JP6969081B2 - Cyclic azine compounds, their production methods, production intermediates, and uses - Google Patents

Description

The present invention relates to a cyclic azine compound useful as a constituent component of an organic electroluminescent device, a method for producing the same, a production intermediate, and an application thereof.

The basic structure of an organic electroluminescent element is that a light emitting layer containing a light emitting material is sandwiched between a hole transport layer and an electron transport layer, and an anode and a cathode are attached to the outside thereof, and the positive is injected into the light emitting layer. It is an element that utilizes the emission of light (fluorescence or phosphorescence) associated with exciton deactivation caused by the recombination of holes and electrons, and is applied to displays and the like. The hole transport layer is divided into a hole transport layer and a hole injection layer, the light emitting layer is divided into an electron block layer, a light emitting layer and a hole block layer, and the electron transport layer is divided into an electron transport layer and an electron injection layer. It may be configured.

In recent years, triazine, pyrimidine, and pyridine compounds (for example, Patent Document 1-7) have been widely used for light emitting layers, electron transport layers, and the like, but they have been completely reported in terms of luminous efficiency characteristics, drive voltage characteristics, and long life characteristics. It cannot be said that it meets the market demand, and even better materials are required.

In addition, many examples have been reported in which triazine (for example, Non-Patent Document 1) and a pyrimidine compound (for example, Patent Document 8) are used for an electron transport layer or the like in an organic electroluminescent device utilizing thermally activated delayed fluorescence (TADF). In terms of emission efficiency characteristics, drive voltage characteristics, and lifetime characteristics, it cannot be said that the market requirements are completely satisfied, and improvement of triazine and pyrimidine compounds is required.

Japanese Unexamined Patent Publication No. 2004-22334 Japanese Unexamined Patent Publication No. 2008-280330 Japanese Unexamined Patent Publication No. 2010-155826 International Publication No. 2010/072300 Pamphlet US Publication No. 2014/376656 Pamphlet Korea Public Publication No. 2012/158474 Pamphlet International Publication No. 2010/080471 Pamphlet Japanese Unexamined Patent Publication No. 2014-22666

Scientific Reports, Volume 3, 2127-2132, 2013

Although organic electroluminescent devices have begun to be used in various display devices, there is a demand for higher performance of the devices such as longer life, higher luminous efficiency, and lower drive voltage. More specifically, there is a demand for the development of carrier transport materials that achieve long life, high luminous efficiency, low drive voltage, and suppression of voltage rise during drive.

Among the carrier transport materials, the electron injection material and the electron transport material are new materials that drive the device at a low voltage due to its excellent electron injection property and electron transport characteristics, and also have high luminous efficiency and drive the device for a long time. It is desired. In particular, in an organic electroluminescent element utilizing phosphorescence emission and TADF, a light emitting material having a high excited triplet level and a carrier transport material are desired in order to realize high emission efficiency at the same time as extending the life and reducing the driving voltage. It is rare.

As a result of diligent studies to solve the above problems, the present inventors have found that the cyclic azine compound represented by the general formula (1) of the present invention has higher electron durability and positive holes than the conventionally known compounds. We have found that the hole durability is significantly improved. Further, the inventors have found that the cyclic azine compound represented by the general formula (1) of the present invention has an improved excited triplet level as compared with a conventionally known compound. Based on these findings, it was found that when the cyclic azine compound is used as an electron transport layer in an organic electroluminescent device, the life of the organic electroluminescent device is extended as compared with the case where a known or general-purpose electron transport material is used. The finding has led to the completion of the present invention.

That is, the present invention relates to a cyclic azine compound represented by the following general formula (1) of the present invention (hereinafter, also referred to as "compound (1)"), a method for producing the same, and an organic electroluminescent element containing the same. be.

{In the formula,
At least two Rs in at least one ring of the benzene rings A, B, C may be independently linked and / or condensed, respectively, and an aromatic hydrocarbon group having 6 to 30 carbon atoms (the group is a group). , Independently, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and an alkyl halide group having 1 to 3 carbon atoms. Alternatively, it may have a halide alkoxy group having 1 to 3 carbon atoms as a substituent).
Rs other than the above are independently hydrogen atom, heavy hydrogen atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, and methylthio group. , Ethylthio group, sulfide group having 3 to 10 carbon atoms, or aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed (the groups are independently fluorine atoms and methyl. Group, ethyl group, alkyl group with 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group with 3 to 10 carbon atoms, alkyl halide group with 1 to 3 carbon atoms, or alkoxy halide with 1 to 3 carbon atoms. It may have a group as a substituent).
One of Y ¹ , Y ² and Y ³ represents = N-, and the others represent = CH- or = N-. }
The present invention also relates to a method for producing the compound (1), a production intermediate extremely useful for industrially producing the compound (1), and uses of the compound (1).

Hereinafter, the present invention will be described in detail.

The substituents in the compound (1) of the present application are defined as follows.

The aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed in R defines only the ring skeleton which may be condensed or linked, and the aromatic hydrocarbon. The carbon number of the group does not include the carbon number of the substituent which may be separately contained. The aromatic hydrocarbon group having 6 to 30 carbon atoms is not particularly limited as long as it is a monocyclic ring or a condensed or linked product thereof.

That is, the aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed has a ring skeleton having a total carbon number of 6 to 30 and is a single ring, and has two or more rings. Condensed or concatenated with two or more rings.

The aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed is not particularly limited, and is, for example, a phenyl group, a biphenylyl group, a turphenyl group, a naphthyl group, or binaphthyl. Group, naphthylphenyl group, phenylnaphthyl group, naphthylbiphenyl group, biphenylnaphthyl group, diphenylnaphthyl group, phenylnaphthylphenyl group, anthryl group, anthrylphenyl group, phenylanthryl group, phenylanthrylphenyl group, phenanthryl group, Fe Nantrilphenyl group, phenylphenanthril group, pyrenyl group, phenylpyrenyl group, pyrenylphenyl group, fluorenyl group, fluorenylphenyl group, phenylfluorenyl group, fluoranthenyl group, phenylfluoranthenyl group, Fluolanthenylphenyl group, perylenelyl group, phenylperyleneyl group, peryleneylphenyl group, triphenylenyl group, phenyltriphenylenyl group, triphenylenylphenyl group, tetrasenyl group, phenyltoterasenyl group, tetrasenylphenyl group , Chrysenyl group, phenylchrysenyl group, chrysenylphenyl group and the like.

The alkyl group having 3 to 10 carbon atoms in R is not particularly limited, but for example, a propyl group (n-propyl group, isopropyl group), a butyl group (n-butyl group, sec-butyl group, isobutyl). Group, tert-butyl group), pentyl group (n-pentyl group, sec-pentyl group, isopentyl group, cyclopentyl group), hexyl group (n-hexyl group, cyclohexyl group), n-heptyl group, n-octyl group, Examples thereof include an n-nonyl group, an n-decyl group, a benzyl group, a phenethyl group and the like.

The alkoxy group having 3 to 10 carbon atoms in R is not particularly limited, but for example, a propoxy group (n-propoxy group, isopropoxy group), a butoxy group (n-butoxy group, sec-butoxy group, etc.) Isobutoxy group, tert-butoxy group), pentyloxy group (n-pentyloxy group, sec-pentyloxy group, isopentyloxy group, cyclopentyloxy group), hexyloxy group (n-hexyloxy group, cyclohexyloxy group), Examples thereof include an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, a benzyloxy group, a phenethyloxy group and the like.

The alkyl halide group having 1 to 3 carbon atoms in R is not particularly limited, and is, for example, chloromethyl group, dichloromethyl group, trichloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloroethyl. Examples thereof include a group, a dichloroethyl group, a trichloroethyl group, a pentachloroethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a pentafluoroethyl group, a chloropropyl group, a fluoropropyl group and the like.

The halogenated alkoxy group having 1 to 3 carbon atoms in R is not particularly limited, and is, for example, a chloromethyloxy group, a dichloromethyloxy group, a trichloromethyloxy group, a fluoromethyloxy group, or a difluoromethyloxy group. Group, trifluoromethyloxy group, chloroethyloxy group, dichloroethyloxy group, trichloroethyloxy group, pentachloroethyloxy group, fluoroethyloxy group, difluoroethyloxy group, trifluoroethyloxy group, pentafluoroethyloxy group Examples thereof include a group, a chloropropyloxy group, a fluoropropyloxy group and the like.

The sulfide group having 3 to 10 carbon atoms in R is not particularly limited, but for example, a propyl sulfide group (n-propyl sulfide group, isopropyl sulfide group), a butyl sulfide group (n-butyl sulfide group, sec). -Butyl sulfide group, isobutyl sulfide group, tert-butyl sulfide group), pentyl sulfide group (n-pentyl sulfide group, sec-pentyl sulfide group, isopen tyl sulfide group, cyclopentyl sulfide group), hexyl sulfide group (n-hexyl sulfide group) Group, cyclohexyl sulfide group), n-heptyl sulfide group, n-octyl sulfide group, n-nonyl sulfide group, n-decyl sulfide group, benzyl sulfide group, phenethyl sulfide group and the like.

In R, the aromatic hydrocarbon groups having 6 to 30 carbon atoms, which may be linked and / or condensed, are independently a fluorine atom, a methyl group, an ethyl group, and an alkyl group having 3 to 10 carbon atoms. It has a substituent selected from the group consisting of a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, and an alkoxy halide group having 1 to 3 carbon atoms. Also, the substituent may be plural. When there are a plurality of substituents on an aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed, each substituent may be the same or different. The definitions of substituents described in this paragraph are as described above.

As the substituent which may be possessed by the aromatic group having 6 to 30 carbon atoms which may be linked and / or condensed, the fluorine atom, the methyl group and the butyl are excellent in the property of the electron transport material. A group, a methoxy group, a butoxy group, a methyl halide group, or a methoxy halide group is preferable, and a methyl group or a fluorine atom is more preferable.

The benzene ring A is preferably any of the following general formulas (A-1) to (A-14) in that it is excellent in electron transport material properties.

(In the general formulas (A-1) to (A-14), R follows the definition of the general formula (1).)
Of the substituents represented by the general formulas (A-1) to (A-14), (A-4) or (A-12) is preferable in terms of excellent electron transport characteristics, and (A-12) is preferable. ) Is more preferable.

The benzene ring B is preferably a substituent represented by any of the following general formulas (B-1) to (B-14) in that it is excellent in electron transport material properties.

(In the general formulas (B-1) to (B-14), R follows the definition of the general formula (1).)
Among the substituents represented by the general formulas (B-1) to (B-14), (B-5), (B-10), (B-12), and (B-12), in that they are excellent in electron transport characteristics. The substituent represented by (B-13) or (B-14) is preferable.

The benzene ring C is preferably a substituent represented by any of the following general formulas (C-1) to (C-14) in that it is excellent in electron transport material properties.

(In the general formulas (C-1) to (C-14), R follows the definition of the general formula (1).)
Among the substituents represented by the general formulas (C-1) to (C-14), (C-1), (C-5), (C-6), and (C-6), in that they are excellent in electron transport characteristics. (C-10), (C-12), (C-13), or (C-14) is preferable, (C-1) or (C-6) is more preferable, and (C-1) is more preferable. ..

{In the formula,
At least two Rs in at least one ring of the benzene rings A, B, C may be independently linked and / or condensed, respectively, and an aromatic hydrocarbon group having 6 to 30 carbon atoms (the group is a group). , Independently, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and an alkyl halide group having 1 to 3 carbon atoms. Alternatively, it may have a halide alkoxy group having 1 to 3 carbon atoms as a substituent).
Rs other than the above are independently hydrogen atom, heavy hydrogen atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, and methylthio group. , Ethylthio group, sulfide group having 3 to 10 carbon atoms, or aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed (the groups are independently fluorine atoms and methyl. Group, ethyl group, alkyl group with 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group with 3 to 10 carbon atoms, alkyl halide group with 1 to 3 carbon atoms, or alkoxy halide with 1 to 3 carbon atoms. It may have a group as a substituent).
One of Y ¹ , Y ² and Y ³ represents = N-, and the others represent = CH- or = N-. }

{In the formula,
At least two Rs in at least one ring of the benzene rings A, B, C may be independently linked and / or condensed, respectively, and an aromatic hydrocarbon group having 6 to 30 carbon atoms (the group is a group). , Independently, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and an alkyl halide group having 1 to 3 carbon atoms. Alternatively, it may have a halide alkoxy group having 1 to 3 carbon atoms as a substituent).
Rs other than the above are independently hydrogen atom, heavy hydrogen atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, and methylthio group. , Ethylthio group, sulfide group having 3 to 10 carbon atoms, or aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed (the groups are independently fluorine atoms and methyl. Group, ethyl group, alkyl group with 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group with 3 to 10 carbon atoms, alkyl halide group with 1 to 3 carbon atoms, or alkoxy halide with 1 to 3 carbon atoms. It may have a group as a substituent).
One of Y ¹ , Y ² and Y ³ represents = N-, and the others represent = CH- or = N-. }
Further, the cyclic azine compound represented by the above general formulas (1), (4), (6) and the like has excellent electron transport characteristics in at least one of the benzene rings A, B and C. At least two Rs may be independently linked and / or fused to an aromatic hydrocarbon group having 6 to 17 carbon atoms (each of which is independently a fluorine atom, a methyl group, or an ethyl). Substitutes a group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a halogenated alkoxy group having 1 to 3 carbon atoms. It may have as a group), and R other than the above independently represents a hydrogen atom, a heavy hydrogen atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, and an ethoxy group. , An alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, a sulfide group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 17 carbon atoms which may be linked and / or condensed. The groups are independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and an alkyl halide having 1 to 3 carbon atoms. It may have a group or a halogenated alkoxy group having 1 to 3 carbon atoms as a substituent), and R ¹ is independently a hydrogen atom, a heavy hydrogen atom, a methyl group, and an ethyl. A group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, a sulfide group having 3 to 10 carbon atoms, or an aromatic having 6 to 17 carbon atoms. A hydrocarbon group (each of which is independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and 1 to 1 carbon atoms. It may have an alkyl halide group of 3 or an alkoxy halide group having 1 to 3 carbon atoms as a substituent), or it preferably represents a linking site with X.

The aromatic hydrocarbon group having 6 to 17 carbon atoms which may be linked and / or condensed in R defines only the ring skeleton which may be condensed or linked, and the aromatic hydrocarbon. The carbon number of the group does not include the carbon number of the substituent which may be separately contained. The aromatic hydrocarbon group having 6 to 17 carbon atoms is not particularly limited as long as it is a monocyclic ring or a condensed or linked product thereof.

That is, the aromatic hydrocarbon group having 6 to 17 carbon atoms which may be linked and / or condensed has a ring skeleton having a total carbon number of 6 to 17 and is a single ring, and has two or more rings. Condensed or concatenated with two or more rings.

The aromatic hydrocarbon group having 6 to 17 carbon atoms which may be linked and / or condensed is not particularly limited, and is, for example, a phenyl group, a biphenylyl group, a naphthyl group, a naphthylphenyl group, or phenyl. Examples thereof include a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a fluorenyl group, a fluoranthenyl group and the like.

Regarding R in the general formula (1), at least two Rs in at least one ring of the benzene rings A, B, and C, and 0, 1, 2, 3 among the other Rs are excellent in terms of excellent electron transport characteristics. , Or an aromatic hydrocarbon group having 6 to 30 carbon atoms, each of which may be independently linked and / or fused, each of which is independently a fluorine atom, a methyl group, or an ethyl. Substitute a group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a halogenated alkoxy group having 1 to 3 carbon atoms. It may have as a group), and R other than the above independently represents a hydrogen atom, a heavy hydrogen atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, and an ethoxy. It preferably represents a group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, or a sulfide group having 3 to 10 carbon atoms, and at least two Rs in at least one of the benzene rings A, B and C. And 0, 1, 2, or 3 of the other Rs may be independently linked and / or condensed to an aromatic hydrocarbon group having 6 to 30 carbon atoms (the group is a group. Independently, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. It may have a halogenated alkoxy group having 1 to 3 carbon atoms as a substituent), and R other than the above independently represents a hydrogen atom, a heavy hydrogen atom, a methyl group, an ethyl group, and a carbon. It is more preferable to represent an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, or a sulfide group having 3 to 10 carbon atoms, and the benzene rings A and B are more preferable. , At least two Rs in at least one ring of C, and 0, 1, or 2 of the other Rs may be independently linked and / or condensed, respectively, with 6 to 30 carbon atoms. Aromatic hydrocarbon groups (each of which is independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and carbon. It may have an alkyl halide group having the number 1 to 3 or an alkoxy group halide having the carbon number 1 to 3 as a substituent), and Rs other than the above are independently hydrogen atoms, respectively. Heavy hydrogen atom, methyl group, ethyl group, alkyl group with 3 to 10 carbon atoms, methoxy group, d It preferably represents a toxi group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, or a sulfide group having 3 to 10 carbon atoms.

Further, among the Rs in the general formula (1), an aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed (the groups are independently a fluorine atom and a methyl group, respectively. An ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an alkoxy halide group having 1 to 3 carbon atoms. Regarding (may have as a substituent), an aromatic hydrocarbon group having 6 to 17 carbon atoms (which may be linked and / or condensed) may be linked and / or condensed in terms of excellent electron transport properties and thermal durability of the compound. Each of the groups independently has a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and a halide having 1 to 3 carbon atoms. It is preferably an alkyl group or a halogenated alkoxy group having 1 to 3 carbon atoms as a substituent), and is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, or a phenanthryl group (of these). The groups may each independently have a fluorine atom, a methyl group, a butyl group, a methoxy group, a butoxy group, a methyl halide group, or a methoxy halide group as a substituent). It is more preferably a phenyl group or a biphenyl group (each of these groups may independently have a fluorine atom or a methyl group as a substituent), and is a phenyl group or a biphenyl group. Is more preferable.

Further, among the Rs in the general formula (1), an aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed at the first specified (the groups are independently fluorine). Atomic, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, alkyl halide group having 1 to 3 carbon atoms, or alkyl group having 1 to 3 carbon atoms. Those that do not fall under (which may have a halogenated alkoxy group as a substituent) are preferably hydrogen atoms, methyl groups, butyl groups, methoxy groups, or butoxy groups, and are preferably hydrogen atoms, methyl groups, or groups. It is more preferably a butyl group and more preferably a hydrogen atom.

That is, with respect to R in the general formula (1), at least two Rs in at least one ring of the benzene rings A, B, and C, and other Rs in terms of excellent electron transport characteristics and thermal durability of the compound. Of these, 0, 1, 2, 3, or 4 may be independently linked and / or fused rings, and each of them may be an aromatic hydrocarbon group having 6 to 17 carbon atoms (each of which is an independent group). , Fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, alkyl halide group having 1 to 3 carbon atoms, or 1 to 1 carbon atoms. 3 may have a halogenated alkoxy group as a substituent), and R other than the above independently represents a hydrogen atom, a heavy hydrogen atom, a methyl group, an ethyl group, and 3 to 10 carbon atoms. It is preferable to represent an alkyl group, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, or a sulfide group having 3 to 10 carbon atoms, and at least one of the benzene rings A, B and C. Of the at least two Rs in one ring and the other Rs, 0, 1, 2, or 3 may be independently linked and / or condensed to an aromatic group having 6 to 17 carbon atoms. A hydrocarbon group (each of which is independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and 1 to 1 carbon atoms. It may have an alkyl halide group of 3 or an alkoxy halide group having 1 to 3 carbon atoms as a substituent), and Rs other than the above are independently hydrogen atoms and deuterium atoms, respectively. , Methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, methylthio group, ethylthio group, or sulfide group having 3 to 10 carbon atoms. More preferably, at least two Rs in at least one of the benzene rings A, B and C, and 0, 1, or 2 of the other Rs are independently linked and / or condensed, respectively. An aromatic hydrocarbon group having 6 to 17 carbon atoms may be used (the groups are independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group and a carbon number of carbon atoms. It may have an alkoxy group of 3 to 10, an alkyl halide group having 1 to 3 carbon atoms, or a halogenated alkoxy group having 1 to 3 carbon atoms as a substituent), and R other than the above is used as a substituent. Each independently has a hydrogen atom, a heavy hydrogen atom, a methyl group, an ethyl group, and 3 to 10 carbon atoms. It is preferable to represent an alkyl group, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, or a sulfide group having 3 to 10 carbon atoms. It should be noted that the aromatic hydrocarbon groups having 6 to 17 carbon atoms which may be linked and / or condensed in this paragraph (the groups are independently a fluorine atom, a methyl group, an ethyl group and 3 carbon atoms). It has an alkyl group of 10 to 10, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an alkoxy halide group having 1 to 3 carbon atoms as a substituent. For (may be), a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, or a phenanthryl group (these groups are independently each of a fluorine atom, a methyl group, a butyl group, a methoxy group, a butoxy group, and a halogen). It is preferably a methyl group or a methoxy halide group as a substituent, preferably a phenyl group or a biphenyl group (each of these groups independently has a fluorine atom or a methyl group. It may have as a substituent)), and more preferably a phenyl group or a biphenyl group. Then, an aromatic hydrocarbon group having 6 to 17 carbon atoms which may be linked and / or condensed in this paragraph (the groups are independently a fluorine atom, a methyl group, an ethyl group and 3 carbon atoms). It has an alkyl group of 10 to 10, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an alkoxy halide group having 1 to 3 carbon atoms as a substituent. R, which does not fall under (may be), is preferably a hydrogen atom, a methyl group, a butyl group, a methoxy group, or a butoxy group, more preferably a hydrogen atom, a methyl group, or a butyl group, and a hydrogen atom. Is more preferable.

Further, in the general formula (1), the R bonded to the C ring is preferably a hydrogen atom because it has excellent lifetime characteristics as an organic electroluminescent device.

In the general formula (1) ^{, any one of Y 1} , Y ² and Y ³ represents = N-, and the other represents = CH- or = N-.

In the general formula (1), Y ² and Y ³ both represent = N-, and Y ¹ is preferably = CH- or = N-, and Y ¹ and Y are preferable in that they are excellent in electron transport characteristics. It is more preferable that both ² and Y ^{3 are = N−.}

Specific examples of the cyclic azine compound represented by the general formula (1) include the following compounds 1 to 554, but the present invention is not limited thereto.

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

The cyclic azine compound (1) of the present invention can be produced by the method represented by the following reaction formula (1) in the presence of a metal catalyst or in the presence of a base and a metal catalyst.

In addition, hereinafter, the compound represented by the general formula (2) is abbreviated as the compound (2). In addition, other compounds including compound (3) have the same meaning.

(During the ceremony,
At least two Rs in at least one ring of the benzene rings A, B, C may be independently linked and / or condensed, respectively, and an aromatic hydrocarbon group having 6 to 30 carbon atoms (the group is a group). , Independently, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and an alkyl halide group having 1 to 3 carbon atoms. Alternatively, it may have a halide alkoxy group having 1 to 3 carbon atoms as a substituent).
Rs other than the above are independently hydrogen atom, heavy hydrogen atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, and methylthio group. , Ethylthio group, sulfide group having 3 to 10 carbon atoms, or aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed (the groups are independently fluorine atoms and methyl. Group, ethyl group, alkyl group with 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group with 3 to 10 carbon atoms, alkyl halide group with 1 to 3 carbon atoms, or alkoxy halide with 1 to 3 carbon atoms. It may have a group as a substituent).
One of Y ¹ , Y ² and Y ³ represents = N-, and the others represent = CH- or = N-.
X and Y represent leaving groups.
Each of R ² is an independently aromatic hydrocarbon group having 6 to 60 carbon atoms (the groups are independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, and a methoxy group. , An ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an alkoxy halide group having 1 to 3 carbon atoms may be used as a substituent).
n represents an integer of 1 to 15.
A represents a substituent represented by the following general formulas (2-1) to (2-18).

(During the ceremony,
Each of R ¹ independently has a hydrogen atom, a heavy hydrogen atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group and an ethylthio. A group, a sulfide group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms (independently, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, It may have an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an alkoxy halide group having 1 to 3 carbon atoms as a substituent), or with X. Represents a connecting site.
One of Y ¹ , Y ² and Y ³ represents = N-, and the others represent = CH- or = N-. )
In addition, A can produce the cyclic azine compound represented by the general formula (1) more efficiently and industrially, and the above general formulas (2-1), (2-3) and (2-4) can be produced. ) Or (2-7) is preferable.

Compound (2) can be produced, for example, by using the method disclosed in Hiroshi Yamanaka, "New Heterocyclic Compound Basics", Kodansha, 2004.

Compound (3) may be described, for example, in J. Am. Tsuji, "Palradium Reagents and Catalysts", John Wiley & Sons, 2004, Journal of Organic Chemistry, Volume 60, 7508-7510, 1995, Journal of Organic Chemistry, Volume 16 , 10, 941-944, 2008, or Chemistry of Materials, 20, 2551-5953, 2008. Further, any hydrogen atom in the compound (3) may be substituted with a deuterium atom.

Aromatic hydrocarbon group having 6 to 60 ring carbon atoms represented by R ² is representative of the components needed to make compounds by linking the A (1) in the compound (2), in particular limited It is not something that is done.
The carbon number of the aromatic hydrocarbon group does not include the carbon number of the substituent. The aromatic hydrocarbon group having 6 to 60 carbon atoms is not particularly limited as long as it is a monocyclic ring or one in which these are condensed and / or linked.

That is, an aromatic hydrocarbon group having 6 to 60 carbon atoms is required to form the compound (1) by linking with A in the compound (2), which has a total carbon number of 6 to 60 in the ring skeleton. If it can form a constituent component, it represents a monocyclic ring, or an aromatic group to which they may be condensed and / or linked. The aromatic group having 6 to 60 carbon atoms does not include the carbon number of the substituent which may be separately contained. The aromatic group having 6 to 60 carbon atoms is not particularly limited as long as it is a monocyclic ring or one in which they are condensed and / or linked.

The aromatic hydrocarbon group having 6 to 60 carbon atoms is not particularly limited, and is, for example, a phenyl group, a biphenylyl group, a terphenyl group, a quaterphenyl group, a kinkphenyl group, a sexiphenyl group, a septiphenylki, or an octi. Phenyl group, nobiphenyl group, desiphenyl group, naphthyl group, binaphthyl group, naphthylphenyl group, phenylnaphthyl group, naphthylbiphenyl group, biphenylnaphthyl group, diphenylnaphthyl group, phenylnaphthylphenyl group, anthryl group, anthrylphenyl group, phenyl Anthryl group, phenylanthrylphenyl group, phenanthryl group, phenanthrylphenyl group, phenylphenanthryl group, pyrenyl group, phenylpyrenyl group, pyrenylphenyl group, fluorenyl group, fluorenylphenyl group, phenylfluore Nyl group, fluoranthenyl group, phenylfluoranthenyl group, fluoranthenylphenyl group, perylenyl group, phenylperyleneyl group, peryleneylphenyl group, triphenylenyl group, phenyltriphenylenyl group, triphenylenylphenyl group, Examples thereof include a tetrasenyl group, a phenyltoterasenyl group, a tetrasenylphenyl group, a chrysenyl group, a phenylcrisenyl group, a chrysenylphenyl group and the like.

The leaving group represented by X and Y represents a group that is eliminated with the reaction, and is not particularly limited, and is, for example, a hydrogen atom, a chlorine atom, a bromine atom, a trifurate, an iodine atom, and a metal-containing group. (For example, Li, Na, MgCl, MgBr, MgI, CuCl, CuBr, CuI, AlCl ₂ , AlBr ₂ , Al (Me) ₂ , Al (Et) ₂ , Al ( ⁱ Bu) ₂ , Sn (Me) ₃ , Sn (Bu) ₃ , SnF ₃ , ZnR ²⁴ (R ²⁴ represents a halogen atom. Examples of ZnR ²⁴ include ZnCl, ZnBr, ZnI, etc.), Si (R ²¹ ) ₃ (for example, SiMe ₃ , SiPh). ₃ , SiMePh ₂ , SiCl ₃ , SiF ₃ , Si (OMe) ₃ , Si (OEt) ₃ , Si (OMe) ₂ OH, etc.), BF ₃ K, B (OR ²² ) ₂ (for example, B (OH) ₂₎ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh) ₂ etc.), B (OR ²³ ) ₃ etc.) and the like can be exemplified.

A ligand such as an ether or an amine may be coordinated to the metal-containing group represented by X and Y, and the type of the ligand may not inhibit the reaction formula (1). There are no restrictions.

Further, as B (OR ²² ) ₂ , those represented by the following (I) to (VII) can be exemplified, and those represented by (II) are preferable in terms of good yield.

Examples of the B (OR ²³ ) ₃ include those shown in the following (I) to (III).

Of these leaving groups, chlorine atom, bromine atom, triflate, iodine atom, B (OR ²² ) ₂ or B (OR ²³ ) ₃ are selected in terms of ease of post-reaction treatment and ease of procurement of raw materials. preferable.

Of the compound (2), the cyclic azine compound represented by the following general formula (5) is preferable as a production intermediate for producing the compound (1).

{In the formula,
Each of X ¹ is independently a desorbing group, a hydrogen atom, a heavy hydrogen atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, and an alkoxy group having 3 to 10 carbon atoms. A methylthio group, an ethylthio group, a sulfide group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed (each of which is an independent fluorine atom). , Methyl group, ethyl group, alkyl group with 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group with 3 to 10 carbon atoms, alkyl halide group with 1 to 3 carbon atoms, or halogen with 1 to 3 carbon atoms. alkoxy group and represents may also) have, as a substituent, at least two of X ¹ is a leaving group.
R ³ is a desorbing group or an aromatic hydrocarbon group having 6 to 60 carbon atoms which may be linked and / or fused (the groups are independently desorbing groups, fluorine atoms and methyl groups, respectively. , Ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, alkyl halide group having 1 to 3 carbon atoms, or alkoxy halide group having 1 to 3 carbon atoms. May have as a substituent).
R ⁴ are each independently a leaving group, hydrogen atom, a deuterium atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, A methylthio group, an ethylthio group, a sulfide group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed (each of which is an independent fluorine atom). , Methyl group, ethyl group, alkyl group with 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group with 3 to 10 carbon atoms, alkyl halide group with 1 to 3 carbon atoms, or halogen with 1 to 3 carbon atoms. It may have a chemicalized alkoxy group as a substituent).
One of Y ¹ , Y ² and Y ³ represents = N-, and the others represent = CH- or = N-. }
The R ³ of the compound (5), in that the compounds of this the (1) can be efficiently produced at low environmental load, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, or a phenanthryl group (These groups may each independently have a halogen atom, a methyl group, a butyl group, a methoxy group, a butoxy group, a methyl halide group, or a methoxy halide group as a substituent), or a halogen. It is preferably an atom, preferably a phenyl group, or a biphenyl group (each of these groups may independently have a halogen atom or a methyl group as a substituent), or a halogen atom. , A phenyl group or a halogen atom which may have a halogen atom is more preferable.

For R ⁴ of the compound (5), in that the compounds of this the (1) can be efficiently produced at low environmental load, each independently, a hydrogen atom, a deuterium atom, a methyl group, butyl A group, a methoxy group, a butoxy group, or an aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed (each of which is independently a fluorine atom, a methyl group, an ethyl group, An alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a halogenated alkoxy group having 1 to 3 carbon atoms is used as a substituent. It is preferable to have), and each independently has a hydrogen atom, a heavy hydrogen atom, a methyl group, a butyl group, a methoxy group, a butoxy group, or a phenyl group (the groups are each independently a fluorine atom, Methyl group, ethyl group, alkyl group with 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group with 3 to 10 carbon atoms, alkyl halide group with 1 to 3 carbon atoms, or halogenation with 1 to 3 carbon atoms. It may have an alkoxy group as a substituent)).

Next, the reaction formula (1) will be described.

As shown in the reaction of the reaction formula (1), the compound (1) of the present invention is a compound represented by the general formula (2) in the presence of a metal catalyst or in the presence of a base and a metal catalyst, and a general formula. It can be synthesized by performing a coupling reaction with the compound represented by (3).

In the reaction of the reaction formula (1), the metal catalyst is preferably a palladium catalyst, a nickel catalyst, an iridium catalyst, a rhodium catalyst or a copper catalyst, and is easy to handle because the efficiency of the coupling reaction is excellent. In some respects, palladium catalysts, nickel catalysts or copper catalysts are more preferred.

In the reaction of the reaction formula (1), it is also possible to add a base to carry out the reaction, and it is preferable to add a base from the viewpoint of improving the reaction yield. However, when X and Y are B (OR ²² ) ₂ or Si (R ²¹ ) ₃ , it is essential to add a base.

Further, a phase transfer catalyst can be added in the reaction of the reaction formula (1). The phase transfer catalyst is not particularly limited, but for example, 18-crown-6-ether or the like can be used. The amount to be added is any amount within a range that does not significantly inhibit the reaction.

The metal catalyst used in the reaction of the reaction formula (1) is not particularly limited, and examples thereof include a palladium catalyst, a nickel catalyst, an iridium catalyst, a rhodium catalyst, and a copper catalyst.

The palladium catalyst is not particularly limited, and examples thereof include salts of palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate. In addition, π-allyl palladium chloride dimer, palladium acetylacetonato, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tri (tert). -Butyl) phosphinpalladium, dichloro (1,1'-bis (diphenylphosphino) ferrocene) palladium and the like can be exemplified. Among them, a palladium complex having a tertiary phosphine as a ligand such as dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, and tri (tert-butyl) phosphine palladium is preferable in terms of good yield and can be obtained. Tri (tert-butyl) phosphine palladium is further preferred in that it is easy.

The nickel catalyst is not particularly limited, but is, for example, nickel chloride, nickel bromide, nickel chloride hydrate, dichloro (dimethoxyethane) nickel, dichloro [1,2-bis (diphenylphosphino) ethane] nickel. , Dichloro [1,3-bis (diphenylphosphino) propane] nickel, dichloro [1,4-bis (diphenylphosphino) butane] nickel, dichloro [1,1'-bis (diphenylphosphino) ferrocene] nickel, [1,2-bis (dicyclohexylphosphino) ethane] Dicarbonylnickel (the above five are examples of nickel complexes having tertiary phosphin as a ligand), dichloro (N, N, N', N'- Tetramethylethylenediamine) Nickel can be mentioned. Among them, dichloro (dimethoxyethane) nickel, dichloro [1,4-bis (diphenylphosphino) butane] nickel, and dichloro (N, N, N', N'-tetramethylethylenediamine) nickel have excellent coupling reaction results. Dichloro (dimethoxyethane) nickel and dichloro [1,4-bis (diphenylphosphino) butane] nickel are more preferable in terms of preference and availability.

The iridium catalyst is not particularly limited, but is, for example, iridium (III) chloride, (2,2'-bipyridine) bis (2-phenylpyridinato) iridium (III) hexafluorophosphate, bis (triphenyl). Phosphin) Iridium (I) carbonyl chloride, tris (triphenylphosphine) iridium (I) carbonyl hydride, di-μ-chlorobis (cyclooctene) iridium (I), dichlorotetra (ethylene) diiridium (I), bis (1) , 5-Cyclooctadien) Diiridium (I) dichloride, bis (1,5-cyclooctadien) di-μ-methoxydiiridium (I), (1,5-cyclooctadien) (pyridine) (tricyclohexyl) Examples include phosphin) iridium (I) hexafluorophosphate, dichloro (pentamethylcyclopentadienyl) iridium (III) (dimer).

The rhodium catalyst is not particularly limited, but is limited to tris (triphenylphosphine) rhodium (I) chloride, tetrakis (triphenylphosphine) rhodium (I) hydride, and bis (1,5-cyclooctadien) dilodium (I). ) Dichloride, chlorobis (cyclooctene) rhodium (I) (dimer), tris (triphenylphosphine) rhodium (I) carbonyl hydride, bis (triphenylphosphine) carbonyl rhodium (I) chloride, bis [η- (2,5) -Norbornadiene] Rhodium (I) Rhodium (I) Rhodium (I), Bis (1,5-Cyclooctadiene) Rhodium (I) Tetrafluoroborate, (Acetylacetonato) (Norbornadiene) Rhodium (I), Bis (ethylene) ( 2,4-Pentandionato) Rhodium (I) can be mentioned.

The copper catalyst is not particularly limited, and examples thereof include copper chloride, copper bromide, copper iodide, copper oxide, and copper trifurate. Among them, copper oxide and copper iodide are preferable in terms of excellent coupling reaction results, and copper iodide or copper oxide is further preferable in that they are easily available.

For the above-mentioned palladium complex having a tertiary phosphine as a ligand and a nickel complex having a tertiary phosphine as a ligand, a tertiary phosphine is added to a palladium salt, a nickel salt or a complex compound thereof. Can be adjusted. The adjustment can be performed separately from the reaction and then added to the reaction system, or can be performed in the reaction system.

The tertiary phosphine is not particularly limited, and is, for example, triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl. -4,5-bis (diphenylphosphine) xanthene, 2- (diphenylphosphine) -2'-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphine) biphenyl, 2- ( Dicyclohexylphosphine) biphenyl, bis (diphenylphosphine) 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-kisilyl) phosphine, (±) -2,2'-bis (±) -2,2'-bis ( Diphenylphosphine) -1,1'-binaphthyl, 2-dicyclohexylphosphine-2', 4', 6'-triisopropylbiphenyl and the like can be exemplified. Of these, (tert-butyl) phosphine or 2-dicyclohexylphosphine-2', 4', 6'-triisopropylbiphenyl is preferable because it is easily available and the yield is good.

When tertiary phosphine is added to a palladium salt, nickel salt or a complex compound thereof, the amount of tertiary phosphine added is 1 mol (palladium or nickel atom equivalent) of the palladium salt, nickel salt or a complex compound thereof. On the other hand, it is preferably 0.1 to 10 times mol, and more preferably 0.3 to 5 times mol from the viewpoint of good yield.

It is also possible to add a ligand to the copper catalyst separately. The ligand to be added to the copper catalyst is not particularly limited, but is, for example, 2,2'-bipyridine, 1,10-phenanthroline, N, N, N', N'-tetramethylethylenediamine, triphenyl. Examples thereof include phosphine and 2- (dicyclohexylphosphino) biphenyl. Of these, 1,10-phenanthroline is preferable because it is easily available and the yield is good.

The base that can be used in the reaction formula (1) is not particularly limited, but for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium acetate, sodium acetate. , Potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, cesium fluoride, silver carbonate and the like can be exemplified. Of these, potassium carbonate, potassium phosphate or sodium hydroxide is preferable in terms of good yield.

The reaction of reaction equation (1) is preferably carried out in a solvent. The solvent is not particularly limited, but for example, water, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF), toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, butanol, xylene and the like. Can be exemplified, and these may be used in combination as appropriate. Of these, a mixed solvent of THF, 1,4-dioxane, xylene, toluene and butanol, or a mixed solvent of xylene and butanol is preferable in terms of good yield.

The compound (3) in the reaction formula (1) is not particularly limited, and for example, the compounds represented by the following 3-13 to 24 can be exemplified.

(These substituents are independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and 1 to 3 carbon atoms. May have a methyl halide group of 1 to 3 or a methoxy halide group having 1 to 3 carbon atoms as a substituent.
Further, Y has the same definition as Y in the above general formula (3). )
The reaction formula (1) is a method for producing the compound (1) of the present invention by reacting the compound (2) with the compound (3) in the presence of a metal catalyst or a base and a metal catalyst. -By applying the reaction conditions of the Miyaura reaction, the desired product can be obtained in high yield.

The amount of the metal catalyst used in the reaction formula (1) is not particularly limited as long as it is a so-called catalyst amount, but is 0.1 to 0.01 with respect to 1 mol of the compound (2) in terms of good yield. It is preferably double molar (in terms of metal atom).

The amount of the base used is not particularly limited, but it is preferably 0.1 to 10 times mol, and 1 to 4 times mol in terms of good yield, with respect to 1 mol of compound (3). Is even more preferable.

The molar ratio of the compound (2) to the compound (3) used in the reaction formula (1) is not particularly limited, but the compound (3) having a molar ratio of 1 to 10 times the molar ratio of the removing group of the compound (2) is 1 mol. ) Is preferable, and it is more preferable to use 1 to 3 times the molar amount of the compound (3) in terms of good yield.

The compound (2) is an excellent material for industrially supplying a compound such as the compound (1), which is remarkably excellent in low drive voltage property, high luminous efficiency, and long life of an organic electroluminescent element. It is industrially very valuable.

The purity of the compound (1) of the present invention can be increased by performing treatments such as reprecipitation, concentration, filtration and purification after the completion of each reaction. In order to further purify the product, it may be purified by recrystallization, silica gel column chromatography, sublimation or the like, if necessary.

The compound (6) of the present invention can be produced by the same method as the above-mentioned reaction formula (1).

(During the ceremony,
At least two Rs in at least one ring of the benzene rings A, B, C may be independently linked and / or condensed, respectively, and an aromatic hydrocarbon group having 6 to 30 carbon atoms (the group is a group). , Independently, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and an alkyl halide group having 1 to 3 carbon atoms. Alternatively, it may have a halide alkoxy group having 1 to 3 carbon atoms as a substituent).
Rs other than the above are independently hydrogen atom, heavy hydrogen atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, and methylthio group. , Ethylthio group, sulfide group having 3 to 10 carbon atoms, or aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed (the groups are independently fluorine atoms and methyl. Group, ethyl group, alkyl group with 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group with 3 to 10 carbon atoms, alkyl halide group with 1 to 3 carbon atoms, or alkoxy halide with 1 to 3 carbon atoms. It may have a group as a substituent).
One of Y ¹ , Y ² and Y ³ represents = N-, and the others represent = CH- or = N-. )
X and Y represent leaving groups.
Each of R ² is an independently aromatic hydrocarbon group having 6 to 60 carbon atoms (the groups are independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, and a methoxy group. , An ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an alkoxy halide group having 1 to 3 carbon atoms may be used as a substituent).
n represents an integer of 1 to 15.
A represents a substituent represented by the following general formulas (2-1') to (2-18').

(During the ceremony,
Each of R ¹ independently has a hydrogen atom, a heavy hydrogen atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group and an ethylthio. A group, a sulfide group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms (independently, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, It may have an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an alkoxy halide group having 1 to 3 carbon atoms as a substituent), or with X. Represents a connecting site.
One of Y ¹ , Y ² and Y ³ represents = N-, and the others represent = CH- or = N-. )
In addition, A can produce the cyclic azine compound represented by the general formula (1) more efficiently and industrially, and the above general formulas (2-1'), (2-3'), (2). It is preferably -4') or (2-7').

The present invention is an organic electroluminescent device containing a cyclic azine compound represented by the general formula (1), and the cyclic azine compound is preferably used for an electron transport layer, an electron injection layer, or a light emitting layer.

The cyclic azine compound represented by the general formula (1) can be preferably used as an electron transporting material (electron transporting material, electron injecting material, etc.) of the organic electroluminescent device. At this time, for the anode, hole injection layer, hole transport layer, electron blocking layer, light emitting layer, light emitting layer dopant, light emitting layer host, cathode, etc. used in combination, generally known materials can be selected by those skilled in the art. Can be used in.

The configuration of the organic electroluminescent device may be any conventionally known one, and is not particularly limited.

The method for producing a thin film for an organic electroluminescent device containing the compound (1) of the present invention is not particularly limited, and a preferable example thereof is film formation by a vacuum vapor deposition method. The film formation by the vacuum vapor deposition method can be performed by using a general-purpose vacuum vapor deposition apparatus. The vacuum degree of the vacuum chamber when forming a film by the vacuum vapor deposition method is generally used for diffusion pumps, turbo molecular pumps, and cryopumps in that the manufacturing tact time for manufacturing organic electric field light emitting elements is short and the manufacturing cost is superior. ^{It is preferably about 1 × 10 − 2} to 1 × 10 ⁻⁶ Pa that can be reached by a pump or the like, and the vapor deposition rate is preferably 0.005 to 10 nm / sec depending on the thickness of the film to be formed. Further, a thin film for an organic electroluminescent device made of the compound (1) can also be produced by a solution coating method. For example, compound (1) is dissolved in an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate or tetrahydrofuran, and a spin coating method, an inkjet method, a casting method or a general-purpose device is used. It is also possible to form a film by the dip method or the like.

Since the cyclic azine compound represented by the general formula (1) of the present invention has high solubility in chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, tetrahydrofuran and the like, spinco using a general-purpose device was used. Chloroform can also be formed by the toluene method, inkjet method, casting method, dip method, or the like.

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

The anode and cathode of the organic electroluminescent device are connected to a power source via an electrical conductor. By applying an electric potential between the anode and the cathode, the organic electroluminescent device operates. 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 overlaid on the substrate and the anode or cathode can be in contact with the substrate. The electrodes that come into contact with the substrate are called lower electrodes for convenience. Generally, 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 emission direction. The light transmission characteristics can be confirmed by electroluminescence emission through the substrate. Generally, transparent glass or plastic is adopted as the substrate. The substrate may have a composite structure including multiple material layers.

When electroluminescence emission is confirmed through an anode, the anode is formed by passing or substantially passing the emission.

Common transparent anode materials used in the present invention include indium-tin oxide (ITO), indium-zinc oxide (IZO), or tin oxide. Further, other metal oxides such as aluminum or indium-doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide are also preferably used. In addition to these oxides, metal nitrides such as gallium nitride, metal seleniums 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.

If electroluminescence emission is confirmed only through the cathode, the transmission properties of the anode are not important and any transparent, opaque or reflective conductive material can be used. Examples of conductors for this application include gold, iridium, molybdenum, palladium, platinum and the like.

The hole injection layer can be provided between the anode and the hole transport layer. The material of the hole injecting layer helps to improve the film forming properties of the organic material layer such as the hole transporting layer and the hole injecting layer and facilitate the injecting holes into the hole transporting layer. Examples of materials suitable for use in the hole infusion layer include porphyrin compounds, plasma-deposited fluorocarbon polymers, and amines with aromatic rings such as biphenyl and carbazole groups, 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, tritrilamine, trildiphenylamine, 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, N, N'-diphenyl-N, N'-bis (9-phenylcarbazole-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 (hole transport materials), for example, an aromatic tertiary amine. An aromatic tertiary amine is a compound containing one or more trivalent nitrogen atoms, the trivalent nitrogen atom being bonded only to a carbon atom, and one or more of these carbon atoms forming an aromatic ring. Is forming. Specifically, the aromatic tertiary amine may be an arylamine, for example, a monoarylamine, a diarylamine, a triarylamine, or a high molecular weight arylamine.

As the hole transport material, an aromatic tertiary amine having one or more amino groups can be used. In addition, polymer hole transport materials can be used. For example, poly (N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline and the like can be used.

Specifically, NPD (N, N'-bis (naphthalene-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-benzimidazole-) 2-yl) benzene)), TPD (N, N'-bis (3-methylphenyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine) and the like can be mentioned.

Dipyrazino [2,3-f: 2', 3'-h] quinoxalin-2,3,6,7,10,11-hexacarbonitrile as a charge generation layer between the hole injection layer and the hole transport layer (HAT-CN), 7,7', 8,8'-Tetracyanoquinodimethane (TCNQ), 2,3,5,6-Tetrafluoro-7,7', 8,8'-Tetracyanoquinodimethane methane (F ₄ -TCNQ) or the like may be provided a layer containing, or may be doped with these compounds in the hole-transporting layer.

The light emitting layer of the organic electroluminescent element contains a phosphorescent material or a fluorescent material, in which case light emission occurs as a result of the recombination of electron-hole pairs in this region. The light emitting layer may be formed from a single material containing both small molecules and polymers, but more generally it is formed from a host material doped with a guest compound, the emission of which originates primarily from the dopant. It can emit any color.

As the host material of the light emitting layer, the cyclic azine compound represented by the general formula (1) can be used, and as other materials, for example, a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group and a pyrenyl. Examples thereof include compounds having a group or an anthranyl group, and these materials can be used alone or mixed with a cyclic azine compound represented by the general formula (1).

Specifically, DPVBi (4,4'-bis (2,2-diphenylvinyl) -1,1'-biphenyl), BCzVBi (4,4'-bis (9-ethyl-3-carbazovinylene) 1,1 '-Biphenyl), TBADN (2-talshalbutyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4'-bis (4,4'-bis) Carbazole-9-yl) biphenyl), CDBP (4,4'-bis (carbazole-9-yl) -2,2'-dimethylbiphenyl), 9,10-bis (biphenyl) anthracene and the like. Further, a compound that expresses Thermally Activated Delayed Fluorescence (TADF) or the like can also be used.

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

Examples of fluorescent dopants include pyrene, anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine and quinacridone, dicyanomethylenepyrine compounds, thiopyran compounds, polymethine compounds, pyrylium, or thiapyrylium compounds, fluorene derivatives, perifrantene derivatives, indeno. Examples thereof include a perylene derivative, a bis (azinyl) amine boron compound, a bis (azinyl) methane compound, a carbostylyl compound, a compound expressing thermal activation delayed fluorescence (TADF), and the like.

Examples of useful phosphorescent dopants include organic metal complexes of transition metals such as iridium, platinum, palladium and osmium.

Examples of dopants are Alq ₃ (tris (8-hydroxyquinoline) aluminum), DPAVBi (4,4'-bis [4- (di-para-tolylamino) styryl] biphenyl), perylene, Ir (PPy) ₃ ( Examples thereof include tris (2-phenylpyridine) iridium (III) and FlrPic (bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III)).

As the thin film forming material used for forming the electron transport layer of the organic electroluminescent device of the present invention, a cyclic azine compound represented by the general formula (1) of the present invention can be used. The electron transport layer may contain other electron transport materials. Examples of other 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, or earth metal complexes include, for example, 8-hydroxyquinolinate lithium (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) berylium, bis (10-hydroxybenzo [h] quinolinate) zinc, bis (2-methyl-8-quinolinate) chlorogallium, bis (2-methyl-8-quinolinate) Examples thereof include (o-cresolate) gallium, bis (2-methyl-8-quinolinate) -1-naphtholate aluminum, and bis (2-methyl-8-quinolinate) -2-naphtholate gallium.

A hole blocking layer may be provided between the light emitting layer and the electron transport layer for the purpose of improving the carrier balance. As the hole blocking layer, a cyclic azine compound represented by the general formula (1) can be used, and as another material, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) can be used. ), Bphenyl (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2-methyl-8-quinolinolate) -4- (phenylphenanthroline) aluminum), bis (10-hydroxybenzo [h] quinolinate) ) Beryllium) and the like.

In the organic electroluminescent element of the present invention, an electron injection layer may be provided for the purpose of improving the electron injection property and the element characteristics (for example, luminous efficiency, low voltage drive, or high durability).

Desirable compounds for the electron injection layer include cyclic azine compounds represented by the general formula (1), fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxazole, oxadiazole, triazole, imidazole, and perylenetetracarboxylic acid. , Freolenilidenemethane, anthracinodimethane, antron and the like. Also, metal complexes and the alkali metal oxides noted above, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth _{halides, SiO X, AlO X, SiN} X, SiON, Various oxides such as AlON, GeO _X , LiO _X , LiON, TiO _X , TiON, TaO _X , TaON, TaN _X , C, and inorganic compounds such as nitrides and oxide nitrides can also be used.

The cathode used in the present invention can be formed from almost any conductive material if the emission is only seen through the anode. Desirable 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 mixture, rare earth metals and the like.

It is sectional drawing of the organic electroluminescence device produced in the evaluation Example 1-1 and the like. It is sectional drawing of the organic electroluminescence device produced in the evaluation Example 2-1 and the like. It is sectional drawing of the organic electroluminescence device produced in the evaluation Example 3-1 and the like. It is sectional drawing of the organic electroluminescence device produced in the evaluation Example 4-1 and the like. It is sectional drawing of the organic electroluminescence device produced in the evaluation Example 5-1 and the like.

11. Glass substrate with ITO transparent electrode 12. Hole injection layer 13. First hole transport layer 14. Second hole transport layer 15. Light emitting layer 16. First electron transport layer 17. Second electron transport layer 18. Cathode layer 21. Glass substrate with ITO transparent electrode 22. Hole injection layer 23. First hole transport layer 24. Second hole transport layer 25. Light emitting layer 26. First electron transport layer 27. Second electron transport layer 28. Cathode layer 31. Glass substrate with ITO transparent electrode 32. Hole injection layer 33. First hole transport layer 34. Second hole transport layer 35. Light emitting layer 36. Electron transport layer 37. Cathode layer 41. Glass substrate with ITO transparent electrode 42. Hole injection layer 43. First hole transport layer 44. Second hole transport layer 45. Light emitting layer 46. First electron transport layer 47. Second electron transport layer 48. Cathode layer 51. Glass substrate with ITO transparent electrode 52. Hole injection layer 53. First hole transport layer 54. Second hole transport layer 55. Electron blocking layer 56. Light emitting layer 57. First electron transport layer 58. Second electron transport layer 59. Cathode layer

Hereinafter, the present invention will be described in more detail with reference to synthetic examples, examples, comparative examples and reference examples, but the present invention is not limited thereto.
Example 1

2,4-Bis (5-bromobiphenyl-3-yl) -6-phenyl-1,3,5-triazine (D-1) (2.0 g), phenylboronic acid (0.95 g) under an argon stream. , Palladium acetate (14.5 mg), and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (92.4 mg) suspended in THF (32 mL), and a 3M-potassium carbonate aqueous solution (5). .2 mL) was added, and the mixture was heated under reflux for 78 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. The obtained solid was washed with water, methanol and hexane, and the desired 2,4-bis [1,1': 3', 1''-terphenyl-5'-yl] -6-phenyl-1,3 , 5-Triazine (E-1) gray powder (yield 1.94 g, yield 98%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.46 (t, J = 7.4Hz, 4H), 7.55-7.58 (m, 8H), 7.59-7.66 (m) , 3H), 7.81 (m, 8H), 8.09 (s, 2H), 8.83 (d, J = 8.0Hz, 2H), 9.01 (s, 4H).
¹³ C-NMR (CDCl ₃ ) δ (ppm): 126.69, 127.45, 127.78, 128.74, 128.99, 129.13, 130.23, 132.70, 136.12, 137 .36, 140.82, 142.32, 171.77, 171.85.
Example 2

2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (D-2) (5.0 g), phenylboronic acid (1.59 g), and Bis (triphenylphosphine) palladium dichloride (166 mg) was suspended in THF (118 mL), a 3M-potassium carbonate aqueous solution (7.9 mL) was further added, and the mixture was heated under reflux for 45 hours. After allowing the reaction mixture to cool, water is added, and the precipitated solid is collected by filtration to remove 2- (3-chlorobiphenyl-5-yl) -4,6-diphenyl-1,3,5-triazine (D-3). Gray powder (yield 4.2 g, yield 85%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.46 (t, J = 7.4Hz, 1H), 7.53-7.57 (m, 2H), 7.59-7.67 (m) , 6H), 7.74 (d, J = 8.3Hz, 2H), 7.82 (s, 1H), 8.73 (s, 1H), 8.80 (d, J = 8.2Hz, 4H) ), 8.88 (s, 1H).
Compound D-3 (1.0 g), 5'-m-terphenylboronic acid (0.72 g), palladium acetate (107 mg) and 2-dicyclohexylphosphino-2', 4', 6'-under an argon stream. Triisopropylbiphenyl (92.1 mg) was suspended in THF (24 mL), a 3M-potassium carbonate aqueous solution (1.6 mL) was further added, and the mixture was heated under reflux for 69 hours. After allowing the reaction mixture to cool, water and methanol are added, and the precipitated solid is collected by filtration to obtain the desired 2- (5 ″ -phenyl-1,1 ′: 5 ′, 1 ″: 3 ″, 1 ′. ''-Quaterphenyl-3'-yl) -4,6-diphenyl-1,3,5-triazine (E-2) gray powder (yield 1.46 g, yield 99%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.41-7.49 (m, 3H), 7.51-7.66 (m, 12H), 7.78 (d, J = 8.3Hz) , 4H), 7.84 (d, J = 8.3Hz, 2H), 7.90 (s, 1H), 7.97 (s, 2H), 8.13 (s, 1H), 8.81- 8.84 (m, 4H), 9.03-9.05 (m, 2H).
Example 3

Under an argon stream, compound D-2 (12.0 g), 3-biphenylboronic acid (6.75 g), and tetrakis (triphenylphosphine) palladium (985 mg) were suspended in THF (250 mL), followed by 2M-potassium carbonate. An aqueous solution (43 mL) was added, and the mixture was heated under reflux for 112 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene 3 times, xylene 1 time), 2- (3-chloro-1,1': 3', 1''-terphenyl-5-yl) -4,6-yl A gray powder of diphenyl-1,3,5-triazine (D-4) (yield 10.9 g, yield 78%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.41 (t, J = 7.3Hz, 1H), 7.50 (t, J = 7.8Hz, 2H), 7.57-7.72 (M, 11H), 7.86 (s, 1H), 7.90 (s, 1H), 8.75 (s, 1H), 8.79 (d, J = 6.3Hz, 4H), 8. 91 (s, 1H).
Compound D-4 (1.5 g), 5'-m-terphenylboronic acid (0.99 g), palladium acetate (6.9 mg) and 2-dicyclohexylphosphino-2', 4', 6 under an argon stream. '-Triisopropylbiphenyl (29.4 mg) was suspended in THF (80 mL), a 2M-potassium carbonate aqueous solution (4.5 mL) was further added, and the mixture was heated under reflux for 20 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), 2- (5'-phenyl-1,1': 3', 1'': 3'', 1''': 3''', 1', A gray powder (yield 1.91 g, yield 92%) of''''-kinkphenyl-5''-yl) -4,6-diphenyl-1,3,5-triazine (E-3) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.37-7.81 (m, 24H), 7.89 (s, 1H), 7.97 (s, 2H), 8.00 (s,, 1H), 8.15 (s, 1H), 8.81 (d, J = 6.3Hz, 4H), 9.05 (s, 2H).
Example 4

Under an argon stream, compound D-2 (12 g), 2-biphenylboronic acid (6.75 g), and tetrakis (triphenylphosphine) palladium (991 mg) were suspended in THF (300 mL), and a 2M-potassium carbonate aqueous solution (2M-potassium carbonate aqueous solution) was added. 42.6 mL) was added, and the mixture was heated under reflux for 75 hours. After allowing the reaction mixture to cool, water, methanol and hexane were added, and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), 2- (3-chloro-1,1': 2', 1''-terphenyl-5-yl) -4,6-diphenyl-1,3 A gray powder of 5-triazine (D-5) (yield 10.58 g, yield 75%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.18 (m, 1H), 7.23-7.29 (m, 4H), 7.39 (s, 1H), 7.49-7. 58 (m, 10H), 8.45 (s, 1H), 8.57 (s, 1H), 8.70 (d, J = 6.5Hz, 4H).
Compound D-5 (1.5 g), 5'-m-terphenylboronic acid (0.99 g), palladium acetate (6.9 mg) and 2-dicyclohexylphosphino-2', 4', 6 under an argon stream. '-Triisopropylbiphenyl (29.3 mg) was suspended in THF (50 mL), a 2M-potassium carbonate aqueous solution (4.5 mL) was further added, and the mixture was heated under reflux for 20 hours. The reaction mixture was concentrated under reduced pressure, water was added, and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), 2- (5'-phenyl-1,1': 3', 1'': 3'', 1''': 2''', 1', A gray powder (yield 1.9 g, yield 90%) of''''-kinkphenyl-5''-yl) -4,6-diphenyl-1,3,5-triazine (E-4) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.18 (m, 1H), 7.27-7.33 (m, 4H), 7.42 (t, J = 7.4Hz, 2H), 7.50-7.65 (m, 16H), 7.69 (d, J = 8.3Hz, 4H), 7.73 (m, 1H), 7.80 (s, 1H), 8.77 ( d, J = 6.4Hz, 4H), 8.79 (s, 1H), 8.88 (s, 1H).
Example 5

Compound D-2 (5.0 g), bis (pinacolato) diboron (3.15 g), potassium acetate (2.44 g), and bis (triphenylphosphine) palladium dichloride (166 mg) were added at 1,4- under an argon stream. It was suspended in dioxane (118 mL) and heated to reflux for 18 hours. After allowing the reaction mixture to cool, the solid was filtered off and the solvent was distilled off under reduced pressure. When the obtained mixture was purified by column chromatography (developing solvent: chloroform, hexane), the desired 2- [3-chloro-5- (4,4,5,5-tetramethyl-1,3,2) was obtained. -Dioxaborolan-2-yl) phenyl] -4,6-diphenyl-1,3,5-triazine (D-6) gray powder (yield 3.62 g, yield 65%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 1.42 (s, 12H), 7.59-7.65 (m, 6H), 8.03 (s, 1H), 8.80 (d, J = 8.8Hz, 4H), 8.83 (s, 1H), 9.01 (s, 1H).
Compound D-6 (1.50 g), 2,6-dichloro-1-iodobenzene (0.96 g), and bis (triphenylphosphine) palladium dichloride (44.8 mg) in THF (16 mL) under an argon stream. It was suspended, and a 3M-potassium carbonate aqueous solution (2.1 mL) was further added, and the mixture was heated under reflux for 20 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. The obtained solid was dissolved in toluene and the insoluble component was filtered off. Then, the filtrate was concentrated and crystallized with MeOH. By filtering this, the desired 2- (2', 5,6'-trichlorobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine (D-7) gray powder was obtained. (Yield 0.99 g, yield 64%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.34 (t, J = 8.1Hz, 1H), 7.49 (d, J = 8.1Hz, 2H), 7.52 (s, 1H) ), 7.60-7.66 (m, 6H), 8.57 (s, 1H), 8.78 (d, J = 8.2Hz, 4H), 8.83 (s, 1H).
Under an argon stream, compound D-7 (0.98 g), phenylboronic acid (1.10 g), palladium acetate (9.0 mg) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl ( 57.3 mg) was suspended in THF (20 mL), a 3M-potassium carbonate aqueous solution (6.0 mL) was further added, and the mixture was heated under reflux for 69 hours. After allowing the reaction mixture to cool, water is added and the precipitated solid is collected by filtration to obtain the desired 2- (6 ″ -phenyl-1,1 ′: 5 ′, 1 ″: 2 ″, 1 ′. ''-Quaterphenyl-3'-yl) -4,6-diphenyl-1,3,5-triazine (E-5) gray powder (yield 1.18 g, yield 96%) was obtained.

^{1 1} H-NMR (THF-d ₈ ) δ (ppm): 7.13-7.26 (m, 12H), 7.30 (s, 1H), 7.31-7.41 (m, 3H), 7.55-7.64 (m, 9H), 8.28 (s, 1H), 8.61 (s, 1H), 8.68 (d, J = 8.2Hz, 4H).
Example 6

Compound D-6 (1.50 g), 2,4-dichloro-1-bromobenzene (0.79 g), and bis (triphenylphosphine) palladium dichloride (44.8 mg) in THF (16 mL) under an argon stream. After suspension, a 3M-potassium carbonate aqueous solution (2.1 mL) was added, and the mixture was heated under reflux for 20 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. The obtained solid was dissolved in toluene and the insoluble component was filtered off. Then, the filtrate was concentrated and crystallized with MeOH. By filtering this, the desired 2- (2', 4', 5-trichlorobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine (D-8) gray powder was obtained. (Yield 1.25 g, yield 80%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.40-7.41 (m, 2H), 7.57-7.66 (m, 8H), 8.69 (s, 1H), 8. 76-8.79 (m, 5H).
Under an argon stream, compound D-8 (1.14 g), phenylboronic acid (1.28 g), palladium acetate (10.5 mg) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl ( 66.9 mg) was suspended in THF (23 mL), a 3M-potassium carbonate aqueous solution (7.0 mL) was further added, and the mixture was heated under reflux for 4 hours. After allowing the reaction mixture to cool, water is added, and the precipitated solid is collected by filtration to remove 2- (4 ″ -phenyl-1, 1 ′: 5 ′, 1 ″: 2 ″, 1''''-qua. A gray powder (yield 1.34 g, yield 93%) of terphenyl-3'-yl) -4,6-diphenyl-1,3,5-triazine (E-6) was obtained.

^{1 1} H-NMR (THF-d ₈ ) δ (ppm): 7.11 (t, J = 7.3Hz, 1H), 7.19-7.41 (m, 12H), 7.46-7.54 (M, 6H), 7.56 (s, 1H), 7.66-7.72 (m, 5H), 8.64 (s, 1H), 8.68 (d, J = 8.1Hz, 4H) ), 8.78 (s, 1H).
Example 7

Under an argon stream, compound D-6 (2.0 g), 2,4,6-trichloro-1-bromobenzene (1.57 g), and bis (triphenylphosphine) palladium dichloride (59.8 mg) were added in THF (21 mL). ), Further 3M-potassium carbonate aqueous solution (2.8 mL) was added, and the mixture was heated under reflux for 19 hours. After allowing the reaction mixture to cool, water and methanol were added, and the precipitated solid was collected by filtration. Then, by recrystallization with toluene, the desired 2- (2', 4', 5,6'-tetrachlorobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine (D) -9) gray powder (yield 1.66 g, yield 75%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.49 (s, 1H), 7.51 (s, 2H), 7.57-7.66 (m, 6H), 8.53 (s, 1H), 8.77 (d, J = 8.2Hz, 4H), 8.83 (s, 1H).
Under an argon stream, compound D-9 (1.64 g), phenylboronic acid (2.29 g), palladium acetate (14.1 mg) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl ( 89.7 mg) was suspended in THF (31 mL), a 3M-potassium carbonate aqueous solution (13 mL) was further added, and the mixture was heated under reflux for 115 hours. After allowing the reaction mixture to cool, the solvent was distilled off under reduced pressure, and the precipitated solid was collected by filtration and washed with water, methanol and hexane. Then, by recrystallizing with toluene. Target 2- (4'', 6''-diphenyl-1,1': 5', 1'': 2'', 1'''-quaterphenyl-3'-yl) -4,6- A gray powder of diphenyl-1,3,5-triazine (E-7) (yield 1.15 g, yield 53%) was obtained.

^{1 1} H-NMR (THF-d ₈ ) δ (ppm): 7.16 (t, J = 7.4Hz, 2H), 7.25-7.43 (m, 14H), 7.45 (s, 1H) ), 7.51 (t, J = 7,4Hz, 2H), 7.59-7.67 (m, 6H), 7.85-7.87 (m, 4H), 8.42 (s, 1H) ), 8.70 (s, 1H), 8.76 (d, J = 8.1Hz, 4H).
Example 8

Compound D-10 (1.5 g), 2,4-dichloro-1-bromobenzene (0.66 g), and bis (triphenylphosphine) palladium dichloride (37.5 mg) in THF (27 mL) under an argon stream. After suspension, a 3M-potassium carbonate aqueous solution (1.8 mL) was added, and the mixture was heated under reflux for 67 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. The obtained solid was dissolved in toluene and the insoluble component was filtered off. Then, the filtrate was concentrated and crystallized with MeOH. By filtering this, the desired 2- (2,2'', 4,4''-tetrachloro-1,1': 3', 1''-terphenyl-5'-yl) -4 , 6-Diphenyl-1,3,5-triazine (D-11) gray powder (yield 0.62 g, yield 39%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.41 (dd, J = 8.2, 2.1 Hz, 2H), 7.49 (d, J = 8.2 Hz, 2H), 7.56 -7.64 (m, 8H), 7.74 (s, 1H), 8.78 (d, J = 8.2Hz, 4H), 8.84 (s, 2H).
Under an argon stream, compound D-11 (0.61 g), phenylboronic acid (0.62 g), palladium acetate (4.6 mg) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl ( 29.3 mg) was suspended in THF (10 mL), a 3M-potassium carbonate aqueous solution (3.4 mL) was further added, and the mixture was heated under reflux for 23 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (4''', 5'-diphenyl-1,1': 2', 1'': 3'', 1''': 2'''', 1''''-Kinkphenyl-3'-yl) -4,6-diphenyl-1,3,5-triazine (E-8) gray powder (yield 45 g, yield 58%) Got

^{1 1} H-NMR (THF-d ₈ ) δ (ppm): 7.08-7.13 (m, 2H), 7.20-7.26 (m, 10H), 7.28 (d, J = 8) .0Hz, 2H), 7.30 (s, 1H), 7.33-7.37 (m, 4H), 7.44-7.51 (m, 6H), 7.60 (dd, J = 8) .0, 2.0Hz, 2H), 7.64 (d, J = 8.2Hz, 4H), 7.65 (d, J = 2.0Hz, 2H), 8.36 (s, 2H), 8 .57 (d, J = 8.2Hz, 4H).
Example 9

Compound D-12 (1.50 g), 2,5-dichloro-1-bromobenzene (0.73 g), and bis (triphenylphosphine) palladium dichloride (41.2 mg) in THF (29 mL) under an argon stream. After suspension, a 3M-potassium carbonate aqueous solution (2.0 mL) was added, and the mixture was heated under reflux for 23 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (2,5-dichloro-1,1': 3', 1''-terphenyl-5'-yl) -4,6- A gray powder of diphenyl-1,3,5-triazine (D-13) (yield 1.39 g, yield 89%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.37 (dd, J = 8.6, 2.5Hz, 1H), 7.46 (t, J = 7.4Hz, 1H), 7.51 (D, J = 8.6Hz, 1H), 7.53-7.64 (m, 9H), 7.80 (d, J = 8.4Hz, 2H), 7.90 (s, 1H), 8 .79-8.82 (m, 5H), 9.05 (s, 1H).
Compound D-13 (1.39 g), 4-biphenylboronic acid (1.24 g), palladium acetate (11.7 mg) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropyl under an argon stream. Biphenyl (74.8 mg) was suspended in THF (26 mL), a 3M-potassium carbonate aqueous solution (4.4 mL) was further added, and the mixture was heated under reflux for 91 hours. After allowing the reaction mixture to cool, water is added, and the precipitated solid is collected by filtration to obtain the desired 2- (5 ″ -biphenyl-4-yl-1,1 ′: 3 ′, 1 ″: 2 ″,. 1''': 4'''', 1''''-kinkphenyl-5'-yl) -4,6-diphenyl-1,3,5-triazine (E-9) gray powder (yield 1. 96 g, yield 98%) was obtained.

¹ H-NMR (THF-d ₈ ) δ (ppm): 7.11 (t, J = 7.3Hz, 1H), 7.18-7.23 (m, 4H), 7.26-7.30 (M, 2H), 7.33 (t, J = 8.5Hz, 4H), 7.38-7.53 (m, 12H), 7.58-7.60 (m, 3H), 7.65 (S, 1H), 7.66 (d, J = 8.5Hz, 2H), 7.78 (dd, J = 8.0, 1.9Hz, 1H), 7.81 (d, J = 8. 5Hz, 2H), 7.94 (d, J = 1.9Hz, 1H), 8.66 (d, J = 8.2Hz, 4H), 8.71 (s, 1H), 8.80 (s, 1H).
Example 10

Compound D-6 (1.36 g), 2,5-dichloro-1-bromobenzene (0.72 g), and bis (triphenylphosphine) palladium dichloride (44.8 mg) in THF (15 mL) under an argon stream. After suspension, a 3M-potassium carbonate aqueous solution (1.9 mL) was added, and the mixture was heated under reflux for 22 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (2', 5,5'-trichlorobiphenyl-3-yl) -4,6-diphenyl-1,3,5-triazine (D) -14) gray powder (yield 1.12 g, yield 79%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.37 (dd, J = 8.6, 2.5Hz, 1H), 7.47 (d, J = 2.5Hz, 1H), 7.49 (D, J = 8.6Hz, 1H), 7.58-7.67 (m, 7H), 8.70 (s, 1H), 8.77-8.81 (m, 5H).
Under an argon stream, compound D-14 (1.12 g), phenylboronic acid (1.26 g), palladium acetate (10.3 mg) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl ( 65.6 mg) was suspended in THF (23 mL), a 3M-potassium carbonate aqueous solution (6.9 mL) was further added, and the mixture was heated under reflux for 122 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (5''-phenyl-1,1': 3', 1'': 2'', 1'''-quaterphenyl- A gray powder of 5'-yl) -4,6-diphenyl-1,3,5-triazine (E-10) (yield 0.88 g, yield 63%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.22-7.26 (m, 1H), 7.29-7.53 (m, 12H), 7.57-7.65 (m, 8H) ), 7.75-7.77 (m, 3H), 7.90 (s, 1H), 8.71 (s, 1H), 8.75 (d, J = 8.1Hz, 4H), 8. 86 (s, 1H).
Example 11

Under an argon stream, compound D-2 (1.50 g), 4-biphenylboronic acid (0.77 g), and bis (triphenylphosphine) palladium dichloride (49.8 mg) were suspended in THF (36 mL) and further 3 M. -Aqueous potassium carbonate solution (2.4 mL) was added, and the mixture was heated and refluxed for 46 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (3-chloro-1,1': 4', 1''-terphenyl-5-yl) -4,6-diphenyl-1 , 3,5-Triazine (D-15) gray powder (yield 1.64 g, yield 93%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.41 (t, J = 7.4Hz, 1H), 7.49-7.53 (m, 2H), 7.59-7.66 (m) , 6H), 7.70 (d, J = 8.3Hz, 2H), 7.78 (d, J = 8.6Hz, 2H), 7.83 (d, J = 8.6Hz, 2H), 7 .87 (s, 1H), 8.75 (s, 1H), 8.82 (d, J = 8.1Hz, 4H), 8.94 (s, 1H).
Compound D-15 (1.45 g), 5'-m-terphenylboronic acid (0.88 g), palladium acetate (13.1 mg) and 2-dicyclohexylphosphino-2', 4', 6 under an argon stream. '-Triisopropylbiphenyl (83.6 mg) was suspended in THF (29 mL), a 3M-potassium carbonate aqueous solution (1.9 mL) was further added, and the mixture was heated and refluxed for 48 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (5'-phenyl-1,1': 3', 1'': 3'', 1''': 4''', 1''''-Kinkphenyl-5''-yl) -4,6-diphenyl-1,3,5-triazine (E-11) gray powder (yield 1.70 g, yield 84%) was obtained. rice field.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.38-7.46 (m, 3H), 7.49-7.55 (m, 6H), 7.58-7.67 (m, 6H) ), 7.72 (d, J = 8.4Hz, 2H), 7.77-7.80 (m, 4H), 7.80 (d, J = 8.5Hz, 2H), 7.91 (s) , 1H), 7.92 (d, J = 8.5Hz, 2H), 7.98 (s, 2H), 8.18 (s, 1H), 8.83 (d, J = 8.0Hz, 4H) ), 9.06 (s, 1H), 9.09 (s, 1H).
Example 12

Compound D-12 (3.0 g), bromo-3,5-dichlorobenzene (1.46 g), and bis (triphenylphosphine) palladium dichloride (82.3 mg) were suspended in THF (59 mL) under an argon stream. Further, a 3M-potassium carbonate aqueous solution (3.9 mL) was added, and the mixture was heated under reflux for 92 hours. After allowing the reaction mixture to cool, water and methanol were added, and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (3,5-dichloro-1,1': 3', 1''-terphenyl-5'-yl) -4,6- A gray powder of diphenyl-1,3,5-triazine (D-16) (yield 2.73 g, yield 88%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.45 (t, J = 1.9Hz, 1H), 7.48 (t, J = 7.4Hz, 1H), 7.56-7.66 (M, 8H), 7.67 (d, J = 1.9Hz, 2H), 7.80 (d, J = 8.3Hz, 2H), 7.97 (s, 1H), 8.81 (d) , J = 8.1Hz, 4H), 8.88 (s, 1H), 9.04 (s, 1H).
Compound D-16 (0.50 g), 2-naphthalene boronic acid (0.39 g), palladium acetate (4.2 mg) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropyl under an argon stream. Biphenyl (27.0 mg) was suspended in THF (9.4 mL), a 3M-potassium carbonate aqueous solution (1.5 mL) was further added, and the mixture was heated under reflux for 116 hours. After allowing the reaction mixture to cool, water and methanol were added, and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- [3,5-di (2-naphthyl) -1,1': 3', 1''-terphenyl-5'-yl) A gray powder of -4,6-diphenyl-1,3,5-triazine (E-12) (yield 0.55 g, yield 82%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.41 (t, J = 7.4Hz, 1H), 7.45-7.59 (m, 12H), 7.79 (d, J = 8) .1Hz, 2H), 7.84-7.93 (m, 6H), 7.95 (d, J = 8.6Hz, 2H), 8.06 (s, 2H), 8.09 (s, 1H) ), 8.13 (s, 1H), 8.20 (s, 2H), 8.76 (d, J = 8.1Hz, 4H), 8.99 (s, 1H), 9.05 (s, 1H).
Example 13

Compound D-12 (1.12 g), 4'-iodo-5'-phenyl-1,1': 2', 1''-terphenyl (1.04 g), and bis (triphenylphosphine) under an argon stream. ) Palladium dichloride (30.8 mg) was suspended in THF (22 mL), a 3M-potassium carbonate aqueous solution (1.5 mL) was further added, and the mixture was heated under reflux for 24 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (4'', 5''-diphenyl-1,1': 3', 1'': 2'', 1'''- A gray powder (yield 1.00 g, yield 66%) of quaterphenyl-5'-yl) -4,6-diphenyl-1,3,5-triazine (E-13) was obtained.

^{1 1} H-NMR (THF-d ₈ ) δ (ppm): 7.21-7.40 (m, 14H), 7.44-7.49 (m, 4H), 7.59-7.68 (m) , 9H), 7.79 (s, 1H), 7.84 (s, 1H), 8.74 (s, 1H), 8.80 (dmJ = 8.2Hz, 4H), 8.94 (s, 1H).
Example 14

Compound D-16 (0.27 g), 2,3-dimethoxyphenylboronic acid (0.22 g), palladium acetate (2.3 mg) and 2-dicyclohexylphosphino-2', 4', 6'under an argon stream. -Triisopropylbiphenyl (14.6 mg) was suspended in THF (2.5 mL), a 3M-potassium carbonate aqueous solution (0.8 mL) was further added, and the mixture was heated under reflux for 22 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (2''', 3'''-dimethoxy-5''- (2,3-dimethoxyphenyl) -1,1': 3 ', 1'': 3'', 1'''-Quaterphenyl-5'-yl) -4,6-diphenyl-1,3,5-triazine (E-14) white solid (yield 0. 28 g, yield 76%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 3.78 (s, 6H), 3.96 (s, 6H), 6.99 (dd, J = 7.7, 2.1Hz, 2H), 7.14 (dd, J = 7.7, 2.1Hz, 2H), 7.18 (t, J = 7.7Hz, 2H), 7.45 (t, J = 7.4Hz, 1H), 7 .54-7.66 (m, 8H), 7.82 (d, J = 8.2Hz, 2H), 7.85 (s, 1H), 8.01 (s, 2H), 8.13 (s) , 1H), 8.02 (d, J = 8.0Hz, 4H), 8.99 (s, 1H), 9.08 (s, 1H).
Example 15

Compound D-16 (1.0 g), bis (pinacolato) diboron (1.0 g), potassium acetate (0.78 g), palladium acetate (8.5 mg) and 2-dicyclohexylphosphino-2', under an argon stream. 4', 6'-triisopropylbiphenyl (53.9 mg) was suspended in THF (9.4 mL) and heated to reflux for 21 hours. After allowing the reaction mixture to cool, water was added. The mixture was filtered and the filtrate was distilled off under reduced pressure. Then, methanol was added, and the precipitate was collected by filtration and washed with water, methanol and hexane. By recrystallizing the sample by filtration (toluene), the desired 2- [3,5-di (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1, 1': 3', 1''-terphenyl-5'-yl] -4,6-diphenyl-1,3,5-triazine (D-17) gray powder (yield 0.74 g, yield 55%) ) Was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 1.39 (s, 24H), 7.46 (t, J = 7.4Hz, 1H), 7.53-7.66 (m, 8H), 7.82 (d, J = 8.2Hz, 2H), 8.07 (s, 1H), 8.31 (s, 2H), 8.37 (s, 1H), 8.83 (d, J = 8.1Hz, 4H), 8.96 (s, 1H), 9.00 (s, 1H).
Compound D-17 (0.28 g), 3,4,5-trifluorobenzene (100 μL), and bis (triphenylphosphine) palladium dichloride (5.4 mg) were applied to THF (3.9 mL) under an argon stream. After turbidity, a 3M-potassium carbonate aqueous solution (0.6 mL) was added, and the mixture was heated under reflux for 93 hours. After allowing the reaction mixture to cool, water and methanol were added, and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- [3,4,5-trifluoro-5'-(3,4,5-trifluorophenyl) -1,1': 3' , 1'': 3'', 1''''-terphenyl-5''-yl] -4,6-diphenyl-1,3,5-triazine (D-15) gray powder (yield 0.10 g) , Yield 36%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.35 (dd, J = 8.5, 6.4 Hz, 4H), 7.49 (t, J = 7.4 Hz, 1H), 7.56 -7.67 (m, 9H), 7.82 (d, J = 8.2Hz, 2H), 7.89 (s, 2H), 8.06 (s, 1H), 8.81 (d, J) = 8.2Hz, 4H), 9.00 (s, 1H), 9.04 (s, 1H).
Example 16

2,4-Bis (5-bromobiphenyl-3-yl) -6-phenyl-1,3,5-triazine (D-1) (1.50 g), 4-biphenylboronic acid (1. 15 g) and bis (triphenylphosphine) palladium dichloride (34.0 mg) were suspended in THF (24 mL), a 3M-potassium carbonate aqueous solution (3.9 mL) was further added, and the mixture was heated under reflux for 143 hours. After allowing the reaction mixture to cool, water and methanol were added, and the precipitated solid was collected by filtration. The obtained solid was washed with water, methanol and hexane and then recrystallized (o-xylene) to obtain the desired 2,4-bis [1,1': 3', 1'': 4'', A gray powder (yield 1.43 g, yield 77%) of 1''''-quaterphenyl-5'-yl] -6-phenyl-1,3,5-triazine (E-16) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.39 (t, J = 7.4Hz, 2H), 7.44-7.52 (m, 6H), 7.58 (dd, J = 7) 8.8, 7.4Hz, 4H), 7.64-7.70 (m, 3H), 7.77 (d, J = 7.8Hz, 4H), 7.87 (d, J = 8.4Hz, 4H), 7.95 (d, J = 8.2Hz, 4H), 8.04 (d, J = 8.4Hz, 4H), 8.30 (s, 2H), 8.94 (d, J = 8.1Hz, 2H), 9.16 (s, 2H), 9.21 (s, 2H).
Example 17

2,4-Bis (5-bromobiphenyl-3-yl) -6-phenyl-1,3,5-triazine (D-1) (0.31 g), 5'-m-terphenylboron under an argon stream Acid (0.30 g) and bis (triphenylphosphine) palladium dichloride (7.0 mg) were suspended in THF (10 mL), a 3M-potassium carbonate aqueous solution (0.7 mL) was added, and the mixture was heated and refluxed for 45 hours. .. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. The obtained solid was washed with water, methanol and hexane and then recrystallized (o-xylene) to obtain the desired 2,4-bis [5 ″ -phenyl-1,1 ′: 3 ′, 1 ′. ': 3'', 1'''-Quaterphenyl-5'-Il] -6-Phenyl-1,3,5-triazine (E-17) gray powder (yield 0.17 g, yield 36%) ) Was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.39 (m, 6H), 7.47-7.53 (m, 12H), 7.58-7.64 (m, 3H), 7. 75 (d, J = 8.2Hz, 8H), 7.82 (d, J = 8.2Hz, 4H), 7.88 (s, 2H), 7.97 (s, 4H), 8.15 ( s, 2H), 8.84 (d, J = 8.0Hz, 2H), 9.06 (s, 2H), 9.09 (s, 2H).
Example 18

Compound F-1 (2.00 g), 4-biphenylboronic acid (1.03 g), and bis (triphenylphosphine) palladium dichloride (66.6 mg) were suspended in THF (47 mL) under an argon stream, and further 3 M. -Aqueous potassium carbonate solution (3.2 mL) was added, and the mixture was heated and refluxed for 21 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (3-chloro-1,1': 4', 1''-terphenyl-5-yl) -4,6-diphenyl-pyrimidine A light brown solid (yield 2.03 g, yield 86%) of (F-2) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.40 (t, J = 7.4Hz, 1H), 7.50 (t, J = 7.6Hz, 2H), 7.56-7.63 (M, 6H), 7.69 (d, J = 8.2Hz, 2H), 7.76 (d, J = 8.5Hz, 2H), 7.78 (s, 1H), 7.82 (d) , J = 8.5Hz, 2H), 8.09 (s, 1H), 8.32 (d, J = 7.7Hz, 4H), 8.71 (s, 1H), 8.90 (s, 1H) ).
Compound F-2 (1.00 g), 5'-m-terphenylboronic acid (0.61 g), palladium acetate (9.1 mg) and 2-dicyclohexylphosphino-2', 4', 6 under an argon stream. '-Triisopropylbiphenyl (57.8 mg) was suspended in THF (20 mL), a 3M-potassium carbonate aqueous solution (1.3 mL) was further added, and the mixture was heated under reflux for 68 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (5'-phenyl-1,1': 3', 1'': 3'', 1''': 4''', A white powder (yield 1.07 g, yield 77%) of 1''''-kinkphenyl-5''-yl) -4,6-diphenyl-pyrimidine (G-1) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.40 (t, J = 7.4Hz, 1H), 7.42 (t, J = 7.4Hz, 2H), 7.48-7.62 (M, 12H), 7.71 (d, J = 8.3Hz, 2H), 7.77-7.79 (m, 6H), 7.89 (s, 1H), 7.92 (d, J) = 8.4Hz, 2H), 7.9 (s, 2H), 8.09 (s, 1H), 8.10 (s, 1H), 8.34 (d, J = 7.7Hz, 4H), 9.03 (s, 1H), 9.04 (s, 1H).
Example-19

Compound F-3 (2.00 g), 5'-m-terphenylboronic acid (1.44 g), palladium acetate (21.4 mg) and 2-dicyclohexylphosphino-2', 4', 6 under an argon stream. '-Triisopropylbiphenyl (136.6 mg) was suspended in THF (48 mL), a 3M-potassium carbonate aqueous solution (3.5 mL) was further added, and the mixture was heated under reflux for 95 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (5''-phenyl-1,1': 5', 1'': 3'', 1'''-quaterphenyl- A white powder of 3'-yl) -4,6-diphenyl-pyrimidine (G-2) (yield 2.66 g, yield 91%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.40-7.47 (m, 3H), 7.50-7.61 (m, 12H), 7.78 (d, J = 8.3Hz) , 4H), 7.84 (d, J = 8.3Hz, 2H), 7.88 (s, 1H), 7.98 (s, 2H), 8.05 (s, 1H), 8.10 ( s, 1H), 8.31-8.35 (m, 4H), 8.99 (s, 1H), 9.02 (s, 1H).
Example-20

Compound D-2 (1.2 g), 5'-m-terphenylboronic acid (2.38 g), palladium acetate (22.0 mg) and 2-dicyclohexylphosphino-2', 4', 6 under an argon stream. '-Triisopropylbiphenyl (126 mg) was suspended in THF (500 mL), a 2M-potassium carbonate aqueous solution (8.6 mL) was further added, and the mixture was heated and refluxed for 186 hours. After allowing the reaction mixture to cool, the solvent was distilled off under reduced pressure, and the precipitated solid was collected by filtration. By recrystallizing (toluene) the obtained solid, 2- (5', 5'''-diphenyl-1,1': 3', 1'': 3'', 1''': 3' '', 1''''-Kinkphenyl-5''-yl) -4,6-diphenyl-1,3,5-triazine (E-18) gray powder (yield 1.37 g, yield 63%) ) Was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.42 (t, J = 7.6Hz, 4H), 7.51 (t, J = 7.8Hz, 8H), 7.56-7.65 (M, 6H), 7.77 (d, J = 6.4Hz, 8H), 7.90 (s, 2H), 7.97 (s, 4H), 8.19 (s, 1H), 8. 81 (d, J = 6.3Hz, 4H), 9.08 (s, 2H).
Example-21

Under an argon stream, compound D-2 (7.33 g), 5'-m-terphenylboronic acid (5.23 g), and bis (triphenylphosphine) palladium dichloride (243 mg) were suspended in THF (346 mL). Further, a 3M-potassium carbonate aqueous solution (12.7 mL) was added, and the mixture was heated and refluxed for 139 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (o-xylene), the desired 2- (5-chloro-5'-phenyl-1,1': 3', 1''-terphenyl-3-yl)- A white powder of 4,6-diphenyl-triazine (D-18) (yield 8.80 g, yield 89%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.44 (t, J = 7.4Hz, 2H), 7.51-7.55 (m, 4H), 7.58-7.67 (m) , 6H), 7.75-7.78 (m, 4H), 7.89-7.91 (m, 4H), 8.78-8.82 (m, 5H), 8.95 (s, 1H) ).
Compound D-18 (2.50 g), 2,4,6-trimethylphenylboronic acid (0.86 g), palladium acetate (19.6 mg) and 2-dicyclohexylphosphino-2', 4', under an argon stream. 6'-Triisopropylbiphenyl (125 mg) was suspended in THF (44 mL), a 3M-potassium carbonate aqueous solution (3.5 mL) was further added, and the mixture was heated under reflux for 24 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (2,4,6-trimethyl-5''-phenyl-1,1': 5', 1'': 3'', 1 A white powder (yield 2.51 g, yield 87%) of''''-quaterphenyl-3'-yl) -4,6-diphenyl-triazine (E-19) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 2.18 (s, 6H), 2.41 (s, 3H), 7.07 (s, 2H), 7.43 (t, J = 7. 4Hz, 2H), 7.50-7.65 (m, 10H), 7.75-7.78 (m, 5H), 7.88 (s, 1H), 7.96 (s, 2H), 8 .64 (s, 1H), 8.80 (dmJ = 8.2Hz, 4H), 9.08 (s, 1H).
Example-22

Compound D-18 (5.00 g), bis (pinacolato) diboron (2.66 g), potassium acetate (2.14 g), palladium acetate (19.6 mg) and 2-dicyclohexylphosphino-2', under an argon stream. 4', 6'-triisopropylbiphenyl (83.3 mg) was suspended in THF (44 mL) and heated to reflux for 22 hours. After allowing the reaction mixture to cool, the solvent was distilled off under reduced pressure. Then, the liquid was separated and extracted with water and chloroform, and the solvent was distilled off under reduced pressure. By producing this by column chromatography (developing solvent: chloroform / hexane), the desired 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5'-Phenyl-1,1': 3', 1 "-Terphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine (D-19) gray powder (yield 3) .99 g, yield 69%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 1.44 (s, 12H), 7.43 (t, J = 7.4Hz, 2H), 7.53 (t, J = 7.4Hz, 4H) ), 7.58-7.66 (m, 6H), 7.78 (d, J = 8.3Hz, 4H), 7.87 (s, 1H), 7.94 (s, 2H), 8. 35 (s, 1H), 8.83 (d, J = 8.0Hz, 4H), 9.15 (s, 1H), 9.17 (s, 1H).
Under an argon stream, compound D-19 (3.99 g), 2,6-dichloro-iodobenzene (1.80 g), and bis (triphenylphosphine) palladium dichloride (84.4 mg) were suspended in THF (30 mL). Further, a 3M-potassium carbonate aqueous solution (4.0 mL) was added, and the mixture was heated under reflux for 96 hours. After allowing the reaction mixture to cool, water and methanol were added, and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (2,6-dichloro-5''-phenyl-1,1': 5', 1'': 3'', 1'' A gray powder (yield 3.27 g, yield 80%) of'-quaterphenyl-3'-yl) -4,6-diphenyl-1,3,5-triazine (D-20) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.34 (dd, J = 8.5,7.7 Hz, 1H), 7.42 (t, J = 7.4 Hz, 2H), 7.50 -7.65 (m, 12H), 7.77 (d, J = 8.3Hz, 4H), 7.85 (s, 1H), 7.88 (s, 1H), 7.96 (s, 2H) ), 8.72 (s, 1H), 8.80 (d, J = 8.1Hz, 4H), 9.14 (s, 1H).
Under an argon stream, compound D-20 (3.27 g), phenylboronic acid (1.23 g), palladium acetate (21.5 mg) and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl ( 137 mg) was suspended in THF (48 mL), a 3M-potassium carbonate aqueous solution (6.7 mL) was further added, and the mixture was heated under reflux for 48 hours. After allowing the reaction mixture to cool, water and methanol were added, and the precipitated solid was collected by filtration. By recrystallizing the obtained solid (toluene), the desired 2- (3', 5'''-diphenyl-1,1': 2', 1'': 5'', 1''': 3'''', 1''''-Kinkphenyl-3''-yl) -4,6-diphenyl-1,3,5-triazine (E-20) gray powder (yield 3.27 g, yield) 89%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.16 (t, J = 7.2Hz, 2H), 7.24-7.32 (m, 8H), 7.42 (t, J = 7) .4Hz, 2H), 7.47 (s, 2H), 7.50-7.67 (m, 14H), 7.78 (d, J = 8.3Hz, 4H), 7.90 (s, 1H) ), 8.40 (s, 1H), 8.74-8.76 (m, 5H).
Example-23

In the atmosphere, 3-bromo-5-chlorobenzaldehyde (10.0 g) and acetophenone (5.55 g) were suspended in acetic acid (92 mL), and concentrated sulfuric acid (22.6 mL) was added dropwise thereto for 16 hours. It was heated to reflux. After allowing the reaction mixture to cool, water was added and the precipitate was collected by filtration. By washing the sample with water, the target (E) -3- (3-bromo-5-chlorophenyl) -1-phenyl-2-propen-1-one (D-21) pale yellow powder (D-21) Yield 13.5 g, yield 91%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.53 (d, J = 15.7Hz, 1H), 7.51-7.56 (m, 4H), 7.63 (t, J = 7) .4Hz, 1H), 7.66 (d, J = 15.7Hz, 1H), 7.67 (s, 1H), 8.02-8.05 (m, 2H).
In the atmosphere, compound D-21 (6.43 g) and 1-phenacylpyridinium bromide (8.34 g) were suspended in DMF (57 mL), acetic acid (57 mL) was added dropwise thereto, and the mixture was added dropwise at 150 ° C. for 16 hours. It was heated and stirred. After cooling the reaction mixture, water was added and the precipitate was filtered. By washing the sample with water, a white powder of the desired 4- (3-bromo-5-chlorophenyl) -2,6-diphenylpyridine (H-1) (yield 6.91 g, yield 82%) was obtained. Got

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.48 (t, J = 7.2Hz, 2H), 7.52-7.56 (m, 4H), 7.63 (s, 1H), 7.66 (s, 1H), 7.77 (s, 1H), 7.81 (s, 2H), 8.21 (d, J = 8.3Hz, 4H).
Compound H-1 (2.10 g), bis (pinacolato) diboron (2.67 g), potassium acetate (2.06 g), palladium acetate (22.4 mg) and 2-dicyclohexylphosphino-2', under an argon stream. 4', 6'-triisopropylbiphenyl (143 mg) was suspended in THF (50 mL) and heated to reflux for 16 hours. After allowing the reaction mixture to cool, the solvent was distilled off under reduced pressure. Then, the liquid was separated and extracted with water and chloroform, and the solvent was distilled off under reduced pressure. By producing this by column chromatography (developing solvent: chloroform / hexane), the desired 4- [3,5-di (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2) -Il) -phenyl] -2,6-diphenylpyridine (H-2) was obtained as a white powder (yield 2.57 g, yield 92%).

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 1.39 (s, 24H), 7.46 (t, J = 7.3Hz, 2H), 7.52-7.56 (m, 4H), 7.95 (s, 2H), 8.22-8.26 (m, 6H), 8.39 (s, 1H).
Compound H-2 (1.12 g), 6'-iodo-1,1': 3', 1''-terphenyl (1.50 g), and tetrakis (triphenylphosphine) palladium (46. 2 g) was suspended in THF (10 mL), a 3M-potassium carbonate aqueous solution (2.7 mL) was further added, and the mixture was heated under reflux for 72 hours. After allowing the reaction mixture to cool, the reaction mixture was separated and extracted with water and chloroform, and the solvent was distilled off under reduced pressure. By producing this by column chromatography (developing solvent: chloroform / hexane), the desired 4- (4''', 5'-diphenyl-1, 1': 2', 1'': 3'', 1''': 2''', 1''''-kinkphenyl-3'-yl) -2,6-diphenylpyridine (I-1) powder (yield 0.26 g, yield 17%) Obtained.

^{1 1} H-NMR (THF-d ₈ ) δ (ppm): 7.19-7.40 (m, 29H), 7.58 (d, J = 8.0Hz, 2H), 7.60-7.63 (M, 6H), 8.05-8.08 (m, 4H).
Example-24

In the atmosphere, compound D-21 (6.75 g) and benzamidine hydrochloride (1.57 g) were suspended in EtOH (40 mL), and an EtOH solution (13 mL) of potassium hydroxide (1.12 g) was added dropwise. , Heated and refluxed for 6 hours. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. By washing the obtained solid with MeOH, the desired white powder of 4- (3-bromo-5-chlorophenyl) -2,6-diphenyl-pyrimidine (F-4) (yield 3.26 g, yield 77) was obtained. %) Was obtained.

^{1 1} H-NMR (THF-d ₈ ) δ (ppm): 7.55-7.61 (m, 6H), 7.69 (s, 1H), 7.96 (s, 1H), 8.22 ( s, 1H), 8.30 (m, 3H), 8.70-8.72 (m, 2H).
Compound F-4 (843 mg), bis (pinacolato) diboron (1.07 g), potassium acetate (824 mg), palladium acetate (9.0 mg) and 2-dicyclohexylphosphino-2', 4', 6 under an argon stream. '-Triisopropylbiphenyl (57.2 mg) was suspended in THF (20 mL) and heated to reflux for 3 hours. Then, 6'-iodine-1,1': 3', 1 "-terphenyl (1.50 g) was added, and a 3M-potassium carbonate aqueous solution (2.7 mL) was further added, and the mixture was heated under reflux for 22 hours. .. After allowing the reaction mixture to cool, the reaction mixture was separated and extracted with water and chloroform, and the solvent was distilled off under reduced pressure. By producing this by column chromatography (developing solvent: chloroform / hexane), the desired 4- (4''', 5'-diphenyl-1,1': 2', 1'': 3'', 1''': 2''', 1''''-kinkphenyl-3'-yl) -2,6-diphenylpyrimidine (G-3) powder (yield 0.87 g, yield 57%) Obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.12-7.45 (m, 25H), 7.50 (s, 1H), 7.56 (d, J = 8.0Hz, 2H), 7.59-7.62 (m, 6H), 7.87 (s, 2H), 8.17 (d, J = 8.1Hz, 2H), 8.50 (d, J = 7.9Hz, 2H) ).
Excited triplet level measurement of the cyclic azine compound of the present invention The excited triplet level of the compound of the present invention and the conventionally known compound was measured.

The excited triplet level was determined as follows. A 0.5-5 mmol / L 2-methyltetrahydrofuran solution of the compound to be evaluated was prepared, and the phosphorescence spectrum at 77K was measured with a spectrofluorometer (FP-6500, manufactured by JASCO Corporation). A tangent line is drawn for the rising edge of the phosphorescence spectrum on the short wavelength side, and the wavelength value (nm) at the intersection of the tangent line and the horizontal axis is calculated. By substituting this wavelength value into the following equation, the excited triplet level was obtained.

Calculation formula: Excited triplet level [eV] = 1240 / wavelength value The excited triplet level measured by the above method is shown in the table below. As conventionally known compounds, ETL-2 and the like shown below were evaluated in the same manner. The results are shown in the table below.

Fabrication and Performance Evaluation of Organic Electroluminescent Device Containing a Cyclic Adin Compound of the Present Invention The present invention will be described with reference to the following test examples, but the present invention is not limited thereto. The structural formulas of the compounds used and their abbreviations are shown below.

Evaluation Example 1-1
As the 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. This substrate was washed with isopropyl alcohol and then surface-treated by oxygen plasma washing. Each layer was vacuum-deposited on the washed substrate by a vacuum-film deposition method to produce an organic electroluminescent device having ^{a light-emitting area of 4 mm 2 as shown in FIG. 1 in a schematic cross-sectional view.}

First, the glass substrate was introduced into the vacuum vapor deposition tank, and the pressure was reduced to ^{1.0 × 10 -4 Pa.}
Then, as an organic compound layer on the glass substrate with an ITO transparent electrode shown in FIG. 1, the hole injection layer 12, the first hole transport layer 13, the second hole transport layer 14, the light emitting layer 15, and the first electron. The transport layer 16 and the second electron transport layer 17 were sequentially formed, and then the cathode layer 18 was formed.

The materials forming each layer of the organic electroluminescent device were vacuum-deposited by a resistance heating method.

As the hole injection layer 12, HIL-1 was vacuum-deposited at a film thickness of 0.15 nm / sec to a film thickness of 65 nm.

As the first hole transport layer 13, HAT-CN was vacuum-deposited at a film thickness of 0.025 nm / sec to a film thickness of 5 nm.

As the second hole transport layer 14, HTL-2 was vacuum-deposited at a film thickness of 0.15 nm / sec to a film thickness of 10 nm.

As the light emitting layer 15, EML-H1 and EML-D1 are co-deposited with a film thickness of 25 nm at a film formation rate of 0.18 nm / sec (EML-H1 / EMLD1 = 95.4 / 4.6 (weight ratio) co-deposition). Vacuum-deposited with.

As the first electron transport layer 16, E-2 synthesized in Example 2 of the present invention was vacuum-deposited at a film thickness of 0.15 nm / sec to a film thickness of 5 nm.

As the second electron transport layer 17, ETL-2 and Liq were vacuum-deposited at a film thickness of 0.15 nm / sec with a film thickness of 25 nm (co-deposited with ETL-2 / Liq = 50/50 (weight ratio)). ..

Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and the cathode layer 18 was formed into a film. In the cathode layer 18, magnesium / silver (weight ratio 80/20) and silver are vacuum-deposited in this order at a film formation rate of 0.5 nm / sec and 0.2 nm / sec, respectively, at a film thickness of 80 nm and 20 nm. It has a two-layer structure.

Each film thickness was measured with a stylus type film thickness measuring meter (DEKTAK, manufactured by Veeco). Further, this element was sealed in a nitrogen atmosphere glove box having an oxygen and water concentration of 1 ppm or less. For sealing, a glass sealing cap and the film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Evaluation Example 1-2
In the first electron transport layer 16 of Evaluation Example 1-1, organic electroluminescence is emitted by the same method as that of Evaluation Example 1-1 except that E-3 synthesized in Example 3 is used instead of E-2. The element was manufactured.

Evaluation Example 1-3
In the first electron transport layer 16 of Evaluation Example 1-1, organic electroluminescence is emitted by the same method as that of Evaluation Example 1-1 except that E-4 synthesized in Example 4 is used instead of E-2. The element was manufactured.

Evaluation Example 1-4
In the first electron transport layer 16 of Evaluation Example 1-1, organic electroluminescence is emitted by the same method as that of Evaluation Example 1-1 except that E-6 synthesized in Example 6 is used instead of E-2. The element was manufactured.

Evaluation Example 1-5
In the first electron transport layer 16 of Evaluation Example 1-1, organic electroluminescence is emitted by the same method as that of Evaluation Example 1-1 except that E-7 synthesized in Example 7 is used instead of E-2. The element was manufactured.

Comparative Example 1-1
In the first electron transport layer 16 of Evaluation Example 1-1, an organic electric field is used in the same manner as in Evaluation Example 1-1 except that ETL-1, which is a known electron transport material, is used instead of E-2. A light emitting element was manufactured.

Reference example 1-1
In the first electron transport layer 16 of Evaluation Example 1-1, an organic electric field is used in the same manner as in Evaluation Example 1-1 except that ETL-2, which is a known electron transport material, is used instead of E-2. A light emitting element was manufactured.

Reference example 1-2
In the first electron transport layer 16 of Evaluation Example 1-1, an organic electric field is used in the same manner as in Evaluation Example 1-1 except that ETL-3, which is a known electron transport material, is used instead of E-2. A light emitting element was manufactured.

A direct current was applied to the organic electroluminescent elements manufactured in Evaluation Examples 1-1 to 1-5, Comparative Examples 1-1 and Reference Examples 1-1 to 1-2, and LUMINANCE METER (BM-9) manufactured by TOPCON Co., Ltd. was applied. The emission characteristics were evaluated using the luminance meter of). As the life characteristic (h), ^{the luminance decay time at the time of continuous lighting when a current density of 10 mA / cm 2} is passed is measured, and the time when the luminance (cd / m ² ) is reduced by 25% is the element lifetime (h). ). The element life of each evaluation example is shown as a relative value with the element life in Comparative Example 1-1 as 100.

It was found that the organic electroluminescent device using the cyclic azine compound of the present invention has excellent life characteristics as compared with Comparative Example 1-1.

Evaluation Example 2-1
As the 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. This substrate was washed with isopropyl alcohol and then surface-treated by oxygen plasma washing. Each layer was vacuum-deposited on the washed substrate by a vacuum-film deposition method to produce an organic electroluminescent device having ^{a light-emitting area of 4 mm 2 as shown in FIG. 2 in a schematic cross-sectional view.}

First, the glass substrate was introduced into the vacuum vapor deposition tank, and the pressure was reduced to ^{1.0 × 10 -4 Pa.}
Then, as an organic compound layer on the glass substrate with an ITO transparent electrode shown in FIG. 2, the hole injection layer 22, the first hole transport layer 23, the second hole transport layer 24, the light emitting layer 25, and the first electron. The transport layer 26 and the second electron transport layer 27 were sequentially formed, and then the cathode layer 28 was formed.

The materials forming each layer of the organic electroluminescent device were vacuum-deposited by a resistance heating method.

As the hole injection layer 22, HIL-1 was vacuum-deposited with a film thickness of 60 nm at a film formation rate of 0.15 nm / sec.

As the first hole transport layer 23, HAT-CN was vacuum-deposited at a film thickness of 0.025 nm / sec to a film thickness of 10 nm.

As the second hole transport layer 24, HTL-2 was vacuum-deposited at a film thickness of 0.15 nm / sec to a film thickness of 10 nm.

As the light emitting layer 25, the film thickness of EML-H2 and Ir (ppy) ₃ was 30 nm at a film thickness rate of 0.18 nm / sec (EML-1 / EML-2 = 90.0 / 10.0 (weight ratio)). Vacuum-deposited by co-depositing).

As the first electron transport layer 26, E-1 synthesized in Example 1 of the present invention was vacuum-deposited at a film thickness of 0.15 nm / sec to a film thickness of 10 nm.

As the second electron transport layer 27, ETL-2 and Liq were vacuum-deposited at a film thickness of 0.15 nm / sec with a film thickness of 40 nm (co-deposited with ETL-2 / Liq = 50/50 (weight ratio)). ..

Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and the cathode layer 28 was formed into a film. The cathode layer 28 vacuum-deposits magnesium / silver (weight ratio 80/20) and silver in this order at a film formation rate of 0.5 nm / sec and 0.2 nm / sec, respectively, at a film thickness of 80 nm and 20 nm. It has a two-layer structure.

Each film thickness was measured with a stylus type film thickness measuring meter (DEKTAK, manufactured by Veeco). Further, this element was sealed in a nitrogen atmosphere glove box having an oxygen and water concentration of 1 ppm or less. For sealing, a glass sealing cap and the film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Evaluation Example 2-2
In the first electron transport layer 26 of Evaluation Example 2-1 the organic electroluminescence was carried out in the same manner as in Evaluation Example 2-1 except that E-2 synthesized in Example 2 was used instead of E-1. The element was manufactured.

Evaluation Example 2-3
In the first electron transport layer 26 of Evaluation Example 2-1 the organic electroluminescence was carried out in the same manner as in Evaluation Example 2-1 except that E-3 synthesized in Example 3 was used instead of E-1. The element was manufactured.

Evaluation Example 2-4
In the first electron transport layer 26 of Evaluation Example 2-1 the organic electroluminescence was carried out in the same manner as in Evaluation Example 2-1 except that E-4 synthesized in Example 4 was used instead of E-1. The element was manufactured.

Evaluation Example 2-5
In the first electron transport layer 26 of Evaluation Example 2-1 organic electroluminescence was performed in the same manner as in Evaluation Example 2-1 except that E-5 synthesized in Example 5 was used instead of E-1. The element was manufactured.

Evaluation Example 2-6
In the first electron transport layer 26 of Evaluation Example 2-1 organic electroluminescence was performed in the same manner as in Evaluation Example 2-1 except that E-6 synthesized in Example 6 was used instead of E-1. The element was manufactured.

Evaluation Example 2-7
In the first electron transport layer 26 of Evaluation Example 2-1 organic electroluminescence was performed in the same manner as in Evaluation Example 2-1 except that E-7 synthesized in Example 7 was used instead of E-1. The element was manufactured.

Evaluation Example 2-8
In the first electron transport layer 26 of Evaluation Example 2-1 organic electroluminescence was performed in the same manner as in Evaluation Example 2-1 except that E-10 synthesized in Example 10 was used instead of E-1. The element was manufactured.

Evaluation Example 2-9
In the first electron transport layer 26 of Evaluation Example 2-1 the organic electroluminescence was carried out in the same manner as in Evaluation Example 2-1 except that E-13 synthesized in Example 13 was used instead of E-1. The element was manufactured.

Reference example 2-1
In the first electron transport layer 26 of Evaluation Example 2-1 the organic electric field is used in the same manner as in Evaluation Example 2-1 except that ETL-2, which is a known electron transport material, is used instead of E-1. A light emitting element was manufactured.

Reference example 2-2
In the first electron transport layer 26 of Evaluation Example 2-1 the organic electric field is used in the same manner as in Evaluation Example 2-1 except that ETL-3, which is a known electron transport material, is used instead of E-1. A light emitting element was manufactured.

A direct current was applied to the organic electroluminescent devices manufactured in Evaluation Examples 2-1 to 2-9, Comparative Example 2-1 and Reference Examples 2-1 to 2-2, and LUMINANCE METER (BM-9) manufactured by TOPCON Co., Ltd. was applied. ) Luminance meter was used to evaluate the emission characteristics. As the life characteristic (h), ^{the luminance decay time at the time of continuous lighting when a current density of 4 mA / cm 2} is passed is measured, and the time when the luminance (cd / m ² ) is reduced by 15% is the element lifetime (h). ). The element life of each evaluation example is shown as a relative value with the element life in Reference Example 2-1 as 100.

It was found that the organic electroluminescent device using the cyclic azine compound of the present invention has excellent life characteristics as compared with Reference Example 2-1.

Evaluation Example 3-1
As the 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. This substrate was washed with isopropyl alcohol and then surface-treated by oxygen plasma washing. Each layer was vacuum-deposited on the washed substrate by a vacuum-film deposition method to produce an organic electroluminescent device having ^{a light-emitting area of 4 mm 2 as shown in FIG. 3 in a schematic cross-sectional view.}

First, the glass substrate was introduced into the vacuum vapor deposition tank, and the pressure was reduced to ^{1.0 × 10 -4 Pa.}
After that, the hole injection layer 32, the first hole transport layer 33, the second hole transport layer 34, the light emitting layer 35, and the electron transport are used as the organic compound layer on the glass substrate with the ITO transparent electrode shown in FIG. The layers 36 were sequentially formed, and then the cathode layer 37 was formed.

The materials forming each layer of the organic electroluminescent device were vacuum-deposited by a resistance heating method.

As the hole injection layer 32, HIL-1 was vacuum-deposited at a film thickness of 0.15 nm / sec to a film thickness of 65 nm.

As the first hole transport layer 33, HAT-CN was vacuum-deposited at a film thickness of 0.025 nm / sec to a film thickness of 5 nm.

As the second hole transport layer 34, HTL-2 was vacuum-deposited at a film thickness of 0.15 nm / sec to a film thickness of 10 nm.

As the light emitting layer 35, EML-H1 and EML-D1 have a film thickness of 25 nm (EML-1 / EML-2 = 95.4 / 4.6 (weight ratio)) at a film thickness rate of 0.18 nm / sec. Vacuum deposition was performed by vapor deposition).

As the electron transport layer 36, a film thickness of 30 nm (ETL-2 / Liq = 50/50 (weight ratio)) of E-2 and Liq synthesized in Example 2 of the present invention at a film thickness rate of 0.15 nm / sec. Vacuum-deposited by co-depositing).

Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and the cathode layer 37 was formed into a film. The cathode layer 37 vacuum-deposits magnesium / silver (weight ratio 80/20) and silver in this order at a film formation rate of 0.5 nm / sec and 0.2 nm / sec, respectively, at a film thickness of 80 nm and 20 nm. It has a two-layer structure.

Each film thickness was measured with a stylus type film thickness measuring meter (DEKTAK, manufactured by Veeco). Further, this element was sealed in a nitrogen atmosphere glove box having an oxygen and water concentration of 1 ppm or less. For sealing, a glass sealing cap and the film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Evaluation Example 3-2
In the first electron transport layer 36 of Evaluation Example 3-1 organic electroluminescence was performed in the same manner as in Evaluation Example 3-1 except that E-3 synthesized in Example 3 was used instead of E-2. The element was manufactured.

Evaluation Example 3-3
Organic electroluminescence was carried out in the same manner as in Evaluation Example 3-1 except that E-4 synthesized in Example 4 was used in place of E-2 in the first electron transport layer 36 of Evaluation Example 3-1. The element was manufactured.

Evaluation Example 3-4
In the first electron transport layer 36 of Evaluation Example 3-1 organic electroluminescence was performed in the same manner as in Evaluation Example 3-1 except that E-6 synthesized in Example 6 was used instead of E-2. The element was manufactured.

Evaluation Example 3-5
In the first electron transport layer 36 of Evaluation Example 3-1 organic electroluminescence was performed in the same manner as in Evaluation Example 3-1 except that E-7 synthesized in Example 7 was used instead of E-2. The element was manufactured.

Comparative Example 3-1
In the first electron transport layer 36 of Evaluation Example 3-1 the organic electric field is used in the same manner as in Evaluation Example 3-1 except that ETL-1, which is a known electron transport material, is used instead of E-2. A light emitting element was manufactured.

Reference example 3-1
In the first electron transport layer 36 of Evaluation Example 3-1 the organic electric field is used in the same manner as in Evaluation Example 3-1 except that ETL-3, which is a known electron transport material, is used instead of E-2. A light emitting element was manufactured.

Luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON Co., Ltd. by applying a direct current to the organic electroluminescent devices manufactured in Evaluation Examples 3-1 to 3-5, Comparative Example 3-1 and Reference Example 3-1. The emission characteristics were evaluated using. As the life characteristic (h), ^{the luminance decay time at the time of continuous lighting when a current density of 10 mA / cm 2} is passed is measured, and the time when the luminance (cd / m ² ) is reduced by 20% is the element lifetime (h). ). The element life of each evaluation example is shown as a relative value with the element life (h) in Comparative Example 3-1 as 100.

It was found that the organic electroluminescent device using the cyclic azine compound of the present invention has excellent life characteristics as compared with Comparative Example 3-1.

Evaluation Example 4-1
As the 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. This substrate was washed with isopropyl alcohol and then surface-treated by oxygen plasma washing. Each layer was vacuum-deposited on the washed substrate by a vacuum-film deposition method to produce an organic electroluminescent device having ^{a light-emitting area of 4 mm 2 as shown in FIG. 4 in a schematic cross-sectional view.}

First, the glass substrate was introduced into the vacuum vapor deposition tank, and the pressure was reduced to ^{1.0 × 10 -4 Pa.}
After that, the hole injection layer 42, the first hole transport layer 43, the second hole transport layer 44, the light emitting layer 45, and the first electron are formed as an organic compound layer on the glass substrate with the ITO transparent electrode shown in FIG. The transport layer 46 and the second electron transport layer 47 were sequentially formed, and then the cathode layer 48 was formed.

The materials forming each layer of the organic electroluminescent device were vacuum-deposited by a resistance heating method.

As the hole injection layer 42, HIL-1 was vacuum-deposited with a film thickness of 60 nm at a film formation rate of 0.15 nm / sec.

As the first hole transport layer 43, HAT-CN was vacuum-deposited at a film thickness of 0.025 nm / sec to a film thickness of 10 nm.

As the second hole transport layer 44, HTL-2 was vacuum-deposited at a film thickness of 0.15 nm / sec to a film thickness of 10 nm.

As the light emitting layer 45, mCBP and 4Cz-IPN, which is a TADF light emitting material known as mCBP, have a film thickness of 30 nm at a film formation rate of 0.18 nm / sec (mCBP / 4Cz-IPN = 85.0 / 15.0 (weight ratio). ) Co-deposited) was vacuum-deposited.

As the first electron transport layer 46, E-1 synthesized in Example 1 of the present invention was vacuum-deposited at a film thickness of 0.15 nm / sec to a film thickness of 10 nm.

As the second electron transport layer 47, ETL-2 and Liq were vacuum-deposited at a film thickness of 0.15 nm / sec with a film thickness of 40 nm (co-deposited with ETL-2 / Liq = 50/50 (weight ratio)). ..

Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and the cathode layer 48 was formed into a film. In the cathode layer 48, magnesium / silver (weight ratio 80/20) and silver are vacuum-deposited in this order at a film formation rate of 0.5 nm / sec and 0.2 nm / sec, respectively, at a film thickness of 80 nm and 20 nm. It has a two-layer structure.

Each film thickness was measured with a stylus type film thickness measuring meter (DEKTAK, manufactured by Veeco). Further, this element was sealed in a nitrogen atmosphere glove box having an oxygen and water concentration of 1 ppm or less. For sealing, a glass sealing cap and the film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Evaluation Example 4-2
In the first electron transport layer 46 of Evaluation Example 4-1 the organic electroluminescence was carried out in the same manner as in Evaluation Example 4-1 except that E-11 synthesized in Example 11 was used instead of E-2. The element was manufactured.

Comparative Example 4-1
In the first electron transport layer 46 of the evaluation example 4-1 except that ETL-1, which is a known electron transport material, was used instead of E-2, the organic electric field was used in the same manner as in the evaluation example 4-1. A light emitting element was manufactured.

A direct current is applied to the organic electroluminescent devices manufactured in Evaluation Examples 4-1 to 4-2 and Comparative Example 4-1. Was evaluated. As the life characteristic (h), ^{the luminance decay time at the time of continuous lighting when a current density of 10 mA / cm 2} is passed is measured, and the time when the luminance (cd / m ² ) is reduced by 15% is the element lifetime (h). ). The element life of each evaluation example is shown as a relative value with the element life (h) in Comparative Example 4-1 as 100.

It was found that the organic electroluminescent device using the cyclic azine compound of the present invention has excellent life characteristics as compared with Comparative Example 4-1.

Evaluation Example 5-1
As the 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. This substrate was washed with isopropyl alcohol and then surface-treated by oxygen plasma washing. Each layer was vacuum-deposited on the washed substrate by a vacuum-film deposition method to produce an organic electroluminescent device having ^{a light-emitting area of 4 mm 2 as shown in FIG. 5 in a schematic cross-sectional view.}

First, the glass substrate was introduced into the vacuum vapor deposition tank, and the pressure was reduced to ^{1.0 × 10 -4 Pa.}
After that, the hole injection layer 52, the first hole transport layer 53, the second hole transport layer 54, the electron blocking layer 55, and the light emitting layer were formed as organic compound layers on the glass substrate with the ITO transparent electrode shown in FIG. 56, the first electron transport layer 57 and the second electron transport layer 58 were sequentially formed, and then the cathode layer 59 was formed.

The materials forming each layer of the organic electroluminescent device were vacuum-deposited by a resistance heating method.

As the hole injection layer 52, HIL-1 was vacuum-deposited with a film thickness of 60 nm at a film formation rate of 0.15 nm / sec.

As the first hole transport layer 53, HAT-CN was vacuum-deposited at a film thickness of 0.025 nm / sec to a film thickness of 10 nm.

As the second hole transport layer 54, HTL-2 was vacuum-deposited at a film thickness of 0.15 nm / sec to a film thickness of 10 nm.

As the electron blocking layer 55, mCBP was vacuum-deposited at a film thickness of 0.15 nm / sec and a film thickness of 5 nm.

As the light emitting layer 56, mCBP and 4Cz-IPN, which is a TADF light emitting material known as mCBP, have a film thickness of 30 nm at a film formation rate of 0.18 nm / sec (mCBP / 4Cz-IPN = 85.0 / 15.0 (weight ratio). ) Co-deposited) was vacuum-deposited.

As the first electron transport layer 57, E-2 synthesized in Example 1 of the present invention was vacuum-deposited at a film thickness of 0.15 nm / sec to a film thickness of 10 nm.

As the second electron transport layer 58, ETL-2 and Liq were vacuum-deposited at a film thickness of 0.15 nm / sec with a film thickness of 40 nm (co-deposited with ETL-2 / Liq = 50/50 (weight ratio)). ..

Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and the cathode layer 59 was formed into a film. In the cathode layer 59, magnesium / silver (weight ratio 80/20) and silver are vacuum-deposited in this order at a film formation rate of 0.5 nm / sec and 0.2 nm / sec, respectively, at a film thickness of 80 nm and 20 nm. It has a two-layer structure.

Each film thickness was measured with a stylus type film thickness measuring meter (DEKTAK, manufactured by Veeco). Further, this element was sealed in a nitrogen atmosphere glove box having an oxygen and water concentration of 1 ppm or less. For sealing, a glass sealing cap and the film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Evaluation Example 5-2
Organic electroluminescence was carried out in the same manner as in Evaluation Example 5-1 except that E-11 synthesized in Example 11 was used in place of E-2 in the first electron transport layer 57 of Evaluation Example 5-1. The element was manufactured.

Evaluation Example 5-3
Organic electroluminescence was carried out in the same manner as in Evaluation Example 5-1 except that G-1 synthesized in Example 18 was used in place of E-2 in the first electron transport layer 57 of Evaluation Example 5-1. The element was manufactured.

Evaluation Example 5-4
In the first electron transport layer 57 of Evaluation Example 5-1, E-11 synthesized in Example 11 was used instead of E-2, and in the second electron transport layer 58, instead of ETL-2, An organic electroluminescent device was produced by the same method as in Evaluation Example 5-1 except that E-11 synthesized in Example 11 was used. Evaluation Example 5-5
In the first electron transport layer 57 of Evaluation Example 5-1, G-1 synthesized in Example 18 was used instead of E-2, and in the second electron transport layer 58, instead of ETL-2, An organic electroluminescent device was produced by the same method as in Evaluation Example 5-1 except that E-11 synthesized in Example 11 was used.

Comparative Example 5-1
In the first electron transport layer 57 of Evaluation Example 5-1, an organic electric field is used in the same manner as in Evaluation Example 5-1 except that ETL-1, which is a known electron transport material, is used instead of E-2. A light emitting element was manufactured.

Comparative Example 5-2
The second electron transport layer 58 of Comparative Example 5-1 uses the same method as that of Evaluation Example 5-1 except that ETL-1, which is a known electron transport material, is used instead of ETL-2. The element was manufactured.

A direct current was applied to the organic electroluminescent devices manufactured in Evaluation Examples 5-1 to 5-5 and Comparative Examples 5-1 to 5-2, and a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON was used. The emission characteristics were evaluated using. As the life characteristic (h), ^{the luminance decay time at the time of continuous lighting when a current density of 10 mA / cm 2} is passed is measured, and the time when the luminance (cd / m ² ) is reduced by 15% is the element lifetime (h). ). The element life of each evaluation example is shown as a relative value with the element life (h) in Comparative Example 5-1 as 100.

It was found that the organic electroluminescent device using the cyclic azine compound of the present invention has excellent lifetime characteristics as compared with Comparative Examples 5-1 and 5-2.

The organic electroluminescent device using the cyclic azine compound of the present invention can be driven for a longer time than the organic electroluminescent device using an existing material. Further, the cyclic azine compound of the present invention can be applied not only to the electron transport layer of the present embodiment but also to a light emitting host layer and the like. Further, it can be applied not only to an element using a fluorescent light emitting material but also to various organic electroluminescent devices using a phosphorescent light emitting material. Further, the cyclic azine compound of the present invention has high solubility, and it is possible to fabricate an element using not only a vacuum vapor deposition method but also a coating method. Further, it is useful not only for applications such as flat panel displays, but also for lighting applications that require low power consumption.

Claims (8)

General formula (1)

{In the formula,
The benzene ring B is as follows.

The benzene ring C is as follows.

At least two Rs in at least one ring of the benzene rings A, B, C may be independently linked and / or condensed, respectively, and an aromatic hydrocarbon group having 6 to 30 carbon atoms (the group is a group). , Independently, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and an alkyl halide group having 1 to 3 carbon atoms. Alternatively, it may have a halide alkoxy group having 1 to 3 carbon atoms as a substituent).
Rs other than the above are independently hydrogen atom, heavy hydrogen atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, and methylthio group. , Ethylthio group, sulfide group having 3 to 10 carbon atoms, or aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed (the groups are independently fluorine atoms and methyl. Group, ethyl group, alkyl group with 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group with 3 to 10 carbon atoms, alkyl halide group with 1 to 3 carbon atoms, or alkoxy halide with 1 to 3 carbon atoms. It may have a group as a substituent).
Y ¹ , Y ² and Y ³ all represent = N−. }
Cyclic azine compound represented by.
However, the following compounds are excluded.

The cyclic azine compound according to claim 1, wherein the benzene ring A is as follows.

(In the formula, R is synonymous with claim 1.) The cyclic azine compound according to claim 1 or 2, wherein the benzene ring C is as follows.

At least two Rs in at least one ring of the benzene rings A, B, C may be independently linked and / or condensed, respectively, and an aromatic hydrocarbon group having 6 to 17 carbon atoms (the group is a group). , Independently, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and an alkyl halide group having 1 to 3 carbon atoms. Alternatively, it may have a halogenated alkoxy group having 1 to 3 carbon atoms as a substituent), and Rs other than the above are independently hydrogen atoms, deuterium atoms, methyl groups, ethyl groups, and carbons. It may be an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, a sulfide group having 3 to 10 carbon atoms, or linked and / or condensed rings. Aromatic hydrocarbon group having 6 to 17 carbon atoms (the group is independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, and 3 to 10 carbon atoms. The alkoxy group, the alkyl halide group having 1 to 3 carbon atoms, or the alkoxy halide group having 1 to 3 carbon atoms may be used as a substituent) according to any one of claims 1 to 3. The cyclic azine compound according to the above. At least two Rs in at least one ring of the benzene rings A, B, C, and 0, 1, 2, 3, or 4 of the other Rs are independently linked and / or condensed. An aromatic hydrocarbon group having 6 to 30 carbon atoms (the groups may independently have a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, and a carbon. It may have an alkoxy group having a number of 3 to 10, an alkyl halide group having 1 to 3 carbon atoms, or a halogenated alkoxy group having 1 to 3 carbon atoms as a substituent), and R other than the above is used. , Independently, hydrogen atom, heavy hydrogen atom, methyl group, ethyl group, alkyl group with 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group with 3 to 10 carbon atoms, methylthio group, ethylthio group, or The cyclic azine compound according to any one of claims 1 to 4 , which represents a sulfide group having 3 to 10 carbon atoms. An aromatic hydrocarbon group having 6 to 30 carbon atoms which may be linked and / or condensed (the groups are independently a fluorine atom, a methyl group, an ethyl group, and an alkyl group having 3 to 10 carbon atoms, respectively. It may have a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or an alkoxy halide group having 1 to 3 carbon atoms as a substituent). A phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, or a phenanthryl group (these groups are independently fluorine atoms, methyl groups, butyl groups, methoxy groups, butoxy groups, methyl halide groups, or halogenated groups. The cyclic azine compound according to any one of claims 1 to 5 , which may have a methoxy group as a substituent). A material for an organic electroluminescent device comprising the cyclic azine compound according to any one of claims 1 to 6. An electron injection material, an electron transport material, or a light emitting material for an organic electroluminescent device containing the cyclic azine compound according to any one of claims 1 to 6.

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