WO2014104235A1

WO2014104235A1 - 1,2,4-tris-substituted benzene compound and method for producing same, and organic electroluminescent element

Info

Publication number: WO2014104235A1
Application number: PCT/JP2013/084972
Authority: WO
Inventors: 華奈藤田; 信道新井; 桂甫野村; 尚志飯田; 田中　剛
Original assignee: 東ソー株式会社
Priority date: 2012-12-28
Filing date: 2013-12-26
Publication date: 2014-07-03
Also published as: TW201443036A; JP6264877B2; JP2014141467A

Abstract

Provided are: an organic electroluminescent element which has high efficiency, can be driven at a low voltage and has a long service life; and a material, particularly an electron-transporting material, which enables the production of the organic electroluminescent element. A 1,2,4-tris-substituted benzene compound represented by formula (1) or (1)'; and an organic electroluminescent element produced using the compound. (In the formulae, Ar¹ represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or the like, Ar² represents a monovalent or bivalent nitrogenated heteroaromatic group having 3 to 17 carbon atoms, and Ar³ represents a nitrogenated heteroaromatic group having 3 to 17 carbon atoms or the like, wherein at least one of Ar¹, Ar² and Ar³ represents a pyridyl group or the like; R¹, R², R³ and R⁴ independently represent a hydrogen atom or the like; m represents 0 or 1; n represents 0, 1 or 2; Y¹ and Y² independently represent a monovalent or bivalent group represented by formula (A) or (A)' (wherein X¹, X² and X³ independently represent CH or the like and at least one of X¹, X² and X³ is CH); and R⁵'s independently represent an alkyl group having 1 to 8 carbon atoms or the like) (in the structure, the total number of pyridyl groups, pyridylene groups and the like is 0 to 3 regardless the presence or absence of substituents; and in the formulae, each of hydrogen atoms may be a deuterium atom)).

Description

1,2,4-Tris-substituted benzene compound, method for producing the same, and organic electroluminescent device

The present invention relates to a 1,2,4-tris-substituted benzene compound, a method for producing the same, and a high-efficiency organic electroluminescent device using the same for at least one organic compound layer and having excellent light emission characteristics.

The organic electroluminescent element has a structure in which a light emitting layer containing a light emitting material is sandwiched between a hole transport layer and an electron transport layer, and an anode and a cathode are attached to the outside, and holes injected into the light emitting layer and It is a self-emitting element that utilizes a light emission phenomenon (fluorescence or phosphorescence) when excitons generated by electron recombination are deactivated. Since it is a self-luminous type, it is excellent in visibility, and since it is a completely solid element, it is easy to handle and manufacture. In addition, since it is a thin film type device, it is attracting attention from the viewpoints of space saving and portability, and is applied to displays, lighting, and the like. At present, the organic electroluminescence device has begun to be used for commercial purposes. However, further improvement in light emission efficiency, reduction in driving voltage, and longer life are required for energy saving.

In order to make the organic electroluminescence device highly efficient, low voltage drive, and long life, it is necessary to efficiently inject and transport holes and electrons to the light emitting layer and recombine them. In this regard, improvement of each material constituting the organic electroluminescent element, particularly an electron transporting material, has been demanded. Tris (8-quinolinolato) aluminum (III) (Alq) is an example of an electron transport material that has already been put to practical use. However, there is a problem that the drive voltage is high. It was sought after.

Patent Document 1 discloses a host material for an electroluminescence element capable of obtaining an organic EL element having a long emission lifetime and excellent heat resistance, and an element using the same. However, when the host material is used as an electron transporting material, the device has been required to be improved because the driving voltage is increased.

WO2005-072017

An object of the present invention is to provide an electron transporting material which is excellent in the lifetime characteristics of the device and excellent in driving the device at a low voltage as compared with a conventionally known electron transporting material for an organic electroluminescence device.

As a result of intensive studies to solve the above problems, the inventors of the present invention have heretofore known an organic electroluminescent device using the 1,2,4-tris-substituted benzene compound shown in the present invention as an electron transport layer. As compared with an organic electroluminescent device using a material for the electron transport layer, the driving voltage is significantly reduced and the lifetime is found, and the present invention has been completed.

That is, the present invention relates to a 1,2,4-tris-substituted benzene compound represented by the following general formula (1) or (1) ′ (hereinafter referred to as “compound (1)” or “compound (1) ′”, respectively). And a manufacturing method thereof, and an organic electroluminescent element including the same as a constituent component.

(Where
Ar ¹ represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, An ester group or an ester alkyl group, or an optionally substituted fluorine atom).
Ar ² in formula (1) is a monovalent nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or fluorine). In formula (1) ′, a divalent nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, An ester group or an ester alkyl group, or an optionally substituted fluorine atom).
Ar ³ may be substituted with a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). ) Or a substituent represented by —Ar ⁴ —Ar ⁵ .
Ar ⁴ is a nitrogen-containing heteroarylene group having 3 to 17 carbon atoms (which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). To express.
Ar ⁵ is an aromatic hydrocarbon group having 6 to 18 carbon atoms, pyridyl group, pyrimidyl group, or pyrazyl group (these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, ester groups or esters). An alkyl group or a fluorine atom which may be substituted).
Note that at least one of Ar ¹ , Ar ² , and Ar ³ is a pyridyl group, a pyrimidyl group, or a condensed ring group having 6 to 17 carbon atoms including a pyridine skeleton or a pyrimidine skeleton (these groups have a carbon number of 1 To 8 alkyl groups, alkoxy groups, alkoxyalkyl groups, ester groups or ester alkyl groups, or a fluorine atom, which may be substituted.
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituent having 1 to 4 carbon atoms, and R ¹ and R ² , R ³ and R ⁴ , or R ¹ and R ² and R ^{Both 3} and R ⁴ may be linked together to form an alicyclic or aromatic ring.
m represents 0 or 1.
n represents 0, 1, or 2.
Y ¹ represents a divalent substituent represented by the following general formula (A), and Y ² is a divalent substituent represented by the following general formula (A) in Formula (1), independently of Y ^1. In the formula (1) ′, a monovalent substituent represented by the following general formula (A) ′ is represented.

(In the formulas (A) and (A) ′, X ¹ , X ² and X ³ each independently represent CH or a nitrogen atom, and at least one is CH.
R ⁵ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group, or an ester alkyl group, a hydrogen atom, a fluorine atom, or a counter electron. )
Note that the total number of pyridyl groups and pyridylene groups, the total number of pyrimidyl groups and pyrimidylene groups, and the total number of pyrazyl groups and pyrazylene groups in the structure are each independently 0, 1 2, or 3.
In addition, each hydrogen atom in the formula may independently be a deuterium atom. )

Since the compound (1) or (1) ′ of the present invention has good charge injection and transport properties, it is useful as an electron transport material of a fluorescent or phosphorescent organic electroluminescence device, and particularly used as an electron transport material. be able to. The organic electroluminescent device having an electron transport layer containing the compound (1) or (1) ′ of the present invention has a significantly lower driving voltage and a higher driving voltage than an organic electroluminescent device using a general-purpose electron transport material. Efficiency and long life.

The band gap of the compound (1) or (1) ′ of the present invention is 3.2 eV or more, and the three primary colors constituting the panel (red: 1.9 eV, green: 2.4 eV, blue: 2.8 eV) This material has a wide band gap sufficient to confine the energy of each color. Therefore, it can be applied to various elements such as a single color display element, a three primary color display element, and a white element for illumination use. Since the compound (1) of the present invention has a high triplet energy, it can be sufficiently applied to phosphorescence. Furthermore, since the solubility can be controlled by changing the substituent, it can be applied not only to a vapor deposition element but also to a coating element.

FIG. 3 is a cross-sectional view of an organic electroluminescent element produced in Test Example-1.

Hereinafter, the present invention will be described in detail.

In the present invention, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group is not particularly limited, and examples thereof include a methyl group (-Me), an ethyl group (- Et), n-propyl group (n-Pr), i-propyl group (i-Pr), n-butyl group (n-Bu), t-butyl group (t-Bu), pentyl group, hexyl group (- Hex), heptyl group, octyl group (above, alkyl group having 1 to 8 carbon atoms), methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, n-butyloxy group, t-butyloxy group, pentyl Oxy group, hexyloxy group, heptyloxy group, octyloxy group (above, alkoxy group having 1 to 8 carbon atoms), methoxymethyl group, methoxyethyl group, metho Cypropyl group, methoxybutyl group, methoxyhexyl group, methoxyheptyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, pentyloxypropyl group (above, alkyl alkoxy group having 1 to 8 carbon atoms), methyl Ester group, ethyl ester group, n-propyl ester group, i-propyl ester group, n-butyl ester group, t-butyl ester group, pentyl ester group, hexyl ester group, heptyl ester group (above, 1 to 8 carbon atoms) Ester group), —CH ₂ COOMe, —CH ₂ COOEt, —CH ₂ COO (n-Pr), —CH ₂ COO (i-Pr), —CH ₂ COO (n-Bu), —CH ₂ COO ( _{_{_{t-Bu), - CH 2}}} COOHex, -CH 2 CH 2 CH 2 COOMe, -CH _{_{_{_{CH 2 CH 2 COOEt, -CH 2}}}} CH 2 CH 2 COO (n-Pr), - CH 2 CH 2 CH 2 COO (i-Pr), - CH 2 CH 2 CH 2 COO (n-Bu), - CH ₂ CH ₂ CH ₂ COO (t-Bu), —Hex-COOMe (an ester alkyl group having 1 to 8 carbon atoms).

Substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom represented by Ar ¹ in the general formula (1) or (1) ′ The aromatic hydrocarbon group having 6 to 18 carbon atoms is not particularly limited, and examples thereof include a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3 -Dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2-ethylphenyl group 3-ethylphenyl group, 4-ethylphenyl group, 2-ethyl-3-methylphenyl group, 2-ethyl-4-methylphenyl group, 2-ethyl-5- Tylphenyl group, 2-ethyl-6-methylphenyl group, 3-ethyl-2-methylphenyl group, 3-ethyl-4-methylphenyl group, 3-ethyl-5-methylphenyl group, 3-ethyl-6-methyl Phenyl group, 4-ethyl-2-methylphenyl group, 4-ethyl-3-methylphenyl group, 2-hexylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 2-hexyl-3-methylphenyl group 2-hexyl-4-ethylphenyl group, 2-hexyloxy-5-methylphenyl group, 2-hexyloxy-6-methylphenyl group, 3-hexyloxy-2-methylphenyl group, 3-hexyloxy-4 -Methylphenyl group, 3-ethoxyethyl-5-methylphenyl group, 3-ethoxyethyl-6-methylphenyl group, 4-ethoxyethyl 2-methylphenyl group, 4-ethoxyethyl-3-methylphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluoro Phenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, perfluorophenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 3-methylnaphthalene-1 -Yl group, 4-methylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 6-methylnaphthalen-1-yl group, 1-methylnaphthalen-2-yl group, 3-methylnaphthalene-2 -Yl group, 4-methylnaphthalen-2-yl group, 5-methylnaphthalen-2-yl group, 6-methylnaphthalen-2-yl group, 2-pentyl Naphthalen-1-yl group, 3-pentoxynaphthalen-1-yl group, 4-methoxyethylnaphthalen-1-yl group, 5-pentylnaphthalen-1-yl group, 6-pentoxynaphthalen-1-yl group, 1-methoxyethylnaphthalen-2-yl group, 3-pentylnaphthalen-2-yl group, 4-pentoxynaphthalen-2-yl group, 5-methoxyethylnaphthalen-2-yl group, 6-pentylnaphthalene-2-yl group Yl group, 2-fluoronaphthalen-1-yl group, 3-fluoronaphthalen-1-yl group, 4-fluoronaphthalen-1-yl group, 5-fluoronaphthalen-1-yl group, 6-fluoronaphthalene-1- Yl group, 1-fluoronaphthalen-2-yl group, 3-fluoronaphthalen-2-yl group, 4-fluoronaphthalen-2-yl group, 5- Fluoronaphthalen-2-yl group, 6-fluoronaphthalen-2-yl group, perfluoronaphthalen-1-yl group, perfluoronaphthalen-2-yl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group Group, 4-phenanthryl group, 9-phenanthryl group, 1-methylphenanthren-2-yl group, 3-methylphenanthren-2-yl group, 4-methylphenanthren-2-yl group, 5-methylphenanthren-2-yl group Group, 6-methylphenanthren-2-yl group, 9-methylphenanthren-2-yl group, 1-methylphenanthren-4-yl group, 2-methylphenanthren-4-yl group, 3-methylphenanthren-4-yl group Group, 5-methylphenanthren-4-yl group, 6-methylphenanthren-4-yl group, 9-methylphenanthren-4-yl group, 1-methylphenanthren-9-yl group, 2-methylphenanthren-9-yl group, 3-methylphenanthren-9-yl group, 4-methylphenanthren-9-yl group, 5-methylphenanthren-9-yl group, 6-methylphenanthren-9-yl group, 1-octylphenanthren-2-yl group, 3-octylphenanthren-2-yl group, 4-octylphenanthren-2-yl group, 5-octylphenanthren-2-yl group, 6-octylphenanthren-2-yl group, 9-octylphenanthren-2-yl group, 1-octyloxyphenanthren-4-yl group, 2-octyloxyphenanthren-4-yl group Group, 3-octyloxyphenanthren-4-yl group, 5-octyloxyphene N-Tren-4-yl group, 6-octyloxyphenanthren-4-yl group, 9-octyloxyphenanthren-4-yl group, 1-methoxypropylphenanthren-9-yl group, 2-methoxypropylphenanthren-9-yl group 3-methoxypropylphenanthren-9-yl group, 4-methoxypropylphenanthren-9-yl group, 5-methoxypropylphenanthren-9-yl group, 6-methoxypropylphenanthren-9-yl group, 1-fluorophenanthrene- 2-yl group, 3-fluorophenanthren-2-yl group, 4-fluorophenanthren-2-yl group, 5-fluorophenanthren-2-yl group, 6-fluorophenanthren-2-yl group, 9-fluorophenanthrene- 2-yl group, 1-fluorophenant N-4-yl group, 2-fluorophenanthren-4-yl group, 3-fluorophenanthren-4-yl group, 5-fluorophenanthren-4-yl group, 6-fluorophenanthren-4-yl group, 9-fluoro Phenanthren-4-yl group, 1-fluorophenanthren-9-yl group, 2-fluorophenanthren-9-yl group, 3-fluorophenanthren-9-yl group, 4-fluorophenanthren-9-yl group, 5-fluoro Examples thereof include a phenanthren-9-yl group, a 6-fluorophenanthren-9-yl group, a perfluorophenanthren-1-yl group, a perfluorophenanthren-2-yl group, and a perfluorophenanthren-9-yl group. Of these, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-phenanthrenyl are preferable in terms of performance as an organic electroluminescent element material. Group, 9-phenanthrenyl group, 1-anthracenyl group, or 9-anthracenyl group is preferable, and phenyl group, 2-methylphenyl group, 3-methylphenyl group, or 4-methylphenyl group is more preferable.

Substitution with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom represented by Ar ¹ and Ar ² described in the general formula (1) or (1) ′ The monovalent nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms which may be used is not particularly limited, and examples thereof include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 3- Methylpyridin-2-yl group, 4-methylpyridin-2-yl group, 5-methylpyridin-2-yl group, 6-methylpyridin-2-yl group, 2-methylpyridin-3-yl group, 4- Methylpyridin-3-yl group, 5-methylpyridin-3-yl group, 6-methylpyridin-3-yl group, 2-methylpyridin-4-yl group, 3-methylpyridin-4-yl group, 3, 4 Dimethylpyridin-2-yl group, 3,5-dimethylpyridin-2-yl group, 3,6-dimethylpyridin-2-yl group, 2,4-dimethylpyridin-3-yl group, 2,5-dimethylpyridine -3-yl group, 2,6-dimethylpyridin-3-yl group, 2,3-dimethylpyridin-4-yl group, 3,5-dimethylpyridin-4-yl group, 2,5-dimethylpyridin-4 -Yl group, 3-butylpyridin-2-yl group, 4-butylpyridin-2-yl group, 5-butylpyridin-2-yl group, 6-butylpyridin-2-yl group, 2-butoxypyridine-3 -Yl group, 4-butoxypyridin-3-yl group, 5-butoxypyridin-3-yl group, 6-butoxypyridin-3-yl group, 2-methoxymethylpyridin-4-yl group, 3-methoxymethylpyridine 4-yl group, 3-fluoropyridin-2-yl group, 4-fluoropyridin-2-yl group, 5-fluoropyridin-2-yl group, 6-fluoropyridin-2-yl group, 2-fluoropyridin- 3-yl group, 4-fluoropyridin-3-yl group, 5-fluoropyridin-3-yl group, 6-fluoropyridin-3-yl group, 2-fluoropyridin-4-yl group, 3-fluoropyridine- 4-yl group, 3,4-difluoropyridin-2-yl group, 3,5-difluoropyridin-2-yl group, 3,6-difluoropyridin-2-yl group, 2,4-difluoropyridin-3- Yl group, 2,5-difluoropyridin-3-yl group, 2,6-difluoropyridin-3-yl group, 2,3-difluoropyridin-4-yl group, 3,5-difluoropyridin-4-yl group Group, 2,5-difluoropyridin-4-yl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 4-methylpyrimidin-2-yl group, 5-methylpyrimidin-2-yl group, 2-methylpyrimidin-4-yl group, 6-methylpyrimidin-4-yl group, 4-propylpyrimidin-2-yl group, 5-propoxypyrimidin-2-yl group, 2-pentoxymethylpyrimidin-4-yl Group, 6-heptylpyrimidin-4-yl group, 4,6-dimethylpyrimidin-2-yl group, 4-fluoropyrimidin-2-yl group, 5-fluoropyrimidin-2-yl group, 2-fluoropyrimidine-4 -Yl group, 6-fluoropyrimidin-4-yl group, 2-pyrazyl group, 3-methylpyrazin-2-yl group, 5-methylpyrazin-2-yl group, 6-methylpi Gin-2-yl group, 3-fluoropyrazin-2-yl group, 5-fluoropyrazin-2-yl group, 6-fluoropyrazin-2-yl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl Group, 3-methylquinolin-2-yl group, 4-methylquinolin-2-yl group, 5-methylquinolin-2-yl group, 6-methylquinolin-2-yl group, 2-methylquinolin-3-yl Group, 4-methylquinolin-3-yl group, 5-methylquinolin-3-yl group, 6-methylquinolin-3-yl group, 2-methylquinolin-4-yl group, 3-methylquinolin-4-yl Group, 5-methylquinolin-4-yl group, 6-methylquinolin-4-yl group, 3-heptylquinolin-2-yl group, 4-heptoxyquinolin-2-yl group, 5-methoxyhexylquinoline-2 -Yl groups, -Heptoxymethylquinolin-2-yl group, 3-fluoroquinolin-2-yl group, 4-fluoroquinolin-2-yl group, 5-fluoroquinolin-2-yl group, 6-fluoroquinolin-2-yl group 2-fluoroquinolin-3-yl group, 4-fluoroquinolin-3-yl group, 5-fluoroquinolin-3-yl group, 6-fluoroquinolin-3-yl group, 2-fluoroquinolin-4-yl group 3-fluoroquinolin-4-yl group, 5-fluoroquinolin-4-yl group, 6-fluoroquinolin-4-yl group, perfluoroquinolin-2-yl group, perfluoroquinolin-3-yl group, perfluoroquinolin-4-yl group Fluoroquinolin-4-yl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 3-methylisoquinolin-1-yl group, 4-methylisoquinolyl group N-1-yl group, 5-methylisoquinolin-1-yl group, 6-methylisoquinolin-1-yl group, 1-methylisoquinolin-3-yl group, 4-methylisoquinolin-3-yl group, 5-methyl Isoquinolin-3-yl group, 6-methylisoquinolin-3-yl group, 1-methylisoquinolin-4-yl group, 3-methylisoquinolin-4-yl group, 5-methylisoquinolin-4-yl group, 6-methyl Isoquinolin-4-yl group, 3-hexylisoquinolin-1-yl group, 4-hexyloxyisoquinolin-1-yl group, 5-ethoxybutylisoquinolin-1-yl group, 6-butoxypropylisoquinolin-1-yl group, 3-fluoroisoquinolin-1-yl group, 4-fluoroisoquinolin-1-yl group, 5-fluoroisoquinolin-1-yl group, 6- Luoisoquinolin-1-yl group, 1-fluoroisoquinolin-3-yl group, 4-fluoroisoquinolin-3-yl group, 5-fluoroisoquinolin-3-yl group, 6-fluoroisoquinolin-3-yl group, 1 -Fluoroisoquinolin-4-yl group, 3-fluoroisoquinolin-4-yl group, 5-fluoroisoquinolin-4-yl group, 6-fluoroisoquinolin-4-yl group, perfluoroisoquinolin-1-yl group, perfluoro Isoquinolin-3-yl group, perfluoroisoquinolin-4-yl group, 1,5-naphthyridin-2-yl group, 1,6-naphthyridin-2-yl group, 1,8-naphthyridin-2-yl group, 1 -Carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 9-β-carbo Ryl group, 1-methyl-β-carbolin-9-yl group, 3-methyl-β-carbolin-9-yl group, 1-fluoro-β-carbolin-9-yl group, 3-fluoro-β-carboline- 9-yl group, 5-acridyl group, 8-acridyl group, 9-acridyl group, 4-phenanthridyl group, 6-phenanthridyl group, 7-phenanthridyl group, 8-phenanthridyl group, 10- Phenanthridyl group, 5- (1,6-phenanthroyl) group, 5- (1,10-phenanthroyl) group, benzo [b] -1,5-naphthyridin-2-yl group, benzo [b] -1, 8-naphthyridin-2-yl group, benzo [c] -1,5-naphthyridin-2-yl group, benzo [c] -1,6-naphthyridin-2-yl group, benzo [c] -1,8- Naphthyridin-2-yl group, 1-ph Nazarite group, 2-Fenajiru group, 2-benzothiazolyl group and the like.
The number of carbon atoms that may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom represented by Ar ² in the general formula (1) ′ The divalent nitrogen-containing heteroaromatic group of 3 to 17 is not particularly limited. For example, pyridinediyl group, methylpyridinediyl group, methoxypyridinediyl group, dimethylpyridinediyl group, ethylpyridinediyl group, Ethoxypyridinediyl group, propylpyridinediyl group, propoxypyridinediyl group, butylpyridinediyl group, butoxypyridinediyl group, methoxymethylpyridinediyl group, fluoropyridinediyl group, difluoropyridinediyl group, pyrimidinediyl group, methylpyrimidinediyl group, Methoxypyrimidine Yl, dimethylpyrimidinediyl, ethylpyrimidinediyl, ethoxypyrimidinediyl, propylpyrimidinediyl, propoxypyrimidinediyl, pentylpyrimidinediyl, pentoxypyrimidinediyl, methylpentoxypyrimidinediyl, fluoropyrimidinediyl , Difluoropyrimidinediyl group, pyrazinediyl group, methylpyrazinediyl group, methoxypyrazinediyl group, dimethylpyrazinediyl group, ethylpyrazinediyl group, ethoxypyrazinediyl group, propylpyrazinediyl group, propoxypyrazinediyl group, hexylpyrazinediyl group, hexyl Oxypyrazinediyl group, fluoropyrazinediyl group, difluoropyrazinediyl group, quinolinediyl group, methylquinolinediyl group, methoxyquinolyl Diyl group, dimethylquinolinediyl group, ethylquinolinediyl group, ethoxyquinolinediyl group, propylquinolinediyl group, propoxyquinolinediyl group, heptylquinolinediyl group, heptoxyquinolinediyl group, hexylmethoxyquinolinediyl group, heptoxymethylquinolinediyl Group, fluoroquinolinediyl group, perfluoroquinolinediyl group, isoquinolinediyl group, methylisoquinolinediyl group, methoxyisoquinolinediyl group, dimethylisoquinolinediyl group, ethylisoquinolinediyl group, ethoxyisoquinolinediyl group, propylisoquinolinediyl group, propoxyisoquinolinediyl Group, octylisoquinolinediyl group, octyloxyisoquinolinediyl group, ethoxybutylisoquinolinediyl group, butoxypropiyl Isoquinolinediyl group, fluoro isoquinoline-diyl group, perfluoro isoquinolinediyl group, and the like.

Ar ¹ and Ar ² are each independently a pyridyl group, a pyrimidyl group, or a condensed ring group having 6 to 17 carbon atoms including a pyridine skeleton or a pyrimidine skeleton in terms of good performance as an organic electroluminescent element material ( These groups are monovalent or divalent, and may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). Each independently, a pyridyl group, a pyrimidyl group, or a condensed ring group having 6 to 9 carbon atoms including a pyridine skeleton or a pyrimidine skeleton (these groups are monovalent or divalent and have 1 to 8 carbon atoms). Substituted with an alkyl group, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom. Each of which is independently a pyridyl group, a pyrimidyl group, or a condensed ring group having 6 to 9 carbon atoms containing a pyridine skeleton (these groups are monovalent or divalent, More preferably, it may be substituted with an alkyl group, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom.

A condensed ring group having 6 to 17 carbon atoms containing the pyridine skeleton or pyrimidine skeleton (these groups are an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom. Is not particularly limited, and examples thereof include quinolyl group, isoquinolyl group, naphthyridyl group, β-carbolyl group, phenanthridyl group, acridyl group, phenanthroyl group, and benzo [b]. A naphthylidyl group, a benzo [c] naphthylidyl group or the like (note that these groups may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom. The present invention is not limited to these examples. There. Of these, quinolyl group, isoquinolyl group, β-carbolyl group, acridyl group, phenanthridyl group, or phenanthroyl group (these groups are alkyl groups having 1 to 8 carbon atoms) because of their good performance as organic electroluminescent device materials. Group, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, which may be substituted with a fluorine atom), a quinolyl group, an isoquinolyl group, a β-carbolyl group, an acridyl group, a phenanthridyl group, or A phenanthroyl group (these groups may be substituted with a methyl group or a fluorine atom) is more preferable.
A bivalent condensed ring group having 6 to 17 carbon atoms containing the pyridine skeleton or pyrimidine skeleton (these groups are an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group; Or may be substituted with a fluorine atom), but is not particularly limited, for example, quinoline diyl group, isoquinoline diyl group, naphthyridine diyl group, β-carboline diyl group, phenanthridine diyl group, acridine diyl group Phenanthrolinediyl group, benzo [b] naphthyridinediyl group, benzo [c] naphthyridinediyl group, etc. (Note that these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, ester groups or ester alkyls) Substituted by a group or fluorine atom Although even it is) and the like, and the present invention is not limited thereto. Of these, a quinoline diyl group or an isoquinoline diyl group (these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, ester groups or ester alkyl groups in terms of good performance as organic electroluminescent element materials. Or an optionally substituted with a fluorine atom), and more preferably a quinolinediyl group or an isoquinolinediyl group (these groups may be substituted with a methyl group or a fluorine atom).

A condensed ring group having 6 to 9 carbon atoms containing the pyridine skeleton or pyrimidine skeleton (these groups are an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom; Is not particularly limited, and examples thereof include a quinolyl group, an isoquinolyl group, or a naphthyridyl group (these groups include an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxy group). An alkyl group, an ester group or an ester alkyl group, which may be substituted with a fluorine atom), but the present invention is not limited thereto. Of these, a quinolyl group or an isoquinolyl group (these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, ester groups or ester alkyl groups; Or may be substituted with a fluorine atom), and more preferably a quinolyl group or an isoquinolyl group (these groups may be substituted with a methyl group or a fluorine atom).
A divalent condensed ring group having 6 to 9 carbon atoms containing the pyridine skeleton or pyrimidine skeleton (these groups are an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group; The group may be substituted with a fluorine atom, but is not particularly limited. For example, a quinoline diyl group, an isoquinoline diyl group, or a naphthyridine diyl group (these groups are alkyl groups having 1 to 8 carbon atoms). , An alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom may be substituted), but the present invention is not limited thereto. Of these, a quinoline diyl group or an isoquinoline diyl group (these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, ester groups or ester alkyls) because of their good performance as organic electroluminescent device materials. A quinoline diyl group or an isoquinoline diyl group (these groups may be substituted with a methyl group or a fluorine atom), more preferably.

Ar ¹ and Ar ² are each independently a pyrimidyl group, a pyridyl group, a quinolyl group, or an isoquinolyl group (these groups are monovalent or divalent, each independently having 1 to 8 carbon atoms). More preferably an alkyl group, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom, each independently, a pyrimidyl group, a pyridyl group, a quinolyl group, Or an isoquinolyl group (these groups are monovalent or divalent and may be substituted with a methyl group or a fluorine atom), and each independently represents a 2-pyrimidyl group, 4-methyl Pyrimidin-2-yl group, 4,6-dimethylpyrimidin-2-yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 6- Tylpyridin-2-yl group, 5-methylpyridin-2-yl group, 6-fluoropyridin-2-yl group, 5-fluoropyridin-2-yl group, 1-isoquinolyl group, or 2-quinolyl group (above, Monovalent), 2,5-pyrimidylene group, 4,6-dimethylpyrimidine-2,5-diyl group, 2,5-pyridylene group, 6-methylpyridine-2,5-diyl group, 6-fluoro Pyridine-2,5-diyl group, isoquinoline-1,4-diyl group, isoquinoline-5,8-diyl group, isoquinoline-3,7-diyl group, or quinoline-5,8-diyl group, quinoline-2, More preferably, it is a 6-diyl group (above, a divalent group).

Ar ¹ and Ar ² are preferably the same substituent as each other regardless of the difference between monovalent and divalent in terms of excellent production efficiency.

In the general formula (1) or (1) ′, Ar ³ represents a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group, or an ester alkyl group). Or a substituent represented by —Ar ⁴ —Ar ^{5 (} which may be substituted with a group or a fluorine atom). Ar ⁴ represents a nitrogen-containing heteroarylene group having 3 to 17 carbon atoms (which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). Ar ⁵ represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a pyridyl group, a pyrimidyl group, or a pyrazyl group (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, Or may be substituted with a fluorine atom).

A nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms in Ar ³ (which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom) Although it does not specifically limit, for example, a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms exemplified for Ar ¹ and Ar ² (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, Examples thereof include the same substituent groups as those of an ester group or an ester alkyl group, which may be substituted with a fluorine atom.

Incidentally, Ar ³ are points performance as good as the organic electroluminescence element material, is Ar ^3, alkyl group, alkoxy group, nitrogen-containing heteroaromatic group (from 1 to 8 carbon atoms of a carbon number of 4 11, an alkoxyalkyl group , An ester group or an ester alkyl group, or a substituent represented by —Ar ⁴ —Ar ⁵ , and Ar ⁴ is a nitrogen-containing heteroarylene group having 4 to 12 carbon atoms Ar ⁵ is an aromatic carbon atom having 6 to 18 carbon atoms (which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). A hydrogen group, a pyridyl group, a pyrimidyl group, or a pyrazyl group (these groups are each independently an alkyl group, alkoxy group, A alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom which may be substituted).

A nitrogen-containing heteroaromatic group having 4 to 11 carbon atoms represented by Ar ³ (substituted with an alkyl group, alkoxy group, alkoxyalkyl group, ester group or ester alkyl group having 1 to 8 carbon atoms, or a fluorine atom) May be, for example, pyridyl group, pyrimidyl group, pyrazyl group, quinolyl group, isoquinolyl group, naphthyridyl group, carbolyl group, benzothiazolyl group (these groups have 1 to 8 carbon atoms). And an alkyl group, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom which may be substituted). Of these, a pyridyl group, pyrimidyl group, isoquinolyl group, or carbolyl group (these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, An ester group or an ester alkyl group, which may be substituted with a fluorine atom) is preferred.

A nitrogen-containing heteroarylene group having 3 to 17 carbon atoms represented by Ar ^{4 (} which may be substituted with a C 1 to C 8 alkyl group, alkoxy group, alkoxyalkyl group, ester group or ester alkyl group, or a fluorine atom) Although it is not particularly limited, for example, a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms exemplified for Ar ¹ and Ar ² (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group) Group, ester group or ester alkyl group, which may be substituted with a fluorine atom) (eg pyrimidinediyl group, pyridinediyl group, quinolinediyl group, isoquinolinediyl group, naphthyridinediyl group, carbazole) Diyl group, β-carboline diyl group, benzothiazole diyl group, phena Tolidinediyl group, acridinediyl group, phenanthrolinediyl group, benzo [b] naphthyridinediyl group, benzo [c] naphthyridinediyl group, indolediyl group, benzimidazolediyl group, pyrrolopyridinediyl group (these groups have 1 to 8 alkyl group, alkoxy group, alkoxyalkyl group, ester group or ester alkyl group, or optionally substituted with a fluorine atom)).

A nitrogen-containing heteroarylene group having 4 to 12 carbon atoms represented by Ar ^{4 (} which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom) Is not particularly limited. Groups, indolediyl groups, benzimidazolediyl groups, pyrrolopyridinediyl groups (these groups are substituted with alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, ester groups or ester alkyl groups, or fluorine atoms). May be) And the like. Among these, a pyridinediyl group, a pyrimidinediyl group, a benzimidazolediyl group, or a carbazolediyl group (these groups are an alkyl group having 1 to 8 carbon atoms, an alkoxy group in view of good performance as an organic electroluminescent element material. , An alkoxyalkyl group, an ester group or an esteralkyl group, which may be substituted with a fluorine atom), a pyrimidine-2,5-diyl group, a 4-methylpyrimidine-2,5-diyl group, 4,6 -Dimethylpyrimidine-2,5-diyl group, pyridine-2,5-diyl group, pyridine-3,6-diyl group, 6-methylpyridine-2,5-diyl group, 4-methylpyridine-2,5- Diyl group, 6-fluoropyridine-2,5-diyl group, 4-fluoropyridine-2,5-diyl group, isoquinoline-1,4 Diyl group, isoquinoline-1,5-diyl group, isoquinoline-1,6-diyl group, quinoline-2,4-diyl group, quinoline-2,5-diyl group, or quinoline-2,6-diyl group preferable.

An aromatic hydrocarbon group having 6 to 18 carbon atoms represented by Ar ^{5 (} which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom) Although not particularly limited, for example, an aromatic hydrocarbon group having 6 to 18 carbon atoms exemplified by Ar ¹ (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group) Alternatively, an ester alkyl group, or the same substituent as that optionally substituted with a fluorine atom can be exemplified.

Ar ⁵ is a phenyl group optionally substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom in terms of good performance as an organic electroluminescent element material. It is preferably a group, and more preferably a phenyl group.

In summary, Ar ³ is 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 6-methylpyridin-2-yl group, 5-methylpyridine- 2-yl group, 6-fluoropyridin-2-yl group, 5-fluoropyridin-2-yl group, 5-phenylpyridin-2-yl group, 6-phenylpyridin-3-yl group, 2-pyrimidyl group, 5-phenylpyrimidin-2-yl group, 3- (2-pyridyl) -9H-carbazol-9-yl group, 2-phenyl-1H-benzimidazol-1-yl group, 1-phenyl-1H-benzimidazole- A 2-yl group, a 2-benzothiazolyl group, a 1-isoquinolyl group, a 2-quinolyl group, or a β-carbolin-9-yl group is preferable.

In General Formula (1) or (1) ′, at least one of Ar ¹ , Ar ² , and Ar ³ has a pyridyl group, a pyrimidyl group, a pyridine skeleton or a pyrimidine skeleton, and has 6 to 17 carbon atoms. A condensed ring group (these groups may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom);

A condensed ring group having 6 to 17 carbon atoms containing the pyridine skeleton or pyrimidine skeleton (these groups are an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom. Is not particularly limited, for example, quinolyl group, isoquinolyl group, quinolidyl group, naphthyridyl group, quinazolinyl group, carbolinyl group, phenanthridinyl group, acridinyl group, phenant And a rolinyl group (these groups may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom).

In addition, at least one of Ar ¹ , Ar ² , and Ar ³ is a pyridyl group, a pyrimidyl group, a quinolyl group, an isoquinolyl group, a naphthyridyl group, a quinazolinyl group, and a carbolinyl group in terms of good performance as an organic electroluminescent element material. , A phenanthridinyl group, an acridinyl group, or a phenanthrolinyl group (these groups are substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom) The pyridyl group, pyrimidyl group, quinolyl group, isoquinolyl group, naphthyridyl group, quinazolinyl group, or carbolinyl group (these groups are substituted with a methyl group, a methoxy group, or a fluorine atom). More preferably).

In the general formula (1) or (1) ′, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituent having 1 to 4 carbon atoms, and R ¹ , R ² and R ³ And R ⁴ , or R ¹ and R ² and R ³ and R ⁴ may be linked to each other to form an alicyclic ring or an aromatic ring. Here, examples of the alicyclic ring include a cyclopentane ring and a cyclohexane ring, and examples of the aromatic ring include, but are not limited to, a benzene ring.

Examples of the substituent having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and an alkenyl group having 2 to 4 carbon atoms (for example, a vinyl group). ) And the like. Among these, a vinyl group or a hydrogen atom, which are connected to each other to form an aromatic ring, is preferable in terms of good performance as an organic electroluminescent element material.

R ¹ , R ² , R ³ and R ⁴ are 1) all hydrogen atoms, 2) both R ¹ and R ² are alkenyl groups having 2 to 4 carbon atoms and are bonded to each other to form an aromatic ring Or 3) all of R ¹ , R ² , R ³ and R ⁴ are alkenyl groups having 2 to 4 carbon atoms, and R ¹ and R ² , and R ³ and R ⁴ are linked to each other It preferably forms an aromatic ring, 1) all are hydrogen atoms, 2) both R ¹ and R ² are vinyl groups and are bonded to each other to form a benzene ring, or 3) R ^More preferably, ¹ , R ² , R ³ and R ⁴ are all vinyl groups, and R ¹ and R ² , and R ³ and R ⁴ are connected to each other to form a benzene ring.

In General Formula (1) or (1) ′, Y ¹ represents a divalent substituent represented by the following General Formula (A), and Y ² is the following in Formula (1) independently of Y ^1. The divalent substituent represented by the general formula (A) is represented. In the formula (1) ′, the monovalent substituent represented by the following general formula (A) ′ is represented.

(In formula (A) or (A) ′, X ¹ , X ² and X ³ each independently represent CH or a nitrogen atom, and at least one is CH.
R ⁵ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group, or an ester alkyl group, a hydrogen atom, a fluorine atom, or a counter electron. )
With regard to the general formulas (A) and (A) ′, X ¹ to X ³ are all CH, or X ¹ is a nitrogen atom in terms of good performance as an organic electroluminescent device material, and X ² and X ³ Is preferably CH.
Regarding the divalent Y ² described in the general formula (1), a 1,4-phenylene group, a 2,5-pyridylene group, or a 2,5-pyrimidylene group ( These groups are preferably each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group, an ester alkyl group, or a fluorine atom. A 1,4-phenylene group, a 2,5-pyridylene group, or a 2,5-pyrimidylene group (these groups may have a methyl group or a fluorine atom) are more preferable.
The monovalent Y ² described in the general formula (1) ′ is a phenyl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, or 2- A pyrimidyl group (these groups may each independently have an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group, an ester alkyl group, or a fluorine atom); A phenyl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, or a 2-pyrimidyl group (these groups may have a methyl group or a fluorine atom) are more preferable.

In the general formula (1) or (1) ′, m represents 0 or 1. Note that m is preferably 1 in terms of good performance as an organic electroluminescent element material.

N in the general formula (1) or (1) 'represents 0, 1, or 2. Note that n is preferably 0 or 1 in terms of good performance as an organic electroluminescent element material.

In addition, when there are too many pyridyl groups or pyridylene groups, pyrimidyl groups or pyrimidylene groups, pyrazyl groups or pyrazylene groups in the molecule, the driving voltage of the organic electroluminescence device is increased and the lifetime is shortened. Therefore, in the structure of the general formula (1) or (1) ′, the total number of pyridyl groups and pyridylene groups, the total number of pyrimidyl groups and pyrimidylene groups, and the total number of pyrazyl groups and pyrazilene groups are based on the presence or absence of the substituent of each group Regardless, each is independently limited to 0, 1, 2, or 3 (see Test Example-17 and Reference Example-3).

In addition, each hydrogen atom in the general formula (1) or (1) ′ may be independently a deuterium atom.

Next, the manufacturing method of the present invention will be described.

The compound (1) or (1) ′ of the present invention has the following reaction formula

(In the general formulas (1), (1) ′, (2), (3), (4), (4) ′ and (5),
Ar ¹ represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, An ester group or an ester alkyl group, or an optionally substituted fluorine atom).
Ar ² may be substituted with a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). ).
Ar ³ may be substituted with a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). ) Or a substituent represented by —Ar ⁴ —Ar ⁵ .
Ar ⁴ is a nitrogen-containing heteroarylene group having 3 to 17 carbon atoms (which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). To express.
Ar ⁵ is an aromatic hydrocarbon group having 6 to 18 carbon atoms, pyridyl group, pyrimidyl group, or pyrazyl group (these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, ester groups or esters). An alkyl group or a fluorine atom which may be substituted).
Note that at least one of Ar ¹ , Ar ² , and Ar ³ is a pyridyl group, a pyrimidyl group, or a condensed ring group having 6 to 17 carbon atoms including a pyridine skeleton or a pyrimidine skeleton (these groups have a carbon number of 1 To 8 alkyl groups, alkoxy groups, alkoxyalkyl groups, ester groups or ester alkyl groups, or a fluorine atom, which may be substituted. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituent having 1 to 4 carbon atoms, and R ¹ and R ² , R ³ and R ⁴ , or R ¹ and R ² and R ^{Both 3} and R ⁴ may be linked together to form an alicyclic or aromatic ring.
m represents 0 or 1.
n represents 0, 1, or 2.
Y ¹ represents a divalent substituent represented by the following general formula (A), and Y ² is a divalent substituent represented by the following general formula (A) in Formula (1), independently of Y ^1. In the formula (1) ′, a monovalent substituent represented by the following general formula (A) ′ is represented.

(In the formulas (A) and (A) ′, X ¹ , X ² and X ³ each independently represent CH or a nitrogen atom, and at least one is CH.
R ⁵ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group, or an ester alkyl group, a hydrogen atom, a fluorine atom, or a counter electron. )
Note that the total number of pyridyl groups and pyridylene groups, the total number of pyrimidyl groups and pyrimidylene groups, and the total number of pyrazyl groups and pyrazylene groups in the structure are each independently 0, 1 2, or 3.
In addition, each hydrogen atom in the formula may independently be a deuterium atom.
Z ¹ , Z ² and Z ³ each independently represent a leaving group.
M ¹ , M ² and M ³ each independently represent a metal group, a boronic acid group, or a boronic ester group. )
It can be manufactured by the method shown in

The compound represented by the general formula (2) is referred to as compound (2). The same applies to the compounds (3), (4), (4) 'and (5). The compound (3), the compound (4), the compound (4) ′ and the compound (5) are produced using, for example, the methods disclosed in JP-A-2008-280330 (0061) to (0076). be able to.

Examples of the compound (3) include the following (A1) to (A178), but the present invention is not limited to these. Here, M ¹ represents a metal group, a boronic acid group, or a boronic acid ester group.

Examples of the compound (4) include the following (B1) to (B84), but the present invention is not limited to these. Here, M ² represents a metal group, a boronic acid group, or a boronic acid ester group.

Examples of the compound (4) ′ include the following (B85) to (B118), but the present invention is not limited to these. Here, M ² represents a metal group, a boronic acid group, or a boronic acid ester group.

Examples of the compound (5) include compounds in which M ² described in (B1) to (B84) is M ³ and the following (C1) to (C105), but the present invention is limited to these. It is not a thing. Here, M ³ represents a metal group, a boronic acid group, or a boronic acid ester group.

Hereinafter, although a specific example is given and demonstrated about "process 1", this invention is not limited to these.

“Step 1” is the step of reacting compound (2) with compound (3), compound (4) or compound (4) ′, and compound (5) in the presence of a metal catalyst or in the presence of a metal catalyst and a base. This is a method for obtaining the compound (1) or (1) ′ of the present invention, and applies general reaction conditions for coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc. By doing so, the target product can be obtained in good yield. The reaction sequence when reacting the compound (3), the compound (4) or the compound (4) ′, and the compound (5) is random, and the intermediates may be taken out by sequentially reacting or reacting simultaneously. Also good.

Examples of M ¹ , M ² and M ³ in compound (3), compound (4), compound (4) ′ and compound (5) are ZnA ¹ , MgA ² , Sn (A ³ ) ₃ , B (OA ⁴ ) ₂ etc. are mentioned. However, A ¹ and A ² each independently represent a chlorine atom, a bromine atom or an iodine atom, A ³ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and A ⁴ represents a hydrogen atom or carbon number 1 4 represents an alkyl group or a phenyl group, and two A ⁴ of B (OA ⁴ ) ₂ may be the same or different. Further, the two A ⁴ can also form a ring containing an oxygen atom and a boron atom together.

As B (OA ⁴ ) ₂ in the compound (3), the compound (4), the compound (4) ′ and the compound (5), B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , Examples thereof include B (OBu) ₂ and B (OPh) ₂ . Examples of B (OA ⁴ ) ₂ in the case where two A ⁴ are united to form a ring containing an oxygen atom and a boron atom include groups represented by the following (D1) to (D6): The group represented by (D2) is preferable because it can be exemplified and the yield is good.

Examples of the leaving group represented by Z ¹ , Z ² and Z ³ in the compound (2) include a chlorine group, a bromine group, an iodine group, a trifluoromethylsulfonyloxy (OTf) group, a methanesulfonyloxy group, and a chloromethanesulfonyl. Examples thereof include an oxy group and a p-toluenesulfonyloxy group. Examples of the compound (2) include the following (E1) to (E5), but the present invention is not limited to these.

Examples of the metal catalyst that can be used in “Step 1” include a palladium catalyst and a nickel catalyst.

Examples of the palladium catalyst that can be used in “Step 1” include salts of palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, and the like. In addition, π-allyl palladium chloride dimer, palladium acetylacetonate, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and dichloro [1,1′-bis (diphenylphosphine). Fino) ferrocene] complex compounds such as palladium. Among these, a palladium complex having a tertiary phosphine as a ligand is preferable in terms of a good reaction yield.

A palladium complex having tertiary phosphine as a ligand can also be prepared in a reaction system by adding tertiary phosphine to a palladium salt or complex compound. The tertiary phosphine that can be used at this time is triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5. -Bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) Biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1 ′ -Bis (diphenylphosphino) Erocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (±) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl and the like. 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl is preferred because it is readily available and the reaction yield is good.

The molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 in terms of good reaction yield.

The nickel catalyst that can be used in “Step 1” includes [1,1′-bis (diphenylphosphino) ferrocene] nickel (II) dichloride, [1,2-bis (diphenylphosphino) ethane] nickel ( II) Dichloride, [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride, [1,1′-bis (diphenylphosphino) propane] nickel (II) dichloride, 1,2-bis (diphenyl) Phosphino) ethane] nickel (II) dichloride, [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride, and the like.

Examples of the base that can be used in “Step 1” include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, tripotassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, Cesium fluoride and the like can be exemplified, and tripotassium phosphate is desirable in terms of a good yield. The molar ratio of the base to the compound (3), the compound (4) and the compound (5) is preferably 1: 2 to 10: 1, and more preferably 1: 1 to 3: 1 in terms of a good yield.

Examples of the solvent that can be used in “Step 1” include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethyl ether, ethanol, methanol, and xylene, and these may be used in appropriate combination. . It is desirable to use a mixed solvent of dioxane and water in terms of a good yield.

“Step 1” can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably performed at 80 ° C. to 100 ° C. in terms of a good yield.

Compound (1) can be obtained by performing a normal treatment after completion of “Step 1”. If necessary, it may be purified by recrystallization, column chromatography or sublimation.

Further, the compound (1) or (1) ′ of the present invention has the following reaction formula:

(In general formulas (1), (1) ′, (3), (4), (4) ′, (6), (7) and (7) ′,
Ar ¹ represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, An ester group or an ester alkyl group, or an optionally substituted fluorine atom).
Ar ² may be substituted with a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). ).
Ar ³ may be substituted with a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). ) Or a substituent represented by —Ar ⁴ —Ar ⁵ .
Ar ⁴ is a nitrogen-containing heteroarylene group having 3 to 17 carbon atoms (which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). To express.
Ar ⁵ is an aromatic hydrocarbon group having 6 to 18 carbon atoms, pyridyl group, pyrimidyl group, or pyrazyl group (these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, ester groups or esters). An alkyl group or a fluorine atom which may be substituted).
Note that at least one of Ar ¹ , Ar ² , and Ar ³ is a pyridyl group, a pyrimidyl group, or a condensed ring group having 6 to 17 carbon atoms including a pyridine skeleton or a pyrimidine skeleton (these groups have a carbon number of 1 To 8 alkyl groups, alkoxy groups, alkoxyalkyl groups, ester groups or ester alkyl groups, or a fluorine atom, which may be substituted.
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituent having 1 to 4 carbon atoms, and R ¹ and R ² , R ³ and R ⁴ , or R ¹ and R ² and R ^{Both 3} and R ⁴ may be linked together to form an alicyclic or aromatic ring.
m represents 0 or 1.
n represents 0, 1, or 2.
Y ¹ represents a divalent substituent represented by the following general formula (A), and Y ² is a divalent substituent represented by the following general formula (A) in Formula (1), independently of Y ^1. In the formula (1) ′, a monovalent substituent represented by the following general formula (A) ′ is represented.

(In the formulas (A) and (A) ′, X ¹ , X ² and X ³ each independently represent CH or a nitrogen atom, and at least one is CH.
R ⁵ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group, or an ester alkyl group, a hydrogen atom, a fluorine atom, or a counter electron. )
Note that the total number of pyridyl groups and pyridylene groups, the total number of pyrimidyl groups and pyrimidylene groups, and the total number of pyrazyl groups and pyrazylene groups in the structure are each independently 0, 1 2, or 3.
In addition, each hydrogen atom in the formula may independently be a deuterium atom.
Z ¹ and Z ² each independently represent a leaving group.
M ¹ and M ² each independently represent a metal group, a boronic acid group, or a boronic ester group.
W represents a substituent necessary for carrying out the heterocycle formation reaction. )
It can be manufactured by the method shown in

The compounds represented by general formula (6), general formula (7), and general formula (7) 'are referred to as compound (6), compound (7), and compound (7)', respectively.

“Step 2” can be performed in the same manner as “Step 1”, and the conditions thereof are the same as those of “Step 1”. “Step 3” is a method of converting the site represented by W of compound (7) and compound (7) ′ to Ar ³ by a heterocycle formation reaction, and includes imidazole synthesis, indole synthesis, oxazole synthesis, and Erdman cyclization. Known methods such as reaction can be applied.

Examples of the substituent necessary for carrying out the heterocycle-forming reaction represented by W in compound (7) and compound (7) ′ include formyl group, amino group, ester group, carbonyl group, nitrile group and the like. Can be mentioned.

In the above reaction formula, for compound (7) and compound (7) ′, the site represented by W is converted to Ar ³ by a heterocyclic reaction, and then compound (3) and compound (4) or A coupling reaction may be performed with compound (4) ′.

Although there is no particular limitation on the method for producing an organic electroluminescent element comprising the compound (1) or (1) ′ of the present invention as a constituent component, film formation by vacuum vapor deposition is possible. 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 reached by a commonly used diffusion pump, turbo molecular pump, cryopump, etc., considering the manufacturing tact time and manufacturing cost of organic electroluminescence device production. It is preferably about 1 × 10 ⁻² to 1 × 10 ⁻⁵ Pa. The deposition rate is preferably 0.005 to 1.0 nm / sec depending on the thickness of the film to be formed.

In addition, the compound (1) or (1) ′ of the present invention can be formed into a film by a spin coat method, an ink jet method, a cast method, a dip method or the like using a general-purpose apparatus.

Hereinafter, the present invention will be described in more detail with reference to experimental examples and test examples, but the present invention is not limited thereto.

Experimental example-1 (Example)

Under an argon stream, 1.5 g (6.64 mmol) of 3,4-dichloro-1-bromobenzene, 6.61 g (33.2 mmol) of 4- (2-pyridyl) phenylboronic acid, 74.5 mg (0. 332 mmol), 317 mg (0.664 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, and 14.1 g (66.4 mmol) of tripotassium phosphate are mixed with 75 mL of dioxane and 20 mL of water. It melt | dissolved in the solvent and heat-stirred at 80 degreeC for 13 hours. After cooling to room temperature, the precipitated solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was purified by recrystallization with toluene, and the desired 4,4 ″ -di (2-pyridyl) -4 ′-[4- (2-pyridyl) phenyl] -1,1 ′: 2 ′, A white solid of 1 ″ -terphenyl (yield 3.35 g, yield 93.8%) was obtained.

¹ H-NMR (CDCl ₃ ): 7.17-7.20 (m, 2H), 7.22-7.25 (m, 1H), 7.33 (d, J = 8.3 Hz, 2H), 7.36 (d, J = 8.4 Hz, 2H), 7.59 (d, J = 8.0 Hz, 1H), 7.68-7.78 (m, 8H), 7.81 (d, J = 8.5 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.89 (d, J = 8.5 Hz, 2H), 8.10 (d, J = 8.3 Hz, 2H), 8.65 (d, J = 4.7 Hz, 2H), 8.71 (d, J = 4.6 Hz, 1H).
Experimental example-2 (Example)

Under an argon stream, 3,4-dichloro-1,1 ′: 4 ′, 1 ″ -terphenyl 2.21 g (7.39 mmol), 4- (2-pyridyl) phenylboronic acid 4.41 g (22.2 mmol) ), Palladium acetate 83.0 mg (0.370 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 352 mg (0.738 mmol), and tripotassium phosphate 9.41 g (44.3 mmol) ) Was dissolved in a mixed solvent of 108 mL of dioxane and 69 mL of water and heated and stirred at 90 ° C. for 22 hours. After cooling to room temperature, the precipitated solid was collected by filtration and washed with water, methanol, and hexane. The obtained solid was purified by recrystallization from toluene, and the desired 4- (2-pyridyl) -2 ′-[4- (2-pyridyl) phenyl] -1,1 ′: 4 ′, 1 ″: 4 A white solid (yield 1.40 g, yield 35.3%) of '', 1 '' '-quaterphenyl was obtained.

1H-NMR (CDCl3): 7.19 (t, J = 5.8 Hz, 2H), 7.33 (d, J = 8.7 Hz, 2H), 7.33-7.36 (m, 1H), 7.36 (d, J = 8.5 Hz, 2H), 7.46 (t, J = 7.8 Hz, 2H), 7.59 (d, J = 8.0 Hz, 1H), 7.65 (d , J = 7.1 Hz, 2H), 7.69-7.74 (m, 7H), 7.76 (d, J = 1.6 Hz, 1H), 7.77 (d, J = 5.1 Hz, 2H), 7.88 (d, J = 8.2 Hz, 2H), 7.89 (d, J = 8.3 Hz, 2H), 8.66 (d, J = 4.6 Hz, 2H).
Experimental Example-3

Under an argon stream, 17.0 g (62.9 mmol) of 1,4-dibromo-2-chlorobenzene, 25.0 g (126 mmol) of 4- (2-pyridyl) phenylboronic acid, 1.45 g of tetrakis (triphenylphosphine) palladium ( 1.26 mmol), and 62.8 mL (188 mmol) of 1 M aqueous potassium carbonate solution were dissolved in 153 mL of dioxane, and the mixture was heated and stirred at 95 ° C. for 21 hours. After cooling to room temperature, 200 mL of pure water was added and filtered, and the resulting solid was washed with water, methanol, and hexane to obtain the target 2′-chloro-4,4 ″ -di (2-pyridyl) -1 , 1 ′: 4 ′, 1 ″ -terphenyl was obtained as a white solid (yield 24.6 g, yield 93.3%).

¹ H-NMR (CDCl ₃ ): δ 8.73 (d, J = 4.71 Hz, 2H), 8.11 (t, J = 8.47 Hz, 4H), 7.81-7.75 (m, 7H) ), 7.63 (d, J = 8.53 Hz, 3H), 7.49 (d, J = 8.03 Hz, 1H), 7.30-7.27 (m, 2H).
Experimental Example-4

2′-chloro-4,4 ″ -di (2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl 24.6 g (58.7 mmol), bis (binacolato) diboron under argon flow 22.3 g (87.8 mmol), bis (dibenzylideneacetone) palladium 537 mg (0.586 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 559 mg (1.17 mmol), and acetic acid 11.5 g (117 mmol) of potassium was dissolved in 231 mL of dioxane, and heated and stirred at 100 ° C. for 14 hours. After cooling to room temperature, 400 mL of pure water was added and filtered. The obtained solid was dispersed in 2 L of hexane, refluxed for 1 hour and filtered at room temperature to obtain the target 2 ′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl). A white solid (yield 24.5 g, yield 81.8%) of -4,4 ″ -di (2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.73 (d, J = 3.33 Hz, 2H), 8.13-8.09 (m, 2H), 8.06-8.02 (m, 3H), 7.81-7.75 (m, 8H), 7.58-7.50 (m, 3H), 7.27-7.25 (m, 1H), 1.25 (s, 12H).
Experimental Example-5 (Example)

Under a stream of argon, 2 ′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1,1 ′: 1.00 g (1.96 mmol) of 4 ′, 1 ″ -terphenyl, 496 mg (2.94 mmol) of 2-chlorobenzothiazole, 22.0 mg (0.0980 mmol) of palladium acetate, 2-dicyclohexylphosphino-2 ′, 93.4 mg (0.196 mmol) of 4 ′, 6′-triisopropylbiphenyl and 9.41 mL (9.41 mmol) of 1M tripotassium phosphate aqueous solution were dissolved in 30 mL of dioxane, and the mixture was heated and stirred at 80 ° C. for 19 hours. . After cooling to room temperature, 300 mL of pure water was added, followed by separation / extraction with chloroform. After distilling off the solvent under reduced pressure, the obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform) to obtain the target 2 ′-(2-benzothiazolyl) -4,4 ″ -di (2-pyridyl). A light yellow solid of -1,1 ′: 4 ′, 1 ″ -terphenyl (yield 321 mg, yield 31.7%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.73 (d, J = 4.64 Hz, 1H), 8.70 (d, J = 4.64 Hz, 1H), 8.37 (d, J = 1.88 Hz) , 1H), 8.13 (d, J = 8.60 Hz, 2H), 8.08 (d, J = 8.16 Hz, 1H), 8.01 (d, J = 8.41 Hz, 2H), 7 .86 (d, J = 8.28 Hz, 3H), 7.80-7.76 (m, 4H), 7.72 (d, J = 8.16 Hz, 1H), 7.58 (d, J = 7.97 Hz, 1H), 7.49 (d, J = 8.41 Hz, 2H), 7.46 (t, J = 7.03 Hz, 1H), 7.32 (t, J = 7.15 Hz, 1H) ).
Experimental Example-6 (Example)

Under a stream of argon, 2 ′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl 1.00 g (1.96 mmol), 2- (4-chlorophenyl) benzothiazole 578 mg (2.35 mmol), palladium acetate 22.0 mg (0.0980 mmol), 2-dicyclohexylphosphino 2 ′, 4 ′, 6′-triisopropylbiphenyl 93.4 mg (0.196 mmol) and 1M tripotassium phosphate aqueous solution 9.41 mL (9.41 mmol) were dissolved in 30 mL dioxane, Stir with heating for hours. After cooling to room temperature, it was diluted with 300 mL of pure water and the solid was filtered off. The obtained crude product was recrystallized with 80 mL of toluene, and the filtrate was recrystallized again with 30 mL of toluene to obtain the desired 4- (2-benzothiazolyl) -4 ″-(2-pyridyl) -5 ′. A white solid (yield 220 mg, yield 18.9%) of-[4- (2-pyridyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was obtained. Further, the solid filtered off by the first recrystallization was recrystallized again with 100 mL of toluene, and the filtrate was distilled off under reduced pressure to obtain the desired product (yield 618 mg, yield 53.1%).

¹ H-NMR (CDCl ₃ ): δ 8.73 (d, J = 4.96 Hz, 1H), 8.67 (d, J = 4.89 Hz, 1H), 8.13 (dt, J = 8.22 Hz) , 7.09 Hz, 2H), 8.04 (d, J = 8.22 Hz, 1H), 7.99 (d, J = 8.22 Hz, 2H), 7.90 (dd, J = 7.97 Hz, 6.02 Hz, 3H), 7.83-7.78 (m, 7H), 7.72-7.70 (m, 2H), 7.62 (d, J = 8.22 Hz, 1H), 7. 47 (t, J = 7.78 Hz, 1H), 7.39 (dt, J = 8.22 Hz, 6.65 Hz, 3H), 7.34 (d, J = 8.22 Hz, 2H), 7.20 (T, J = 6.90 Hz, 1H).
Experiment-7 (Example)

Under a stream of argon, 2 ′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1,1 ′: 909 mg (1.78 mmol) of 4 ′, 1 ″ -terphenyl, 747 mg (2.14 mmol) of 1- (4-bromophenyl) -2-phenyl-1H-benzimidazole, 20.0 mg (0.0890 mmol) of palladium acetate , 84.8 mg (0.178 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl and 8.54 mL (8.54 mmol) of 1M aqueous tripotassium phosphate solution in 28 mL of dioxane And stirred at 80 ° C. for 5 hours. After cooling to room temperature, 300 mL of pure water was added, followed by liquid separation extraction with chloroform. After the solvent was distilled off under reduced pressure, the resulting crude product was purified by silica gel column chromatography (developing solvent: chloroform: ethyl acetate = 12: 1) to obtain the desired 4- (2-phenyl-1H-benzimidazol-1- Yl) -4 ″-(2-pyridyl) -5 ′-[4- (2-pyridyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl pale yellow solid (yield 803 mg, yield) Rate 69.1%).

¹ H-NMR (CDCl ₃ ): δ 8.73 (dd, J = 5.40 Hz, 4.89 Hz, 2H), 8.14 (d, J = 8.47 Hz, 2H), 7.95 (d, J = 8.47 Hz, 2H), 7.88-7.73 (m, 9H), 7.63 (d, J = 7.78 Hz, 1H), 7.56 (d, J = 7.34 Hz, 2H) , 7.39-7.29 (m, 8H), 7.21 (d, J = 8.60 Hz, 3H).
Experimental Example-8 (Example)

Under a stream of argon, 2 ′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl 1.00 g (1.96 mmol), 2- (4-bromophenyl) -1-phenyl-1H-benzimidazole 889 mg (2.55 mmol), palladium acetate 22.0 mg (0. 0980 mmol), 9-3.4 mg (0.196 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, and 9.41 mL (9.41 mmol) of 1M aqueous tripotassium phosphate solution in 30 mL of dioxane. And heated and stirred at 80 ° C. for 6 hours. After cooling to room temperature, 300 mL of pure water was added, followed by liquid separation extraction with chloroform. After distilling off the solvent under reduced pressure, the obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform) to obtain the desired 4- (1-phenyl-1H-benzimidazol-2-yl) -4 ″- Pale yellow solid of (2-pyridyl) -5 ′-[4- (2-pyridyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl (yield 1.18 g, yield 92.2%) )

¹ H-NMR (CDCl ₃ ): δ 8.73 (d, J = 4.71 Hz, 1H), 8.70 (d, J = 4.27 Hz, 1H), 8.11 (d, J = 8.47 Hz) , 2H), 7.86 (d, J = 8.47 Hz, 3H), 7.81-7.72 (m, 8H), 7.57 (d, J = 8.60 Hz, 1H), 7.47. -7.41 (m, 4H), 7.34-7.18 (m, 12H).
Experimental example-9

Under a stream of argon, 1.50 g (6.83 mmol) of 2-bromo-5-chloro-benzoic acid, 3.40 g (17.1 mmol) of 4- (2-pyridyl) phenylboronic acid, 76.7 mg (0. 342 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (326 mg, 0.683 mmol), and 1M aqueous tripotassium phosphate solution (32.8 mL, 32.8 mmol) are dissolved in 90 mL of dioxane. And stirred at 80 ° C. for 4 hours. After cooling to room temperature, 900 mL of pure water was added, followed by liquid separation extraction with chloroform. After the solvent was distilled off under reduced pressure, the obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform: ethyl acetate = 9: 1) to obtain the desired 2′-formyl-4,4 ″ -di (2 -Pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl white solid (yield 1.98 g, yield 70.3%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 10.13 (s, 1H), 8.73 (dd, J = 4.58 Hz, 4.39 Hz, 2H), 8.35 (d, J = 1.82 Hz, 1H) ), 8.14 (dd, J = 6.65 Hz, 1.82 Hz, 4H), 7.97 (dd, J = 5.96 Hz, 2.20 Hz, 1H), 7.83-7.76 (m, 7H), 7.61 (d, J = 8.03 Hz, 1H), 7.55 (d, J = 8.47 Hz, 2H), 7.30-7.28 (m, 1H).
Experimental Example-10 (Example)

2′-formyl-4,4 ″ -di (2-pyridyl) -1,1 ′: 1.98 g (4.80 mmol) of 4 ′, 1 ″ -terphenyl, and N-phenyl-1,2- 1.33 g (7.20 mmol) of phenylenediamine was dissolved in a mixed solvent of 51 mL of toluene and 13 mL of acetic acid, and heated and stirred at 100 ° C. for 20 hours. After cooling to room temperature, 150 mL of pure water was added, followed by separation / extraction with chloroform, and the organic layer was separated and washed twice with pure water. After distilling off the solvent under reduced pressure, the obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform: ethyl acetate = 9: 1) to obtain the desired 2 ′-[2- (1-phenyl-1H-benzimidazolyl). )]-4,4 ″ -di (2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl was obtained as a white solid (yield 1.84 g, 66.4%).

¹ H-NMR (CDCl ₃ ): δ 8.73 (d, J = 4.58 Hz, 1H), 8.68 (d, J = 3.76 Hz, 1H), 8.26 (d, J = 1.88 Hz) , 1H), 8.14 (d, J = 8.47 Hz, 2H), 7.96 (d, J = 7.84 Hz, 1H), 7.89 (d, J = 8.47 Hz, 2H), 7 .85-7.66 (m, 7H), 7.40-7.34 (m, 2H), 7.27-7.17 (m, 5H), 7.10 (t, J = 8.16 Hz, 2H), 6.85 (d, J = 8.28 Hz, 2H), 6.55 (d, J = 7.28 Hz, 2H).
Experimental Example-11 (Example)

Under an argon stream, 340 mg (1.08 mmol) of 1,2,4-tribromobenzene, 100 mg (0.0865 mmol) of tetrakis (triphenylphosphine) palladium, and 4.86 mL (4.86 mmol) of 1M aqueous potassium carbonate solution were added to dioxane. Dissolved in 12.5 mL and heated to 100 ° C. There, 1.25 g (3.78 mmol) of 1- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] isoquinoline dissolved in 25 mL of dioxane Was added dropwise over 3 hours, and the mixture was further stirred for 1 hour. After cooling to room temperature, 400 mL of pure water was added and liquid separation extraction was performed with chloroform. After the solvent was distilled off under reduced pressure, the obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform: ethyl acetate = 7: 3) to obtain the desired 4,4 ″ -di (1-isoquinolyl) -4. A pale yellow solid (yield 536 mg, yield 72.2%) of “-[4- (1-isoquinolyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.64 (d, J = 5.77 Hz, 1H), 8.59 (d, J = 5.71 Hz, 2H), 8.21 (d, J = 9.29 Hz) , 1H), 8.10 (d, J = 8.60 Hz, 2H), 7.91-7.82 (m, 8H), 7.73-7.42 (m, 19H).
Experimental example-12

Under an argon stream, 1- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] isoquinoline (1.00 g, 3.02 mmol), 1,4-dibromo 370 mg (1.37 mmol) of -2-chlorobenzene, 83.9 mg (0.0726 mmol) of tetrakis (triphenylphosphine) palladium, and 5.45 mL (5.45 mmol) of 1M aqueous potassium carbonate solution were dissolved in 40 mL of dioxane, and 100 ° C. And stirred with heating. After cooling to room temperature, 400 mL of pure water was added and liquid separation extraction was performed with chloroform. After distilling off the solvent under reduced pressure, the obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform) to obtain the target 2′-chloro-4,4 ″ -di (1-isoquinolyl) -1,1. A pale yellow solid (yield 490 mg, yield 68.9%) of “: 4 ′, 1 ″ -terphenyl was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.65 (d, J = 5.83 Hz, 2H), 8.25 (d, J = 8.66 Hz, 1H), 8.20 (d, J = 8.85 Hz) , 1H), 7.92 (d, J = 8.41 Hz, 2H), 7.85 (dd, J = 11.6 Hz, J = 9.35 Hz, 7H), 7.75-7.68 (m, 7H), 7.62-7.55 (m, 3H).
Experimental Example-13 (Example)

Under a stream of argon, 2′-chloro-4,4 ″ -di (1-isoquinolyl) -1,1 ′: 4 ′, 1 ″ -terphenyl 490 mg (0.944 mmol), 4- (2-phenyl- 1H-benzoimidazol-1-yl) phenylboronic acid 356 mg (1.13 mmol), palladium acetate 10.6 mg (0.0472 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 0 mg (0.0944 mmol) and 4.53 mL (4.53 mmol) of 1M aqueous potassium carbonate solution were dissolved in 15 mL of dioxane, and the mixture was heated and stirred at 100 ° C. for 4 hours. After cooling to room temperature, 150 mL of pure water was added, followed by liquid separation extraction with chloroform. After distilling off the solvent under reduced pressure, the resulting crude product was purified by silica gel column chromatography (developing solvent: chloroform) to obtain the desired 4- (2-phenyl-1H-benzimidazol-1-yl) -4 ″- A pale yellow solid of (1-isoquinolyl) -5 ′-[4- (1-isoquinolyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl (yield 531 mg, yield 74.7%) Obtained.

¹ H-NMR (CDCl ₃ ): δ 8.32 (d, J = 8.47 Hz, 2H), 8.28 (d, J = 4.14 Hz, 1H), 8.26 (d, J = 4.14 Hz) , 1H), 8.22-8.14 (m, 4H), 7.96 (d, J = 8.14 Hz, 1H), 7.92-7.83 (m, 9H), 7.78-7 .72 (m, 2H), 7.67 (d, J = 8.34 Hz, 1H), 7.59-7.54 (m, 4H), 7.42 (t, J = 8.09 Hz, 4H) , 7.36-7.23 (m, 6H), 7.15 (t, J = 7.59 Hz, 1H).
Experimental Example-14

Under an argon stream, 857 mg (5.24 mmol) of 1-chloroisoquinoline, 500 mg (2.62 mmol) of 3,4-dichlorophenylboronic acid, 242 mg (0.210 mmol) of tetrakis (triphenylphosphine) palladium, and 1M aqueous potassium carbonate solution 11 .8 mL (11.8 mmol) was dissolved in 30 mL of dioxane, and heated and stirred at 80 ° C. for 5 hours. After cooling to room temperature, 300 mL of pure water was added and liquid separation extraction was performed with chloroform. After the solvent was distilled off under reduced pressure, the resulting crude product was purified by silica gel column chromatography (developing solvent: chloroform: hexane = 1: 20 → 2: 3) to obtain the desired 1- (3,4-dichlorophenyl) isoquinoline. A white solid (yield 512 mg, yield 71.4%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.60 (d, J = 5.71 Hz, 1H), 8.03 (d, J = 7.53 Hz, 1H), 7.91 (d, J = 8.09 Hz) , 1H), 7.83 (d, J = 1.82 Hz, 1H), 7.73 (t, J = 6.96 Hz, 1H), 7.69 (d, J = 5.71 Hz, 1H), 7 62-7.54 (m, 3H).
Experimental Example-15 (Example)

Under an argon stream, 269 mg (0.982 mmol) of 1- (3,4-dichlorophenyl) isoquinoline, 8.8 mg (0.0393 mmol) of palladium acetate, 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 37.4 mg (0.0786 mmol), and 3.44 mL (3.44 mmol) of 1M aqueous tripotassium phosphate solution were dissolved in 10 mL of dioxane and heated to 80 ° C. Thereto was added 813 mg (2.46 mmol) of 1- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] isoquinoline dissolved in 5 mL of dioxane. The solution was added dropwise over a period of time and stirred for another hour after the completion of the addition. After cooling to room temperature, 200 mL of pure water was added and liquid separation extraction was performed with chloroform. After the solvent was distilled off under reduced pressure, the obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform: ethyl acetate = 3: 2) to obtain the desired 4,4 ′, 4 ″ -tris (1-isoquinolyl). ) -1,1 ′: 2 ′, 1 ″ -terphenyl white solid (yield 343 mg, yield 57.1%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.68 (d, J = 5.52 Hz, 1H), 8.60 (d, J = 5.71 Hz, 1H), 8.59 (d, J = 5.65 Hz) , 1H), 8.33 (d, J = 8.53 Hz, 1H), 8.12 (d, J = 8.66 Hz, 1H), 8.07 (d, J = 8.41 Hz, 1H), 7 .94-7.84 (m, 6H), 7.77-7.62 (m, 13H) 7.51 (d, J = 8.03 Hz, 4H).
Experimental Example-16 (Example)

Under an argon stream, 1.50 g (6.02 mmol) of 4- (2-quinolyl) phenylboronic acid, 542 mg (1.72 mmol) of 1,2,4-tribromobenzene, 159 mg of tetrakis (triphenylphosphine) palladium. 138 mmol) and 7.74 mL (7.74 mmol) of 1 M aqueous potassium carbonate solution were dissolved in 60 mL of dioxane, and the mixture was heated and stirred at 100 ° C. After cooling to room temperature, 500 mL of pure water was added and liquid separation extraction was performed with chloroform. After distilling off the solvent under reduced pressure, the obtained crude product was recrystallized twice using toluene as a solvent to obtain the desired 4,4 ″ -di (2-quinolyl) -4 ′-[4- (2-quinolyl). Phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was obtained as a white solid (yield 680 mg, yield 57.5%).

¹ H-NMR (CDCl ₃ ): δ 8.31 (d, J = 8.16 Hz, 2H), 8.26-8.08 (m, 11H), 7.95 (d, J = 8.66 Hz, 1H) ), 7.90-7.69 (m, 11H), 7.64 (d, J = 7.72 Hz, 1H), 7.56-7.22 (m, 7H).
Experimental Example-17

Under an argon stream, 1.00 g (4.01 mmol) of 4- (2-quinolyl) phenylboronic acid, 493 mg (1.82 mmol) of 1,4-dibromo-2-chlorobenzene, 126 mg (0.002 mmol) of tetrakis (triphenylphosphine) palladium. 109 mmol) and 8.19 mL (8.19 mmol) of 1M aqueous potassium carbonate solution were dissolved in 50 mL of dioxane, and the mixture was heated and stirred at 100 ° C. After cooling to room temperature, 500 mL of pure water was added and liquid separation extraction was performed with chloroform. After distilling off the solvent under reduced pressure, the obtained crude product was recrystallized using toluene as a solvent to obtain the desired 2′-chloro-4,4 ″ -di (2-quinolyl) -1,1 ′: 4 ′, A light yellow solid of 1 ″ -terphenyl (yield 833 mg, yield 88.1%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.31-8.25 (m, 6H), 8.20 (d, J = 8.72 Hz, 2H), 7.96 (dd, J = 8.41 Hz, 1 .94 Hz, 2H), 7.87-7.80 (m, 5H), 7.75 (t, J = 8.41 Hz, 2H), 7.71-7.66 (m, 3H), 7.57 -7.52 (m, 3H).
Experimental Example-18 (Example)

Under a stream of argon, 2′-chloro-4,4 ″ -di (2-quinolyl) -1,1 ′: 4 ′, 1 ″ -terphenyl 832 mg (1.60 mmol), 4- (2-phenyl- 1H-benzoimidazol-1-yl) phenylboronic acid 604 mg (1.92 mmol), palladium acetate 18.0 mg (0.0802 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 76. 4 mg (0.160 mmol) and 7.69 mL (7.69 mmol) of 1M potassium carbonate aqueous solution were dissolved in 25 mL of dioxane, and the mixture was heated and stirred at 100 ° C. for 4 hours. After cooling to room temperature, 200 mL of pure water was added and filtered, and the resulting solid was washed with pure water, methanol, and hexane. The obtained crude product was dried and recrystallized twice using chlorobenzene as a solvent to obtain the desired 4- (2-phenyl-1H-benzimidazol-1-yl) -4 ″-(2-quinolyl) -5. A pale yellow solid (yield 763 mg, yield 63.2%) of “-[4- (2-quinolyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.66 (t, J = 5.77 Hz, 2H), 8.21 (d, J = 7.65 Hz, 1H), 8.07 (d, J = 8.53 Hz) , 1H), 7.93-7.85 (m, 10H), 7.75-7.66 (m, 8H), 7.61-7.55 (m, 3H), 7.52-7.40. (M, 6H), 7.34-7.20 (m, 4H), 7.07 (t, J = 7.60 Hz, 1H).
Experimental Example-19

Under an argon stream, 1.00 g (3.70 mmol) of 1,4-dibromo-2-chlorobenzene, 5-methyl-2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) -2-yl) phenyl) pyridine 2.18 g (7.40 mmol), tetrakis (triphenylphosphine) palladium 85.5 mg (0.0740 mmol), and 1 M aqueous potassium carbonate solution 11.1 mL (11.1 mmol) in 9 mL It melt | dissolved in dioxane and heated and stirred at 100 degreeC for 18 hours. After cooling to room temperature, 20 mL of pure water was added, followed by liquid separation extraction with chloroform. After distilling off the solvent under reduced pressure, the obtained crude product was washed with chloroform, and the desired 2′-chloro-4,4 ″ -di (5-methylpyridin-2-yl) -1,1 ′: 4 A white solid of ', 1 ″ -terphenyl (yield 1.22 g, yield 73.8%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.55 (d, J = 2.26 Hz, 2H), 8.07 (t, J = 8.41 Hz, 4H), 7.79 (d, J = 1.76 Hz) , 1H), 7.74-7.68 (m, 4H), 7.63-7.58 (m, 5H), 7.48 (d, J = 7.97 Hz, 1H), 2.40 (s) , 6H).
Experimental Example-20 (Example)

Under an argon stream, 2′-chloro-4,4 ″ -di (5-methylpyridin-2-yl) -1,1 ′: 4 ′, 1 ″ -terphenyl 600 mg (1.34 mmol), 4- (2-Phenyl-1H-benzimidazol-1-yl) phenylboronic acid 506 mg (1.61 mmol), palladium acetate 15.0 mg (0.0670 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′- 63.9 mg (0.134 mmol) of triisopropylbiphenyl and 6.43 mL (6.43 mmol) of 1M aqueous potassium carbonate solution were dissolved in 21 mL of dioxane, and the mixture was heated and stirred at 100 ° C. for 4 hours. After cooling to room temperature, 200 mL of pure water was added for liquid separation extraction. After the solvent was distilled off under reduced pressure, the resulting crude product was purified by silica gel column chromatography (developing solvent: chloroform: ethyl acetate = 10: 1) to obtain the desired 4- (5-methylpyridin-2-yl) -4. ''-(2-Phenyl-1H-benzimidazol-1-yl) -4 '-[4- (5-methylpyridin-2-yl) phenyl] -1,1': 2 ', 1' '-tel A white solid of phenyl (yield 561 mg, yield 61.6%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.55 (t, J = 5.33 Hz, 2H), 8.10 (d, J = 8.03 Hz, 2H), 7.92 (d, J = 8.03 Hz) , 2H), 7.87 (d, J = 8.03 Hz, 1H), 7.83-7.78 (m, 4H), 7.71 (d, J = 9.35 Hz, 1H), 7.65 -7.55 (m, 7H), 7.39-7.27 (m, 8H), 7.22-7.19 (m, 3H), 2.40 (s, 6H).
Experimental Example 21 (Example)

Under an argon stream, 821 mg (3.63 mmol) of 1-bromo-3,4-dichlorobenzene, 1.00 g (3.63 mmol) of 4 ′-(2-pyridyl) biphenyl-4-boronic acid, 30.2 mg of palladium acetate ( 0.135 mmol), 138 mg (0.289 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, and 15 mL (15 mmol) of 1M aqueous tripotassium phosphate solution were dissolved in 36 mL of dioxane, The mixture was stirred with heating at ° C for 2 hours. Thereto was added 1.59 g (7.99 mmol) of 4- (2-pyridyl) phenylboronic acid, and the mixture was heated and stirred at 100 ° C. for 5 days. After cooling to room temperature, 200 mL of pure water was added and filtered, and the resulting solid was washed with pure water, methanol, and hexane. The obtained crude product was dried and recrystallized twice using toluene as a solvent to obtain the desired 4,4 ′ ″-di (2-pyridyl) -2 ′-[4- (2-pyridyl) phenyl]- A white solid of 1,1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-quaterphenyl (yield 777 mg, yield 34.9%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.73 (d, J = 4.14 Hz, 1H), 8.67 (d, J = 3.58 Hz, 2H), 8.11 (d, J = 8.28 Hz) , 2H), 7.92 (dd, J = 8.47 Hz, 8.78 Hz, 4H), 8.12 (m, 15H), 7.61 (d, J = 7.91 Hz, 1H), 7.38. (D, J = 8.47 Hz, 2H), 7.35 (d, J = 8.53 Hz, 2H), 7.21 (m, 2H).
Experimental Example-22 (Example)

Under an argon stream, 1.00 g (3.02 mmol) of 2- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthyl] pyridine, 1-bromo-3 , 4-dichlorobenzene 682 mg (3.02 mmol), palladium acetate 15.0 mg (0.0668 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 64.0 mg (0.134 mmol), And 13.6 mL (13.6 mmol) of 1 M aqueous tripotassium phosphate solution was dissolved in 30 mL of dioxane and heated at 80 ° C. for 2 hours. Thereto was added dropwise 1.32 g (6.64 mmol) of 4- (2-pyridyl) phenylboronic acid dissolved in 10 mL of dioxane over 2 hours, and the mixture was further stirred for 2 hours after completion of the addition. After cooling to room temperature, 200 mL of pure water was added and liquid separation extraction was performed with chloroform. After the solvent was distilled off under reduced pressure, the obtained crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 1) to obtain the desired 4 ′-[(2-pyridyl) naphthalen-4-yl. ] -4,4 ″ -di (2-pyridyl) -1,1 ′: 2 ′, 1 ″ -terphenyl white solid (yield 508 mg, yield 28.6%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.83 (d, J = 3.07 Hz, 1H), 8.67 (dd, J = 9, 79 Hz, 9.73 Hz, 2H), 8.16 (dd, J = 6.46 Hz, 6.71 Hz, 2H), 7.93-7.85 (m, 5H), 7.74-7.61 (m, 11H), 7.51 (dd, J = 6.78 Hz, 6.58 Hz, 2H), 7.42-7.35 (m, 4H), 7.23-7.18 (m, 2H),
Experimental Example-23 (Example)

Under a stream of argon, 2 ′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl 1.50 g (2.94 mmol), 1- (6-chloropyridyl-3-yl) -2-phenyl-1H-benzimidazole 680 mg (2.22 mmol), palladium acetate 33. 46 mL of 0 mg (0.147 mmol), 140 mg (0.294 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, and 14.1 mL (14.1 mmol) of 1M tripotassium phosphate aqueous solution Was dissolved in dioxane and heated and stirred at 80 ° C. for 7 hours. After cooling to room temperature, 50 mL of pure water was added and filtered, and the resulting solid was washed with pure water. The obtained crude product was dried, and filtered while hot using toluene as a solvent, and a black solid was separated by filtration. After collecting the filtrate and distilling off the solvent under reduced pressure, the obtained crude product was recrystallized using toluene as a solvent to obtain the desired 2 ′-[5- (2-phenyl-1H-benzimidazol-1-yl]. ) Pyridin-2-yl] -4,4 ″-(2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl white solid (yield 730 mg, yield 38.0%) It was.

¹ H-NMR (CDCl ₃ ): δ 8.71 (t, J = 5.65 Hz, 2H), 8.66 (d, J = 2.32 Hz, 1H), 8.24 (d, J = 7.53 Hz) , 1H), 8.08-7.91 (m, 10H), 7.81-7.77 (m, 2H), 7.68 (d, J = 8.34 Hz, 1H), 7.51 (d , J = 7.34 Hz, 2H), 7.43-7.25 (m, 12H).
Experimental Example-24 (Example)

Under a stream of argon, 2 ′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1,1 ′: 863 mg (1.69 mmol) of 4 ′, 1 ″ -terphenyl, 650 mg (1.69 mmol) of 1- (4-bromo-3,5-difluorophenyl) -2-phenyl-1H-benzimidazole, palladium acetate 19. 0 mg (0.0845 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 80.6 mg (0.169 mmol), and 1M tripotassium phosphate aqueous solution 8.11 mL (8.11 mmol) Was dissolved in 26 mL of dioxane and stirred with heating at 80 ° C. for 18 hours. After cooling to room temperature, 50 mL of pure water was added, followed by liquid separation extraction with chloroform. After distilling off the solvent under reduced pressure, the obtained crude product was recrystallized using toluene as a solvent to obtain the target 2 ′-[2,6-difluoro-4- (2-phenyl-1H-benzimidazol-1-yl). Phenyl] -4,4 ″-(2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl white solid (yield 438 mg, yield 38.8%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.67 (m, 2H), 8.06 (td, J = 8.47 Hz, 8.91 Hz, 2H), 7.93 (d, J = 8.47 Hz, 2H) ), 7.81-7.70 (m, 10H), 7.59 (d, J = 8.22 Hz, 1H), 7.46-7.44 (m, 2H), 7.30-7.21 (M, 8H), 7.13 (t, J = 8.22 Hz, 2H), 6.77 (d, J = 6.53 Hz, 1H).
Experimental example-25 (Example)

Under a stream of argon, 2 ′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1,1 ′: 1.2 'g (2.40 mmol) of 4 ′, 1 ″ -terphenyl, 800 mg (2.88 mmol) of 9- (4-chlorophenyl) -β-carboline, 27.0 mg (0.120 mmol) of palladium acetate, 2-dicyclohexyl Phosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (114 mg, 0.240 mmol) and 1M aqueous potassium carbonate solution (11.5 mL, 11.5 mmol) were dissolved in 37 mL dioxane and heated at 100 ° C. for 5 hours. Stir. After cooling to room temperature, 100 mL of pure water was added, followed by liquid separation extraction with chloroform. After distilling off the solvent under reduced pressure, the obtained crude product was recrystallized using methanol as a solvent to obtain the desired 4- (β-carbolin-9-yl) -4 ″-(2-pyridyl) -5 ′-[ A white solid (yield 1.36 g, yield 90.8%) of 4- (2-pyridyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.85 (d, J = 0.82 Hz, 1H), 8.74 (d, J = 4.33 Hz, 1H), 8.69 (d, J = 4.71 Hz) , 1H), 8.51 (d, J = 5.46 Hz, 1H), 8.18 (d, J = 7.84 Hz, 1H), 8.14 (d, J = 8.34 Hz, 2H), 8 .00 (dd, J = 5.46 Hz, 1.13 Hz, 1H), 7.97 (d, J = 8.41 Hz, 2H), 7.88-7.86 (m, 3H), 7.83- 7.79 (m, 3H), 7.76-7.75 (m, 2H), 7.65 (d, J = 8.09 Hz, 1H), 7.56-7.47 (m, 6H), 7.40 (d, J = 8.53 Hz, 2H), 7.34 (t, J = 8.03 Hz, 1H), 7.28 (dd, J = 4.52 Hz, 1.88 Hz, 1 ), 7.23 (dt, J = 4.33Hz, 4.39Hz, 1H).
Experimental Example-26 (Example)

Under a stream of argon, 2 ′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl 713 mg (1.40 mmol), 9- (6-chloropyridin-3-yl) -β-carboline 430 mg (1.54 mmol), palladium acetate 16.0 mg (0.070 mmol), 2-Dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (66 mg, 0.140 mmol) and 1M aqueous potassium carbonate solution (6.72 mL, 6.72 mmol) were dissolved in 22 mL of dioxane at 100 ° C. The mixture was heated and stirred for 8 hours. After cooling to room temperature, 50 mL of pure water was added, followed by liquid separation extraction with chloroform. The organic layer was filtered to remove the black solid, and then the solvent was distilled off under reduced pressure. The obtained crude product was recrystallized using methanol as a solvent to obtain the target 2 ′-[5- (β-carbolin-9-yl) pyridin-2-yl] -4,4 ″-(2-pyridyl). A white solid of -1,1 ′: 4 ′, 1 ″ -terphenyl (yield 583 mg, yield 66.5%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 8.99 (d, J = 2.13 Hz, 1 H), 8.83 (d, J = 0.94 Hz, 1 H), 8.73 (d, J = 0.08 Hz) , 1H), 8.70 (d, J = 4.89 Hz, 1H), 8.54 (d, J = 5.33 Hz, 1H), 8.21-8.19 (m, 2H), 8.14 (D, J = 8.47 Hz, 2H), 8.02-8.00 (m, 3H), 7.89 (d, J = 8.47 Hz, 2H), 7.87 (d, J = 5. 96 Hz, 1H), 7.83-7.76 (m, 4H), 7.69-7.66 (m, 2H), 7.55 (t, J = 7.09 Hz, 1H), 7.46 ( d, J = 8.47 Hz, 1H), 7.44 (d, J = 8.47 Hz, 2H), 7.36 (t, J = 7.84 Hz, 1H), 7.19 (d, J = 8 .03 z, 1H), 8.27 (d, J = 5.14Hz, 1H), 7.23 (dt, J = 4.52Hz, 4.33Hz, 1H).
Experimental Example-27 (Example)

Under an argon stream, 1.00 g (3.22 mmol) of 2- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] pyridine, 1,2,4 -305 mg (0.977 mmol) of bromobenzene, 90.0 mg (0.078 mmol) of tetrakis (triphenylphosphine) palladium, and 4.40 mL (4.40 mmol) of 1M aqueous potassium carbonate solution were dissolved in 30 mL of dioxane, And stirred for 8 hours. After cooling to room temperature, 50 mL of pure water was added and filtered, and the resulting solid was washed with pure water, methanol, and hexane. The obtained crude product was dried and recrystallized twice using toluene as a solvent to obtain the desired 4,4 ″ -di (4,6-dimethylpyrimidin-2-yl) -4 ′-[4- (4 , 6-Dimethylpyrimidin-2-yl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was obtained as a white solid (yield 503 mg, yield 82.4%).

¹ H-NMR (CDCl ₃ ): δ 8.54 (d, J = 8.47 Hz, 2H), 8.31 (t, J = 8.85 Hz, 4H), 7.82-7.75 (m, 4H) ), 7.60 (d, J = 8.03 Hz, 1H), 7.36 (d, J = 8.47 Hz, 2H), 7.33 (d, J = 8.28 Hz, 2H), 6.94. (S, 1H), 6.89 (s, 2H), 2.56 (s, 6H), 2.51 (s, 12H).
Example 28

Under an argon stream, 1.00 g (4.09 mmol) of 3- (2-pyridyl) -9H-carbazole, 1.34 g (4.91 mmol) of 1,4-dichloro-2-iodobenzene, copper (I) iodide 78 0.0 mg (0.409 mmol) 1,10-phenanthroline 73.0 mg (0.409 mmol) and potassium carbonate 565 mg (4.09 mmol) were dissolved in 24 mL of xylene, and the mixture was heated and stirred at 130 ° C. for 48 hours. After cooling to room temperature, 50 mL of pure water was added, followed by liquid separation extraction with chloroform. After distilling off the solvent under reduced pressure, the obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform) to obtain the target 9- (1,4-dichlorophenyl-2-yl) -3- (2-pyridyl). A yellow solid of -9H-carbazole (yield 150 mg, yield 9.4%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 9.00 (d, J = 1.32 Hz, 1H), 8.67 (d, J = 3.89 Hz, 1H), 8.37 (d, J = 7.60 Hz) , 1H), 8.21 (dd, J = 8.85 Hz, 1.88 Hz, 1H), 8.09 (d, J = 8.26 Hz, 1H), 7.96 (d, J = 2.57 Hz, 1H), 7.92-7.89 (m, 2H), 7.78 (dd, J = 8.72 Hz, 2.51 Hz, 1H), 7.46 (t, J = 7.34 Hz, 1H), 7.36-7.31 (m, 2H), 7.19 (d, J = 8.85 Hz, 1H), 7.12 (d, J = 8.22 Hz, 1H).
Experimental Example-29 (Example)

Under an argon stream, 9- (1,4-dichlorophenyl-2-yl) -3- (2-pyridyl) -9H-carbazole 150 mg (0.385 mmol), 4- (2-pyridyl) phenylboronic acid 169 mg (0. 849 mmol), 1.70 mg (0.0077 mmol) of palladium acetate, 7.30 mg (0.0154 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, and 0.770 mL of 1M aqueous potassium carbonate solution (0.770 mmol) was dissolved in 2.6 mL of dioxane and heated and stirred at 80 ° C. for 21 hours. After cooling to room temperature, 10 mL of pure water was added, followed by liquid separation extraction with chloroform. After distilling off the solvent under reduced pressure, the obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform) to obtain the desired 2 ′-[3- (2-pyridyl) -9H-carbazol-9-yl]- A white solid of 4,4 ″-(2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl was obtained (yield 80 mg, yield 33.1%).

¹ H-NMR (DMCO-d ⁶ ): δ 9.03 (d, J = 1.69 Hz, 1H), 8.70-0.67 (m, 3H), 8.40 (d, J = 7.65 Hz) , 1H), 8, 22 (td, J = 8.72 Hz, 1.82 Hz, 3H), 8.16 (d, J = 2.51 Hz, 1H), 8.12-8.08 (m, 4H) , 8.04 (d, J = 7.91 Hz, 1H), 7.98-7.87 (m, 7H), 7.52-7.43 (m, 3H), 7.39-7.32 ( m, 4H), 7.25 (d, J = 8.60 Hz, 1H), 7.18 (d, J = 8.09 Hz, 1H).
Experimental example-30 (Example)

Under a stream of argon, 6 ′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl 210 mg (0.490 mmol), 2-chloro-5-phenylpyridine 111 mg (0.588 mmol), palladium acetate 2.2 mg (0.00980 mmol), 2-dicyclohexylphosphino-2 ′ , 4 ′, 6′-triisopropylbiphenyl 9.3 mg (0.0196 mmol) and potassium carbonate 135 mg (0.980 mmol) are dissolved in a mixed solvent of 3.2 mL of dioxane and 330 μL of water, and heated at 80 ° C. for 18 hours. Stir. After cooling to room temperature, 10 mL of pure water was added, followed by liquid separation extraction with chloroform. After the solvent was distilled off under reduced pressure, the obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform: methanol = 99: 1) to obtain the desired 6 ′-(5-phenylpyridin-2-yl) -4. , 4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl was obtained as a white solid (yield 20 mg, yield 7.6%).
¹ H-NMR (CDCl ₃ ): 8.85 (d, J = 1.65 Hz, 1H), 8.64 (d, J = 4.83 Hz, 1H), 8.60 (d, J = 4.77 Hz) , 1H), 8.04 (d, J = 8.44 Hz, 2H), 7.87 (d, J = 8.31 Hz, 2H), 7.83 (d, J = 8.01 Hz, 1H), 7 .76-7.64 (m, 8H), 7.52 (dd, J = 8.50 Hz, 7.89 Hz, 3H), 7.39-7.27 (m, 5H), 7.18-7. 12 (m, 2H), 6.96 (d, J = 8.13 Hz, 1H).
Experimental Example-31 (Example)

Under a stream of argon, 6 ′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl 210 mg (0.490 mmol), 3-chloro-6-phenylpyridine 111 mg (0.588 mmol), palladium acetate 2.2 mg (0.00980 mmol), 2-dicyclohexylphosphino-2 ′ , 4 ′, 6′-triisopropylbiphenyl 9.3 mg (0.0196 mmol) and potassium carbonate 135 mg (0.980 mmol) are dissolved in a mixed solvent of 3.2 mL of dioxane and 330 μL of water, and heated at 80 ° C. for 18 hours. Stir. After cooling to room temperature, 10 mL of pure water was added, followed by liquid separation extraction with chloroform. After the solvent was distilled off under reduced pressure, the resulting crude product was purified by silica gel column chromatography (developing solvent: chloroform: methanol = 99: 1) to obtain the desired 6 ′-(6-phenylpyridin-3-yl) -4. , 4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl was obtained as a white solid (yield 100 mg, yield 38.0%).
¹ H-NMR (CDCl ₃ ): 8.73 (d, J = 4.65 Hz, 1H), 8.67 (d, J = 4.65 Hz, 1H), 8.66 (d, J = 1.65 Hz) , 1H), 8.13 (d, J = 8.50 Hz, 2H), 7.98 (d, J = 7.03 Hz, 2H), 7.94 (d, J = 8.44 Hz, 2H), 7 .83-7.78 (m, 6H), 7.76-7.70 (m, 2H), 7.60 (dd, J = 7.83 Hz, 7.64 Hz, 2H), 7.51 (dd, J = 8.25 Hz, 2.26 Hz, 1H), 7.47-7.43 (m, 2H), 7.41-7.37 (m, 3H), 7.28-7.25 (m, 1H) ), 7.22 (dt, J = 6.11 Hz, 2.08 Hz, 1H).
Test Example-1 (Example)
Preparation and evaluation of the organic electroluminescent element were performed as follows. As the substrate, a glass substrate with an ITO transparent electrode in which a 2 mm-wide indium-tin oxide (ITO) film was patterned in a stripe shape 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 deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm ² as shown in FIG.

First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was 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 (1-naphthyl) -N, N′-diphenylbenzidine (NPD) was vacuum-deposited with a film thickness of 45 nm. As the light emitting layer 4, 2-tert-butyl-9,10-di (2-naphthyl) anthracene (TBADN) and 4,4′-bis [4- (di-p-tolylamino) phenylethen-1-yl] Biphenyl (DPAVBi) was vacuum-deposited at a thickness of 40 nm at a ratio of 95: 5 (mass%). The electron transport layer 5 is 4,4 ″ -di (2-pyridyl) -4 ′-[4- (2-pyridyl) phenyl] -1,1 ′: 2 synthesized in Experimental Example-1 of the present invention. ', 1''-Terphenyl was vacuum deposited with a film 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 0.6 to 3.0 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 deposition of lithium fluoride and aluminum with a thickness of 1.0 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. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

A direct current was applied to the produced 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 passed were measured.

The measured values of the fabricated element were 4.49 V, 2020 cd / m ² , 10.1 cd / A, 7.07 lm / W.

Test Example-2 (Example)
2 ′-(2-benzothiazolyl) -4,4 ″ -di (2-pyridyl) -1,1 ′: 4 ′ obtained in Experimental Example-5 instead of the electron transporting layer 5 in Test Example-1. An organic electroluminescent device obtained by vacuum-depositing 1,1 ″ -terphenyl was prepared and evaluated in the same manner as in Test Example-1. The measured values of the fabricated elements were 4.98 V, 1428 cd / m ² , 7.14 cd / A, and 4.50 lm / W, respectively.

Test Example 3 (Example)
4- (2-benzothiazolyl) -4 ″-(2-pyridyl) -5 ′-[4- (2-pyridyl) obtained in Experimental Example-6 instead of the electron transport layer 5 of Test Example-1 An organic electroluminescent device in which phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was vacuum-deposited was prepared and evaluated in the same manner as in Test Example-1. The measured values of the fabricated elements were 4.83 V, 1472 cd / m ² , 7.36 cd / A, and 4.79 lm / W, respectively.

Test Example 4 (Example)
4- (2-Phenyl-1H-benzoimidazol-1-yl) -4 ″-(2-pyridyl) -5 ′ obtained in Experimental Example-7 in place of the electron transport layer 5 of Test Example-1 An organic electroluminescent device obtained by vacuum-depositing — [4- (2-pyridyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was prepared and evaluated in the same manner as in Test Example-1. The measured values of the fabricated elements were 4.65 V, 1944 cd / m ² , 9.72 cd / A, and 6.57 lm / W, respectively.

Test Example-5 (Example)
The 4- (1-phenyl-1H-benzoimidazol-2-yl) -4 ″-(2-pyridyl) -5 ′ obtained in Experimental Example-8 was used in place of the electron transport layer 5 in Test Example-1. An organic electroluminescent device obtained by vacuum-depositing — [4- (2-pyridyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was prepared and evaluated in the same manner as in Test Example-1. The measured values of the fabricated elements were 5.42 V, 1824 cd / m ² , 9.12 cd / A, and 5.29 lm / W, respectively. Further, the luminance 20% deterioration time during continuous lighting of this element was 35 hours.

Test Example-6 (Example)
Instead of the electron transport layer 5 of Test Example-1, 4,4 ″ -di (2-quinolyl) -4 ′-[4- (2-quinolyl) phenyl] -1, obtained in Experimental Example-16 An organic electroluminescent device obtained by vacuum-depositing 1 ′: 2 ′, 1 ″ -terphenyl was prepared and evaluated in the same manner as in Test Example-1. The measured values of the fabricated elements were 5.84 V, 2020 cd / m ² , 10.1 cd / A, and 5.43 lm / W, respectively.

Comparative Example-1
In place of the electron transport layer 5 in Test Example 1, an organic electroluminescent device in which Alq was vacuum-deposited was produced and evaluated in the same manner as in Test Example-1. The measured values of the fabricated elements were 7.47 V, 1661 cd / m ² , 8.31 cd / A, and 3.49 lm / W, respectively. Further, the luminance 20% deterioration time during continuous lighting of this element was 34 hours.
The measurement results of Test Examples 1 to 6 and Comparative Example 1 are summarized in the following table.

Test Example-7 (Example)
4- (2-Phenyl-1H-benzoimidazol-1-yl) -4 ″-(1-isoquinolyl) -5 ′ obtained in Experimental Example-13 instead of the electron transport layer 5 in Test Example-1 -[4- (1-Isoquinolyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl is changed to the light-emitting layer 4 to produce 2-tert-butyl-9,10-di (3-biphenyl) ) Anthracene (formula below, see EML-1) and N, N′-diphenyl-N, N′-bis (4-biphenyl) pyrene-1,6-diamine (formula below, see EML-2) 95: 5 An organic electroluminescent device vacuum-deposited at a ratio of (% by mass) was produced and evaluated in the same manner as in Test Example-1. The measured values of the fabricated elements were 5.87 V, 1244 cd / m ² , 6.22 cd / A, and 3.33 lm / W, respectively. Further, the 30% luminance degradation time during continuous lighting of this element was 58 hours.

Test Example-8 (Example)
The 4- (5-methylpyridin-2-yl) -4 ″-(2-phenyl-1H-benzoimidazole-1-) obtained in Experimental Example-20 was used instead of the electron transporting layer 5 in Test Example-7. Yl) -4 ′-[4- (5-methylpyridin-2-yl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was vacuum-deposited and an organic electroluminescent device was tested in Test Example 7 Were prepared and evaluated. The measured values of the fabricated elements were 4.72 V, 1407 cd / m ² , 7.04 cd / A, and 4.68 lm / W, respectively.

Test Example-9 (Example)
4,4 ′ ″-di (2-pyridyl) -2 ′-[4- (2-pyridyl) phenyl] -1 obtained in Experiment 21 instead of the electron transport layer 5 in Test Example-7 , 1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-Quaterphenyl was vacuum-deposited and an organic electroluminescent device was produced and evaluated in the same manner as in Test Example-7. The measured values of the fabricated elements were 5.32 V, 1465 cd / m ² , 7.33 cd / A, and 4.33 lm / W, respectively.

Test Example-10 (Example)
4 ′-[(2-Pyridyl) naphthalen-4-yl] -4,4 ″ -di (2-pyridyl)-obtained in Experimental Example-22 instead of Electron Transport Layer 5 in Test Example-7 An organic electroluminescent device obtained by vacuum-depositing 1,1 ′: 2 ′, 1 ″ -terphenyl was prepared and evaluated in the same manner as in Test Example-7. The measured values of the fabricated elements were 6.24 V, 1379 cd / m ² , 6.90 cd / A, and 3.47 lm / W, respectively.

Test Example-11 (Example)
2 ′-[5- (2-Phenyl-1H-benzimidazol-1-yl) pyridin-2-yl] -4,4 obtained in Experimental Example-23 instead of the electron transport layer 5 in Test Example-7 An organic electroluminescent device obtained by vacuum-depositing ″-(2-pyridyl) -1,1 ′: 4 ′, 1 ″ -terphenyl was prepared and evaluated in the same manner as in Test Example-7. The measured values of the fabricated elements were 4.96 V, 1332 cd / m ² , 6.66 cd / A, and 4.22 lm / W, respectively. Further, the 30% luminance degradation time when the device was continuously lit was 40 hours.

Reference Example-1
In place of the electron transport layer 5 of Test Example-7, 2,4-diphenyl-6- [4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 described in Patent No. WO20081299912 ''-Terphenyl-5'-yl] -1,3,5-triazine (see formula ETL-1 below)

An organic electroluminescent device obtained by vacuum deposition was prepared and evaluated in the same manner as in Test Example-7. The measured values of the fabricated elements were 6.79 V, 1193 cd / m ² , 5.97 cd / A, and 2.76 lm / W, respectively. Further, the 30% luminance degradation time during continuous lighting of this element was 50 hours.
The measurement results of Test Examples 7 to 11 and Reference Example 1 are summarized in the following table.

Test Example-12 (Example)
4- (2-pyridyl) -2 ′-[4- (2-pyridyl) phenyl] -1,1 ′: 4 ′ obtained in Experiment Example 2 instead of the electron transport layer 5 in Test Example 1 , 1 ″: 4 ″, 1 ′ ″-quaterphenyl is changed to the light-emitting layer 4, and 2-tert-butyl-9,10-di (2-naphthyl) anthracene (TBADN) and 4,4 An organic electroluminescence device obtained by vacuum-depositing '-bis [4- (di-p-tolylamino) phenylethen-1-yl] biphenyl (DPAVBi) at a ratio of 93: 7 (mass%) was the same as in Test Example 1. Were prepared and evaluated. The measured values of the fabricated elements were 4.53 V, 2130 cd / m ² , 10.65 cd / A, and 7.39 lm / W, respectively.

Comparative Example-2
In place of the electron transport layer 5 in Test Example-12, an organic electroluminescent device in which Alq was vacuum-deposited was produced and evaluated in the same manner as in Test Example-12. The measured values of the fabricated elements were 6.04 V, 1902 cd / m ² , 9.51 cd / A, and 4.95 lm / W, respectively.
The measurement results of Test Example 12 and Comparative Example 2 are summarized in the following table.

Test Example-13 (Example)
Instead of the electron transport layer 5 of Test Example-1, 4,4 ″ -di (1-isoquinolyl) -4 ′-[4- (1-isoquinolyl) phenyl] -1, obtained in Experiment Example-11, An organic electroluminescent device obtained by vacuum-depositing 1 ′: 2 ′, 1 ″ -terphenyl was prepared in the same manner as in Test Example 1, except that the substrate surface treatment method was changed from ozone ultraviolet cleaning to oxygen plasma cleaning. evaluated. The measured values of the fabricated elements were 5.70 V, 1779 cd / m ² , 8.90 cd / A, and 4.90 lm / W, respectively.

Comparative Example-3
In place of the electron transport layer 5 of Test Example-13, an organic electroluminescent device in which Alq was vacuum-deposited was produced and evaluated in the same manner as Test Example-13. The measured values of the fabricated elements were 6.20 V, 1957 cd / m ² , 9.79 cd / A, and 4.96 lm / W, respectively.
The measurement results of Test Example 13 and Comparative Example 3 are summarized in the following table.

Test Example-14 (Example)
Instead of the hole injection layer 2 of Test Example 1, the sublimated and purified HIL is changed to a thickness of 45 nm and changed to the hole transport layer 3, and HAT and HTL are changed to a thickness of 5 nm and 30 nm, respectively. In place of EML-1 and EML-2 (same as above) at a ratio of 958: 42 (mass%) with a film thickness of 20 nm, the electron transport layer 5 was used and synthesized in Experimental Example 27 of the present invention. 4,4 ″ -di (4,6-dimethylpyrimidin-2-yl) -4 ′-[4- (4,6-dimethylpyrimidin-2-yl) phenyl] -1,1 ′: 2 ′, 1 ″ -Organic electroluminescent device in which Liq, silver magnesium, and silver were vacuum-deposited in thicknesses of 0.45 nm, 80 nm, and 20 nm, respectively, by changing the cathode layer 6 to a thickness of 30 nm and the cathode layer 6 were tested. 1 was produced. The structural formulas and abbreviations of the compounds used are shown below.

The evaluation results when a current density of 10 mA / cm ² is applied to the fabricated device are shown in the table below.

Test Example-15 (Example)
4- (β-carbolin-9-yl) -4 ″-(2-pyridyl) -5 ′-[4] synthesized in Experimental Example-25 of the present invention instead of the electron transport layer 5 in Test Example-14 An organic electroluminescent device in which — (2-pyridyl) phenyl] -1,1 ′: 2 ′, 1 ″ -terphenyl was vacuum-deposited was prepared and measured in the same manner as in Test Example-14. The evaluation results of the fabricated devices are shown in the table below.

Test Example-16 (Example)
Instead of the electron transport layer 5 in Test Example-14, 2 ′-[5- (β-carbolin-9-yl) pyridin-2-yl] -4,4 ′ obtained in Experiment Example-26 of the present invention was used. An organic electroluminescent device obtained by vacuum-depositing '-(2-pyridyl) -1,1': 4 ', 1''-terphenyl was prepared and measured in the same manner as in Test Example-14. The evaluation results of the fabricated devices are shown in the table below.

Reference example-2
Instead of the electron transport layer 5 of Test Example-14, 2,4-diphenyl-6- [4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 described in Patent No. WO20081299912 An organic electroluminescent device obtained by vacuum-depositing ″ -terphenyl-5′-yl] -1,3,5-triazine (see the following formula ETL-1) was prepared and measured in the same manner as in Test Example-14. The evaluation results of the fabricated devices are shown in the table below.

Test Example-17 (Example)
The thickness of the hole injection layer 2 in Test Example-14 was changed to 65 nm, the thickness of the hole transport layer 3HTL was changed to 10 nm, and the light emitting layer 4 was changed to 954 for EML-1 and EML-2 (shown in Chemical Formula 53): The thickness of the film was 25 nm at a ratio of 46 (mass%), and instead of the

electron transport layer

5, 4,4 ″ -di (2-pyridyl) -4 ′-[4- (2 -Pyridyl) phenyl] -1,1 ': 2', 1 ''-terphenyl was vacuum-deposited with a cathode layer 6Liq having a thickness of 0.5 nm to produce an organic electroluminescent device in the same manner as in Test Example-14 And measured. The measured value evaluation results of the fabricated devices are shown in the table below. Further, the 20% luminance deterioration time during continuous lighting of this element was 105 hours.

Reference Example-3
Instead of the electron transport layer 5 in Test Example-17, 1,3,5-tri (2,2′-bipyridin-5-yl) benzene (see the following formula ETL-2) described in Patent No. WO2009107651 is vacuum deposited. The produced organic electroluminescent device was produced and measured in the same manner as in Test Example-17. The evaluation results of the fabricated devices are shown in the table below. Further, the luminance 20% deterioration time during continuous lighting of this element was 48 hours.

The thin film comprising the compound (1) or (1) ′ of the present invention has high thin film stability, heat resistance, electron transport properties, hole blocking ability, redox resistance, water resistance, oxygen resistance, electron injection properties, etc. Therefore, it can be suitably used as an organic electroluminescent element material, particularly as an electron transporting material. Further, the compound (1) or (1) ′ of the present invention has a wide energy gap and triplet energy, and can be used in combination with a fluorescent or phosphorescent organic electroluminescent material. In addition, the compound (1) or (1) ′ of the present invention can be used for a light-emitting host layer and the like in addition to the electron transport layer because of its characteristics. Moreover, it can be used even if it mixes or laminates with another compound as an electron carrying layer. Furthermore, this compound has high solubility, and can be used for coating elements in addition to vapor deposition. From these effects, these elements are expected to have significant effects such as suppression of battery consumption by reducing power consumption, improvement of product life by extending life, and reduction of burden on the drive circuit.
The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2012-287908 filed on Dec. 28, 2012 are cited here as disclosure of the specification of the present invention. Incorporated.

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

A 1,2,4-tris-substituted benzene compound represented by the general formula (1) or (1) ′.

(Where
Ar 1 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, An ester group or an ester alkyl group, or an optionally substituted fluorine atom).
Ar 2 in formula (1) is a monovalent nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or fluorine). In formula (1) ′, a divalent nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, An ester group or an ester alkyl group, or an optionally substituted fluorine atom).
Ar 3 may be substituted with a nitrogen-containing heteroaromatic group having 3 to 17 carbon atoms (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). ) Or a substituent represented by —Ar 4 —Ar 5 .
Ar 4 is a nitrogen-containing heteroarylene group having 3 to 17 carbon atoms (which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). To express.
Ar 5 is an aromatic hydrocarbon group having 6 to 18 carbon atoms, pyridyl group, pyrimidyl group, or pyrazyl group (these groups are alkyl groups having 1 to 8 carbon atoms, alkoxy groups, alkoxyalkyl groups, ester groups or esters). An alkyl group or a fluorine atom which may be substituted).
Note that at least one of Ar 1 , Ar 2 , and Ar 3 is a pyridyl group, a pyrimidyl group, or a condensed ring group having 6 to 17 carbon atoms including a pyridine skeleton or a pyrimidine skeleton (these groups have a carbon number of 1 To 8 alkyl groups, alkoxy groups, alkoxyalkyl groups, ester groups or ester alkyl groups, or a fluorine atom, which may be substituted.
R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a substituent having 1 to 4 carbon atoms, and R 1 and R 2 , R 3 and R 4 , or R 1 and R 2 and R Both 3 and R 4 may be linked together to form an alicyclic or aromatic ring.
m represents 0 or 1.
n represents 0, 1, or 2.
Y 1 represents a divalent substituent represented by the following general formula (A), and Y 2 is a monovalent substituent represented by the following general formula (A) in formula (1) independently of Y 1. In the formula (1) ′, a substituent represented by the following general formula (A) ′ is represented.

(In formulas (A) and (A) ′, X 1 , X 2 and X 3 each independently represent CH or a nitrogen atom, and at least one represents CH.)
R 5 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group, or an ester alkyl group, a hydrogen atom, a fluorine atom, or a counter electron.
Note that the total number of pyridyl groups and pyridylene groups, the total number of pyrimidyl groups and pyrimidylene groups, and the total number of pyrazyl groups and pyrazylene groups in the structure are each independently 0, 1 2, or 3.
In addition, each hydrogen atom in the formula may independently be a deuterium atom.
The 1,2,4-tris-substituted benzene compound according to claim 1 represented by the general formula (1).
Ar 2 is a pyrimidyl group, or a condensed ring group having 6 to 17 carbon atoms including a pyridine skeleton or a pyrimidine skeleton (these groups are monovalent or divalent, each independently an alkyl group having 1 to 8 carbon atoms) The 1,2,4-tris-substituted benzene compound according to claim 1 or 2, which may be substituted with an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom.
Ar 1 and Ar 2 are each independently a pyridyl group, a pyrimidyl group, or a condensed ring group having 6 to 17 carbon atoms including a pyridine skeleton or a pyrimidine skeleton (these groups are monovalent or divalent, and each independently Or an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom, which may be substituted). 1,2,4-tris-substituted benzene compound.
Ar 1 and Ar 2 are each independently a pyridyl group, a pyrimidyl group, or a condensed ring group having 6 to 9 carbon atoms including a pyridine skeleton or a pyrimidine skeleton (these groups are monovalent or divalent, each independently And optionally substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). 1,2,4-tris-substituted benzene compound.
The 1,2,4-tris-substituted benzene compound according to any one of claims 1 to 5, wherein Ar 1 and Ar 2 are the same substituent regardless of the difference between monovalent and divalent.
2. Ar 2 is an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a monovalent or divalent pyridyl group optionally substituted with a fluorine atom. The 1,2,4-tris-substituted benzene compound according to any one of 1 to 6.
Ar 3 may be substituted with a nitrogen-containing heteroaromatic group having 4 to 11 carbon atoms (an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). ) Or —Ar 4 —Ar 5 , and Ar 4 is a nitrogen-containing heteroarylene group having 4 to 12 carbon atoms (an alkyl group, alkoxy group, alkoxyalkyl group, ester having 1 to 8 carbon atoms) Ar 5 is an aromatic hydrocarbon group having 6 to 18 carbon atoms, a pyridyl group, a pyrimidyl group, or a pyrazyl group (which may be substituted with a fluorine atom or an ester alkyl group). Each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl. Group or 1,2,4-tris-substituted benzene compound according to any one of claims 1 to 7, also may) be substituted by a fluorine atom.
Ar 5 is a phenyl group or a pyridyl group (these groups may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group, or a fluorine atom). The 1,2,4-tris-substituted benzene compound according to any one of claims 1 to 8.
1) R 1 , R 2 , R 3 and R 4 are hydrogen atoms, 2) both R 1 and R 2 are alkenyl groups having 2 to 4 carbon atoms and bonded to each other to form an aromatic ring Or 3) R 1 , R 2 , R 3 , and R 4 are all alkenyl groups having 2 to 4 carbon atoms, and R 1 and R 2 , and R 3 and R 4 are connected to each other to form an aromatic ring The 1,2,4-tris-substituted benzene compound according to any one of claims 1 to 9, wherein
The 1,2,4-tris-substituted benzene compound according to any one of claims 1 to 10, wherein n is 0 or 1.
The 1,2,4-tris-substituted benzene compound according to any one of claims 1 to 10, wherein m is 1.
A method for producing a 1,2,4-tris-substituted benzene compound represented by the general formula (1) or (1) 'according to claim 1, wherein the compound is present in the presence of a metal catalyst or in the presence of a metal catalyst and a base. The compound represented by the general formula (3), (4) or (4) ′, and (5) is converted to the compound represented by the general formula (2) in one step, two steps, or three steps. A production method characterized by carrying out a coupling reaction (when the reaction is carried out in two steps or three steps, the order of the coupling reaction may be any combination).

(For each symbol in formulas (1), (1) ′, (2), (3), (4), (4) ′, and (5), the same as defined in claim 1 is the same as that) And Z 1 , Z 2 and Z 3 each independently represent a leaving group, and M 1 , M 2 and M 3 each independently represent a metal group, a boronic acid group or a boronic acid ester group.)
A method for producing a 1,2,4-tris-substituted benzene compound represented by the general formula (1) or (1) 'according to claim 1, represented by the general formula (7) or (7)' A production method comprising converting a substituent W of a compound into Ar 3 by a heterocycle formation reaction.

(For each symbol in the formulas (1) and (7), what is defined in claim 1 is the same as above, and W represents a substituent necessary for carrying out the heterocycle formation reaction.)
A method for producing a 1,2,4-tris-substituted benzene compound represented by the general formula (1) or (1) 'according to claim 1, wherein the compound is present in the presence of a metal catalyst or in the presence of a metal catalyst and a base. The compound represented by the general formula (3) and the compound represented by the formula (4) or (4) ′ is coupled to the compound represented by the general formula (6) in one step or two steps (reacted in two steps). The order of the coupling reaction may be any combination) to produce a compound represented by general formula (7) or (7) ′, and further represented by general formula (7) The manufacturing method characterized by converting the substituent represented by W of the compound to Ar 3 by a hetero ring formation reaction.
(Each symbol in the formulas (1), (1) ′, (3), (4), (4) ′, (6), (7), (7) ′) is defined in claim 1 Are the same, Z 1 and Z 2 each independently represent a leaving group, M 1 and M 2 each independently represent a metal group, a boronic acid group, or a boronic ester group, and W is It represents a substituent necessary for carrying out the heterocycle formation reaction.)
An organic electroluminescent device comprising a 1,2,4-tris-substituted benzene compound represented by the general formula (1) or (1) 'according to claim 1.
An organic electroluminescent device comprising a 1,2,4-tris-substituted benzene compound represented by the general formula (1) according to claim 2.
The organic electroluminescent element according to claim 16 or 17, comprising a 1,2,4-tris-substituted benzene compound in the electron transport layer.