efficiency is low, so that the power consumption is high.

  This problem is caused by insufficient properties of materials constituting the organic electroluminescent element, particularly electron transport materials. A wide variety of hole transport materials are known, mainly triarylamine derivatives, but there are few reported examples of electron transport materials. There is tris (8-quinolinolato) aluminum (III) (Alq) as a material that has already been put into practical use, but N, N′-bis (1-naphthyl) -N, N′-diphenyl-, which is a hole transport material, is used. Since the performance is lower than that of 4,4′-biphenyl (NPD), the characteristics of the organic electroluminescent device are limited.

  Examples of reports of other electron transport materials include oxadiazole derivatives (see, for example, Patent Document 1), quinoxaline derivatives (for example, see Patent Document 2), triazole derivatives (for example, see Patent Document 3), and silacyclopentadiene derivatives. (For example, refer patent document 4), a quinoline derivative (for example, refer patent document 5), a benzimidazole derivative (for example, refer patent document 6), a benzothiazole derivative (for example, refer nonpatent literature 1), etc. However, there are still many practical problems such as high driving voltage, easy thin film crystallization, and short life.

  Recently, examples using a compound having a 1,3,5-triazine skeleton have been disclosed (see, for example, Patent Documents 7 to 12).

  Furthermore, an organic electroluminescent element using a phosphorescent material has been proposed for the purpose of further improving the light emission efficiency with the aim of lowering the power consumption of the panel and applying it to lighting (for example, see Non-Patent Document 2).

  This is because the conventional phosphor material can theoretically obtain only 25% of luminous efficiency, whereas the phosphorescent material can theoretically obtain 100% of luminous efficiency. As a result, the organic electroluminescent element containing a phosphorescent material can obtain a luminous efficiency four times that of the fluorescent element at the maximum. The reason why the luminous efficiency of phosphorescent material shows four times the luminous efficiency of fluorescent material is that the excited state of fluorescent material is an excited singlet state in which only 25% of the recombination energy of electrons and holes is generated. This is because the excited state of the phosphorescent material is an excited triplet state capable of generating 100% of the recombination energy.

  On the other hand, it has also been reported that it is not sufficient to change the configuration of the light emitting layer when fabricating a phosphorescent device. For example, the luminous efficiency is improved by changing the hole transport layer constituting the organic electroluminescent element (for example, see Non-Patent Document 3).

  This is because the higher the excited triplet state of the material constituting the organic electroluminescent element, the greater the effect of confining the excited triplet state of the phosphorescent material.

JP-A-6-136359 JP-A-6-207169 International Publication No. 95/25097 Pamphlet JP 2005-104986 A JP 2006-199677 A International Publication No. 2004/080975 Pamphlet JP 2003-045662 A JP 2003-282270 A JP 2004-022334 A US Pat. No. 6,225,467 US Pat. No. 6,325,791 Applied Physics Letters, 89, 063504, 2006 Applied Physics Letters, 77, 904, 1999 Journal of Applied Physics, 95, 7798, 2004

  However, these 1,3,5-triazine compounds, like the conventional electron transport materials, are not sufficient in reducing the driving voltage and increasing the efficiency of the organic electroluminescent device, in particular, improving the efficiency of the phosphorescent device. It was.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have found that the phenyl group-substituted 1,3,5-triazine compound (1) of the present invention is not used in any of vacuum deposition and spin coating methods. It is possible to form crystalline thin films, and organic electroluminescent devices using these as electron transport layers have lower driving voltage, higher efficiency, and longer life than general-purpose phosphorescent organic electroluminescent devices. The present invention has been completed by finding that it can be achieved and that it has an excited triplet state necessary for the construction of a phosphorescent organic electroluminescent device. That is, the present invention relates to the general formula (1)

[Wherein, Ar ¹ and Ar ² each independently represent a phenyl group, a naphthyl group or a biphenylyl group, and these groups are substituted with one or more alkyl groups or trifluoromethyl groups having 1 to 6 carbon atoms. May be. R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group. X ¹ and X ² each independently represent a phenylene group, a naphthylene group or a pyridylene group, and these groups may be substituted with one or more alkyl groups having 1 to 4 carbon atoms or fluorine atoms. p and q each independently represent an integer of 0 to 2. When p is 2, the linked X ¹ may be the same or different. When q is 2, the linked X ² may be the same or different. Ar ³ and Ar ⁴ each independently represent a pyridyl group or a phenyl group, and these groups may be substituted with one or more alkyl groups having 1 to 4 carbon atoms or fluorine atoms. ]
The present invention relates to a phosphorescent organic electroluminescent device characterized in that a phenyl group-substituted 1,3,5-triazine compound represented by the formula (1) is used in at least one organic compound layer.

  Hereinafter, the present invention will be described in detail.

Ar ¹ and Ar ² each independently represent a phenyl group, a naphthyl group or a biphenylyl group, and these groups may be substituted with one or more alkyl groups or trifluoromethyl groups having 1 to 6 carbon atoms.

Specific examples of the phenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms or a trifluoromethyl group represented by Ar ¹ and Ar ² include a phenyl group, a p-tolyl group, an m-tolyl group, o-tolyl group, p-trifluoromethylphenyl group, m-trifluoromethylphenyl group, o-trifluoromethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, mesityl group, 2- Ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl group, 3,5-dipropylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4 Isopropylphenyl group, 2,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5- Dibutylphenyl group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2,4-di-tert-butylphenyl group, 3,5-di-tert-butylphenyl Group, 2-pentylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 2,4-dipentylphenyl group, 3,5-dipentylphenyl group, 2-neopentylphenyl group, 3-neopentylphenyl group, 4-neopentylphenyl group, 2,4-dineopentylphenyl group, 3,5-dineopentylphenol Nyl group, 2-hexylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 2,4-dihexylphenyl group, 3,5-dihexylphenyl group, 2-cyclohexylphenyl group, 3-cyclohexylphenyl group, 4 -Cyclohexylphenyl group, 2,4-dicyclohexylphenyl group, 3,5-dicyclohexylphenyl group, etc. are mentioned. A phenyl group, a p-tolyl group, an m-tolyl group, a 4-ethylphenyl group, a 4-propylphenyl group, a 4-isopropylphenyl group, 4 in terms of good performance as a phosphorescent organic electroluminescent element material. -Butylphenyl group, 4-tert-butylphenyl group, 4-pentylphenyl group, 4-hexylphenyl group or 4-cyclohexylphenyl group are desirable, phenyl group, p-tolyl group, m-tolyl group, 3,5- A dimethylphenyl group, a 4-butylphenyl group or a 4-tert-butylphenyl group is more desirable.

Specific examples of the naphthyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms or a trifluoromethyl group represented by Ar ¹ and Ar ² include a 1-naphthyl group, 4-methylnaphthalen-1-yl Group, 4-trifluoromethylnaphthalen-1-yl group, 4-ethylnaphthalen-1-yl group, 4-propylnaphthalen-1-yl group, 4-butylnaphthalen-1-yl group, 4-tert-butylnaphthalene -1-yl group, 4-hexylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 5-trifluoromethylnaphthalen-1-yl group, 5-ethylnaphthalen-1-yl group, 5- Propylnaphthalen-1-yl group, 5-butylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl group, 5-hexylnaphthalene-1- Group, 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-trifluoromethylnaphthalen-2-yl group, 6-ethylnaphthalen-2-yl group, 6-propylnaphthalen-2-yl group, 6-butylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 6-hexylnaphthalen-2-yl group, 7-methylnaphthalen-2-yl group, 7-trifluoromethylnaphthalene-2 -Yl group, 7-ethylnaphthalen-2-yl group, 7-propylnaphthalen-2-yl group, 7-butylnaphthalen-2-yl group, 7-tert-butylnaphthalen-2-yl group or 7-hexylnaphthalene And 2-yl group. 1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, and 5-methylnaphthalene- are preferable in terms of performance as a phosphorescent organic electroluminescent device material. 1-yl group, 5-tert-butylnaphthalen-1-yl group, 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalene-2 A -yl group or a 7-tert-butylnaphthalen-2-yl group is desirable, and a 1-naphthyl group or 2-naphthyl group is more desirable.

Specific examples of the biphenylyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms or a trifluoromethyl group represented by Ar ¹ and Ar ² include a 4-biphenylyl group, 4′-methylbiphenyl-4- Yl group, 4'-trifluoromethylbiphenyl-4-yl group, 2,5-dimethylbiphenyl-4-yl group, 2 ', 5'-dimethylbiphenyl-4-yl group, 4'-ethylbiphenyl-4- Yl group, 4′-propylbiphenyl-4-yl group, 4′-butylbiphenyl-4-yl group, 4′-tert-butylbiphenyl-4-yl group, 4′-hexylbiphenyl-4-yl group, 3 -Biphenylyl group, 3'-methylbiphenyl-3-yl group, 3'-trifluoromethylbiphenyl-3-yl group, 3'-ethylbiphenyl-3-yl group, 3'-propylbiphenyl-3 Yl group, 3'-butyl-3-yl group, 3'-tert-butyl-biphenyl-3-yl group or 3'-hexyl-3-yl group. A 4-biphenylyl group, a 4′-methylbiphenyl-4-yl group, a 4′-tert-butylbiphenyl-4-yl group, and a 3-biphenylyl group in terms of good performance as a phosphorescent organic electroluminescent element material. A group, 3′-methylbiphenyl-3-yl group or 3′-tert-butylbiphenyl-3-yl group is desirable, and 4-biphenylyl group or 3-biphenylyl group is more desirable.

R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group. Among these, a hydrogen atom is desirable because of its good performance as a phosphorescent organic electroluminescent element material.

X ¹ and X ² each independently represent a phenylene group, a naphthylene group or a pyridylene group, and these groups may be substituted with one or more alkyl groups having 1 to 4 carbon atoms or fluorine atoms.

Specific examples of these groups represented by X ¹ and X ² include 1,3-phenylene group, 2-methyl-1,3-phenylene group, 4-methyl-1,3-phenylene group, and 5-methyl. -1,3-phenylene group, 2-tert-butyl-1,3-phenylene group, 4-tert-butyl-1,3-phenylene group, 5-tert-butyl-1,3-phenylene group, 1,4 -Phenylene group, 2-methyl-1,4-phenylene group, 2-tert-butyl-1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6-tetrafluoro-1,4-phenylene group, 2,5-dimethyl-1,4-phenylene group, 1,4-naphthylene group, 2-methyl-1,4-naphthylene group, 5 -Methyl-1,4-naphthylene group 6-methyl-1,4-naphthylene group, 2-tert-butyl-1,4-naphthylene group, 5-tert-butyl-1,4-naphthylene group, 6-tert-butyl-1,4-naphthylene group, 1,5-naphthylene group, 2-methyl-1,5-naphthylene group, 3-methyl-1,5-naphthylene group, 4-methyl-1,5-naphthylene group, 2-tert-butyl-1,5- Naphthylene group, 3-tert-butyl-1,5-naphthylene group, 4-tert-butyl-1,5-naphthylene group, 2,6-naphthylene group, 1-methyl-2,6-naphthylene group, 3-methyl -2,6-naphthylene group, 4-methyl-2,6-naphthylene group, 1-tert-butyl-2,6-naphthylene group, 3-tert-butyl-2,6-naphthylene group, 4-tert-butyl -2,6-Na Butylene group, 2,4-pyridylene group, 3-methyl-2,4-pyridylene group, 5-methyl-2,4-pyridylene group, 6-methyl-2,4-pyridylene group, 3-tert-butyl-2 , 4-pyridylene group, 5-tert-butyl-2,4-pyridylene group, 6-tert-butyl-2,4-pyridylene group, 2,5-pyridylene group, 3-methyl-2,5-pyridylene group, 4-methyl-2,5-pyridylene group, 6-methyl-2,5-pyridylene group, 3-tert-butyl-2,5-pyridylene group, 4-tert-butyl-2,5-pyridylene group, 6- tert-butyl-2,5-pyridylene group, 2,6-pyridylene group, 3-methyl-2,6-pyridylene group, 4-methyl-2,6-pyridylene group, 3-tert-butyl-2,6- Pyridylene group, 4-te t-butyl-2,6-pyridylene group, 3,5-pyridylene group, 2-methyl-3,5-pyridylene group, 4-methyl-3,5-pyridylene group, 6-methyl-3,5-pyridylene group 2-tert-butyl-3,5-pyridylene group, 4-tert-butyl-3,5-pyridylene group, 6-tert-butyl-3,5-pyridylene group, 3,6-pyridylene group, 2-methyl -3,6-pyridylene group, 4-methyl-3,6-pyridylene group, 5-methyl-3,6-pyridylene group, 2-tert-butyl-3,6-pyridylene group, 4-tert-butyl-3 , 6-pyridylene group, 5-tert-butyl-3,6-pyridylene group, 4,6-pyridylene group, 2-methyl-4,6-pyridylene group, 3-methyl-4,6-pyridylene group, 5- Methyl-4,6-pyridyl Group, 2-tert-butyl-4,6-pyridylene group, can be exemplified 3-tert-butyl-4,6-pyridylene group or 5-tert-butyl-4,6-pyridylene group. In terms of good performance as a phosphorescent organic electroluminescent element material, 1,3-phenylene group, 1,4-phenylene group, 2,3,5,6-tetrafluoro-1,4-phenylene group, 2,5-dimethyl-1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, 2,4-pyridylene group, 2,6-pyridylene group, 3, A 5-pyridylene group, a 3,6-pyridylene group or a 4,6-pyridylene group is desirable.

Ar ³ and Ar ⁴ each independently represent a pyridyl group or a phenyl group, and these groups may be substituted with one or more alkyl groups having 1 to 4 carbon atoms or fluorine atoms.

Specific examples of the pyridyl group optionally substituted by one or more alkyl groups having 1 to 4 carbon atoms or fluorine atoms represented by Ar ³ and Ar ⁴ include 2-pyridyl group, 3-methylpyridin-2-yl Group, 4-methylpyridin-2-yl group, 5-methylpyridin-2-yl group, 6-methylpyridin-2-yl group, 3-ethylpyridin-2-yl group, 4-ethylpyridin-2-yl group Group, 5-ethylpyridin-2-yl group, 6-ethylpyridin-2-yl group, 3-propylpyridin-2-yl group, 4-propylpyridin-2-yl group, 5-propylpyridin-2-yl group Group, 6-propylpyridin-2-yl group, 3-butylpyridin-2-yl group, 4-butylpyridin-2-yl group, 5-butylpyridin-2-yl group, 6-butylpyridin-2-yl group Group 3 tert-butylpyridin-2-yl group, 4-tert-butylpyridin-2-yl group, 5-tert-butylpyridin-2-yl group, 6-tert-butylpyridin-2-yl group, 3-fluoropyridine 2-yl group, 4-fluoropyridin-2-yl group, 5-fluoropyridin-2-yl group, 6-fluoropyridin-2-yl group, 3-pyridyl group, 2-methylpyridin-3-yl group 4-methylpyridin-3-yl group, 5-methylpyridin-3-yl group, 6-methylpyridin-3-yl group, 2-ethylpyridin-3-yl group, 4-ethylpyridin-3-yl group 5-ethylpyridin-3-yl group, 6-ethylpyridin-3-yl group, 2-propylpyridin-3-yl group, 4-propylpyridin-3-yl group, 5-propylpyridin-3- Yl group, 6-propylpyridin-3-yl group, 2-butylpyridin-3-yl group, 4-butylpyridin-3-yl group, 5-butylpyridin-3-yl group, 6-butylpyridin-3- Yl group, 2-tert-butylpyridin-3-yl group, 4-tert-butylpyridin-3-yl group, 5-tert-butylpyridin-3-yl group, 6-tert-butylpyridin-3-yl group 2-fluoropyridin-3-yl group, 2-fluoropyridin-4-yl group, 2-fluoropyridin-5-yl group, 2-fluoropyridin-6-yl group, 4-pyridyl group, 2-methylpyridine -4-yl group, 3-methylpyridin-4-yl group, 2-ethylpyridin-4-yl group, 3-ethylpyridin-4-yl group, 2-propylpyridin-4-yl group, 3-propylpi Gin-4-yl group, 2-butylpyridin-4-yl group, 3-butylpyridin-4-yl group, 2-tert-butylpyridin-4-yl group, 3-tert-butylpyridin-4-yl group , 1-fluoropyridin-4-yl group, 2-fluoropyridin-4-yl group, and the like.

Specific examples of the alkyl group having 1 to 4 carbon atoms represented by Ar ³ and Ar ⁴ or a phenyl group optionally substituted with one or more fluorine atoms include a phenyl group, an o-tolyl group, an m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2-butylphenyl group, 3-butyl Phenyl group, 4-butylphenyl group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group Etc. can be illustrated.

Ar ³ and Ar ⁴ are each independently a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a phenyl group or a 4-tert group in terms of good performance as a phosphorescent organic electroluminescent device material. -A butylphenyl group is preferred.

In addition, at least one of Ar ^{3 and} Ar ⁴ is a 2-pyridyl group, a 3-pyridyl group, or a 4-pyridyl group in terms of good performance as a phosphorescent organic electroluminescent element material. Desirable, particularly 2-pyridyl group is more desirable.

The substituents -X ¹ -Ar ³ and -X ¹ -X ¹ -Ar ³ consisting of the above X ¹ and Ar ^{3 wherein} p is 1 or 2 are the following basic skeletons of (I) to (LXXVI): Although the group shown can be illustrated, this invention is not limited to these.

The substituents -X ² -Ar ⁴ and -X ² -X ² -Ar ⁴ consisting of the above X ² and Ar ^{4 in} which q is 1 or 2 are the basic skeletons of the above (I) to (LXXVI) Although the group shown can be illustrated, this invention is not limited to these.

There is no particular limitation on the method for producing a phosphorescent thin film for an organic electroluminescence device comprising the phenyl group-substituted 1,3,5-triazine compound (1), but the film can be formed by a vacuum deposition method. Film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The vacuum degree of the vacuum chamber when forming a film by the vacuum evaporation method is determined by taking into account the manufacturing tact time and manufacturing cost of manufacturing the organic electroluminescence device, and commonly used diffusion pumps, turbo molecular pumps, cryopumps, etc. 1 × 10 ⁻² to 1 × 10 ⁻⁵ Pa which can be reached by the above is desirable. The deposition rate is preferably 0.005 to 1.0 nm / second, depending on the thickness of the film to be formed. In addition, since the phenyl group-substituted 1,3,5-triazine compound (1) has high solubility in chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, tetrahydrofuran, or the like, a spin copolymer using a general-purpose apparatus is used. -Film formation by the GOT method, ink jet method, cast method or dipping method is also possible.

  The thin film comprising the phenyl group-substituted 1,3,5-triazine compound (1) of the present invention has high surface smoothness, amorphousness, heat resistance, electron transport ability, hole blocking ability, redox resistance, water resistance, acid resistance. It is useful as a material for phosphorescent organic electroluminescence devices because it has features, electron injection characteristics, high excited triplet levels, etc., and is especially used as an electron transport material, hole blocking material, light emitting host material, etc. Can do. Accordingly, the thin film comprising the phenyl group-substituted 1,3,5-triazine compound (1) of the present invention is expected to be used as a constituent component of a phosphorescent organic electroluminescence device.

  Hereinafter, evaluation of a phosphorescent organic electroluminescent device using the phenyl group-substituted 1,3,5-triazine compound (1) and the phenyl group-substituted 1,3,5-triazine compound (1) of the present invention as an electron transport layer will be described. Reference examples and examples will be described, but the present invention is not limited to these examples.

  Reference Example 1 Synthesis of 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine

  9.1 g of 3-bromo-5-chlorobenzoic acid chloride and 7.4 g of benzonitrile were dissolved in 200 mL of chloroform under argon. To the resulting solution, 10.7 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 1 hour and then refluxed for 12 hours. After cooling to room temperature, low-boiling components were removed under reduced pressure, and 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-oxa-3,5-diazinium hexachloroantimony (V) acid was converted into a yellow solid. Got as. The resulting yellow solid was pulverized in a stream of argon and slowly added to a 28% aqueous ammonia solution at 0 ° C. The resulting suspension was stirred for an additional hour at room temperature. The precipitated solid was collected by filtration and washed successively with water and methanol. The solid was dried and extracted with a Soxhlet extractor (extraction solvent: tetrahydrofuran). The extract was allowed to cool, and the precipitated solid was collected by filtration and dried to give a white powder of 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (yield 5.6 g). Yield 44%).

¹ H-NMR (CDCl ₃ ): δ 7.57-7.70 (m, 6H), 7.75 (dd, J = 1.7, 1.7 Hz, 1H), 8.66 (brs, 1H), 8.74 (d, J = 7.2 Hz, 4H), 8.76 (brs, 1H).
¹³ C-NMR (CDCl ₃ ): δ 123.2, 127.7, 128.8, 129.1, 130.1, 132.9, 134.9, 135.7, 135.7, 139.5, 169 .3, 172.0.
Example 1 Synthesis of 2- [5-chloro-4 ′-(2-pyridyl) -1,1′-biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine

  Under an argon stream, 350 mg of 2- (4-bromophenyl) pyridine was dissolved in 20 mL of tetrahydrofuran and cooled to -78 ° C. To this was slowly added 1.04 mL of a hexane solution containing 1.65 mmol of butyl lithium, and the mixture was stirred at this temperature for 30 minutes. To this mixture, 454 mg of dichloro (tetramethylethylenediamine) zinc (II) was added, stirred at −78 ° C. for 10 minutes, and then stirred at room temperature for 1.5 hours. To this was added 350 mg of 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine synthesized by the method of Reference Example 1 and 46 mg of tetrakis (triphenylphosphine) palladium (0). And heated to reflux for 18 hours. After allowing to cool, the reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (developing solvent hexane: chloroform = 1: 1 to 0: 1), recrystallized again from dichloromethane-methanol, and 2- [5-chloro-4 ′-( A white solid (yield 339 mg, yield 68%) of 2-pyridyl) -1,1′-biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.28-7.32 (m, 1H), 7.59-7.67 (m, 2H), 7.62 (d, J = 7.6 Hz, 4H), 7.81-7.87 (m, 2H), 7.85 (d, J = 8.3 Hz, 2H), 7.88 (brs, 1H), 8.20 (d, J = 8.3 Hz, 2H) ), 8.74 (brs, 1H), 8.75-8.80 (m, 1H), 8.80 (d, J = 7.6 Hz, 4H), 8.94 (brs, 1H).
¹³ C-NMR (CDCl ₃ ): δ 120.6, 122.4, 125.9, 127.6, 127.7, 127.8, 128.8, 129.1, 130.9, 132.8, 135 4, 136.0, 136.9, 138.6, 139.3, 140.0, 142.4, 149.9, 156.8, 171.5, 172.0.
Example 2 2- {4- (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl} -4,6-diphenyl-1,3,5-triazine Synthesis of

  Under an argon stream, 73 mg of phenylboronic acid, 5.8 mg of tris (dibenzalacetone) dipalladium complex and 12 mg of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl were added to 15 mL of 1,4-dioxane. Suspended, 0.6 mL of 3N potassium phosphate aqueous solution was added, and the mixture was stirred for 10 minutes at room temperature. To this mixture, 2- [5-chloro-4 ′-(2-pyridyl) -1,1′-biphenyl-3-yl] -4,6-diphenyl-1,3,5- obtained in Example 1 was added. 149 mg of triazine was added, and the mixture was heated to reflux at 110 ° C. for 48 hours. After allowing to cool, the reaction solution is concentrated under reduced pressure, and the resulting solid is purified by silica gel column chromatography (developing solvent hexane: chloroform = 1: 1 to 0: 1), recrystallized from dichloromethane-methanol, 2- { White solid of 4- (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl} -4,6-diphenyl-1,3,5-triazine (yield 162 mg) Yield 99% <).

¹ H-NMR (CDCl ₃ ): δ 7.28-7.32 (m, 1H), 7.49 (brt, J = 7.4 Hz, 1H), 7.56-7.72 (m, 8H), 7.80-7.89 (m, 2H), 7.85 (d, J = 8.5 Hz, 2H), 7.95 (d, J = 8.3 Hz, 2H), 8.12 (brs, 1H) ), 8.22 (d, J = 8.3 Hz, 2H), 8.79 (brd, J = 4.5 Hz, 1H), 8.83 (d, J = 8.2 Hz, 4H), 9.02. (Brs, 1H), 9.06 (brs, 1H).
¹³ C-NMR (CDCl ₃ ): δ 120.5, 122.3, 126.7, 126.9, 127.5, 127.6, 127.8, 128.7, 129.0, 129.1, 130 1, 132.6, 136.2, 136.9, 137.5, 138.8, 140.9, 141.4, 141.7, 142.5, 149.9, 157.0, 171.6 171.8.
Example 3 2- {4- (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl} -4,6-diphenyl-1,3,5-triazine In an argon stream, 73 mg of phenylboronic acid, 2.9 mg of palladium acetate, 195 mg of cesium carbonate and 12 mg of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl were suspended in 15 mL of 1,4-dioxane. Stir for 10 minutes at room temperature. To this mixture, 2- [5-chloro-4 ′-(2-pyridyl) -1,1′-biphenyl-3-yl] -4,6-diphenyl-1,3,5- obtained in Example 1 was added. 149 mg of triazine was added, and the mixture was heated to reflux at 110 ° C. for 48 hours. After allowing to cool, the reaction solution is concentrated under reduced pressure, and the resulting solid is purified by silica gel column chromatography (developing solvent hexane: chloroform = 1: 1 to 0: 1), recrystallized from dichloromethane-methanol, 2- { White solid of 4- (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl} -4,6-diphenyl-1,3,5-triazine (yield 153 mg) Yield 95%).

  Reference Example 2 Synthesis of 2- (3,5-dibromophenyl) -4,6-di-m-tolyl-1,3,5-triazine

  26.57 g of 3,5-dibromobenzoyl chloride and 20.85 g of 3-methylbenzonitrile were dissolved in 200 mL of chloroform, and 26.61 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 10 minutes and then refluxed for 12 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. The obtained 2- (3,5-dibromophenyl) -4,6-di-m-tolyl-1,3,5-oxadiazinyl-1-ium hexachloroantimonate was gradually added to 500 mL of 28% aqueous ammonia solution at 0 ° C. A white precipitate formed upon addition. This was stirred at room temperature for 1 hour, and after filtration, the resulting white precipitate was washed with water and methanol. After drying the white precipitate, 200 mL of chloroform was added thereto, and this suspension was stirred under heating to reflux and filtered. Furthermore, 200 mL of chloroform was added to the insoluble component separated by filtration, and this was stirred under heating and refluxing, and then filtered twice. All the filtrates were collected, chloroform was distilled off under reduced pressure, and the obtained solid was recrystallized from dichloromethane-methanol to give 2- (3,5-dibromophenyl) -4,6-di-m-tolyl-1. , 3,5-triazine was obtained as a white solid (yield 26.23 g, yield 60%).

¹ H-NMR (CDCl ₃ ): δ 2.54 (s, 6H), 7.42-7.46 (m, 2H), 7.48 (dd, J = 7.5, 7.5 Hz, 2H), 7.89 (t, J = 1.8 Hz, 1H), 8.52 (s, 2H), 8.54 (d, J = 7.5 Hz, 2H), 8.80 (d, J = 1.8 Hz) , 2H).
¹³ C-NMR (CDCl ₃ ): δ 21.6, 123.3, 126.3, 128.6, 129.4, 130.6, 133.7, 135.6, 137.5, 138.5, 139 .8, 169.2, 172.0.
Example 4 2- {4,4 ″ -bis (2-pyridyl)-[1,1 ′; 3 ′, 1 ″]-terphenyl-5′-yl} -4,6-di-m- Synthesis of tolyl-1,3,5-triazine

  Under an argon stream, 10.0 mL of a hexane solution containing 15.8 mmol of butyllithium was slowly added to 80 mL of tetrahydrofuran dissolved in 3.51 g of 2- (4-bromophenyl) pyridine and cooled to -78 ° C. After stirring at −78 ° C. for 20 minutes, 4.55 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 2.48 g of 2- (3,5-dibromophenyl) -4,6-di-m-tolyl-1,3,5-triazine obtained in Reference Example 2 and tetrakis (triphenylphosphine) palladium (0 ) 0.05 g and 40 mL of tetrahydrofuran were added, and the mixture was stirred for 17 hours with heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (eluent hexane: chloroform = 1: 2 to 0: 1) and recrystallized from dichloromethane-methanol to obtain the desired 2- {4,4 ″ -bis. White solid of (2-pyridyl)-[1,1 ′; 3 ′, 1 ″]-terphenyl-5′-yl} -4,6-di-m-tolyl-1,3,5-triazine ( Yield 2.98 g, 93% yield).

¹ H-NMR (CDCl ₃ ): δ 2.54 (s, 6H), 7.27 (ddd, J = 7.3, 4.8, 1, 1 Hz, 2H), 7.42-7.45 (m , 2H), 7.49 (dd, J = 7.5, 7.5 Hz, 2H), 7.78-7.83 (m, 2H), 7.83-7.87 (m, 2H), 7 .94 (d, J = 8.3 Hz, 4H), 8.14 (t, J = 1.7 Hz, 1H), 8.20 (d, J = 8.3 Hz, 4H), 8.60 (s, 2H), 8.62 (d, J = 7.5 Hz, 2H), 8.76 (brd, J = 4.8 Hz, 2H), 9.04 (d, J = 1.7 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 21.7, 120.6, 122.3, 126.4, 126.9, 127.5, 127.9, 128.7, 129.5, 129.9, 133 5, 136.2, 136.9, 137.7, 138.4, 138.9, 141.4, 141.9, 149.9, 157.0, 171.5, 172.0.
Example 5 2- [4,4 ″ ″-bis (2-pyridyl)-[1,1 ′: 4 ′, 1 ″: 3 ″, 1 ′ ″: 4 ′ ″, 1 ′ Synthesis of ''']-kinkphenyl-5''-yl] -4,6-di-m-tolyl-1,3,5-triazine

  Under an argon stream, 2.9 mL of a hexane solution containing 4.5 mmol of butyllithium was dissolved in 1.32 g of 4-bromo-4 ′-(2-pyridyl) biphenyl and slowly added to 120 mL of tetrahydrofuran cooled to −78 ° C. . After stirring at −78 ° C. for 20 minutes, 1.29 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 0.70 g of 2- (3,5-dibromophenyl) -4,6-di-m-tolyl-1,3,5-triazine obtained in Reference Example 2 and tetrakis (triphenylphosphine) palladium (0 ) 0.035 g was added and stirred under reflux for 14 hours. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (eluent hexane: chloroform = 1: 1 to 0: 1) and recrystallized from toluene to obtain the desired 2- [4,4 ″ ″-bis. (2-pyridyl)-[1,1 ′: 4 ′, 1 ″: 3 ″, 1 ′ ″: 4 ′ ″, 1 ″ ″]-kinkphenyl-5 ″ -yl]- A white solid (yield: 0.97 g, yield: 86%) of 4,6-di-m-tolyl-1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ 2.55 (s, 6H), 7.24-7.29 (m, 2H), 7.43-7.47 (m, 2H), 7.50 (dd, J = 7.5, 7.5 Hz, 2H), 7.76-7.84 (m, 4H), 7.84 (d, J = 8.3 Hz, 4H), 7.87 (d, J = 8 .3 Hz, 4H), 7.93 (d, = 8.3 Hz, 4H), 8.12-8.17 (m, 1H), 8.15 (d, J = 8.3 Hz, 4H), 8. 61 (s, 2H), 8.63 (d, J = 7.5 Hz, 2H), 8.74 (brd, J = 4.6 Hz, 2H), 9.04 (d, J = 1.7 Hz, 2H) ).
¹³ C-NMR (CDCl ₃ ): δ 21.7, 120.5, 122.2, 126.4, 126.7, 127.5, 127.7, 128.0, 128.7, 129.5, 129 .9, 133.5, 136.3, 136.8, 137.7, 138.4, 138.6, 140.0, 140.1, 141.1, 141.9, 149.8, 157.1 171.6, 172.0.
Reference Example 3 Synthesis of 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine

  3.97 g of 3,5-dibromobenzoyl chloride and 4.12 g of benzonitrile were dissolved in 50 mL of chloroform, and 5.98 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 10 minutes and then refluxed for 22 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. When the obtained 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-oxadiazinyl-1-ium hexachloroantimonate was gradually added to 300 mL of 28% aqueous ammonia solution at 0 ° C., white precipitation was observed. Generated. This was stirred at room temperature for 1 hour, and after filtration, the resulting white precipitate was washed with water and methanol. After drying the white precipitate, 150 mL of chloroform was added thereto, and the suspension was stirred under heating to reflux and filtered. Furthermore, 100 mL of chloroform was added to the insoluble component separated by filtration, and this was stirred under heating and refluxing, and then filtered twice. All the filtrates were collected, chloroform was distilled off under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol to give 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5. -A white solid of triazine (yield 6.32 g, yield 68%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.56-7.61 (m, 4H), 7.61-7.67 (m, 2H), 7.90 (t, J = 1.8 Hz, 1H), 8.72-8.78 (m, 4H), 8.82 (d, J = 1.8 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 123.4, 128.8, 129.1, 130.6, 133.0, 135.7, 137.6, 139.8, 169.3, 172.0.
Example 6 2,4-Diphenyl-6- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl] -1, Synthesis of 3,5-triazine

  Under an argon stream, 8.2 mL of a hexane solution containing 13.0 mmol of butyllithium was slowly added to 50 mL of tetrahydrofuran dissolved in 2.81 g of 2- (4-bromophenyl) pyridine and cooled to -78 ° C. After stirring at −78 ° C. for 20 minutes, 3.64 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 1.87 g of 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine obtained in Reference Example 3 and 0.046 g of tetrakis (triphenylphosphine) palladium (0) were obtained. And tetrahydrofuran (50 mL) were added, and the mixture was stirred for 19 hours under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (eluent hexane: chloroform = 1: 2 to 0: 1) and recrystallized again with dichloromethane-methanol and then with toluene to obtain the desired 2,4-diphenyl- 6- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl] -1,3,5-triazine white solid ( Yield 2.14 g, yield 87%).

¹ H-NMR (CDCl ₃ ): δ 7.25 (ddd, J = 7.2, 4.8, 1, 2 Hz, 2H), 7.57-7.67 (m, 6H), 7.78-7 .82 (m, 2H), 7.82-7.86 (m, 2H), 7.94 (d, J = 8.3 Hz, 4H), 8.15 (t, J = 1.7 Hz, 1H) , 8.20 (d, J = 8.3 Hz, 4H), 8.76 (brd, J = 4.8 Hz, 2H), 8.79-8.85 (m, 4H), 9.05 (d, J = 1.7 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 120.6, 122.3, 126.9, 127.5, 127.9, 128.8, 129.1, 129.9, 132.7, 136.2, 136 9, 137.5, 138.9, 141.3, 141.9, 149.9, 157.0, 171.5, 171.8.
Reference Example 4 Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3,5-triazine

  3.98 g of 3,5-dibromobenzoyl chloride and 3.18 g of 4-tert-butylbenzonitrile were dissolved in 30 mL of chloroform, and 2.99 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 10 minutes and then refluxed for 17 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. The obtained 2- (3,5-dibromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3,5-oxadiazinyl-1-ium hexachloroantimonate was dissolved in 200 mL of 28% aqueous ammonia solution. When added slowly at 0 ° C., a white precipitate formed. This was stirred at room temperature for 1 hour, and after filtration, the resulting white precipitate was washed with water and methanol. After drying the white precipitate, 150 mL of chloroform was added thereto, and the suspension was stirred under heating to reflux and filtered. Furthermore, 100 mL of chloroform was added to the insoluble component separated by filtration, and this was stirred while heating under reflux and filtered. All the filtrates were collected, chloroform was distilled off under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol to give 2- (3,5-dibromophenyl) -4,6-bis (4-tert-butyl). A white solid of phenyl) -1,3,5-triazine (yield 4.46 g, yield 77%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 1.41 (s, 18H), 7.61 (d, J = 8.5 Hz, 4H), 7.88 (t, J = 1.8 Hz, 1H), 8. 65 (d, J = 8.5 Hz, 4H), 8.80 (d, J = 1.8 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 31.2, 35.1, 123.3, 125.7, 128.9, 130.5, 133.1, 137.4, 140.0, 156.5, 169 0.0, 171.8.
Reference Example 5 Synthesis of 2,4-bis (biphenyl-4-yl) -6- (3,5-dibromophenyl) -1,3,5-triazine

  3.98 g of 3,5-dibromobenzoyl chloride and 3.58 g of 4-biphenylcarbonitrile were dissolved in 40 mL of chloroform, and 2.99 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 10 minutes and then refluxed for 14 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. The obtained 2,4-bis (biphenyl-4-yl) -6- (3,5-dibromophenyl) -1,3,5-oxadiazinyl-1-ium hexachloroantimonate was added to 150 mL of 28% aqueous ammonia solution at 0 ° C. Was slowly added to form a white precipitate. This was stirred at room temperature for 1 hour, and after filtration, the resulting white precipitate was washed with water and methanol. After drying the white precipitate, 200 mL of chloroform was added thereto, and this suspension was stirred under heating to reflux and filtered. Further, 150 mL of chloroform was added to the insoluble component separated by filtration, and the operation of stirring and heating under reflux was performed twice. All the filtrates were collected, chloroform was distilled off under reduced pressure, and the obtained solid was recrystallized from dichloromethane-methanol to give 2,4-bis (biphenyl-4-yl) -6- (3,5-dibromophenyl). ) -1,3,5-triazine was obtained as a white solid (yield 5.14 g, yield 83%).

¹ H-NMR (CDCl ₃ ): δ 7.40-7.45 (m, 2H), 7.49-7.54 (m, 4H), 7.70-7.75 (m, 4H), 7. 83 (d, J = 8.5 Hz, 4H), 7.91 (t, J = 1.8 Hz, 1H), 8.83 (d, J = 8.5 Hz, 4H), 8.85 (d, J = 1.8 Hz, 2H), 8.91 (d, J = 8.5 Hz, 4H), 9.09 (d, J = 1.7 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 123.4, 127.3, 127.5, 128.2, 129.0, 129.7, 130.7, 134.7, 137.6, 139.9, 140 .3, 145.7, 169.3, 171.8.
Reference Example 6 Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (1-naphthyl) -1,3,5-triazine

  3.98 g of 3,5-dibromobenzoyl chloride and 3.06 g of 1-naphthonitrile were dissolved in 30 mL of chloroform, and 2.99 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 10 minutes and then refluxed for 22 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. The obtained 2- (3,5-dibromophenyl) -4,6-bis (1-naphthyl) -1,3,5-oxadiazinyl-1-ium hexachloroantimonate was gradually added to 100 mL of 28% aqueous ammonia solution at 0 ° C. To form a white precipitate. This was stirred at room temperature for 1 hour, and after filtration, the resulting white precipitate was washed with water and methanol. The white precipitate was dried, purified by silica gel column chromatography (eluent hexane: chloroform = 3: 1 to 1: 1), recrystallized from dichloromethane-methanol, 2- (3,5-dibromophenyl) -4, A white solid (yield 1.73 g, yield 29%) of 6-bis (1-naphthyl) -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.60 (ddd, J = 8.0, 6.8, 1.2 Hz, 2H), 7.65 (ddd, J = 8.6, 6.8, 1. 5 Hz, 2H), 7.69 (dd, J = 8.1, 7.4 Hz, 2H), 7.92 (t, J = 1.8 Hz, 1H), 7.99 (brd, J = 8.0 Hz) , 2H), 8.11 (brd, J = 8.1 Hz, 2H), 8.58 (dd, J = 7.4, 1.3 Hz, 2H), 8.84 (d, J = 1.8 Hz, 2H), 9.16 (brd, J = 8.6 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 123.6, 125.2, 125.9, 126.3, 127.5, 128.8, 130.7, 131.1, 131.3, 132.8, 133 3, 134.3, 137.8, 139.7, 168.9, 174.5.
Example 7 2,4-bis (1-naphthyl) -6- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′- Yl] -1,3,5-triazine

  Under an argon stream, 4.0 mL of a hexane solution containing 6.3 mmol of butyllithium was slowly added to 30 mL of tetrahydrofuran dissolved in 1.40 g of 2- (4-bromophenyl) pyridine and cooled to −78 ° C. After stirring at −78 ° C. for 20 minutes, 1.82 g of dichloro (tetramethylethylenediamine) zinc (II) was added, followed by stirring at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 1.13 g of 2- (3,5-dibromophenyl) -4,6-bis (1-naphthyl) -1,3,5-triazine obtained in Reference Example 6 and tetrakis (triphenylphosphine) palladium ( 0) 0.046 g and 30 mL of tetrahydrofuran were added, and the mixture was stirred for 19 hours with heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (eluent hexane: chloroform = 2: 3 to 0: 1), recrystallized again from dichloromethane-methanol, and purified by sublimation. Bis (1-naphthyl) -6- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl] -1,3 A white solid of 5-triazine (yield 1.12 g, yield 78%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.27 (ddd, J = 7.1, 4.8, 1.4 Hz, 2H), 7.60 (ddd, J = 8.0, 6.8, 1. 2 Hz, 2H), 7.66 (ddd, J = 8.6, 6.8, 1.5 Hz, 2H), 7.69 (dd, J = 8.1, 7.2 Hz, 2H), 7.76. −7.81 (m, 2H), 7.81-7.85 (m, 2H), 7.94 (d, J = 8.5 Hz, 4H), 7.99 (brd, J = 8.0 Hz, 2H), 8.11 (brd, J = 8.1 Hz, 2H), 8.18 (d, J = 8.5 Hz, 4H), 8.21 (t, J = 1.7 Hz, 1H), 8. 65 (dd, J = 7.2, 1.2 Hz, 2H), 8.75 (ddd, J = 4.8, 1.7, 1.0 Hz, 2H), 9.11 (d, J = 1. 7Hz, 2H), 9.3 (D, J = 8.6Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 120.5, 122.2, 125.2, 126.2, 126.8, 127.3, 127.5, 127.7, 128.8, 130.0, 131 0.0, 131.4, 132.6, 133.7, 134.3, 136.8, 137.4, 138.8, 141.0, 141.9, 149.8, 156.9, 171.1 , 174.3.
Reference Example 7 Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine

  4.1 g of 3,5-dibromo-benzoic acid chloride and 5.0 g of 3-phenylbenzonitrile were dissolved in 100 mL of chloroform under argon. To the obtained solution, 4.2 g of antimony pentachloride was added dropwise at 0 ° C. The mixture was stirred at room temperature for 1 hour and then refluxed for 12 hours. After cooling to room temperature, low-boiling components were removed under reduced pressure, and 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -oxa-3,5-diazinium hexachloroantimony (V ) The acid was obtained as a red solid. The resulting red solid was pulverized in a stream of argon and slowly added to a 28% aqueous ammonia solution at 0 ° C. The resulting suspension was stirred for an additional hour at room temperature. The precipitated solid was collected by filtration and washed successively with water and methanol. The solid was dried and extracted with a Soxhlet extractor (extraction solvent: chloroform). The extract was allowed to cool, and the precipitated solid was collected by filtration and dried to give white white 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine. A powder (yield 2.8 g, yield 32%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.46 (brt, J = 7.4 Hz, 2H), 7.52-7.58 (m, 4H), 7, 67 (dd, J = 7.8, 7 .7 Hz, 2H), 7.76 (brd, J = 7.7 Hz, 4H), 7.86 (d, J = 7.7 Hz, 2H), 7.90 (brd, 1H), 8.72 (d , J = 7.8 Hz, 2H), 8.81 (d, J = 1.8 Hz, 2H), 8.95 (s, 2H).
¹³ C-NMR (CDCl ₃ ): δ 123.4, 127.4, 127.7, 127.8, 128.1, 130.7, 131.7, 136.2, 137.7, 139.7, 140 .7, 141.9, 169.4, 172.0.
Example 8 2,4-Bis (biphenyl-3-yl) -6- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5 Synthesis of '-yl] -1,3,5-triazine

  Under an argon stream, 1.38 g of 2- (4-bromophenyl) pyridine was dissolved in 100 mL of tetrahydrofuran and cooled to -78 ° C. To this was slowly added 3.99 mL of a hexane solution containing 6.30 mmol of butyllithium, and the mixture was stirred at this temperature for 30 minutes. To this mixture, 1.82 g of dichloro (tetramethylethylenediamine) zinc (II) was added, stirred at −78 ° C. for 10 minutes, and then stirred at room temperature for 1.5 hours. Here, 1.24 g of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine obtained in Reference Example 7, tetrakis (triphenylphosphine) palladium (0) 0.185 g was added and heated to reflux for 18 hours. After allowing to cool, the reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The resulting crude product was purified by silica gel column chromatography (developing solvent hexane: chloroform = 1: 1 to 0: 1), recrystallized from hot toluene, and 2,4-bis (biphenyl-3-yl)- 6- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl] -1,3,5-triazine white solid ( Yield 1.08 g, yield 70%).

¹ H-NMR (CDCl ₃ ): δ 7.30-7.35 (m, 2H), 7.43-7.49 (m, 2H), 7.56 (dd, J = 7.8, 7.6 Hz) 4H), 7.72 (dd, J = 7.7, 7.7 Hz, 2H), 7.80 (d, J = 7.8 Hz, 4H), 7.82-7.93 (m, 6H) , 7.98 (d, J = 8.3 Hz, 4H), 8.21 (t, J = 1.7 Hz, 1H), 8.23 (d, J = 8.3 Hz, 4H), 8.79 ( d, J = 4.9 Hz, 2H), 8.83 (d, J = 7.7 Hz, 2H), 9.09 (s, 2H), 9.10 (d, J = 1.7 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 120.6, 122.3, 126.9, 127.4, 127.6, 127.7, 127.8, 127.8, 128.1, 129.0, 129 3, 130.1, 131.4, 136.8, 136.9, 137.6, 138.9, 140.8, 141.3, 141.8, 141.9, 149.9, 157.0 , 171.7, 171.9.
Example 9 2- {4,4 ″ -bis (2-pyridyl)-[1,1 ′; 3 ′, 1 ″]-terphenyl-5′-yl} -4,6-di-m- Fabrication and performance evaluation of green phosphorescent organic electroluminescent device comprising tril-1,3,5-triazine as a constituent component A 2 mm wide indium tin oxide (ITO) film was patterned in a stripe pattern on the substrate A glass substrate with an ITO transparent electrode was used. The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum evaporation method, and an organic electroluminescent device having a light-emitting area of 4 mm ² as shown in FIG.

First, the said glass substrate was introduce | transduced in the vacuum evaporation tank and it pressure-reduced to 1.0 * 10 <^-4> Pa. Thereafter, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4 and an electron transport layer 5 are sequentially formed as an organic compound layer on the glass substrate indicated by 1 in FIG. Filmed. As the hole injection layer 2, sublimation-purified phthalocyanine copper (II) was vacuum-deposited with a film thickness of 25 nm. As the hole transport layer 3, N, N′-di (naphthylene-1-yl) -N, N′-diphenylbenzidine (NPD) was vacuum-deposited with a film thickness of 45 nm. 4,4′-bis (carbazol-9-yl) biphenyl (CBP) is used as the host material of the light-emitting layer 4, and tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3) is used as the dopant. The film was co-deposited to a film thickness of 40 nm using a dope concentration of 6%. As the electron transport layer 5, 2- {4,4 ″ -bis (2-pyridyl)-[1,1 ′; 3 ′, 1 ″]-terphenyl-5′- obtained in Example 4 was used. Ir} -4,6-di-m-tolyl-1,3,5-triazine was vacuum deposited with a thickness of 20 nm. Each organic material was formed into a film by a resistance heating method, and the heated compound was vacuum-deposited at a film formation rate of 0.3 to 0.5 nm / second. Finally, a metal mask was disposed so as to be orthogonal to the ITO stripe, and the cathode layer 6 was formed. The cathode layer 6 was made into a two-layer structure by vacuum-depositing lithium fluoride and aluminum with thicknesses of 0.5 nm and 100 nm, respectively. Each film thickness was measured with a stylus type film thickness meter (DEKTAK). Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. Sealing was performed using a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation).

A direct current was applied to the produced green phosphorescent organic electroluminescence device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As light emission characteristics, voltage (V), luminance (cd / m ² ), current efficiency (cd / A), and power efficiency (lm / W) when a current density of 20 mA / cm ² was applied were measured. The measured values of the manufactured element were 8.8 V, 2730 cd / m ² , 13.3 cd / A, and 5.3 lm / W. The luminance half time of this element was 841 hours.

Example 10
4,4′-bis (carbazol-9-yl) biphenyl (CBP) was used as the host material of the light-emitting layer 4 of Example 9, and bis (2- (2′-benzo [4,5-a ] Thienyl) pyridinate-N, C3 ′) iridium (acetylacetonate) (Btp2Ir (acac)) was co-deposited to a thickness of 40 nm using a doping concentration of 6%. As the electron transport layer 5, 2- {4,4 ″ -bis (2-pyridyl)-[1,1 ′; 3 ′, 1 ″]-terphenyl-5′- obtained in Example 4 was used. Il} -4,6-di-m-tolyl-1,3,5-triazine was vacuum-deposited to a thickness of 20 nm, and a red phosphorescent organic electroluminescent device was produced in the same manner as in Example 9.

The measured values of the fabricated element were 6.5 V, 3710 cd / m ² , 12.4 cd / A, 5.5 lm / W. The luminance half time of this element was 422 hours.

Example 11
Instead of the electron transport layer 5 of Example 9, 2- [4,4 ″ ″-bis (2-pyridyl)-[1,1 ′: 4 ′, 1 ″ obtained in Example 5: 3 ″, 1 ′ ″: 4 ′ ″, 1 ″ ″]-kinkphenyl-5 ″ -yl] -4,6-di-m-tolyl-1,3,5-triazine at 20 nm A green phosphorescent organic electroluminescent device was produced in the same manner as in Example 9.

The measured values of the manufactured element were 9.3 V, 3040 cd / m ² , 13.1 cd / A, and 4.8 lm / W. The luminance half time of this device was 783 hours.

Example 12
Instead of the electron transport layer 5 of Example 10, 2- [4,4 ″ ″-bis (2-pyridyl)-[1,1 ′: 4 ′, 1 ″: 3 ″, 1 ″ ': 4''', 1 '''']-kinkphenyl-5''-yl] -4,6-di-m-tolyl-1,3,5-triazine was vacuum deposited to a thickness of 20 nm. A red phosphorescent organic electroluminescent device was produced in the same manner as in Example 10.

The measured values of the fabricated element were 6.5 V, 3190 cd / m ² , 11.5 cd / A, and 5.2 lm / W. The luminance half time of this device was 374 hours.

Example 13
Instead of the electron transport layer 5 of Example 9, 2,4-diphenyl-6- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, obtained in Example 6] 1 ″]-Terphenyl-5′-yl] -1,3,5-triazine was vacuum-deposited with a film thickness of 20 nm, and a green phosphorescent organic electroluminescent device was produced in the same manner as in Example 9.

The measured values of the manufactured element were 8.9 V, 3660 cd / m ² , 13.4 cd / A, 5.5 lm / W. The luminance half time of this device was 851 hours.

Example 14
In place of the electron transport layer 5 of Example 10, 2,4-diphenyl-6- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl -5′-yl] -1,3,5-triazine was vacuum-deposited with a thickness of 20 nm, and a red phosphorescent organic electroluminescent device was produced in the same manner as in Example 10.

The measured values of the fabricated element were 6.4 V, 3210 cd / m ² , 12.0 cd / A, 5.6 lm / W. The luminance half time of this device was 443 hours.

Example 15
Instead of the electron transport layer 5 of Example 9, 2,4-bis (1-naphthyl) -6- [4,4 ″ -bis (2-pyridyl)-[1,1] obtained in Example 7 was used. ': 3', 1 ″]-terphenyl-5′-yl] -1,3,5-triazine was vacuum-deposited to a film thickness of 20 nm, and a green phosphorescent organic electroluminescent device was formed as in Example 9. It produced similarly.

The measured values of the fabricated element were 9.1 V, 2950 cd / m ² , 13.5 cd / A, 5.1 lm / W. The luminance half time of this device was 812 hours.

Example 16
Instead of the electron transport layer 5 of Example 10, 2,4-bis (1-naphthyl) -6- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ′ '] -Terphenyl-5'-yl] -1,3,5-triazine was vacuum-deposited to a thickness of 20 nm, and a red phosphorescent organic electroluminescent device was produced in the same manner as in Example 10.

The measured values of the manufactured element were 6.6 V, 3310 cd / m ² , 11.8 cd / A, and 5.2 lm / W. The luminance half time of this element was 402 hours.

Example 17
Instead of the electron transport layer 5 of Example 9, 2,4-bis (biphenyl-3-yl) -6- [4,4 ″ -bis (2-pyridyl)-[1] obtained in Example 8 was used. , 1 ′: 3 ′, 1 ″]-terphenyl-5′-yl] -1,3,5-triazine is vacuum-deposited with a thickness of 20 nm to produce a green phosphorescent organic electroluminescent device. 9 was produced.

The measured values of the fabricated element were 9.5 V, 2750 cd / m ² , 13.8 cd / A, and 4.9 lm / W. The luminance half time of this device was 824 hours.

Example 18
In place of the electron transport layer 5 of Example 10, 2,4-bis (biphenyl-3-yl) -6- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-Terphenyl-5′-yl] -1,3,5-triazine was vacuum-deposited with a thickness of 20 nm, and a red phosphorescent organic electroluminescent device was produced in the same manner as in Example 10.

The measured values of the manufactured element were 6.6 V, 3040 cd / m ² , 11.9 cd / A, and 5.4 lm / W. The luminance half time of this device was 425 hours.

Comparative Example 1
2- {4,4 ″ -bis (2-pyridyl)-[1,1 ′; 3 ′, 1 ″]-terphenyl-5′-yl} -4,6-di-m of Example 9 -Instead of tolyl-1,3,5-triazine, Alq, which is a general-purpose electron transport material, was vacuum deposited as an electron transport layer 5 to a thickness of 20 nm, and a green phosphorescent organic electroluminescent device was It produced similarly.

The measured values of the manufactured element were 9.1 V, 3100 cd / m ² , 13.3 cd / A, and 4.9 lm / W. The luminance half time of this device was 797 hours.

Comparative Example 2
2- {4,4 ″ -bis (2-pyridyl)-[1,1 ′; 3 ′, 1 ″]-terphenyl-5′-yl} -4,6-di-m of Example 10 -Instead of tolyl-1,3,5-triazine, Alq, which is a general-purpose electron transporting material, was vacuum-deposited as an electron transporting layer 5 to a thickness of 20 nm, and a red phosphorescent organic electroluminescent device was It produced similarly.

The measured values of the fabricated element were 7.8 V, 2930 cd / m ² , 9.4 cd / A, and 4.3 lm / W. The luminance half time of this device was 309 hours.

  As described above, when the phenyl group-substituted 1,3,5-triazine compound of the present invention is used in an organic electroluminescent device, the red phosphorescent light-emitting device has remarkable effects of low voltage, high efficiency, and long life. there were.

Example 19
2- {4,4 ″ -bis (2-pyridyl)-[1,1 ′; 3 ′, 1 ″ obtained in Example 4 on a silicon substrate by the vacuum deposition method described in Example 9. ] -Terphenyl-5'-yl} -4,6-di-m-tolyl-1,3,5-triazine was vacuum deposited with a film thickness of 50 nm.

  The deposited substrate was set in a cooling system for optical and electrical measurement (PS11SS) manufactured by Nagase Electronic Equipment Service Co., Ltd., and cooled to 5K under a vacuum using a refrigerator (RDK-101D) manufactured by Sumitomo Heavy Industries, Ltd.

  The excitation triplet level was measured with a streak camera (C4334) manufactured by Hamamatsu Photonics using a nitrogen gas laser (MNL200, wavelength 337 nm) manufactured by Laser Tech Berlin Berlin as an excitation light source. The obtained excited triplet level was 2.48 eV.

Example 20
The 2,4-diphenyl-6- [4,4 ″ -bis (2-pyridyl)-[obtained in Example 6 was replaced with the compound of Example 19 by the vacuum evaporation method described in Example 9. 1,1 ′: 3 ′, 1 ″]-Terphenyl-5′-yl] -1,3,5-triazine was vacuum deposited with a film thickness of 50 nm.

  The obtained excited triplet level was 2.45 eV.

Example 21
The 2,4-bis (biphenyl-3-yl) -6- [4,4 ″ -bis obtained in Example 8 was replaced with the compound of Example 19 by the vacuum deposition method described in Example 9. (2-Pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl] -1,3,5-triazine was vacuum deposited to a thickness of 50 nm.

  The excited triplet level obtained was 2.44 eV.

Comparative Example 3
Alq which is a general-purpose electron transport material was vacuum-deposited with a film thickness of 50 nm by the vacuum evaporation method described in Example 9 instead of the compound of Example 19.

  The obtained excited triplet level was 2.00 eV.

Comparative Example 4
A film thickness of 50 nm of tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3), which is a green phosphorescent material, was used instead of the compound of Example 19 by the vacuum evaporation method described in Example 9. Was vacuum deposited.

  The excited triplet level obtained was 2.42 eV.

Comparative Example 5
According to the vacuum evaporation method described in Example 9, in place of the compound of Example 19, bis (2- (2′-benzo [4,5-a] thienyl) pyridinate-N, C3, which is a red phosphorescent material, is used. ') Iridium (acetylacetonate) (Btp2Ir (acac)) was vacuum-deposited with a film thickness of 50 nm.

  The obtained excited triplet level was 1.99 eV.

  As described above, the 1,3,5-triazine compound used in the present invention has a higher excited triplet state than Alq, which is a general-purpose electron transport material, and a phosphorescent material, and therefore has a confinement effect in the excited triplet state. It is considered that the light emission efficiency is high.

  Since the organic electroluminescence device having the 1,3,5-triazine compound of the present invention can be expected to improve luminous efficiency, it is possible to achieve low power consumption and long life for panel applications. Furthermore, the present invention can also be applied to lighting applications that require high luminous efficiency.

10 is a cross-sectional view of an organic electroluminescent element produced in Example 9. FIG.

Explanation of symbols

1. 1. Glass substrate with ITO transparent electrode 2. hole injection layer Hole transport layer 4. 4. Light emitting layer Electron transport layer 6. Cathode layer

Claims (3)

General formula (1)

[Wherein, Ar ¹ and Ar ² each independently represent a phenyl group, a naphthyl group or a biphenylyl group, and these groups are substituted with one or more alkyl groups or trifluoromethyl groups having 1 to 6 carbon atoms. May be. R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group. X ¹ and X ² each independently represent a phenylene group, a naphthylene group or a pyridylene group, and these groups may be substituted with one or more alkyl groups having 1 to 4 carbon atoms or fluorine atoms. p and q each independently represent an integer of 0 to 2. When p is 2, the linked X ¹ may be the same or different. When q is 2, the linked X ² may be the same or different. Ar ³ and Ar ⁴ each independently represent a pyridyl group or a phenyl group, and these groups may be substituted with one or more alkyl groups having 1 to 4 carbon atoms or fluorine atoms. ]
A phosphorescent organic electroluminescent device, wherein a phenyl group-substituted 1,3,5-triazine compound represented by the formula: is used in at least one organic compound layer. 2. The phosphorescence according to claim 1, wherein at least one of Ar ^{3 and} Ar ⁴ is an alkyl group having 1 to 4 carbon atoms or a pyridyl group optionally substituted with one or more fluorine atoms. Organic electroluminescent device. 3. The phosphorescent organic electroluminescent device according to claim 1, wherein a phenyl group-substituted 1,3,5-triazine compound having an excited triplet level of 2.4 eV or more is used.

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