JP6515684B2 - Benzoquinazoline compound, method for producing the same, and use thereof - Google Patents

Description

  The present invention provides a benzoquinazoline compound represented by the general formula (1-1) and the general formula (1-2) for providing a highly efficient organic electroluminescent device excellent in drivability and light emission characteristics, and a method for producing the same It is about

  The organic electroluminescent element has a structure in which a light emitting layer containing a light emitting material is sandwiched between a hole transporting layer and an electron transporting layer, and further, an anode and a cathode are attached to the outside. It is a self-emission device that utilizes the light emission phenomenon (fluorescence or phosphorescence) when the excitons generated by electron recombination are deactivated. Since it is a self-luminous type, it has excellent visibility, and since it is a completely solid element, it is easy to handle and manufacture. Moreover, since it is a thin film type element, it attracts attention from a viewpoint of space saving, portability, etc., and is applied to a display, illumination, etc. At present, organic electroluminescent devices have begun to be used commercially for various applications, but there is a demand for further improvement of luminous efficiency, reduction of driving voltage and prolongation of life for energy saving.

  In order to make the organic electroluminescent element have high efficiency, low voltage drive, and long lifetime, it is necessary to efficiently inject and transport holes and electrons to the light emitting layer for recombination. In this regard, there has been a demand for improvement of each material constituting an organic electroluminescent device, in particular, an electron transporting material.

  Patent Document 1 discloses an electron transport layer host material capable of obtaining an organic EL device having a long light emission lifetime and a low driving voltage, and a device using the same. However, in order to use this material for an organic electroluminescent device, a doped material is essential, and when it is used as a single electron transport layer which does not contain a doped material, the device has a high driving voltage. In addition, the luminous efficiency of the device is low, and improvement has been demanded.

  Although the electron transport material for providing an organic electroluminescent element with sufficient luminous efficiency is disclosed by patent document 2, the organic electroluminescent element using the benzoquinazoline compound disclosed by the said document is benzoquinazoline. There is a problem that it is difficult to lower the driving voltage due to the influence of the substituent at the 2nd position.

WO 2006/104118 WO 2013/180376

  Organic electroluminescent devices are used in various display devices, but in order to put a large display and illumination into practical use, more efficient light emission is required. An object of the present invention is to provide an electron transporting material which is excellent in the life characteristics of the device and is further excellent in the luminous efficiency of the device as compared with the conventionally known electron transporting material for an organic electroluminescent device.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have found that the organic electroluminescent device using the benzoquinazoline compound shown in the present invention as the electron transport layer uses a conventionally known material for the electron transport layer. The inventors have found that the driving voltage is lower, the light emission efficiency is improved, and the life becomes longer as compared with the organic electroluminescent device, and the present invention is completed.

  That is, the present invention relates to benzoquinazoline compounds represented by the following general formula (1-1) and general formula (1-2) (hereinafter, also referred to as “compound (1-1)” and “compound (1-2)”) , Its manufacturing method, and its application.

(In the formula,
Ar ¹¹ and Ar ^{21 each} represent an aromatic hydrocarbon group having 6 to 12 carbon atoms (a methyl group, a methoxy group, a pyridyl group, a pyrimidyl group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group , An ester group or an ester alkyl group).
Each of Ar ¹² , Ar ¹³ , Ar ²² and Ar ²³ independently represents a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with a C 6-18 aromatic hydrocarbon group, or a benzene ring and / or An aromatic group consisting of only a 6-membered ring in which 2 to 6 pyridine rings are linked and / or fused {these groups are methyl, methoxy, fluorine atom, pyrimidyl group (the pyrimidyl group is methyl, carbon And at least one substituent selected from the group consisting of an alkyl group of 2 to 10 and an aromatic hydrocarbon group of 6 to 18 carbon atoms), or an alkyl group of 2 to 10 carbon atoms, And R 4 represents an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.
^{R 11, R 12, R 13} , R 14, R 15, R 16, R 21, R 22, R 23, R 24, R 25 and ^{R 26,} each independently, a hydrogen atom, a methyl group, a methoxy group And a phenyl group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.
Each hydrogen atom in the formula may be independently a deuterium atom. )

  The compound (1-1) and the compound (1-2) of the present invention are useful as materials for fluorescent or phosphorescent organic electroluminescent devices because they have good charge injection and transport properties, and in particular, an electron transport material, It can be used as a host material. An organic electroluminescent device having an electron transporting layer containing the compound (1-1) and the compound (1-2) of the present invention is excellent in low driving voltage as compared with an organic electroluminescent device using a general-purpose electron transporting material, It has excellent luminous efficiency and long life.

  The band gap of the compound (1-1) and the compound (1-2) of the present invention is 3.0 eV or more, and the three primary colors (red: 1.9 eV, green: 2.4 eV, blue: A material having a wide band gap sufficient to confine energy of each color of 2.8 eV). Therefore, application to various elements such as a display element of single color, a color display element of three primary colors, and a white element such as a lighting application is possible. Since the compound (1-1) and the compound (1-2) of the present invention also have high triplet energy, application to phosphorescent applications is sufficiently possible. Furthermore, since the solubility can be controlled by changing the substituent, not only vapor deposition elements but also application to coating elements are possible.

It is a cross-sectional schematic diagram of the organic electroluminescent element produced by test example-1.

  Hereinafter, the present invention will be described in detail.

Ar ¹¹ and Ar ^{21 each} represent an aromatic hydrocarbon group having 6 to 12 carbon atoms (a methyl group, a methoxy group, a pyridyl group, a pyrimidyl group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group , An ester group or an ester alkyl group).

  Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include, but are not limited to, phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenyl group, 3-biphenyl group, or 4- for example A biphenyl group etc. are mentioned.

  Although it does not specifically limit as a pyridyl group, For example, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group is mentioned.

  Although it does not specifically limit as a pyrimidyl group, For example, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group is mentioned.

The alkyl group having 2 to 10 carbon atoms, alkoxy group, alkoxyalkyl group, ester group or ester alkyl group is not particularly limited, and examples thereof include ethyl group (-Et) and n-propyl group (n- Pr), i-propyl group (i-Pr), n-butyl group (n-Bu), t-butyl group (t-Bu), pentyl (-Pent), hexyl group (-Hex), heptyl group (- Hept), octyl group (-Oct) (above, alkyl group having 2 to 10 carbon atoms), ethoxy group, n-propyloxy group, i-propyloxy group, n-butyloxy group, t-butyloxy group, pentyloxy group , Hexyloxy group, heptyloxy group, octyloxy group (above, alkoxy group having 2 to 10 carbon atoms), methoxymethyl group, methoxyethyl group, methoxy propy group Group, methoxybutyl group, methoxyhexyl group, methoxyheptyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, pentyloxypropyl group (above, alkyl alkoxy group having 2 to 10 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, having 2 to 10 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 2 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 ( or, an ester group having 2 to 10 carbon atoms) and the like.

The substituent represented by Ar ¹¹ and Ar ²¹ is not particularly limited, and examples thereof include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, and 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-methylphenyl group, 2-ethyl-6-methylphenyl group Group, 3-ethyl-2-methylphenyl group, 3-ethyl-4-methylphenyl group, 3-ethyl-5-methylphenyl group, 3-ethyl-6-methylphenyl group Group, 4-ethyl-2-methylphenyl group, 4-ethyl-3-methylphenyl group, 2-hexylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 4-hexyl-2-methylphenyl group, 4-hexyl-3-ethylphenyl group, 4-hexyloxy-2-propylphenyl group, 4-hexyloxy-3-butylphenyl group, 3-ethoxyethyl-5-methylphenyl group, 3-ethoxyethyl-6- Methylphenyl group, 2-methyl ester phenyl group, 3-methyl ester phenyl group, 4-methyl ester phenyl group, 2-hexyl ester phenyl group, 3-hexyl ester phenyl group, 4-hexyl ester phenyl group, 2-(-) 2-pyridyl) phenyl group, 3- (2-pyridyl) phenyl group, 4- (2-pyridyl) phenyl group 3,5-bi (2-pyridyl) phenyl group, 2- (3-pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 3,5-bi ( 3-pyridyl) phenyl group, 2- (4-pyridyl) phenyl group, 3- (4-pyridyl) phenyl group, 4- (4-pyridyl) phenyl group, 3,5-bi (4-pyridyl) phenyl group, 2- (2-Pyrimidyl) phenyl group, 3- (2-Pyrimidyl) phenyl group, 4- (2-Pyrimidyl) phenyl group, 2- (4-Pyrimidyl) phenyl group, 3- (4-Pyrimidyl) phenyl group, 4- (4-Pyrimidyl) phenyl group, 2- (5-Pyrimidyl) phenyl group, 3- (5-Pyrimidyl) phenyl group, 4- (5-Pyrimidyl) phenyl group, 2-fluorophenyl group, 3-fluorophenyl Group 4- Fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, perfluorophenyl group, 1-naphthyl group, 2-naphthyl group , 2-methylnaphthalen-1-yl group, 3-methylnaphthalen-1-yl group, 4-methylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 6-methylnaphthalen-1-yl group 1-methylnaphthalen-2-yl group, 3-methylnaphthalen-2-yl group, 4-methylnaphthalen-2-yl group, 5-methylnaphthalen-2-yl group, 6-methylnaphthalen-2-yl group , 2-hexylnaphthalen-1-yl group, 3-hexyloxynaphthalen-1-yl group, 4-methoxyethylnaphthalen-1-yl group, 5-hexy Ester naphthalen-1-yl group, 6-pentoxynaphthalen-1-yl group, 1-methoxyethyl naphthalen-2-yl group, 3-pentyl naphthalen-2-yl group, 4-pentoxy naphthalen-2-yl group 5-methoxyethyl naphthalen-2-yl group, 6-butyl naphthalen-2-yl group, 3- (2-pyridyl) naphthalen-1-yl group, 4- (2-pyridyl) naphthalen-1-yl group, 3- (3-Pyridyl) naphthalen-1-yl group, 4- (3-pyridyl) naphthalen-1-yl group, 3- (4-pyridyl) naphthalen-1-yl group, 4- (4-pyridyl) naphthalene -1-yl group, 4- (2-pyridyl) naphthalen-2-yl group, 6- (2-pyridyl) naphthalen-2-yl group, 7- (2-pyridyl) naphthalen-2-yl group, 4- ( -Pyridyl) naphthalen-2-yl group, 6- (3-pyridyl) naphthalen-2-yl group, 7- (3-pyridyl) naphthalen-2-yl group, 4- (4-pyridyl) naphthalen-2-yl group Group, 6- (4-pyridyl) naphthalen-2-yl group, 7- (4-pyridyl) naphthalen-2-yl group, 3- (2-pyrimidyl) naphthalen-1-yl group, 4- (2-pyrimidyl) ) Naphthalen-1-yl group, 3- (4-pyrimidyl) naphthalen-1-yl group, 4- (4-pyrimidyl) naphthalen-1-yl group, 3- (5-pyrimidyl) naphthalen-1-yl group, 4- (5-Pyrimidyl) naphthalen-1-yl group, 4- (2-pyrimidyl) naphthalen-2-yl group, 6- (2-pyrimidyl) naphthalen-2-yl group, 7- (2-pyrimidyl) naphthalene -2-yl Group, 4- (4-pyrimidyl) naphthalen-2-yl group, 6- (4-pyrimidyl) naphthalen-2-yl group, 7- (4-pyrimidyl) naphthalen-2-yl group, 4- (5-pyrimidyl) ) Naphthalen-2-yl group, 6- (5-pyrimidyl) naphthalen-2-yl group, 7- (5-pyrimidyl) naphthalen-2-yl group, 2-fluoronaphthalen-1-yl group, 3-fluoronaphthalene -1-yl group, 4-fluoronaphthalen-1-yl group, 5-fluoronaphthalen-1-yl group, 6-fluoronaphthalen-1-yl group, 1-fluoronaphthalen-2-yl group, 3-fluoronaphthalene -2-yl group, 4-fluoronaphthalen-2-yl group, 5-fluoronaphthalen-2-yl group, 6-fluoronaphthalen-2-yl group, perfluoronaphthalene-1 Group, perfluoronaphthalen-2-yl group, 3-biphenyl group, 4-biphenyl group, 2-methylbiphenyl-3-yl group, 4-methylbiphenyl-3-yl group, 5-methylbiphenyl-3-yl group Group, 6-methylbiphenyl-3-yl group, 2'-methylbiphenyl-3-yl group, 3'-methylbiphenyl-3-yl group, 4'-methylbiphenyl-3-yl group, 2,6-dimethyl Biphenyl-3-yl group, 2 ′, 6′-dimethylbiphenyl-3-yl group, 2-methylbiphenyl-4-yl group, 3-methylbiphenyl-4-yl group, 2′-methylbiphenyl-4-yl group Group, 3'-methylbiphenyl-4-yl group, 4'-methylbiphenyl-4-yl group, 2,6-dimethylbiphenyl-4-yl group, 2 ', 6'-dimethylbiphenyl-4-yl group, 2-hexi Biphenyl-3-yl group, 4-hexyloxybiphenyl-3-yl group, 5-ethylethoxyethylbiphenyl-3-yl group, 6-hexyl ester biphenyl-3-yl group, 2′-pentylbiphenyl-3-yl group Group, 3'-pentyloxybiphenyl-3-yl group, 4'-propyloxymethyl-3-yl group, 2-butylbiphenyl-4-yl group, 3-butoxybiphenyl-4-yl group, 2'-ethoxy Methylbiphenyl-4-yl group, 3′-butyl ester biphenyl-4-yl group, 4′-pentylbiphenyl-4-yl group, 3 ′-(2-pyridyl) biphenyl-3-yl group, 3 ′-( 3-pyridyl) biphenyl-3-yl group, 3 '-(4-pyridyl) biphenyl-3-yl group, 4'-(2-pyridyl) biphenyl-3-yl group, 4 '-(3-pyridyl group ) Biphenyl-3-yl group, 4 ′-(4-pyridyl) biphenyl-3-yl group, 3 ′-(2-pyridyl) biphenyl-4-yl group, 3 ′-(3-pyridyl) biphenyl-4- Yl, 3 '-(4-pyridyl) biphenyl-4-yl, 4'-(2-pyridyl) biphenyl-4-yl, 4 '-(3-pyridyl) biphenyl-4-yl, 4' -(4-pyridyl) biphenyl-4-yl group, 3 '-(2-pyrimidyl) biphenyl-3-yl group, 3'-(4-pyrimidyl) biphenyl-3-yl group, 3 '-(5-pyrimidyl group ) Biphenyl-3-yl group, 4 ′-(2-pyrimidyl) biphenyl-3-yl group, 4 ′-(4-pyrimidyl) biphenyl-3-yl group, 4 ′-(5-pyrimidyl) biphenyl-3- Yl, 3 '-(2-pyrimidyl) biphenyl-4-yl, '-(4-Pyrimidyl) biphenyl-4-yl group, 3'-(5-pyrimidyl) biphenyl-4-yl group, 4 '-(2-pyrimidyl) biphenyl-4-yl group, 4'-(4-) Pyrimidyl) biphenyl-4-yl group, 4 ′-(5-pyrimidyl) biphenyl-4-yl group, 2-fluorobiphenyl-3-yl group, 4-fluorobiphenyl-3-yl group, 5-fluorobiphenyl-3 -Yl, 6-fluorobiphenyl-3-yl, 2'-fluorobiphenyl-3-yl, 3'-fluorobiphenyl-3-yl, 4'-fluorobiphenyl-3-yl, 2, 6 -Difluorobiphenyl-3-yl group, 2 ', 6'-difluorobiphenyl-3-yl group, 2-fluorobiphenyl-4-yl group, 3-fluorobiphenyl-4-yl group, 2'-fluorobiphenyl 4-yl group, 3'-fluorobiphenyl-4-yl group, 4'-fluorobiphenyl-4-yl group, 2,6-difluorobiphenyl-4-yl group, 2 ', 6'-difluorobiphenyl-4- And the like.

As for Ar ¹¹ and Ar ²¹ , an aromatic hydrocarbon group having 6 to 12 carbon atoms (a methyl group, a methoxy group, a pyridyl group, a pyrimidyl group, a fluorine atom, or a carbon number) in terms of good performance as an organic electroluminescent element material It is preferable that it may be substituted by 2-10 alkyl groups or alkoxy groups.

  The preferred substituent is a phenyl group, a naphthyl group or a biphenyl group (these groups may be substituted with a methyl group, a methoxy group, a pyridyl group, a pyrimidyl group or a fluorine atom). preferable.

  Further, a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 1-naphthyl group, 2-naphthyl group, 3-biphenyl group, 4-biphenyl group, 2,6-dimethylbiphenyl- 3-yl group, 2,6-dimethylbiphenyl-4-yl group, 2 ′, 6′-dimethylbiphenyl-3-yl group, 2 ′, 6′-dimethylbiphenyl-4-yl group, 3- (2- (2-) Pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 3- (4-pyridyl) phenyl group, 4- (2-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 4- (4-pyridyl) phenyl group More preferably, it is pyridyl) phenyl group, 3- (2-pyrimidyl) phenyl group or 4- (2-pyrimidyl) phenyl group.

  Further, among these substituents, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-biphenyl group, 4-biphenyl group, 1-naphthyl group, or 2-naphthyl group It is more preferable that

Further, for Ar ¹¹ and Ar ²¹ , a phenyl group, a naphthyl group or a biphenyl group (these groups are a methyl group, a methoxy group, a pyridyl group, a pyrimidyl group, a fluorine group, It is preferable that it may be substituted with an atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.

Each of Ar ¹² , Ar ¹³ , Ar ²² and Ar ²³ independently represents a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with a C 6-18 aromatic hydrocarbon group, or a benzene ring and / or An aromatic group consisting of only a 6-membered ring in which 2 to 6 pyridine rings are linked and / or fused {these groups are methyl, methoxy, fluorine atom, pyrimidyl group (the pyrimidyl group is methyl, carbon And at least one substituent selected from the group consisting of an alkyl group of 2 to 10 and an aromatic hydrocarbon group of 6 to 18 carbon atoms), or an alkyl group of 2 to 10 carbon atoms, And R 4 represents an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.

As the pyridyl group and the pyrimidyl group, the same substituents as those exemplified for Ar ¹¹ and Ar ²¹ can be exemplified.

  The pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms is not particularly limited, and examples thereof include a 4-phenylpyrimidin-2-yl group and a 5-phenylpyrimidin-2-yl group, 2-phenylpyrimidin-4-yl group, 6-phenylpyrimidin-4-yl group, 2-phenylpyrimidin-5-yl group, 4,6-diphenylpyrimidin-2-yl group, 4-naphthylpyrimidin-2-yl group Group, 5-naphthylpyrimidin-2-yl group, 2-naphthylpyrimidin-4-yl group, 6-naphthylpyrimidin-4-yl group, 2-naphthylpyrimidin-5-yl group, 6-naphthyl-4-phenylpyrimidine -2-yl group, 4-anthracylpyrimidin-2-yl group, 5-anthracylpyrimidin-2-yl group, 2-anthracyl pyrimidine-4- Group, 6-anthracylpyrimidin-4-yl group, 2-anthracylpyrimidin-5-yl group, 4-phenanthrylpyrimidin-2-yl group, 5-phenanthrylpyrimidin-2-yl group, 2 -Phenanthrylpyrimidin-4-yl group, 6-phenanthrylpyrimidin-4-yl group, 2-phenanthrylpyrimidin-5-yl group, 4-pyrenylpyrimidin-2-yl group, 5-pyrenyl group Pyrimidin-2-yl group, 2-pyrenylpyrimidin-4-yl group, 6-pyrenylpyrimidin-4-yl group, 2-pyrenylpyrimidin-5-yl group and the like can be mentioned.

  Among these, a pyrimidyl group substituted with a phenyl group, a biphenyl group, or a condensed aromatic hydrocarbon group having 10 to 18 carbon atoms consisting only of a 6-membered ring, from the viewpoint of good performance as an organic electroluminescent element material The substituent is not particularly limited, and is more preferably, for example, a phenyl group, a biphenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, or a pyrimidyl group substituted with a pyrenyl group.

  As for the preferred substituents, 5-phenylpyrimidin-2-yl group, 4,6-diphenylpyrimidin-2-yl group, 5-naphthylpyrimidin-2-yl group, 4,6-dinaphthylpyrimidin-2-yl group The groups, 5-phenanthrylpyrimidin-2-yl group, 5-anthracylpyrimidin-2-yl group, and 5-pyrenylpyrimidin-2-yl group are more preferable.

  Moreover, among these substituents, 5-phenylpyrimidin-2-yl group, 4,6-diphenylpyrimidin-2-yl group, and 4,6-dinaphthylpyrimidin-2-yl group are more preferable.

  The aromatic group consisting of only a 6-membered ring in which 2 to 6 benzene rings and / or pyridine rings are linked and / or fused is not particularly limited, but, for example, the following (A1) to (A186) The substituent represented by can be illustrated (* represents a connection part).

Among these, only a 6-membered ring in which 2 to 6 benzene rings and / or pyridine rings are linked and / or fused (condensed rings are 4 or less rings) from the viewpoint of good performance as an organic electroluminescent element material The aromatic group is preferably composed of 2 to 6 benzene rings and / or pyridine rings linked and / or fused (condensed rings are 4 or less rings, and linkage is up to 4) 6 It is more preferable that it is an aromatic group consisting only of member rings.

  About the said preferable substituent, (A1)-(A19), (A21), (A28), (A30), (A32), (A36), (A38), (A40), (A42)-(A60) , (A63), (A64), (A66) to (A74), (A76), (A78), (A80), (A82), (A84), (A86) to (A124), (A129), (A A130), (A145) to (A154), and (A156) to (A179) are more preferable.

  Among these substituents, (A1) to (A19), (A28), (A30), (A32), (A36), (A38), (A40), (A42) to (A44), (A44) A47), (A49), (A51), (A54) to (A60), (A63), (A66), (A67), (A72), (A73), (A86) to (A100), (A103) -(A118), (A145)-(A150), (A156)-(A176) are more preferable.

  The pyrimidyl group having at least one substituent selected from the group consisting of a methyl group, an alkyl group having 2 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms is not particularly limited. For example, 4-methylpyrimidin-2-yl group, 5-methylpyrimidin-2-yl group, 2-methylpyrimidin-4-yl group, 6-methylpyrimidin-4-yl group, 2-methylpyrimidin-5-yl group Group, 4,6-dimethylpyrimidin-2-yl group, 4-ethylpyrimidin-2-yl group, 5-ethylpyrimidin-2-yl group, 2-ethylpyrimidin-4-yl group, 6-ethylpyrimidin-4 group -Yl, 2-ethylpyrimidin-5-yl, 4,6-diethylpyrimidin-2-yl, 4-propylpyrimidin-2-yl, 5-butylpyrimidin-2-yl Group, 2-pentylpyrimidin-4-yl group, 6-hexylpyrimidin-4-yl group, 2-octylpyrimidin-5-yl group, 4-phenylpyrimidin-2-yl group, 5-phenylpyrimidin-2-yl group -Yl, 2-phenylpyrimidin-4-yl, 6-phenylpyrimidin-4-yl, 2-phenylpyrimidin-5-yl, 4,6-diphenylpyrimidin-2-yl, 4-naphthylpyrimidine- 2-yl group, 5-naphthylpyrimidin-2-yl group, 2-naphthylpyrimidin-4-yl group, 6-naphthylpyrimidin-4-yl group, 2-naphthylpyrimidin-5-yl group, 6-naphthyl-4 -Phenylpyrimidin-2-yl group, 4,6-dinaphthylpyrimidin-2-yl group, 4-anthracylpyrimidin-2-yl group, 5-anthracyl Limidin-2-yl group, 2-anthracylpyrimidin-4-yl group, 6-anthracylpyrimidin-4-yl group, 2-anthracylpyrimidin-5-yl group, 4-phenanthrylpyrimidin-2-yl Group, 5-phenanthrylpyrimidin-2-yl group, 2-phenanthrylpyrimidin-4-yl group, 6-phenanthrylpyrimidin-4-yl group, 2-phenanthrylpyrimidin-5-yl group, 4-pyrenylpyrimidin-2-yl group, 5-pyrenylpyrimidin-2-yl group, 2-pyrenylpyrimidin-4-yl group, 6-pyrenylpyrimidin-4-yl group, 2-pyrenylpyrimidine- 5-yl group, 4-methyl-6-phenylpyrimidin-2-yl group and the like can be mentioned.

  Among these, a pyrimidyl group having at least one substituent selected from the group consisting of a methyl group and an aromatic hydrocarbon group having 6 to 18 carbon atoms is preferable from the viewpoint of good performance as an organic electroluminescent element material More preferred is a pyrimidyl group having at least one substituent selected from the group consisting of methyl group, biphenyl group, phenyl group, naphthyl group, anthracyl group, phenanthryl group, and pyrenyl group.

  As for the preferred substituents, 5-methylpyrimidin-2-yl group, 4,6-dimethylpyrimidin-2-yl group, 4-phenylpyrimidin-2-yl group, 5-phenylpyrimidin-2-yl group, 2 -Phenylpyrimidin-5-yl group, 4,6-diphenylpyrimidin-2-yl group, 5-naphthylpyrimidin-2-yl group, 6-naphthyl-4-phenylpyrimidin-2-yl group, 5-anthracyl pyrimidine -2-yl group, 5-phenanthrylpyrimidin-2-yl group, 5-pyrenylpyrimidin-2-yl group are more preferable.

  Further, among these substituents, 5-methylpyrimidin-2-yl group, 4,6-dimethylpyrimidin-2-yl group, 4-phenylpyrimidin-2-yl group, 5-phenylpyrimidin-2-yl group The 2-phenylpyrimidin-5-yl group, the 4,6-diphenylpyrimidin-2-yl group, and the 5-naphthylpyrimidin-2-yl group are more preferable.

As the alkyl group having 2 to 10 carbon atoms, the alkoxy group, the alkoxyalkyl group, the ester group or the ester alkyl group, the same substituents as those exemplified for Ar ¹¹ and Ar ²¹ can be exemplified.

The substituents represented by Ar ¹² , Ar ¹³ , Ar ²² and Ar ²³ are not particularly limited, but in addition to the substituents shown above, they are represented by the following (B1) to (B137) Can be exemplified (* represents a linking moiety).

Ar ¹² , Ar ¹³ , Ar ²² and Ar ²³ are each substituted by a phenyl group, a pyridyl group, a pyrimidyl group, or an aromatic hydrocarbon group having 6 to 18 carbon atoms in terms of good performance as a compound organic electroluminescent element material Or an aromatic group consisting of only a 6-membered ring in which 2 to 6 benzene rings and / or pyridine rings are linked and / or fused (these groups are methyl, methoxy, and having 2 to 2 carbon atoms) 10 alkyl group, alkoxy group having 2 to 10 carbon atoms, fluorine atom, or pyrimidyl group (wherein the pyrimidyl group is a group consisting of methyl group, phenyl group, biphenyl group, naphthyl group, anthracyl group, phenanthryl group, and pyrenyl group) And the like.) Which may be substituted with at least one substituent selected from

  Among the above-mentioned substituents, a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or 2 to 5 benzene rings and / or pyridine rings are linked and / or Or an aromatic group consisting of only a condensed six-membered ring {these groups are methyl, methoxy, alkyl having 2 to 10 carbons, alkoxy having 2 to 10 carbons, fluorine, or pyrimidyl ( The pyrimidyl group may be substituted by at least one substituent selected from the group consisting of methyl group, phenyl group, biphenyl group, naphthyl group, anthracyl group, phenanthryl group, and pyrenyl group) Is more preferable.

  Among these, a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or 2 to 4 benzene rings and / or pyridine rings are linked and / or fused Aromatic group consisting of only 6-membered rings {these groups are methyl group, methoxy group, alkyl group having 2 to 10 carbon atoms, alkoxy group having 2 to 10 carbon atoms, fluorine atom, or pyrimidyl group Is optionally substituted with at least one substituent selected from the group consisting of methyl, phenyl, biphenyl, naphthyl, anthracyl, phenanthryl and pyrenyl)} It is more preferable that

In addition, with respect to Ar ¹² , Ar ¹³ , Ar ²² and Ar ²³ , a phenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, a pyrenyl group, a pyridyl group and a pyrimidyl group are preferable because they have good performance as organic electroluminescent element materials of compounds. , Quinolyl group, isoquinolyl group, naphthyridyl group, benzoquinolyl group, phenanthridyl group, acridyl group, phenanthrolyl group, biphenyl group, terphenyl group, naphthylphenyl group, phenanthrylphenyl group, anthracylphenyl group, pyrenylphenyl group , Naphthylbiphenyl group, phenanthrylbiphenyl group, anthracylbiphenyl group, phenylnaphthyl group, binaphthyl group, phenanthrylnaphthyl group, anthracylnaphthyl group, phenylanthracyl group, phenylphenanthryl group, pyridyl phenyl group Group, pyridyl biphenyl group, pyridyl naphthyl group, pyridyl anthracyl group, pyridyl phenanthryl group, quinolyl phenyl group, quinolyl biphenyl group, quinolyl naphthyl group, quinolyl anthracyl group, quinolyl phenanthryl group, isoquino Rylphenyl group, isoquinolylbiphenyl group, isoquinolylnaphthyl group, isoquinolyl anthracyl group, isoquinolyl phenanthryl group, naphthyridyl phenyl group, naphthyridyl biphenyl group, benzoquinolyl phenyl group, phenanthridyl Phenyl group, acridyl phenyl group, phenanthrolyl phenyl group, phenyl pyridyl group, diphenyl pyridyl group, biphenyl pyridyl group, naphthyl pyridyl group, phenanthryl pyridyl group, anthracyl pyridyl group, phenyl quinolyl group, biphenyl Aryl group, phenylisoquinolyl group, biphenylisoquinolyl group, bipyridyl group, quinolylpyridyl group, isoquinolylpyridyl group, pyridylquinolyl group, pyridylisoquinolyl group, phenylbipyridyl group, bipyridylphenyl group, phenylpyridylphenyl group, phenyl Pyridyl naphthyl group, diphenyl pyridyl phenyl group, dinaphthyl pyridyl phenyl group, phenyl pyrimidyl group, diphenyl pyrimidyl group, biphenyl pyrimidyl group, naphthyl pyrimidyl group, phenanthryl pyrimidyl group, or anthracyl Pyrimidyl group {these groups are methyl group, methoxy group, fluorine atom, pyrimidyl group (where the pyrimidyl group is methyl group, alkyl group having 2 to 10 carbon atoms, and aromatic hydrocarbon having 6 to 18 carbon atoms) Less substituents selected from the group consisting of It may be substituted by one or two alkyl groups having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group}.

  The preferred substituents described above include phenyl group, naphthyl group, anthracyl group, phenanthryl group, pyrenyl group, pyridyl group, pyrimidyl group, quinolyl group, isoquinolyl group, naphthyridyl group, benzoquinolyl group, phenanthridyl group, acridyl group, phenanthrolyl group. Group, biphenyl group, terphenyl group, naphthylphenyl group, phenanthrylphenyl group, anthracylphenyl group, pyrenylphenyl group, naphthylbiphenyl group, phenanthrylbiphenyl group, anthracylbiphenyl group, phenylnaphthyl group, binaphthyl group Phenanthrylnaphthyl group, anthracylnaphthyl group, phenyl anthracyl group, phenylphenanthryl group, pyridylphenyl group, pyridylbiphenyl group, pyridylnaphthyl group, pyridyl anthracyl group, pyridin Phenanthryl group, quinolyl phenyl group, quinolyl biphenyl group, quinolyl naphthyl group, quinolyl anthracyl group, quinolyl phenanthryl group, isoquinolyl phenyl group, isoquinolyl biphenyl group, isoquinolyl naphthyl group, isoquinolyl Anthracyl group, isoquinolyl phenanthryl group, naphthyridyl phenyl group, naphthyridyl biphenyl group, benzoquinolyl phenyl group, phenanthridyl phenyl group, acridyl phenyl group, phenanthrolyl phenyl group, phenyl pyridyl group, Diphenyl pyridyl, biphenyl pyridyl, naphthyl pyridyl, phenanthryl pyridyl, anthracyl pyridyl, phenyl quinolyl, biphenyl quinolyl, phenyl iso quinolyl, biphenyl iso quinolyl, bipyridyl, quinolyl Lysyl group, isoquinolyl pyridyl group, pyridyl quinolyl group, pyridyl isoquinolyl group, phenyl bipyridyl group, bipyridyl phenyl group, phenyl pyridyl phenyl group, phenyl pyridyl naphthyl group, diphenyl pyridyl phenyl group, di naphthyl pyridyl phenyl group, phenyl pyrimi Zyl group, diphenyl pyrimidyl group, biphenyl pyrimidyl group, naphthyl pyrimidyl group, phenanthryl pyrimidyl group, or anthracyl pyrimidyl group {these groups are methyl group, methoxy group, fluorine atom A pyrimidyl group (the pyrimidyl group may have at least one substituent selected from the group consisting of a methyl group, a phenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a pyrenyl group), or a carbon number 2-10 alkyl group, alkoxy group More preferably an alkoxyalkyl group, an ester group or an ester alkyl.

  Furthermore, phenyl group, naphthyl group, anthracyl group, phenanthryl group, pyrenyl group, pyridyl group, pyrimidyl group, quinolyl group, isoquinolyl group, naphthyridyl group, benzoquinolyl group, phenanthridyl group, acridyl group, phenanthrolyl group, biphenyl group, ter Phenyl group, naphthylphenyl group, phenanthrylphenyl group, anthracylphenyl group, phenylnaphthyl group, phenylanthracyl group, pyridylphenyl group, pyridylbiphenyl group, pyridylnaphthyl group, quinolylphenyl group, quinolylbiphenyl group, iso Quinolyl phenyl group, isoquinolyl biphenyl group, naphthyridyl phenyl group, naphthyridyl biphenyl group, benzoquinolyl phenyl group, phenanthridyl phenyl group, acridyl phenyl group, phenanthrolyl phenyl group Group, phenyl pyridyl group, diphenyl pyridyl group, biphenyl pyridyl group, naphthyl pyridyl group, phenyl quinolyl group, phenyl isoquinolyl group, bipyridyl group, phenyl bipyridyl group, bipyridyl phenyl group, phenyl pyridyl phenyl group, diphenyl pyridyl phenyl group, Phenyl pyrimidyl group, diphenyl pyrimidyl group, biphenyl pyrimidyl group or naphthyl pyrimidyl group {these groups are methyl group, methoxy group, fluorine atom, pyrimidyl group (where the pyrimidyl group is methyl group, phenyl Group, naphthyl group, anthracyl group, phenanthryl group, and at least one substituent selected from the group consisting of pyrenyl groups), or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group , Ester group or And more preferably substituted also be} with ether alkyl.

  In addition, an aromatic group consisting of only a 6-membered ring in which 2 to 5 benzene rings and / or pyridine rings are linked and / or condensed, and 2 or 4 benzene rings and / or pyridine rings are linked and / or condensed rings The aromatic group consisting of only the 6-membered ring is not particularly limited, but an aromatic group consisting only of the 6-membered ring in which 2 to 6 benzene rings and / or pyridine rings described above are linked and / or condensed. Substituents similar to the substituents exemplified for the group can be exemplified.

As preferred substituents of Ar ¹² , Ar ¹³ , Ar ²² and Ar ²³ , phenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group , 5-phenylpyrimidin-2-yl group, 4,6-diphenylpyrimidin-2-yl group, 5-naphthylpyrimidin-2-yl group, 4,6-dinaphthylpyrimidin-2-yl group, 5-phenan Tolylpyrimidin-2-yl group, 5-anthracylpyrimidin-2-yl group, 5-pyrenylpyrimidin-2-yl group, or (A1) to (A19), (A21), (A28), (A30) , (A32), (A36), (A38), (A40), (A42) to (A60), (A63), (A64), (A66) to (A74), (A76), (A78) , (A80), (A82), (A84), (A86) to (A124), (A129), (A130), (A145) to (A154), (A156) to (A179), (B1), (A). B8), (B10), (B20), (B26) to (B28), (B30), (B33), (B38), (B52), (B63) to (B70), (B79) to (B82) , (B84), (B85), (B89), (B93), (B98), (B109), (B110), (B117), (B119) to (B126), or (B129) to (B137). The substituent represented is more preferable.

  Also, among these substituents, phenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 5-phenylpyrimidin-2-yl Group, 4,6-diphenylpyrimidin-2-yl group, 4,6-dinaphthylpyrimidin-2-yl group, or (A1) to (A19), (A28), (A30), (A32), (A36) ), (A38), (A40), (A42) to (A44), (A47), (A49), (A51), (A54) to (A60), (A63), (A66), (A67), (A72), (A73), (A86) to (A100), (A103) to (A118), (A145) to (A150), (A156) to (A176), (B1), (B26), (B27) ), (B33), (B) 8), (B52), (B63) to (B67), (B79) to (B81), (B93), (B98), (B117), (B119) to (B126), or (B129) to (B136) The substituent represented by) is more preferable.

^{R 11, R 12, R 13} , R 14, R 15, R 16, R 21, R 22, R 23, R 24, R 25 and ^{R 26,} each independently, a hydrogen atom, a methyl group, a methoxy group And a phenyl group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.

An alkyl group having 2 to 10 carbon atoms, alkoxy represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ The group, alkoxyalkyl group, ester group or ester alkyl group is not particularly limited, but the same ones as exemplified for Ar ¹¹ and Ar ¹² can be exemplified.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ have good performance as a compound organic electroluminescent element material In terms of point, each of them is preferably a hydrogen atom, a methyl group, a methoxy group, a phenyl group or a fluorine atom, more preferably a hydrogen atom, a methyl group, a methoxy group or a phenyl group, and a hydrogen atom It is more preferable that

  In addition, each hydrogen atom in the general formula (1-1) and the general formula (1-2) may be independently a deuterium atom.

  The general formula (1-1) and the general formula (1-2) are not particularly limited, but can be exemplified by the following (C1) to (C508).

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

  The compound (1-1) and the compound (1-2) of the present invention have the following reaction formulas

(In the formulas (1-1), (1-2), (2-1), (2-2), (3-1), (3-2), (4-3) and (4-2) , Z ¹¹ , Z ¹² , Z ²¹ and Z ²² each independently represent a leaving group, and M ¹¹ , M ¹² , M ²¹ and M ²² each independently represent a metal group, a boronic acid group, or a boronic ester And each other symbol is as defined above).

  The compound represented by General formula (2-1) is called a compound (2-1). The same applies to compound (3-1), compound (4-1), compound (2-2), compound (3-2), and compound (4-2). The compound (3-1), the compound (4-1), the compound (3-2) and the compound (4-2) are disclosed in, for example, JP-A-2008-280330 (0061) to (0076). It can be manufactured using the following methods.

As the compound (3-1), the compound (4-1), the compound (3-2) and the compound (4-2), * in the above (A1) to (A186) and (B1) to (B137) the compound was changed to M ^1, and although the following the (D1) ~ (D19) can be exemplified, the present invention is not limited thereto. Here, M ¹ represents a metal group, a boronic acid group, or a boronic ester group.

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

  "Step 1" is a step of synthesizing a compound (1-1) or a compound (1-2).

  The compound (1-1) is prepared by reacting the compound (2-1) with the compound (3-1) in the presence of a metal catalyst or in the presence of a metal catalyst and a base and then reacting the compound (4-1). And are synthesized. By applying reaction conditions of general coupling reaction such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction to the reaction, a target product can be obtained with good yield.

  In the step 1, the reaction order may be reversed for the compound (3-1) and the compound (4-1). In addition, the compound (3-1) and the compound (4-1) may be sequentially reacted in one pot, or the intermediate product is once taken out at the stage where the compound (3-1) has been reacted, and the compound (4- 1) can also be reacted.

  The compound (1-2) is prepared by reacting the compound (2-2) with the compound (3-2) in the presence of a metal catalyst or in the presence of a metal catalyst and a base, and then reacting the compound (4-2). And are synthesized. By applying reaction conditions of general coupling reaction such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction to the reaction, a target product can be obtained with good yield.

  In the step 1, the reaction order may be reversed for the compound (3-2) and the compound (4-2). In addition, the compound (3-2) and the compound (4-2) may be sequentially reacted in one pot, or the intermediate product is once taken out at the stage where the compound (3-2) has reacted, and the compound (4- 2) can also be reacted.

Examples of M ¹¹ , M ¹² , M ²¹ and M ^{22 in} the compound (3-1), the compound (4-1), the compound (3-2) and the compound (4-2) are not particularly limited. For example, ZnA ¹ , MgA ² , Sn (A ³ ) ₃ , B (OA ⁴ ) ₂ etc. may be 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, A ⁴ represents a hydrogen atom, 1 carbon atom To 4 alkyl groups or phenyl groups, and two A ⁴ of B (OA ⁴ ) ₂ may be the same or different. Also, two A ⁴ can be united together to form a ring including an oxygen atom and a boron atom.

Examples of B (OA ⁴ ) ₂ in the compound (3-1), the compound (4-1), the compound (3-2) and the compound (4-2) include, but are not limited to, for example, B (OH) _{^{) 2, B (OMe) 2}} , B (O i Pr) 2, B (OBu) 2, B (OPh) 2 and the like. Moreover, as an example of B (OA ⁴ ) ₂ when two A ⁴ together form an oxygen atom and a boron atom to form a ring, the groups represented by (E 1) to (E 6) below are The group represented by (E2) is preferable because it can be exemplified and the yield is good.

The leaving group represented by Z ¹¹ , Z ¹² , Z ²¹ and Z ²² in the compound (2-1) and the compound (2-2) is not particularly limited, and examples thereof include a chlorine group and a bromine group. And iodine group, trifluoromethylsulfonyloxy (OTf) group, methanesulfonyloxy group, chloromethanesulfonyloxy group, p-toluenesulfonyloxy group and the like.

  As a metal catalyst which can be used at "the process 1", a palladium catalyst or a nickel catalyst etc. are mentioned.

  Although it does not specifically limit as a palladium catalyst which can be used at "the process 1", For example, salts, such as palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, etc. can be illustrated. Furthermore, π-allylpalladium chloride dimer, palladium acetylacetonato, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and dichloro [1,1′-bis (diphenylphos)] Complex compounds such as (Fino) ferrocene] palladium can be exemplified. Among them, a palladium complex having a tertiary phosphine as a ligand is preferable in that the reaction yield is good.

  A palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or complex compound. The tertiary phosphines that can be used in this case are not particularly limited, and examples thereof include triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine and 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) ferrocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (±) -2,2′-bis (diphenylphos) Fino) -1,1′-binaphthyl, 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl etc. can be exemplified. 2-Dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl is preferred in view of easy availability and good reaction yield.

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

  Moreover, the nickel catalyst that can be used in “Step 1” is not particularly limited, and examples thereof include [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 (diphenylphosphino) ethane] nickel (II) dichloride, [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride and the like.

  The base that can be used in “Step 1” is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, tripotassium phosphate, and phosphoric acid. Examples thereof include sodium fluoride, sodium fluoride, potassium fluoride, cesium fluoride and the like, 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.

  A solvent can also be used for "Step 1", and it is preferable to use a solvent in terms of reaction control. Examples of the solvent that can be used in “Step 1” include, but are not limited to, water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethyl ether, ethanol, methanol or xylene, etc. These may be used in combination as appropriate. It is desirable to use a mixed solvent of dioxane and water, a mixed solvent of tetrahydrofuran and water from the viewpoint of a good yield.

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

  Compound (1-1) and compound (1-2) can be obtained by performing ordinary treatments (separation operation and the like) performed by those skilled in the art after completion of “Step 1”. Furthermore, if necessary, purification may be performed by recrystallization, column chromatography, sublimation or the like.

  The compound (2-1) and the compound (2-2) of the present invention can be produced by the method shown by the following reaction scheme.

(Wherein, W ¹¹ , W ¹² , W ¹³ , W ²¹ , W ²² and W ²³ represent substituents necessary for carrying out the pyrimidine ring formation reaction. Substituents represented by other symbols) Is the same as described above.)
Hereinafter, the compound represented by General formula (5-1) is called compound (5-1). The same applies to compound (5-2), compound (6-1) and compound (6-2).

  Hereinafter, although a specific example is given and demonstrated about "the process 2", this invention is not limited to these.

  "Step 2" is a step of obtaining a compound (2-1) or a compound (2-2).

  Compound (2-1) can be used in the presence of a catalyst, in the presence of an acid, in the presence of a base, in the presence of a catalyst and an acid, or in the presence of a catalyst and a base, in the presence or absence of a nitrogen source And the compound (5-1) and the compound (6-1) are reacted.

  Compound (2-2) can be used in the presence of a catalyst, in the presence of an acid, in the presence of a base, in the presence of a catalyst and an acid, or in the presence of a catalyst and a base, in the presence or absence of a nitrogen source The compound (5-2) is synthesized by reacting the compound (5-2) with the compound (6-2).

Pyrimidines represented by W ¹¹ , W ¹² , W ¹³ , W ²¹ , W ²² and W ²³ in the compound (5-1), the compound (5-2), the compound (6-1) and the compound (6-2) Examples of substituents necessary for carrying out the ring formation reaction include, but are not limited to, for example, formyl group, carbonyl group, carboxyl group, ester group, amide group, amino group, imino group, amidyl group Or its hydrochloride, nitrile group, halogen and the like. Among these, an amidyl group or a hydrochloride thereof, a formyl group, a nitrile group, a carbonyl group, an amino group and an imino group are preferable in terms of easiness of synthesis.

  Examples of the acid that can be used in “Step 2” include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, acetic anhydride, formic acid, oxalic acid, ammonium chloride, fluorosulfonic acid, benzene, for example. A sulfonic acid, p-toluenesulfonic acid, etc. can be illustrated.

  Examples of the base that can be used in “Step 2” include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, tripotassium phosphate, phosphoric acid Trisodium, sodium fluoride, potassium fluoride, cesium fluoride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like can be exemplified.

  Examples of the catalyst that can be used in “Step 2” include, but are not limited to, halogen, Lewis acid, Lewis base, catalytic amount of the above-mentioned acid, base and the like. Examples of the halogen include iodine, bromine and chlorine. Examples of the Lewis acid and the Lewis base include metal complexes of indium, ytterbium, zinc, copper, iron, hafnium, aluminum and the like.

  The nitrogen source that can be used in “Step 2” is not particularly limited, and examples thereof include ammonium acetate, ammonium chloride, ammonium formate, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium iodide, ammonium fluoride, hydrogen carbonate Ammonium, ammonium dihydrogen phosphate, ammonium benzenesulfonate, or ammonium p-toluenesulfonate may, for example, be mentioned.

  A solvent can also be used for "Step 2", and it is preferable to use a solvent in terms of reaction control. Although it does not specifically limit as a solvent which can be used at "the process 2", For example, water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethyl ether, ethanol, methanol, or xylene etc. are mentioned. .

  “Step 2” can be carried out at a temperature appropriately selected from 0 ° C. to 150 ° C.

  Compound (2-1) and compound (2-2) can be obtained by performing ordinary treatments (separation operation and the like) performed by those skilled in the art after completion of “Step 2”. If necessary, purification may be performed by recrystallization, column chromatography, sublimation or the like.

  Further, the compound (2-1) and the compound (2-2) of the present invention have the following reaction formula

(The substituent represented by each symbol in the formula is the same as described above.)
It can manufacture also by the method shown by.

  The compound represented by General Formula (7-1) is referred to as Compound (7-1). The same applies to compound (7-2), compound (8-1) and compound (8-2).

  "Step 3" is a step of obtaining compound (8-1) or compound (8-2).

  Compound (8-1) is formed in the presence of a nitrogen source in the presence of a catalyst, in the presence of an acid, in the presence of a base, in the presence of a catalyst and an acid, or in the presence of a catalyst and a base To be synthesized by reacting compound (5-1) with compound (7-1).

  Compound (8-2) is formed in the presence of a nitrogen source in the presence of a catalyst, in the presence of an acid, in the presence of a base, in the presence of a catalyst and an acid, or in the presence of a catalyst and a base The compound (5-2) is synthesized by reacting the compound (5-2) with the compound (7-2).

  The reaction conditions in “Step 3” are the same as in Step 2.

  The compound (7-1) or compound (7-2) obtained in "Step 3" is not purified, or after purification by recrystallization, column chromatography, sublimation or the like, the raw material for "Step 4" It can be used as

  Hereinafter, although a specific example is given and demonstrated about "the process 4", this invention is not limited to these.

  "Step 4" is a step of obtaining compound (2-1) or compound (2-2).

  Compound (2-1) is synthesized by oxidizing the dihydrobenzoquinazolyl group of compound (8-1) in the presence of an acid and in the presence of an acid or in the presence of a base.

  Compound (2-2) is synthesized by oxidizing the dihydrobenzoquinazolyl group of compound (8-2) in the presence of an acid and in the presence of an acid or in the presence of a base.

  Examples of the oxidizing agent that can be used in "Step 4" include potassium permanganate, manganese dioxide, chromium (IV) oxide, sodium dichromate, potassium dichromate, potassium chromate, chromate ester, hydrogen peroxide, 2, 3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetrachloro-1,4-benzoquinone (chloranil), tetrachloro-1,2-benzoquinone (o-chloranil), or nitrobenzene etc. Be

  As the acid or base that can be used in "Step 4", the compounds listed in "Step 2" can be used.

  A solvent can also be used for "Step 4", and it is preferable to use a solvent in terms of reaction control. Examples of the solvent that can be used in “Step 4” include, but are not limited to, water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethyl ether, ethanol, methanol or xylene.

  “Step 4” can be carried out at a temperature appropriately selected from 0 ° C. to 150 ° C.

  Compound (2-1) and compound (2-2) can be obtained by performing ordinary treatments (separation operation and the like) performed by those skilled in the art after completion of “Step 4”. Furthermore, if necessary, purification may be performed by recrystallization, column chromatography, sublimation or the like.

  The benzoquinazoline compound shown by General formula (1-1) or General formula (1-2) of this application is used suitably as a material for organic electroluminescent elements.

  Furthermore, the benzoquinazoline compound shown by General formula (1-1) or General formula (1-2) of this application is used suitably as an electron transport material or electron injection material for organic electroluminescent elements.

Although there is no limitation in particular in the manufacturing method of the thin film for organic electroluminescent elements containing the benzoquinazoline compound shown by General formula (1-1) or General formula (1-2) of this invention, A vacuum evaporation method is preferable as a preferable example Can be mentioned. The film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The degree of vacuum of the vacuum chamber at the time of forming a film by a vacuum evaporation method is a diffusion pump, a turbo molecular pump, a cryo which is generally used in that the manufacturing tact time for manufacturing an organic electroluminescent device is short and the manufacturing cost is superior. About 1 * 10 ^<-2 > ^-1 * 10 ^{< -6>} Pa which can reach | attain by a pump etc. is preferable, More preferably, it is 1 * 10 < ^-3 > ^-10 <^-6> Pa. The deposition rate is preferably 0.005 to 10 nm / second, more preferably 0.01 to 1 nm / second, depending on the thickness of the film to be formed. Further, a thin film for an organic electroluminescent device comprising the compound A can also be produced by a solution coating method. For example, the compound A is dissolved in an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate or tetrahydrofuran, and a spin coat method, an ink jet method, a cast method or a dip method using a general-purpose device It is also possible to form a film by the like.

  Typical structures of the organic electroluminescent device from which the effects of the present invention can be obtained include a substrate, an anode, a hole injection layer, a light emitting layer of a hole transport layer, an electron transport layer, and a cathode.

  The anode and the cathode of the organic electroluminescent element are connected to a power source via an electrical conductor. The organic electroluminescent device operates by applying a potential between the anode and the cathode. Holes are injected into the organic electroluminescent device from the anode and electrons are injected into the organic electroluminescent device at the cathode.

  The organic electroluminescent device is typically coated on a substrate, and the anode or the cathode can be in contact with the substrate. The electrode in contact with the substrate is conveniently referred to as the lower electrode. In general, the lower electrode is an anode, but the organic electroluminescent device of the present invention is not limited to such a form. The substrate may be light transmissive or opaque depending on the intended light emission direction. Light transmission properties are desirable for viewing the electroluminescent emission through the substrate. Transparent glass or plastic is commonly employed as such a base. The substrate may be a composite structure comprising multiple material layers.

  If electroluminescent emission is viewed through the anode, the anode should either pass or substantially transmit the emission. Typical transparent anode (anode) materials used in the present invention are indium-tin oxide (ITO), indium-zinc oxide (IZO), or tin oxide, but other metal oxides, for example Also useful are aluminum or indium-doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide. In addition to these oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or metal sulfides such as zinc sulfide can be used as the anode. The anode can be modified with plasma deposited fluorocarbons. For applications where electroluminescence is only seen through the cathode, the transmission properties of the anode are not critical and any conductive material transparent, opaque or reflective can be used. Examples of conductors for this application include gold, iridium, molybdenum, palladium and platinum.

  A hole injection layer can be provided between the anode and the hole transport layer. The hole injection material can serve to improve the film forming properties of the subsequent organic layer and facilitate the injection of holes into the hole transport layer. Examples of materials suitable for use in the hole injection layer include porphyrin compounds, plasma deposited fluorocarbon polymers, and amines having an aromatic ring such as biphenyl or carbazole, such as m-MTDATA (4,4 ') , 4 ''-tris [(3-methylphenyl) phenylamino] triphenylamine), 2T-NATA (4,4 ', 4' '-tris [(N-naphthalen-2-yl) -N-phenylamino] Triphenylamine), triphenylamine, tolylamine, tolyldiphenylamine, N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine, N, N, N'N'-tetrakis (4-methylphenyl) -1,1'-biphenyl-4,4'-diamine, MeO-TPD N, N, N'N'-tetrakis (4-methoxyphenyl) -1,1'-biphenyl-4,4'-diamine), N, N'-diphenyl-N, N'-dinaphthyl-1,1 ' -Biphenyl-4,4'-diamine, N, N'-bis (methylphenyl) -N, N'-bis (4-normalbutylphenyl) phenanthrene-9,10-diamine, or N, N'-diphenyl- N, N'-bis (9-phenylcarbazol-3-yl) -1,1'-biphenyl-4,4'-diamine and the like can be mentioned.

  The hole transport layer of the organic electroluminescent device preferably contains one or more hole transport compounds, such as an aromatic tertiary amine. Aromatic tertiary amines are meant to be compounds containing one or more trivalent nitrogen atoms, which trivalent nitrogen atoms are bonded only to carbon atoms, and one or more of these carbon atoms are It forms an aromatic ring. In particular, the aromatic tertiary amines may be arylamines, such as monoarylamines, diarylamines, triarylamines or polymeric arylamines.

  As the hole transport material, aromatic tertiary amines having one or more amine groups can be used. In addition, polymeric hole transport materials can be used. For example, poly (N-vinylcarbazole) (PVK), polythiophene, polypyrrole, or polyaniline can be used. For example, NPD (N, N'-bis (naphthalen-1-yl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine), α-NPD (N, N'-di) (1-Naphthyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine), TPBi (1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) And benzene), or TPD (N, N'-bis (3-methylphenyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine) and the like.

  Dipyrazino [2,3-f: 2 ', 3'-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile as charge generation layer between hole injection layer and hole transport layer A layer containing (HAT-CN) may be provided.

  The light emitting layer of the organic electroluminescent device contains a phosphorescent material or a fluorescent material, and in this case, light emission occurs as a result of recombination of electron-hole pairs in this region. The light emitting layer may consist of a single material containing both small molecules and polymers, but more generally consists of a host material doped with a guest compound, in which case the emission mainly consists of dopants And can have any color.

  Examples of the host material of the light emitting layer include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, or an anthranyl group. For example, DPVBi (4,4'-bis (2,2-diphenylvinyl) -1,1'-biphenyl), BCzVBi (4,4'-bis (9-ethyl-3-carbazovinylene) 1,1'-biphenyl ), TBADN (2-tert-butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4'-bis (carbazole-9) -Yl) biphenyl), CDBP (4,4'-bis (carbazol-9-yl) -2,2'-dimethylbiphenyl), 9,10-bis (biphenyl) anthracene and the like.

  The host material in the light emitting layer may be an electron transport material as defined below, a hole transport material as defined above, or another material supporting hole-electron recombination or a combination of these materials.

  Examples of useful fluorescent dopants include anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine and quinacridone, dicyanomethylene pyran compound, thiopyran compound, polymethine compound, pyrilium or thiapyrilium compound, fluorene derivative, periflanthene derivative, indeno Perylene derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, carbostyril compounds and the like can be mentioned.

  One example of a useful phosphorescent dopant is an organometallic complex of a transition metal of iridium, platinum, palladium or osmium.

Examples of dopants include Alq ₃ (tris (8-hydroxyquinoline) aluminum), DPAVBi (4,4′-bis [4- (di-para-tolylamino) styryl] biphenyl), perylene, Ir (PPy) ₃ ( Tris (2-phenylpyridine) iridium (III), or FlrPic (bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III), etc. may be mentioned.

  The thin film forming material used to form the electron transporting layer of the organic electroluminescent device of the present invention is a benzoquinazoline compound represented by the general formula (1-1) or the general formula (1-2) of the present application. The electron transporting layer may contain other electron transporting materials, and examples of the electron transporting materials include alkali metal complexes, alkaline earth metal complexes, earth metal complexes and the like. Desirable alkali metal complexes, alkaline earth metal complexes, earth metal complexes such as lithium 8-hydroxyquinolinate (Liq), bis (8-hydroxyquinolinate) zinc, bis (8-hydroxyquinolinate) Copper, bis (8-hydroxyquinolinate) manganese, tris (8-hydroxyquinolinate) aluminum, tris (2-methyl-8-hydroxyquinolinate) aluminum, tris (8-hydroxyquinolinate) gallium, Bis (10-hydroxybenzo [h] quinolinate) beryllium, bis (10-hydroxybenzo [h] quinolinate) zinc, bis (2-methyl-8-quinolinate) chlorogallium, bis (2-methyl-8-quinolinate) ( o-Cresolato) gallium, bis (2-methyl-8-quinolina) G) -1-naphthoquinone Trad aluminum or bis (2-methyl-8-quinolinato) -2-naphthoquinone Trad gallium, and the like.

  A hole blocking layer may be provided between the light emitting layer and the electron transporting layer for the purpose of improving carrier balance. Preferred compounds for the hole element layer are BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2 And -methyl-8-quinolinolato) -4- (phenylphenolate) aluminum), or bis (10-hydroxybenzo [h] quinolinate) beryllium) and the like.

  In the organic electroluminescent device of the present invention, an electron injecting layer may be provided for the purpose of improving the electron injecting property and improving the device characteristics (for example, luminous efficiency, constant voltage driving, or high durability).

Desirable compounds for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, or anthrone. Etc. Also, the above-mentioned metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO _x , AlO _x , SiN _x , SiON, _{AlON, GeO X, LiO X,} LiON, TiO X, TiON, TaO X, TaON, TaN X, C and various oxides, nitrides, and inorganic compounds (shown here x such as oxynitride is positive Can also be used).

When light emission is only seen through the anode, the cathode used in the present invention can be formed from almost any conductive material. Preferred cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium , Lithium / aluminum mixtures, rare earth metals and the like.

  Hereinafter, the present invention will be described in more detail by way of experimental examples and test examples, but the present invention is not limited thereto.

  Experimental Example 1 (Example)

7.31 g (50.0 mmol) of α-tetralone and 5.31 g (50.0 mmol) of benzaldehyde were added to 100 mL of acetic acid, and 24.5 g (250 mmol) of concentrated sulfuric acid was added thereto and stirred for 14 hours. Then, 200 mL of water was added to the reaction mixture. The precipitated solid is collected by filtration, and washed with water to obtain a light brown powder (yield 10.6 g, yield) of 2-benzylidene-3,4-dihydro-2H-naphthalen-1-one (A-1). 91%).

¹ H-NMR (CDCl ₃ ), δ (ppm): 2.98 (t, J = 6.5 Hz, 2 H), 3.16 (t, J = 6.5 Hz, 2 H), 7.28 (d, J = 7.5 Hz, 1 H), 7.33-7.49 (m, 6 H), 7.52 (t, J = 7.5 Hz, 1 H), 7. 90 (s, 1 H), 8. 16 ( d, J = 7.8 Hz, 1 H).
2-benzylidene-3,4-dihydro-2H-naphthalen-1-one (A-1) 7.26 g (31.0 mmol), 3-bromo-5-chlorobenzamidine hydrochloride 2.70 g (10.0 mmol) Was added to 10 mL of ethanol, and 15 mL of an ethanol solution of 1.12 g (20.0 mmol) of potassium hydroxide was added thereto, and the mixture was refluxed for 18 hours. After cooling to room temperature, water is added, and the precipitated solid is collected by filtration to give the desired 2- (3-bromo-5-chlorophenyl) -4-phenyl-5,6-dihydrobenzo [h] quinazoline (A A pale yellow powder (yield 3.96 g, 88%) of -2) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 2.94 (t, J = 7.2 Hz, 2H), 3.13 (t, J = 7.2 Hz, 2H), 7.30 (d, J = 6.4 Hz, 1 H), 7.45-7. 60 (m, 5 H), 7.63 (s, 1 H), 7.73 (d, J = 7.7 Hz, 2 H), 8.58 ( d, J = 6.8 Hz, 1 H), 8. 60 (s, 1 H), 8. 70 (s, 1 H).
2- (3-bromo-5-chlorophenyl) -4-phenyl-5,6-dihydrobenzo [h] quinazoline (A-2) 3.00 g (6.7 mmol), 2,3-dichloro-5,6- 3.04 g (13.4 mmol) of dicyano-1,4-benzoquinone (DDQ) was added to 33 mL of o-dichlorobenzene, and the mixture was heated and stirred at 120 ° C. for 3 hours. After cooling to room temperature, the precipitated solid was collected by filtration and washed with toluene and methanol. The obtained solid is recrystallized with toluene to obtain a target white powder (yield 1.22 g of 2- (3-bromo-5-chlorophenyl) -4-phenylbenzo [h] quinazoline (A-3)). A yield of 41% was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.64-7.67 (m, 3H), 7.68 (s, 1H), 7.85-7.88 (m, 3H), 7 .91-7.93 (m, 2 H), 7.95-7.99 (m, 1 H), 8.00 (d, J = 9.1 Hz, 1 H), 8.79 (s, 1 H), 8 .90 (s, 1 H), 9.52-9.55 (m, 1 H).
Experimental Example 2 (Example)

Under argon flow, 554 mg (2.91 mmol) of copper iodide and 577 mg (3.20 mmol) of 1,10-phenanthroline are added to 58 mL of DMF, 3.00 g (29.1 mmol) of benzonitrile, 4.25 g of α-tetralone ( 29.1 mmol) and 16.0 g (116 mmol) of sodium-t-butoxide were added and stirred at 80 ° C. for 10 hours. After cooling to room temperature, water was added, and the precipitated solid was collected by filtration, washed with water and hexane. The resulting crude product is purified by silica gel column chromatography (developing solvent chloroform) to obtain the desired 2- (α-aminobenzylidene) -3,4-dihydro-2H-naphthalen-1-one (A′-1) The light brown powder (yield 4.46 g, 61%) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 2.50 (t, J = 6.6 Hz, 2H), 2.75 (t, J = 6.6 Hz, 2H), 7.15 (d, J = 7.2 Hz, 1H), 7.35 (td, J = 7.6 Hz, 1.5 Hz, 1 H), 7.36 (dd, J = 7.2 Hz, 1.5 Hz, 1 H), 7.39 -7.48 (m, 5H), 8.06 (dd, J = 7.5 Hz, 1.7 Hz, 1 H).
Under an argon stream, 232 mg (0.924 mmol) of 2- (α-aminobenzylidene) -3,4-dihydro-2H-naphthalen-1-one (A′-1), 300 mg of 3-bromo-5-chlorobenzonitrile 1.39 mmol) and 588 mg (2.77 mmol) of tripotassium phosphate were added to 3 mL of DMF, and the mixture was heated and stirred at 80 ° C. for 17 hours. After cooling to room temperature, water was added, and the precipitated solid was collected by filtration, washed with water and methanol. The resulting crude product is purified by silica gel column chromatography (developing solvent chloroform) to obtain the target white powder of 2- (3-bromo-5-chlorophenyl) -4-phenylbenzo [h] quinazoline (A-3). The body (yield 103 mg, 25%) was obtained.

  Experimental Example 3 (Example)

Under an argon stream, 2- (3-bromo-5-chlorophenyl) -4-phenylbenzo [h] quinazoline (A-3) 1.20 g (2.69 mmol), 4- (2-pyridyl) phenylboronic acid. 18 g (5.92 mmol), 12.1 mg (0.0548 mmol) of palladium acetate, and 76.9 mg (0.161 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl are added to 19 mL of THF. Then, 4.0 mL of 3 M aqueous potassium carbonate solution was added, and the mixture was heated to reflux for 14 hours. After cooling to room temperature, water is added, and the precipitated solid is collected by filtration and washed with water, methanol and hexane to obtain the desired 4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) Light brown powder (yield 1.72 g, 100%) of) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] benzo [h] quinazoline (A-4) was obtained .

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.29 (dd, J = 7.1, 4.8 Hz, 2 H), 7.63-7.69 (m, 3 H), 7.80 7.89 (m, 7 H), 7.95-8.00 (m, 7 H), 8.04 (d, J = 9.1 Hz, 1 H), 8.10 (s, 1 H), 8.21 ( d, J = 8.4 Hz, 4 H), 8.77 (d, J = 4.8 Hz, 2 H), 9.17 (s, 2 H), 9.60-9.62 (m, 1 H).
Experimental Example 4 (Example)

Under an argon stream, 1.11 g (2.5 mmol) of 2- (3-bromo-5-chlorophenyl) -4-phenylbenzo [h] quinazoline (A-3), 738 mg (3.0 mmol) of 1-pyreneboronic acid, and 35.1 mg (0.050 mmol) of bis (triphenylphosphino) palladium (II) dichloride was added to 25 mL of THF, and 2.0 mL of 3 M aqueous potassium carbonate solution was further added, followed by heating to reflux for 13 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. Gray powder of desired 2- [3-chloro-5- (1-pyrenyl) phenyl] -4-phenylbenzo [h] quinazoline (B-1) by recrystallizing the obtained solid with 25 mL of o-xylene (Yield 1.12 g, yield 79%) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.61 to 7.64 (m, 3H), 7.77 to 7.83 (m, 3H), 7.85 (d, J = 9. 1 Hz, 1 H), 7.92-7.94 (m, 2 H), 7.96 (d, J = 8.3 Hz, 1 H), 8.02 (d, J = 9.1 Hz, 1 H), 8. 07 (t, J = 7.6 Hz, 1 H), 8. 10 (d, J = 9.5 Hz, 1 H), 8. 14 (d, J = 7.8 Hz, 1 H), 8. 17 (s, 2 H) ), 8.21 to 8.29 (m, 3H), 8.32 (d, J = 7.8 Hz, 1H), 8.97 to 9.01 (m, 2H), 9.50 (d, J) = 7.6 Hz, 1 H).
Under an argon stream, 2- [3-chloro-5- (1-pyrenyl) phenyl] -4-phenylbenzo [h] quinazoline (B-1) 1.10 g (1.94 mmol), 4- (2-pyridyl) 425 mg (2.13 mmol) of phenylboronic acid, 8.7 mg (0.039 mmol) of palladium acetate, and 55.8 mg (0.117 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl in THF The mixture was added to 19 mL, and further 1.4 mL of 3 M aqueous potassium carbonate solution was added, and the mixture was heated to reflux for 6 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting solid is recrystallized from toluene to give the desired 4-phenyl-2- [5- (1-pyrenyl) -4 ′-(2-pyridyl) biphenyl-3-yl] benzo [h] quinazoline ( A light brown powder (yield 1.19 g, 90%) of B-2) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.26-7.29 (m, 1 H), 7.54-7.64 (m, 4 H), 7.78-7.85 (m, 5) 3H), 7.94-7.96 (m, 3H), 8.03 (d, J = 9.2 Hz, 2H), 8.06-8.23 (m, 9H), 8.26 (d, J) J = 7.5 Hz, 1 H), 8, 31-8.39 (m, 4 H), 8. 91 (d, J = 4.6 Hz, 1 H), 9. 15 (s, 1 H), 9. 29 (m, 4 H) s, 1 H), 9.53-9.56 (m, 1 H).
Experimental Example 5 (Example)

Under an argon stream, 2- (3-bromo-5-chlorophenyl) -4-phenylbenzo [h] quinazoline (A-3) 5.0 g (11.2 mmol), 9-phenanthreneboronic acid 2.62 g (11.8 mmol) And tetrakis (triphenylphosphine) palladium 259 mg (0.224 mmol) were added to 110 mL of THF, and 7.48 mL of 3 M aqueous potassium carbonate solution was further added, and the mixture was heated to reflux for 22 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The obtained solid was recrystallized with 70 mL of toluene to obtain gray powder (yield) of desired 2- [3-chloro-5- (9-phenanthryl) phenyl] -4-phenylbenzo [h] quinazoline (C-1) 5.26 g (yield 86%) were obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.56 to 7.62 (m, 4 H), 7.64 to 7.74 (m, 4 H), 7.75 to 7.83 (m, 5) 4H), 7.89-8.00 (m, 6H), 8.77 (d, J = 8.4 Hz, 1 H), 8.82 (d, J = 8.0 Hz, 1 H), 8.89 (8 t, J = 1.2 Hz, 1 H), 8.94 (t, J = 1.6 Hz, 1 H), 9.48 (dd, J = 7.6 Hz, 1.6 Hz, 1 H).
Under an argon stream, 1.00 g (1.84 mmol) of 2- [3-chloro-5- (9-phenanthryl) phenyl] -4-phenylbenzo [h] quinazoline (C-1), 5- (4,4, 5, 5-Tetramethyl-1,3,2-dioxaborolan-2-yl) -2-phenylpyridine 569 mg (2.02 mmol), palladium acetate 8.3 mg (0.037 mmol), and 2-dicyclohexylphosphino-2 52.6 mg (0.110 mmol) of ', 4', 6'-triisopropylbiphenyl was added to 35 mL of THF, and 1.2 mL of 3 M aqueous potassium carbonate solution was further added, followed by heating to reflux for 16 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting solid is recrystallized with 200 mL of toluene to give the desired 2- [3- (9-phenanthryl) -5- (6-phenylpyridin-3-yl) phenyl] -4-phenylbenzo [h] quinazoline. The white powder (yield 872 mg, 72%) of (C-2) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.45 (t, J = 7.3 Hz, 1 H), 7.52 (t, J = 8.0 Hz, 2 H), 7.57-7. 63 (m, 4 H), 7.67 (t, J = 7.3 Hz, 1 H), 7.72 (t, J = 7.7 Hz, 2 H), 7.78-7.84 (m, 3 H), 7.88-8.02 (m, 8 H), 8.09 (t, J = 8.7 Hz, 3 H), 8, 20 (dd, J = 7.7 Hz, 2.3 Hz, 1 H), 8.79 (D, J = 8.0 Hz, 1 H), 8.84 (d, J = 8.0 Hz, 1 H), 9.05 (t, J = 1.6 Hz, 1 H), 9.23 (d, J = 1.9 Hz, 1 H), 9.26 (t, J = 1.5 Hz, 1 H), 9.52 (dd, J = 7.3 Hz, 2.3 Hz, 1 H).
Experimental Example 6 (Example)

Under an argon stream, 1.00 g (1.84 mmol) of 2- [3-chloro-5- (9-phenanthryl) phenyl] -4-phenylbenzo [h] quinazoline (C-1), 401 mg of 4-biphenylboronic acid ( 2.03 mmol), 8.4 mg (0.037 mmol) of palladium acetate, and 35.7 mg (0.074 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl are added to 37 mL of THF, After adding 1.2 mL of 3 M aqueous potassium carbonate solution, the mixture was heated to reflux for 38 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The obtained solid is recrystallized twice with 200 mL of toluene to obtain the target 2- [5- (9-phenanthryl) -1,1 ′: 4 ′, 1 ′ ′-terphenyl-3-yl] -4. -White powder (yield 673 mg, 55% yield) of phenylbenzo [h] quinazoline (C-3) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.37 (t, J = 7.3 Hz, 1 H), 7.47 (t, J = 7.6 Hz, 2 H), 7.56-7. 63 (m, 4 H), 7.64-7. 83 (m, 10 H), 7. 9-8. 02 (m, 9 H), 8.09 (d, J = 8.2 Hz, 1 H), 8. 79 (d, J = 8.2 Hz, 1 H), 8.84 (d, J = 8.5 Hz, 1 H), 9.00 (t, J = 1.5 Hz, 1 H), 9.23 (t, J = 1.8 Hz, 1 H), 9.53 (dd, J = 6.4 Hz, 1.7 Hz, 1 H).
Experimental Example 7 (Example)

Under an argon stream, 820 mg (1.51 mmol) of 2- [3-chloro-5- (9-phenanthryl) phenyl] -4-phenylbenzo [h] quinazoline (C-1), 223 mg (1-.1) of 3-pyridineboronic acid. 81 mmol), 6.8 mg (0.030 mmol) of palladium acetate, and 43.1 mg (0.091 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl are added to 30 mL of THF, and 3 M- 1.0 mL of aqueous potassium carbonate solution was added and heated to reflux for 38 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting solid is recrystallized with 15 mL of toluene to give the desired 2- [3- (9-phenanthryl) -5- (3-pyridyl) phenyl] -4-phenylbenzo [h] quinazoline (C-4) White powder (yield 689 mg, 78%) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.44 (dd, J = 7.9 Hz, 4.8 Hz, 1 H), 7.56-7.62 (m, 4 H), 7.65 ( t, J = 7.1 Hz, 1H), 7.69-7.74 (m, 2H), 7.75-7.83 (m, 3H), 7.90-7.94 (m, 5H), 7.97 (t, J = 7.7 Hz, 1 H), 8.00 (d, J = 9.0 Hz, 1 H), 8.04 (d, J = 8.2 Hz, 1 H), 8.13 (dt , J = 8.2 Hz, 1.8 Hz, 1 H), 8.65 (dd, J = 4.8 Hz, 1.8 Hz, 1 H), 8.78 (d, J = 8.1 Hz, 1 H), 8. 83 (d, J = 8.4 Hz, 1 H), 9.05 (t, J = 1.6 Hz, 1 H), 9.12 (d, J = 1.6 Hz, 1 H), 9.18 (t, J = 1.6 Hz, 1 H , 9.50 (dd, J = 7.1Hz, 2.4Hz, 1H).
Experimental Example 8 (Example)

Under an argon stream, 2- [3-chloro-5- (9-phenanthryl) phenyl] -4-phenylbenzo [h] quinazoline (C-1) 1.50 g (2.76 mmol), bis (binacolato) diboron 912 mg ( 3.59 mmol), bis (dibenzylideneacetone) palladium 51 mg (0.055 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 53 mg (0.110 mmol), and potassium acetate 542 mg (5) .52 mmol) was added to 50 mL of THF and heated to reflux for 20 hours. After cooling to room temperature, water is added and the precipitated solid is collected by filtration and then washed with water, methanol and hexane to obtain the desired 2- [3- (4,4,5,5-tetramethyl- Gray powder (yield 1.28 g, 73%) of 1,3,2-dioxaborolan-2-yl) -5- (9-phenanthryl) phenyl] -4-phenylbenzo [h] quinazoline (D-1) I got

¹ H-NMR (CDCl ₃ ), δ (ppm): 1.14 (s, 12 H), 7.52-7.61 (m, 4 H), 7.64 (t, J = 7.6 Hz, 1 H) , 7.67-7.72 (m, 2H), 7.73-7.81 (m, 3H), 7.84 (s, 1H), 7.90-7.99 (m, 6H), 8 .13 (t, J = 1.5 Hz, 1 H), 8.76 (d, J = 8.3 Hz, 1 H), 8.81 (d, J = 8.0 Hz, 1 H), 9.08 (t, J = 1.8 Hz, 1 H), 9.29 (t, J = 1.5 Hz, 1 H), 9.52 (dd, J = 6.8 Hz, 2.0 Hz, 1 H).
Under an argon stream, 2- [3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5- (9-phenanthryl) phenyl] -4-phenylbenzo [h 1.00 g (1.58 mmol) of quinazoline (D-1), 323 mg (1.73 mmol) of 3-bromo-2,6-dimethylpyridine, and 36.5 mg (0.035 mmol) of tetrakis (triphenylphosphine) palladium in THF The mixture was added to 32 mL, and further 1.1 mL of 3 M aqueous potassium carbonate solution was added, and the mixture was heated to reflux for 40 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The target solid 2- [3- (2,6-dimethylpyridin-3-yl) -5- (9-phenanthryl) phenyl is obtained by washing the obtained solid with 50 mL of a mixed solvent of hexane: chloroform = 9: 1. A white powder (yield 809 mg, 84%) of] -4-phenylbenzo [h] quinazoline (D-2) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 2.62 (s, 3 H), 2. 70 (s, 3 H), 7. 13 (d, J = 7.7 Hz, 1 H), 7.56 -7.60 (m, 4H), 7.63-7.77 (m, 6H), 7.77-7.82 (m, 2H), 7.89-7.93 (m 4 H), 7.96 (D, J = 7.7 Hz, 1 H), 8.00 (d, J = 9.3 Hz, 1 H), 8.06 (d, J = 8.4 Hz, 1 H), 8.77 (d, J = 8.0 Hz, 1 H), 8.83 (d, J = 8.0 Hz, 1 H), 8.89 (t, J = 1.9 Hz, 1 H), 9.00 (t, J = 1.9 Hz, 1 H ), 9.47 (d, J = 7.7 Hz, 1 H).
Experimental Example 9 (Example)

Under an argon stream, 8.44 g (18.9 mmol) of 2- (3-bromo-5-chlorophenyl) -4-phenylbenzo [h] quinazoline (A-3), 2.42 g (19.9 mmol) of phenylboronic acid, And 97.1 mg (0.379 mmol) of tetrakis (triphenylphosphine) palladium were added to 189 mL of THF, and 12.6 mL of 3 M aqueous potassium carbonate solution was further added, followed by heating to reflux for 24 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The obtained solid was recrystallized with 100 mL of toluene to obtain gray powder (yield: 7.54 g) of desired 2- (5-chlorobiphenyl-3-yl) -4-phenylbenzo [h] quinazoline (E-1). Yield 90%).

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.43 (t, J = 7.5 Hz, 1 H), 7.54 (t, J = 7.5 Hz, 2 H), 7.59-7. 66 (m, 3 H), 7.72-7. 76 (m, 3 H), 7.81-7. 85 (m, 3 H), 7. 90-7. 96 (m, 3 H), 7.99 (m, 3 H) d, J = 9.0 Hz, 1 H), 8. 80 (t, J = 1.9 Hz, 1 H), 8. 95 (t, J = 1.5 Hz, 1 H), 9.5 4 (d, J = 9 .0 Hz, 1 H).
Under an argon stream, 2- [5-chlorobiphenyl-3-yl] -4-phenylbenzo [h] quinazoline (E-1) 7.54 g (17.0 mmol), 4- (4,6-diphenylpyridine-2) 6.24 g (18.7 mmol) phenylboronic acid, 76.0 mg (0.340 mmol) palladium acetate, and 324 mg (0.681 mmol) 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl ) Was added to 340 mL of THF, and 11.3 mL of 3 M aqueous potassium carbonate solution was further added, and the mixture was heated to reflux for 24 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting solid is recrystallized twice with 100 mL of toluene to give the desired 4-phenyl-2- [4- (4,6-diphenylpyridin-2-yl) -1,1 ′: 3 ′, 1 ′. A white powder (yield 11.6 g, 96%) of '-terphenyl-5'-yl] -benzo [h] quinazoline (E-2) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.44 to 7.50 (m, 2H), 7.51 to 7.59 (m, 7H), 7.61 to 7.67 (m, 7) 3H), 7.79-7.87 (m, 7H), 7.93-8.02 (m, 8H), 8.05 (t, J = 1.8 Hz, 1 H), 8.26 (dd, J = 8.3 Hz, 1.4 Hz, 2 H), 8, 39 (d, J = 8.4 Hz, 2 H), 9.09 (t, J = 1.6 Hz, 1 H), 9. 15 (t, J = 1.6 Hz, 1 H), 9. 60 (dd, J = 7.0 Hz, 2.4 Hz, 1 H).
Experimental Example-10 (Example)

Under an argon stream, 3.66 g (8.26 mmol) of 2- [5-chlorobiphenyl-3-yl] -4-phenylbenzo [h] quinazoline (E-1), 2.73 g (10.2) of bis (binacolato) diboron. 7 mmol), 151 mg (0.165 mmol) of bis (dibenzylideneacetone) palladium, 158 mg (0.331 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, and 1.62 g of potassium acetate (16 .5 mmol) was added to 165 mL THF and heated to reflux for 17 h. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting solid is recrystallized with a mixed solvent of 100 mL of toluene and 100 mL of methanol to give the desired 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl] Gray powder (yield 3.87 g, 88%) of (biphenyl-3-yl) -4-phenylbenzo [h] quinazoline (F-1) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 1.40 (s, 12 H), 7.38 (t, J = 7.3 Hz, 1 H), 7.49 (t, J = 7.6 Hz, 2H), 7.56-7.64 (m, 3H), 7.77-7.85 (m, 5H), 7.89-7.92 (m, 3H), 7.95 (d, J = 8.9 Hz, 1 H), 8. 18 (t, J = 1.3 Hz, 1 H), 9.14-9.16 (m, 2 H), 9.58 (dd, J = 7.0 Hz, 2.2 Hz , 1 H).
2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) biphenyl-3-yl] -4-phenylbenzo [h] quinazoline (F) under argon stream -1) 1.00 g (1.87 mmol), 547 mg (2.06 mmol) of 2- (4-chlorophenyl) -5-phenylpyridine, 8.4 mg (0.037 mmol) of palladium acetate, and 2-dicyclohexylphosphino-2 35.7 mg (0.075 mmol) of ', 4', 6'-triisopropylbiphenyl was added to 37 mL of THF, and further 1.3 mL of 3 M aqueous potassium carbonate solution was added and the mixture was heated to reflux for 24 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting solid is recrystallized with 200 mL of toluene to give the desired 4-phenyl-2- [4- (5-phenylpyridin-2-yl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl A white powder (yield: 953 mg, 80%) of -5'-yl] benzo [h] quinazoline (F-2) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.42 to 7.46 (m, 2 H), 7.50 to 7.57 (m, 4 H), 7.61 to 7.69 (m, 5) 5H), 7.82-7.87 (m, 5H), 7.92 (d, J = 8.3 Hz, 1 H), 7.94-8.04 (m, 8 H), 8.23 (d, 7 H) J = 8.3 Hz, 2 H), 8, 99 (d, J = 2.3 Hz, 1 H), 9.08 (t, J = 1.7 Hz, 1 H), 9. 14 (t, J = 1.8 Hz) , 1 H), 9.58 (dd, J = 7.4 Hz, 2.9 Hz, 1 H).
Experimental Example 11 (Example)

2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) biphenyl-3-yl] -4-phenylbenzo [h] quinazoline (F) under argon stream -1) 1.00 g (1.87 mmol), 547 mg (2.06 mmol) of 2- (4-chlorophenyl) -6-phenylpyridine, 8.4 mg (0.037 mmol) of palladium acetate, and 2-dicyclohexylphosphino-2 35.7 mg (0.075 mmol) of ', 4', 6'-triisopropylbiphenyl was added to 37 mL of THF, and further 1.3 mL of 3 M aqueous potassium carbonate solution was added and the mixture was heated to reflux for 24 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting crude product is purified by silica gel column chromatography (developing solvent: chloroform: hexane = 1: 1) to give the desired 4-phenyl-2- [4- (6-phenylpyridin-2-yl) -1, White powder (yield 943 mg, 79%) of 1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] benzo [h] quinazoline (F-3) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.43 to 7.47 (m, 2 H), 7.54 (dt, J = 8.3 Hz, 4 H), 7.61 to 7.67 (d) m, 3H), 7. 73 (d, J = 7.5 Hz, 1 H), 7.79-7.89 (m, 7 H), 7.94-8.04 (m, 7 H), 8.20 (m d, J = 7.2 Hz, 2 H), 8, 33 (d, J = 7.9 Hz, 2 H), 9.08 (t, J = 1.5 Hz, 1 H), 9. 14 (t, J = 1 .5 Hz, 1 H), 9.59 (dd, J = 5.9 Hz, 2.3 Hz, 1 H).
Experimental Example 12 (Example)

Under an argon stream, 10.0 g (22.4 mmol) of 2- (3-bromo-5-chlorophenyl) -4-phenylbenzo [h] quinazoline (A-3), 5.33 g (26.9 mmol) of 4-biphenylboronic acid And tetrakis (triphenylphosphine) palladium 518 mg (0.449 mmol) were added to 449 mL of THF, and 15.0 mL of 3 M aqueous potassium carbonate solution was further added, followed by heating to reflux for 32 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting solid is recrystallized twice with 800 mL of toluene to give the desired 2- [5-chloro-1,1 ': 4', 1 ''-terphenyl-3-yl] -4-phenylbenzo [h ] A gray powder of quinazoline (G-1) (yield 9.72 g, 83%) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.39 (t, J = 7.3 Hz, 1 H), 7.49 (t, J = 7.8 Hz, 2 H), 7.63 (d, J = 6.8 Hz, 3H), 7.68 (d, J = 7.0 Hz, 2H), 7.75-7.78 (m, 3H), 7.82-7.86 (m, 5H), 7.87-7.92 (m, 3 H), 8.00 (d, J = 9.1 Hz, 1 H), 8.82 (t, J = 1.8 Hz, 1 H), 9.0 (t, J = 1.6 Hz, 1 H), 9. 55 (d, J = 9.4 Hz, 1 H).
Under an argon stream, 2- [5-chloro-1,1 ′: 4 ′, 1 ′ ′-terphenyl-3-yl] -4-phenylbenzo [h] quinazoline (G-1) 894 mg (1.72 mmol) , 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2-phenylpyridine 508 mg (1.81 mmol), palladium acetate 8.7 mg (0.038 mmol), And 36.8 mg (0.078 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl are added to 34 mL of THF, and further 1.3 mL of 3 M aqueous potassium carbonate solution is added, and the solution is heated to reflux for 48 hours did. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting solid is recrystallized with 50 mL of toluene to give the desired 4-phenyl-2- [5- (6-phenylpyridin-3-yl) -1,1 ′: 4 ′, 1 ′ ′-terphenyl A white powder (yield 820 mg, 75%) of 3-yl] benzo [h] quinazoline (G-2) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.40 (t, J = 7.2 Hz, 1 H), 7.44-7.56 (m, 5 H), 7.61-7.68 ( m, 3 H), 7. 71 (d, J = 7.1 Hz, 2 H), 7.79 (d, J = 8.7 Hz, 2 H), 7.82-7.87 (m, 3 H), 7. 91-7.98 (m, 6 H), 8, 02 (d, J = 9.0 Hz, 1 H), 8.05 (t, J = 1.5 Hz, 1 H), 8.11 (d, J = 6) 8 Hz, 2 H), 8.21 (dd, J = 8.3 Hz, 2.3 Hz, 1 H), 9.14 (t, J = 1.5 Hz, 1 H), 8.17 (t, J = 1. 5 Hz, 1 H), 9.21 (d, J = 1.9 Hz, 1 H), 9.59 (dd, J = 6.8 Hz, 2.6 Hz, 1 H).
Experimental Example 13 (Example)

Under an argon stream, 2- [5-chloro-1,1 ′: 4 ′, 1 ′ ′-terphenyl-3-yl] -4-phenylbenzo [h] quinazoline (G-1) 5.50 g (10. 6 mmol), bis (binacolato) diboron 3.50 g (13.8 mmol), bis (dibenzylideneacetone) palladium 194 mg (0.212 mmol), 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl 202 mg (0.424 mmol) and 2.08 g (21.2 mmol) of potassium acetate were added to 212 mL of THF, and the mixture was heated to reflux for 46 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting solid is recrystallized with 150 mL of toluene to give the desired 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,1 ′. Gray powder (yield 5.63 g, 87%) of 4 ′, 1 ′ ′-terphenyl-3-yl] -4-phenylbenzo [h] quinazoline (H-1) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.38 (t, J = 7.4 Hz, 1 H), 7.47 (t, J = 7.9 Hz, 2 H), 7.60-7. 67 (m, 3 H), 7.69 (d, J = 7.1 Hz, 2 H), 7. 74 (d, J = 8.5 Hz, 2 H), 8.80-8.86 (m, 3 H), 7.90 (d, J = 8.5 Hz, 2 H), 7.94 (d, J = 8.0 Hz, 3 H), 7.98 (d, J = 9.0 Hz, 1 H), 8. 25 (d , J = 2.0 Hz, 1 H), 9.19 (t, J = 1.7 Hz, 1 H), 9.22 (t, J = 1.7 Hz, 1 H), 9. 61 (d, J = 7. 1 Hz, 1 H).
Under an argon stream, 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,1 ′: 4 ′, 1 ′ ′-terphenyl-3 -Yl] -4-phenylbenzo [h] quinazoline (H-1) 1.00 g (1.64 mmol), 4- (4-chlorophenyl) isoquinoline 432 mg (1.80 mmol), palladium acetate 7.4 mg (0.033 mmol) ), And 31.3 mg (0.066 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl are added to 33 mL of THF, and further 1.1 mL of 3 M aqueous potassium carbonate solution is added, and 19 hours Heated to reflux. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The obtained solid is recrystallized with 100 mL of toluene to obtain the target 4-phenyl-2- [4- (4-isoquinolyl) -1,1 ′: 3 ′, 1 ′ ′: 4 ′ ′, 1 ′ ′ A white powder (yield 793 mg, 70%) of '-quaterphenyl-5'-yl] benzo [h] quinazoline (H-2) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.39 (t, J = 7.4 Hz, 1 H), 7.50 (t, J = 7.8 Hz, 2 H), 7.60-7. 76 (m, 9 H), 7.79 (d, J = 8.6 Hz, 2 H), 7.83-7.89 (m, 3 H), 7.95-7.98 (m, 5 H), 8. 00-8.03 (m, 3 H), 8, 08 (t, J = 6.8 Hz, 2 H), 8.1 1 (t, J = 1.8 Hz, 1 H), 8.6 1 (s, 1 H), 9.16 (dd, J = 1.7 Hz, 0.86 Hz, 2 H), 9.30 (s, 1 H), 9. 61 (dd, J = 6.4 Hz, 2.6 Hz, 1 H).
Experimental Example 14 (Example)

Under an argon stream, 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,1 ′: 4 ′, 1 ′ ′-terphenyl-3 -Yl] -4-phenylbenzo [h] quinazoline (H-1) 1.00 g (1.64 mmol), 8- (4-chlorophenyl) quinoline 432 mg (1.80 mmol), palladium acetate 7.4 mg (0.033 mmol) ), And 31.3 mg (0.066 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl are added to 33 mL of THF, and further 1.1 mL of 3 M aqueous potassium carbonate solution is added, and 19 hours Heated to reflux. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting solid is recrystallized with 100 mL of toluene to obtain the desired 4-phenyl-2- [4- (8-quinolyl) -1,1 ′: 3 ′, 1 ′ ′: 4 ′ ′, 1 ′ ′ A white powder (yield 770 mg, 68%) of '-quaterphenyl-5'-yl] benzo [h] quinazoline (H-3) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.39 (t, J = 7.3 Hz, 1 H), 7.45-7.53 (m, 3 H), 7.63-7.73 ( m, 6H), 7.80 (td, J = 8.6 Hz, 2.9 Hz, 2 H), 7.85-7.92 (m, 7 H), 7.93-8.00 (m, 7 H), 8.02 (dd, J = 8.8 Hz, 2.9 Hz, 1 H), 8, 11 (dt, J = 2.8 Hz, 1.8 Hz, 1 H), 8. 25 (dt, J = 8.7 Hz, 2.5 Hz, 1 H), 9.04 (dt, J = 4.2 Hz, 9.2 Hz, J = 2.3 Hz, 1 H), 9. 13 (dt, J = 2.8 Hz, 1.8 Hz, 1 H) , 9.19 (dt, J = 2.8 Hz, 1.6 Hz, 1 H), 9.63 (dt, J = 7.0 Hz, 2.1 Hz, 1 H).
Experimental Example 15 (Example)

Under an argon stream, 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,1 ′: 4 ′, 1 ′ ′-terphenyl-3 -Yl] -4-phenylbenzo [h] quinazoline (H-1) 1.00 g (1.64 mmol), 2-chloro-5-phenylpyridine 342 mg (1.80 mmol), palladium acetate 7.4 mg (0.033 mmol) ), And 31.3 mg (0.066 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl are added to 33 mL of THF, and further 1.1 mL of 3 M aqueous potassium carbonate solution is added for 48 hours. Heated to reflux. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting solid is recrystallized with 30 mL of toluene to give the desired 4-phenyl-2- [5- (5-phenylpyridin-2-yl) -1,1 ′: 4 ′, 1 ′ ′-terphenyl. A white powder (yield 476 mg, 45%) of 3-yl] benzo [h] quinazoline (H-4) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.40 (t, J = 7.4 Hz, 1 H), 7.45 (t, J = 7.3 Hz, 1 H), 7.52 (td, J = 8.1 Hz, 4 H), 7.62-7.68 (m, 3 H), 7. 70-7. 73 (m, 4 H), 7. 78-7. 80 (d, J = 8.4 Hz) , 2H), 7.82-7.87 (m, 3H), 7.96-7.99 (m, 5H), 8.01 (d, J = 9.3 Hz, 1 H), 8.05-8 .13 (m, 2H), 8.58 (t, J = 1.9 Hz, 1 H), 9.05 (d, J = 2.4 Hz, 1 H), 9.21 (t, J = 1.3 Hz, 1H), 9.44 (t, J = 1.4 Hz, 1 H), 9.62 (dd, J = 6.8 Hz, 2.5 Hz, 1 H).
Experimental Example 16 (Example)

Under an argon stream, 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,1 ′: 4 ′, 1 ′ ′-terphenyl-3 -Yl] -4-phenylbenzo [h] quinazoline (H-1) 1.00 g (1.64 mmol), 2-bromo-6-phenylpyridine 552 mg (1.97 mmol), and tetrakis (triphenylphosphine) palladium 38 .0 mg (0.033 mmol) was added to 33 mL of THF, and further 1.1 mL of 3 M aqueous potassium carbonate solution was added, and the mixture was heated to reflux for 37 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The resulting solid is recrystallized with 450 mL of toluene to give the desired 4-phenyl-2- [5- (6-phenylpyridin-2-yl) -1,1 ′: 4 ′, 1 ′ ′-terphenyl White powder (yield 906 mg, 87%) of 3-yl] benzo [h] quinazoline (H-5) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.39 (tt, J = 7.3 Hz, 1.2 Hz, 1 H), 7.45-7.52 (m, 3 H), 7.55 ( t, J = 7.2 Hz, 2 H), 7.62-7.68 (m, 3 H), 7.71 (dd, J = 8.3 Hz, 1.5 Hz, 2 H), 7.79-7.87 (M, 6 H), 7.93 (t, J = 7.5 Hz, 1 H), 7.96-8.00 (m, 6 H), 8.03 (d, J = 9.2 Hz, 1 H), 8 .28 (dd, J = 8.6 Hz, 1.5 Hz, 2 H), 8.66 (t, 1.8 Hz, 1 H), 9.19 (t, J = 1.8 Hz, 1 H), 9.61 ( t, J = 1.8 Hz, 1 H, 9.64 (dd, J = 7.2 Hz, 2.3 Hz, 1 H).
Experimental Example 17 (Example)

Under an argon stream, 2- (3-bromo-5-chlorophenyl) -4-phenylbenzo [h] quinazoline (A-3) 5.0 g (11.2 mmol), 4-biphenylboronic acid 4.89 g (24.7 mmol) ), 50.4 mg (0.224 mmol) of palladium acetate, and 214 mg (0.449 mmol) of 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl are added to 200 mL of THF, and 3 M aqueous potassium carbonate 15.0 mL was added and heated to reflux for 72 hours. After cooling to room temperature, water was added and the precipitated solid was collected by filtration and then washed with water, methanol and hexane. The obtained solid is recrystallized twice with 800 mL of toluene to give the desired 2- (1,1 ': 4', 1 '': 3 '', 1 ''':4''', 1 ''. A white powder (yield 6.23 g, 87%) of '' -quincphenyl-5 ''-yl) -4-phenylbenzo [h] quinazoline (H-6) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.38 (t, J = 7.3 Hz, 2H), 7.50 (t, J = 7.3 Hz, 3H), 7.60-7. 65 (m, 4 H), 7.67-7.69 (t, J = 8.6 Hz, 3 H), 7.7 4-7. 79 (m, 4 H), 7.8 2-7. 86 (m, 6 H) ) 7.92-8.02 (m, 6 H), 8.81 (t, J = 1.8 Hz, 1 H), 9.00 (t, J = 1.5 Hz, 1 H), 9. 11 (d , J = 1.8 Hz, 1 H), 9. 55 (dd, J = 5.9 Hz, 2.9 Hz, 1 H).
Test Example 1 (Example)
The preparation and evaluation of the organic electroluminescent device were performed as follows. As a substrate, a glass substrate with an ITO transparent electrode in which an indium tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. The substrate was washed with isopropyl alcohol and then surface-treated by oxygen plasma washing. Each layer was vacuum deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescent device having a light emitting area of 4 mm ² as shown in FIG. 1 was produced.

First, the glass substrate was introduced into a vacuum deposition 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 shown at 1 in FIG. 1, and then a cathode layer 6 is formed. I made a film.
As the hole injection layer 2, HIL of sublimation purification was vacuum deposited with a film thickness of 65 nm.
As the hole transport layer 3, HAT and HTL were vacuum deposited with film thicknesses of 5 nm and 10 nm, respectively.
As the light emitting layer 4, EML-1 and EML-2 were vacuum deposited at a thickness of 25 nm at a ratio of 954: 46 (% by mass).
As the electron transport layer 5, 4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-obtained in Experimental Example 3 of the present invention Terphenyl-5'-yl] benzo [h] quinazoline (A-4) was vacuum deposited at a thickness of 30 nm.
Finally, a metal mask was disposed to be orthogonal to the ITO stripes, and the cathode layer 6 was formed. As the cathode layer 6, Liq and silver magnesium and silver were vacuum-deposited with film thicknesses of 0.5 nm, 80 nm and 20 nm, respectively, to form a three-layer structure.

  Each organic material was formed into a film by a resistance heating method, and the heated compound was vacuum deposited at a film forming rate of 0.6 to 3.0 nm / sec.

  Each film thickness was measured with a stylus type film thickness measurement meter (DEKTAK). Furthermore, this element was sealed in a nitrogen atmosphere glove box with an oxygen and water concentration of 1 ppm or less. Sealing used the sealing cap made from glass, and the said film-forming board | substrate epoxy-type ultraviolet-ray cured resin (made by Nagase ChemteX Corp.). The structural formulas and abbreviations of the compounds used are shown below.

A direct current was applied to the produced organic electroluminescent device, and the luminescence characteristics were evaluated using a luminance meter manufactured by TOPCON, LUMINANCE METER (BM-9). As light emission characteristics, voltage (V), luminance (cd / m ² ), current efficiency (cd / A), and power efficiency (lm / W) were measured at a current density of 10 mA / cm ² .

Test Example 2 (Example)
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 4-phenyl-2- [5- (1-pyrenyl) -4 ′-(2-pyridyl) biphenyl-3-yl obtained in Experimental Example 4 in place of benzo [h] quinazoline (A-4) An organic electroluminescent element was produced in the same manner as in Test Example 1 except that benzo [h] quinazoline (B-2) was used, and was evaluated in the same manner as in Test example-1.

Test Example 3 (Example)
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 2- [3- (9-phenanthryl) -5- (6-phenylpyridin-3-yl) phenyl] -4- 4 obtained in Experimental Example 5 in place of benzo [h] quinazoline (A-4) An organic electroluminescent device was produced in the same manner as in Test Example 1 except that phenylbenzo [h] quinazoline (C-2) was used, and was evaluated in the same manner as in Test Example-1.

Test Example 4 (Example)
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 2- [3- (9-phenanthryl) -5- (3-pyridyl) phenyl] -4-phenylbenzo [h] obtained in Experimental Example 7 in place of benzo [h] quinazoline (A-4) An organic electroluminescent device was produced in the same manner as in Test Example 1 except that quinazoline (C-4) was used, and was evaluated in the same manner as in Test Example 1.

Test Example 5 (Example)
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 4-phenyl-2- [4- (4,6-diphenylpyridin-2-yl) -1,1 ′: 3 obtained in Experimental Example 9 in place of benzo [h] quinazoline (A-4) An organic electroluminescent device was produced in the same manner as in Test Example 1 except that ', 1'-terphenyl-5'-yl] -benzo [h] quinazoline (E-2) was used, and Test Example- It evaluated similarly to 1.

Test Example 6 (Example)
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 4-phenyl-2- [4- (5-phenylpyridin-2-yl) -1,1 ′: 3 ′ obtained in Experimental Example 10 in place of benzo [h] quinazoline (A-4) An organic electroluminescent device was produced in the same manner as in Test Example 1 except that 1 ′ ′-terphenyl-5′-yl] benzo [h] quinazoline (F-2) was used, and in the same manner as in Test Example-1. Evaluated.

Test Example 7 (Example)
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 4-phenyl-2- [4- (6-phenylpyridin-2-yl) -1,1 ′: 3 ′, obtained in Experimental Example 11 in place of benzo [h] quinazoline (A-4) An organic electroluminescent device was produced in the same manner as in Test Example 1 except that 1 ′ ′-terphenyl-5′-yl] benzo [h] quinazoline (F-3) was used, and in the same manner as in Test Example 1. Evaluated.

Test Example 8 (Example)
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 4-phenyl-2- [5- (6-phenylpyridin-3-yl) -1,1 ′: 4 ′ obtained in Experimental Example 12 in place of benzo [h] quinazoline (A-4) An organic electroluminescent device was produced in the same manner as in Test Example 1 except that 1 ′ ′-terphenyl-3-yl] benzo [h] quinazoline (G-2) was used, and in the same manner as in Test Example 1. evaluated.

Test Example 9 (Example)
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 4-phenyl-2- [4- (4-isoquinolyl) -1,1 ′: 3 ′, 1 ′ ′: 4 obtained in Experimental Example 13 in place of benzo [h] quinazoline (A-4) An organic electroluminescent device was produced and tested in the same manner as in Test Example 1 except that '', 1 '''-quaterphenyl-5'-yl] benzo [h] quinazoline (H-2) was used. It evaluated similarly to Example-1.

Test Example 10 (Example)
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 4-phenyl-2- [4- (8-quinolyl) -1,1 ′: 3 ′, 1 ′ ′: 4 obtained in Experimental Example 14 in place of benzo [h] quinazoline (A-4) An organic electroluminescent device was produced and tested in the same manner as in Test Example 1 except that '', 1 '''-quaterphenyl-5'-yl] benzo [h] quinazoline (H-3) was used. It evaluated similarly to Example-1.

Test Example 11 (Example)
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 4-phenyl-2- [5- (5-phenylpyridin-2-yl) -1,1 ′: 4 ′ obtained in Experimental Example 15 in place of benzo [h] quinazoline (A-4) An organic electroluminescent device was produced in the same manner as in Test Example 1 except that 1 ′ ′-terphenyl-3-yl] benzo [h] quinazoline (H-4) was used, and in the same manner as in Test Example 1. evaluated.

Test Example 12 (Example)
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 2- (1,1 ′: 4 ′, 1 ′ ′: 3 ′ ′, 1 ′ ′ ′: 4 ′ ′ ′ obtained in Experimental Example 17 in place of benzo [h] quinazoline (A-4) An organic electroluminescent device was produced in the same manner as in Test Example 1, except that And evaluated in the same manner as in Test Example-1.

Reference Example 1
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 In place of the benzo [h] quinazoline (A-4), 2,4-diphenyl-6- [4,4 ′ ′-di (2-pyridyl) -1,1 ′: 3 described in Patent No. WO2008 / 129912 The organic electroluminescent element which vacuum-deposited ', 1''-terphenyl5'-yl] -1, 3, 5- triazine (represented by a following formula) was produced similarly to Test example 1, and it measured. did.

Comparative Example 1
4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] of the electron transport layer 5 of Test Example 1 Test Example-An organic electroluminescent device in which 2,4-diphenylbenzoquinazoline (represented by the following formula) described in Patent No. WO 2006/104118 (which is represented by the following formula) is vacuum-deposited instead of benzo [h] quinazoline (A-4) It was prepared and measured in the same manner as 1.

The measurement results of Test Examples 1 to 12, Reference Example 1 and Comparative Example 1 are summarized in the following table.

  The thin film comprising the compound (1-1) or the compound (1-2) of the present invention has high thin film stability, heat resistance, electron transportability, hole blocking ability, redox resistance, water resistance, oxygen resistance, In order to exhibit an electron injection property etc., it can be used suitably as an electron transport material especially as a material of an organic electroluminescent element. In addition, the compound (1-1) and the compound (1-2) of the present invention have a wide energy gap and triplet energy, and can be used in combination with a fluorescent or phosphorescent organic electroluminescent material. In addition to the electron transport layer, the compound (1-1) and the compound (1-2) of the present invention can also be used for a light emitting host layer and the like because of their properties. Moreover, even if it mixes with another compound as an electron carrying layer or it can laminate, it can be used. Furthermore, the compound is highly soluble, and can be used for coated elements other than vapor deposition. From these effects, these elements are expected to have significant effects such as suppression of battery consumption by reduction of power consumption, improvement of product life by extension of life, reduction of load on drive circuits, and the like.

1. Glass substrate with ITO transparent electrode Hole injection layer 3. Hole transport layer 4. Light emitting layer 5. Electron transport layer 6. Cathode layer

Claims (12)

The benzoquinazoline compound shown by General formula (1-1) or General formula (1-2).
(In the formula,
Ar ¹¹ and Ar ^{21 each} represent an aromatic hydrocarbon group having 6 to 12 carbon atoms (a methyl group, a methoxy group, a pyridyl group, a pyrimidyl group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group , An ester group or an ester alkyl group).
Each of Ar ¹² , Ar ¹³ , Ar ²² and Ar ²³ independently represents a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with a C 6-18 aromatic hydrocarbon group, or a benzene ring and / or An aromatic group consisting of only a 6-membered ring in which 2 to 6 pyridine rings are linked and / or fused {these groups are methyl, methoxy, fluorine atom, pyrimidyl group (the pyrimidyl group is methyl, carbon And at least one substituent selected from the group consisting of an alkyl group of 2 to 10 and an aromatic hydrocarbon group of 6 to 18 carbon atoms), or an alkyl group of 2 to 10 carbon atoms, An alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group).
^{R 11, R 12, R 13} , R 14, R 15, R 16, R 21, R 22, R 23, R 24, R 25 and ^{R 26,} each independently, a hydrogen atom, a methyl group, a methoxy group And a phenyl group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.
Each hydrogen atom in the formula may be independently a deuterium atom. ) Ar ¹² , Ar ¹³ , Ar ²² and Ar ²³ each independently represent a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a benzene ring and / or Aromatic groups consisting of only 6-membered rings in which 2 to 6 pyridine rings are linked and / or fused {these groups are methyl, methoxy, alkyl having 2 to 10 carbon atoms, 2 to 10 carbon atoms An alkoxy group, a fluorine atom or a pyrimidyl group (wherein the pyrimidyl group has at least one substituent selected from the group consisting of a methyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a pyrenyl group) The benzoquinazoline compound according to claim 1, which is optionally substituted). Ar ¹² , Ar ¹³ , Ar ²² and Ar ²³ each independently represent a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a benzene ring and / or Aromatic groups consisting of only 6-membered rings in which 2 to 5 pyridine rings are linked and / or fused {these groups are methyl, methoxy, alkyl having 2 to 10 carbon atoms, 2 to 10 carbon atoms An alkoxy group, a fluorine atom or a pyrimidyl group (wherein the pyrimidyl group has at least one substituent selected from the group consisting of a methyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a pyrenyl group) The benzoquinazoline compound according to claim 1 or 2, which is optionally substituted). Ar ¹² , Ar ¹³ , Ar ²² and Ar ²³ each independently represent a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a benzene ring and / or Aromatic groups consisting of only 6-membered rings in which 2 to 4 pyridine rings are linked and / or fused {these groups are methyl, methoxy, alkyl having 2 to 10 carbon atoms, 2 to 10 carbon atoms An alkoxy group, a fluorine atom or a pyrimidyl group (wherein the pyrimidyl group has at least one substituent selected from the group consisting of a methyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a pyrenyl group) Which may be substituted), and the benzoquinazoline compound as described in any one of Claims 1-3. Ar ¹¹ and Ar ²¹ each represent an aromatic hydrocarbon group having 6 to 12 carbon atoms (these groups are methyl, methoxy, alkyl having 2 to 10 carbons or alkoxy, pyridyl, pyrimidyl, or fluorine atom The benzoquinazoline compound according to any one of claims 1 to 4, which is optionally substituted. Ar ¹¹ and Ar ^{21 each} represent a phenyl group, a naphthyl group or a biphenyl group (these groups are methyl, methoxy, pyridyl, pyrimidyl, fluorine, or an alkyl group having 2 to 10 carbon atoms, alkoxy, alkoxy The 2,4-substituted benzoquinazoline compound according to any one of claims 1 to 4, which is an alkyl group, an ester group or an ester alkyl group. The benzoquinazoline compound as described in any one of Claims 1-4 whose Ar < ¹¹ > and Ar < ²¹ > is a phenyl group, a naphthyl group, or a biphenyl group. The benzoquinazoline compound as described in any one of Claims 1-4 whose Ar < ¹¹ > and Ar < ²¹ > is a phenyl group. The R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are hydrogen atoms. The benzoquinazoline compound according to one aspect. The material for organic electroluminescent elements containing the benzoquinazoline compound of any one of Claims 1-9. A light emitting layer host material, an electron injecting material or an electron transporting material comprising the benzoquinazoline compound according to claim 1. An electron injecting material or an electron transporting material comprising the benzoquinazoline compound according to claim 1.