Cyclic azine compound, method for producing the same, and use thereof

Abstract

To provide a cyclic azine compound that contributes to making an organic electroluminescent element with high current efficiency and long service life.SOLUTION: For example, a cyclic azine compound of the following structural formula is illustrated.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a cyclic azine compound, a method for producing the same, and an organic electroluminescent device using the same.

Background Art

[0002] Organic electroluminescent devices are used not only for small displays but also for applications such as large TVs and lighting, and their development is being actively carried out. For example, Patent Document 1 discloses a cyclic azine compound having a specific substituent, which is excellent in heat resistance, reduces the driving voltage, and contributes to providing an organic electroluminescent device with a long lifespan as a material for an organic electroluminescent device.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, in recent years, the market requirements for organic electroluminescent devices have become increasingly high, and materials that are excellent in any of the luminous efficiency characteristics, driving voltage characteristics, and long lifespan characteristics are demanded. Here, although the organic electroluminescent device using the cyclic azine compound disclosed in Patent Document 1 exhibits excellent driving voltage characteristics, further improvement is required for the device lifespan and current efficiency. One aspect of the present disclosure is directed to providing a cyclic azine compound and a material for an organic electroluminescent device that contribute to the production of an organic electroluminescent device excellent in durability and current efficiency. Another aspect of the present disclosure is directed to providing a method for producing the cyclic azine compound. Still another aspect of the present disclosure is directed to providing an organic electroluminescent device excellent in durability and current efficiency.

Means for Solving the Problem

[0005] According to one aspect of the present disclosure, cyclic azine compounds represented by formulas (1-A) to (1-E) are provided:

[0006]

Chemical formula

[0007] In the formula, Ar 1 and Ar 2 each independently represents (i) an aromatic hydrocarbon group of a monocyclic, linked, or condensed ring having 6 to 20 carbon atoms, (ii) an aromatic heterocyclic group of a monocyclic, linked, or condensed ring having 4 to 20 carbon atoms, or (iii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; R represents (iv) a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (v) an aromatic hydrocarbon group of a monocyclic, linked, or condensed ring having 6 to 30 carbon atoms, (vi) an aromatic heterocyclic group of a monocyclic, linked, or condensed ring having 4 to 30 carbon atoms, or (vii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; Ra represents (a1) a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (a2) A monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, (a3) A monocyclic, linked, or fused aromatic heterocyclic group having 4 to 30 carbon atoms, or (a4) A group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; n represents an integer from 1 to 8, provided that when Ra is a hydrogen atom, n represents an integer from 2 to 8; The plurality of Rs may be the same or different; Y 1 and Y 2 each independently represents a nitrogen atom or CH, Y 1 and Y 2 at least one of which is a nitrogen atom.

[0008] [Chemical formula]

[0009] In the formula, Ar 1 and Ar 2 each independently represents (i) A monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 20 carbon atoms, (ii) A monocyclic, linked, or fused aromatic heterocyclic group having 4 to 20 carbon atoms, or (iii) A group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; R is (iv) A halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (v) an aromatic hydrocarbon group of a monocyclic, linked ring, or condensed ring having 6 to 30 carbon atoms, (vi) an aromatic heterocyclic group of a monocyclic, linked ring, or condensed ring having 4 to 30 carbon atoms, or (vii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; Rb is (b1) a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (b2) an aromatic hydrocarbon group of a monocyclic, linked ring, or condensed ring having 6 to 30 carbon atoms, (b3) an aromatic heterocyclic group of a monocyclic, linked ring, or condensed ring having 4 to 30 carbon atoms, or (b4) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; n represents an integer from 1 to 8, provided that when Rb is a hydrogen atom, n represents an integer from 2 to 8; A plurality of Rs may be the same or different; Y 1 and Y 2 each independently represents a nitrogen atom or CH, Y 1 and Y 2 at least one of them is a nitrogen atom.

[0010]

Chemical formula

[0011] In the formula, Ar 1 and Ar2 each independently, (i) an aromatic hydrocarbon group of a monocyclic, linked, or condensed ring having 6 to 20 carbon atoms, (ii) an aromatic heterocyclic group of a monocyclic, linked, or condensed ring having 4 to 20 carbon atoms, or (iii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; R is (iv) a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (v) an aromatic hydrocarbon group of a monocyclic, linked, or condensed ring having 6 to 30 carbon atoms, (vi) an aromatic heterocyclic group of a monocyclic, linked, or condensed ring having 4 to 30 carbon atoms, or (vii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms, provided that when Rc is an aromatic hydrocarbon group of a monocyclic or linked ring having 6 to 30 carbon atoms, or a group in which the aromatic hydrocarbon group of the monocyclic or linked ring is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms, and the 9-position of phenanthrene is substituted with R, R substituted at the 9-position of the phenanthrene represents a group other than an unsubstituted phenyl group; Rc is (c1) a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (c2) an aromatic hydrocarbon group of a monocyclic, linked, or condensed ring having 6 to 30 carbon atoms, (c3) an aromatic heterocyclic group of a monocyclic, linked ring, or condensed ring having 4 to 30 carbon atoms, or (c4) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; n represents an integer from 1 to 8, provided that when Rc is a hydrogen atom, n represents an integer from 2 to 8; the plurality of Rs may be the same or different, provided that the 9-position and the 10-position of phenanthrene are different; Y 1 and Y 2 each independently represents a nitrogen atom or CH, Y 1 and Y 2 at least one of them is a nitrogen atom.

[0012]

Chemical formula

[0013] In the formula, Ar 1 and Ar 2 each independently is (i) an aromatic hydrocarbon group of a monocyclic, linked ring, or condensed ring having 6 to 20 carbon atoms, (ii) an aromatic heterocyclic group of a monocyclic, linked ring, or condensed ring having 4 to 20 carbon atoms, or (iii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; R is (iv) a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (v) an aromatic hydrocarbon group of a monocyclic, linked ring, or condensed ring having 6 to 30 carbon atoms, (vi) an aromatic heterocyclic group of a monocyclic, linked ring, or condensed ring having 4 to 30 carbon atoms, or (vii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms, provided that when R substituted at the 10-position of phenanthrene is an aromatic hydrocarbon group of a monocyclic or linked ring having 6 to 30 carbon atoms, or a group in which the aromatic hydrocarbon group of the monocyclic or linked ring is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms, and when the 9-position of phenanthrene is substituted with R, R substituted at the 9-position of the phenanthrene represents a group other than an unsubstituted phenyl group; Rd is (d1) a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (d2) an aromatic hydrocarbon group of a monocyclic, linked ring, or condensed ring having 6 to 30 carbon atoms, (d3) an aromatic heterocyclic group of a monocyclic, linked ring, or condensed ring having 4 to 30 carbon atoms, or (d4) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; n represents an integer from 1 to 8, provided that when Rd is a hydrogen atom, n represents an integer from 2 to 8; a plurality of Rs may be the same or different, provided that the 9-position and the 10-position of phenanthrene are different; Y 1 and Y 2 each independently represents a nitrogen atom or CH, Y 1 and Y 2 at least one of which is a nitrogen atom.

[0014]

Chemical formula

[0015] In the formula, Ar 1 and Ar 2 each independently represents (i) an aromatic hydrocarbon group of a monocyclic, linked, or fused ring having 6 to 20 carbon atoms, (ii) an aromatic heterocyclic group of a monocyclic, linked, or fused ring having 4 to 20 carbon atoms, or (iii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; R represents (iv) a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (v) an aromatic hydrocarbon group of a monocyclic, linked, or fused ring having 6 to 30 carbon atoms, (vi) an aromatic heterocyclic group of a monocyclic, linked, or fused ring having 4 to 30 carbon atoms, or (vii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. However, when R substituted at the 10-position of phenanthrene is a monocyclic or fused-ring aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group in which the monocyclic or fused-ring aromatic hydrocarbon group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms, and when the 9-position of phenanthrene is substituted with R, R substituted at the 9-position of the phenanthrene represents a group other than an unsubstituted phenyl group; Re is (e1) a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (e2) a monocyclic, fused-ring, or condensed-ring aromatic hydrocarbon group having 6 to 30 carbon atoms, (e3) a monocyclic, fused-ring, or condensed-ring aromatic heterocyclic group having 4 to 30 carbon atoms, or (e4) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; n represents an integer from 1 to 8, provided that when Re is a hydrogen atom, n represents an integer from 2 to 8; The plurality of Rs may be the same or different, provided that the 9-position and the 10-position of phenanthrene are different; Y 1 and Y 2 each independently represents a nitrogen atom or CH, Y 1 and Y 2 at least one of which is a nitrogen atom.

[0016] According to another aspect of the present disclosure, there is provided a material for an organic electroluminescent device including the cyclic azine compound represented by the above formula (1). According to another aspect of the present disclosure, there is provided an organic electroluminescent device including the cyclic azine compound represented by the above formula (1).

[0017] According to another aspect of the present disclosure, there is provided a method for producing a cyclic azine compound represented by formula (1), including subjecting a compound represented by formula (2) and a compound represented by formula (3) to a coupling reaction in the presence of a metal catalyst, wherein the cyclic azine compound represented by the above formula (1) is the cyclic azine compound, and a method for producing a cyclic azine compound is provided:

[0018]

Chemical formula

[0019] In the formula, Ar 1 and Ar 2 R, n, Y 1 and Y 2 are synonymous with formulas (1-A) to (1-E); L represents a group corresponding to the phenanthrenyl group of the cyclic azine compound of formulas (1-A) to (1-E); X 1 represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom; M 1 represents ZnZ 1 MgZ 2 Sn(Z 3 )3, or B(OZ 4 )2; Z 1 and Z 2 each independently represents a chlorine atom, a bromine atom or an iodine atom; Z 3 represents the same or different alkyl groups having 1 to 4 carbon atoms or a phenyl group; Z 4 represents the same or different hydrogen atoms, alkyl groups having 1 to 4 carbon atoms or a phenyl group; However, when M 1 is B(OZ 4)When representing 2, the two (OZ 4 ) groups may together form a ring with a boron atom.

[0020] According to another aspect of the present disclosure, there is provided a method for producing a cyclic azine compound represented by formula (1), which includes subjecting a compound represented by formula (4) and a compound represented by formula (5) to a coupling reaction in the presence of a metal catalyst, wherein the cyclic azine compound represented by formula (1) is the above cyclic azine compound, and a method for producing a cyclic azine compound is provided:

[0021]

Chemical formula

[0022] In the formula, Ar 1 , Ar 2 , R, n, Y 1 and Y 2 are synonymous with formulas (1-A) to (1-E); L represents a group corresponding to the phenanthrenyl group of the cyclic azine compound of formulas (1-A) to (1-E); X 2 represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom.; M 2 represents ZnZ 1 , MgZ 2 , Sn(Z 3 )3, or B(OZ 4 )2; Z 1 and Z 2 each independently represent a chlorine atom, a bromine atom or an iodine atom; Z 3 represents the same or different alkyl groups having 1 to 4 carbon atoms or phenyl groups; Z 4 represents the same or different hydrogen atoms, alkyl groups having 1 to 4 carbon atoms or phenyl groups; However, when M 2 is B(OZ4 ) When representing 2, the two (OZ 4 ) groups may combine to form a ring together with the boron atom.

Advantages of the Invention

[0023] According to one aspect of the present disclosure, a cyclic azine compound and a material for an organic electroluminescent device, which contribute to the production of an organic electroluminescent device excellent in durability and current efficiency, can be provided. According to another aspect of the present disclosure, a method for producing the cyclic azine compound can be provided. According to still another aspect of the present disclosure, an organic electroluminescent device excellent in durability and current efficiency can be provided.

Brief Description of the Drawings

[0024]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0025] Hereinafter, the cyclic azine compound according to one aspect of the present disclosure will be described in detail.

[0026] <Cyclic Azine Compound> The cyclic azine compound according to one aspect of the present disclosure is represented by Formulas (1 - A) to (1 - E):

[0027]

Chemical Formula

[0028]

Chemical Formula

[0029] [Chemical]

[0030] [Chemical]

[0031] [Chemical]

[0032] In the formula, Ar 1 and Ar 2 each independently represents (i) an aromatic hydrocarbon group of a monocyclic, linked ring, or condensed ring having 6 to 20 carbon atoms, (ii) an aromatic heterocyclic group of a monocyclic, linked ring, or condensed ring having 4 to 20 carbon atoms, or (iii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; R represents (iv) a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (v) an aromatic hydrocarbon group of a monocyclic, linked ring, or condensed ring having 6 to 30 carbon atoms, (vi) an aromatic heterocyclic group of a monocyclic, linked ring, or condensed ring having 4 to 30 carbon atoms, or (vii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; Ra to Re represent (a1) to (e1) a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (a2) to (e2) an aromatic hydrocarbon group of a monocyclic, linked ring, or condensed ring having 6 to 30 carbon atoms, (a3) to (e3) an aromatic heterocyclic group of a monocyclic, linked ring, or condensed ring having 4 to 30 carbon atoms, or (a4) to (e4) the aromatic hydrocarbon group or aromatic heterocyclic group is represented by a group substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms; n represents an integer from 1 to 8, provided that when Ra to Re are hydrogen atoms, n represents an integer from 2 to 8; A plurality of Rs may be the same or different, Y 1 and Y 2 each independently represents a nitrogen atom or CH, Y 1 and Y 2 at least one of them is a nitrogen atom.

[0033] However, in formulas (1-C) to (1-E), the R substituted at the 10th position of phenanthrene is an aromatic hydrocarbon group of a monocyclic or linked ring having 6 to 30 carbon atoms, or the aromatic hydrocarbon group of the monocyclic or linked ring is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms, and when the 9th position of phenanthrene is substituted with R, the R substituted at the 9th position of the phenanthrene represents a group other than an unsubstituted phenyl group.

[0034] Hereinafter, the cyclic azine compounds according to one embodiment of the present disclosure represented by Formula (1-A) to (1-E) may also be collectively referred to as cyclic azine compound (1). The definitions of the substituents in cyclic azine compound (1), as well as their preferred embodiments and preferred specific examples, are as follows respectively.

[0035] [Ar 1 、Ar 2 について] Ar 1 およびAr 2 are each independently (i) an aromatic hydrocarbon group of a monocyclic, linked, or condensed ring having 6 to 20 carbon atoms, (ii) an aromatic heterocyclic group of a monocyclic, linked, or condensed ring having 4 to 20 carbon atoms, or (iii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms.

[0036] [[(i): Regarding the aromatic hydrocarbon group]] The aromatic hydrocarbon group of a monocyclic, linked, or condensed ring having 6 to 20 carbon atoms is not particularly limited, but examples include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthylphenyl group, a naphthyl group, an acenaphthylenyl group, a phenanthryl group, an anthryl group, a fluoranthenyl group, a pyrenyl group, a triphenylenyl group, a chrysenyl group, a fluorenyl group, a tripchysenyl group, a perylenyl group, etc. Among these, a phenyl group, a naphthyl group, or a biphenylyl group is preferable in terms of excellent characteristics as an electron transporting material.

[0037] [[(ii): Regarding the aromatic heterocyclic group]] The aromatic heterocyclic group of a monocyclic, linked ring, or condensed ring having 4 to 20 carbon atoms is not particularly limited, and examples thereof include a thienyl group, a furyl group, a benzofuranyl group, a benzothienyl group, a dibenzofuranyl group, a dibenzothienyl group, a pyrimidyl group, a pyrazinyl group, a pyridyl group, a bipyridyl group, a terpyridinyl group, a quinolinyl group, an isoquinolinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, an acridinyl group, a phenanthrolinyl group, a phthalazinyl group, and the like.

[0038] [[(iii): a group in which (i) and (ii) are substituted with a predetermined group]] · a group in which (i) is substituted with a predetermined group The monocyclic, linked ring, or condensed ring aromatic hydrocarbon group having 6 to 20 carbon atoms may be substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. Specific examples include, but are not particularly limited to, for example, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-trifluoromethylphenyl group, m-trifluoromethylphenyl group, o-trifluoromethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl group, 3,5-dipropylphenyl group, 2-(1-methylethyl)phenyl group, 3-(1-methylethyl)phenyl group, 4-(1-methylethyl)phenyl group, 2,4-di(1-methylethyl)phenyl group, 3,5-di(1-methylethyl)phenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl group, 2-t-butylphenyl group, 3-t-butylphenyl group, 4-t-butylphenyl group, 2,4-di-t-butylphenyl group, 3,5-di-t-butylphenyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, 2-methylbiphenyl-4-yl group, 3-methylbiphenyl-4-yl group, 2'-methylbiphenyl-4-yl group, 4'-methylbiphenyl-4-yl group, 2,2'-dimethylbiphenyl-4-yl group, 2',4',6'-trimethylbiphenyl-4-yl group, 6-methylbiphenyl-3-yl group, 5-methylbiphenyl-3-yl group, 2'-methylbiphenyl-3-yl group, 4'-methylbiphenyl-3-yl group, 6,2'-dimethylbiphenyl-3-yl group, 2',4',6'-trimethylbiphenyl-3-yl group, 5-methylbiphenyl-2-yl group, 6-methylbiphenyl-2-yl group, 2'-methylbiphenyl-2-yl group, 4'-methylbiphenyl-2-yl group, 6,2'-dimethylbiphenyl-2-yl group, 2',4',6'-Trimethylbiphenyl-2-yl group, 2-trifluoromethylbiphenyl-4-yl group, 3-trifluoromethylbiphenyl-4-yl group, 2'-trifluoromethylbiphenyl-4-yl group, 4'-trifluoromethylbiphenyl-4-yl group, 6-trifluoromethylbiphenyl-3-yl group, 5-trifluoromethylbiphenyl-3-yl group, 2'-trifluoromethylbiphenyl-3-yl group, 4'-trifluoromethylbiphenyl-3-yl group, 5-trifluoromethylbiphenyl-2-yl group, 6-trifluoromethylbiphenyl-2-yl group, 2'-trifluoromethylbiphenyl-2-yl group, 4'-trifluoromethylbiphenyl-2-yl group, 3-ethylbiphenyl-4-yl group, 4'-ethylbiphenyl-4-yl group, 2',4',6'-triethylbiphenyl-4-yl group, 6-ethylbiphenyl-3-yl group, 4'-ethylbiphenyl-3-yl group, 5-ethylbiphenyl-2-yl group, 4'-ethylbiphenyl-2-yl group, 2',4',6'-triethylbiphenyl-2-yl group, 3-propylbiphenyl-4-yl group, 4'-propylbiphenyl-4-yl group, 2',4',6'-tripropylbiphenyl-4-yl group, 6-propylbiphenyl-3-yl group, 4'-propylbiphenyl-3-yl group, 5-propylbiphenyl-2-yl group, 4'-propylbiphenyl-2-yl group, 2',4',6'-tripropylbiphenyl-2-yl group, 3-(1-methylethyl)biphenyl-4-yl group, 4'-(1-methylethyl)biphenyl-4-yl group, 2',4',6'-tri(1-methylethyl)biphenyl-4-yl group, 6-(1-methylethyl)biphenyl-3-yl group, 4'-(1-methylethyl)biphenyl-3-yl group, 5-(1-methylethyl)biphenyl-2-yl group, 4'-(1-methylethyl)biphenyl-2-yl group, 2',4',6'-tri(1-methylethyl)biphenyl-2-yl group, 3-butylbiphenyl-4-yl group, 4'-butylbiphenyl-4-yl group, 2',4',6'-tributylbiphenyl-4-yl group, 6-butylbiphenyl-3-yl group, 4'-butylbiphenyl-3-yl group, 5-butylbiphenyl-2-yl group, 4'-butylbiphenyl-2-yl group, 2',4',6'-tributylbiphenyl-2-yl group, 3-t-butylbiphenyl-4-yl group, 4'-t-butylbiphenyl-4-yl group, 2',4',6'-tri-t-butylbiphenyl-4-yl group, 6-t-butylbiphenyl-3-yl group, 4'-t-butylbiphenyl-3-yl group, 5-t-butylbiphenyl-2-yl group, 4'-t-butylbiphenyl-2-yl group, 2',4',6'-tri-t-butylbiphenyl-2-yl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, 1-naphthyl group, 4-trifluoromethylnaphthalen-1-yl group, 4-ethylnaphthalen-1-yl group, 4-propylnaphthalen-1-yl group, 4-butylnaphthalen-1-yl group, 4-t-butylnaphthalen-1-yl group, 5-trifluoromethylnaphthalen-1-yl group, 5-ethylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group, 5-butylnaphthalen-1-yl group, 5-t-butylnaphthalen-1-yl group, 2-naphthyl group, 6-trifluoromethylnaphthalen-2-yl group, 6-ethylnaphthalen-2-yl group, 6-propylnaphthalen-2-yl group, 6-butylnaphthalen-2-yl group, 6-t-butylnaphthalen-2-yl group, 7-trifluoromethylnaphthalen-2-yl group, 7-ethylnaphthalen-2-yl group, 7-propylnaphthalen-2-yl group, 7-butylnaphthalen-2-yl group, 7-t-butylnaphthalen-2-yl group, 1-phenylnaphthalen-2-yl group, 1-phenylnaphthalen-3-yl group, 1-phenylnaphthalen-4-yl group, 1-phenylnaphthalen-5-yl group, 1-phenylnaphthalen-6-yl group, 1-phenylnaphthalen-7-yl group, 1-phenylnaphthalen-8-yl group, 2-phenylnaphthalen-1-yl group, 2-phenylnaphthalen-3-yl group, 2-phenylnaphthalen-4-yl group, 2-phenylnaphthalen-5-yl group, 2-phenylnaphthalen-6-yl group, 2-phenylnaphthalen-7-yl group, 2-phenylnaphthalen-8-yl group, 1-methylnaphthalen-4-yl group, 1-methylnaphthalen-5-yl group, 1-methylnaphthalen-6-yl group, 1-methylnaphthalen-7-yl group, 1-methylnaphthalen-8-yl group, 2-methylnaphthalen-1-yl group, 2-methylnaphthalen-3-yl group, 2-methylnaphthalen-4-yl group, 2-methylnaphthalen-5-yl group, 2-methylnaphthalen-6-yl group, 2-methylnaphthalen-7-yl group, 2-methylnaphthalen-8-yl group, 1,1':4',1''-terphenyl-2'-yl group, 1,1':3',1''-terphenyl-2'-yl group, 1,1':3',1”-terphenyl-4’-yl group, 1,1’:3’,1”-terphenyl-5’-yl group, 1,1’:2’,1”-terphenyl-3’-yl group, 1,1’:2’,1”-terphenyl-4’-yl group, 1-phenanthrenyl group, 2-phenanthrenyl group, 3-phenanthrenyl group, 4-phenanthrenyl group, 9-phenanthrenyl group, 10-phenylphenanthren-9-yl group, 10-(2-naphthyl)phenanthren-9-yl group, 7-(9-phenanthrenyl)phenanthren-2-yl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 10-methylanthracen-9-yl group, 10-phenylanthracen-9-yl group, 10-(2-naphthyl)anthracen-9-yl group and the like can be mentioned. Among these groups, a phenyl group, a biphenyl-3-yl group, a biphenyl-4-yl group, a 1-naphthyl group, or a 2-naphthyl group is more preferable in terms of excellent characteristics as an electron transporting material.,

[0039] · A group in which (ii) is substituted with a predetermined group The aromatic heterocyclic group of a monocyclic, linked ring, or condensed ring having 4 to 20 carbon atoms may be substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. Specific examples include, but are not particularly limited to, for example, 2-thienyl group, 5-methylthiophen-2-yl group, 2-furyl group, 5-methylfuran-2-yl group, 2-benzothienyl group, 3-benzothienyl group, 4-benzothienyl group, 5-benzothienyl group, 6-benzothienyl group, 7-benzothienyl group, 2-benzofuranyl group, 5-benzofuranyl group, 1-dibenzothienyl group, 2-dibenzothienyl group, 3-dibenzothienyl group, 4-dibenzothienyl group, 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3-dibenzofuranyl group, 4-dibenzofuranyl group, 2-pyrimidyl group, 3,5-dimethylpyrimidin-2-yl group, 3,5-diphenylpyrimidin-2-yl group, 3,5-bis(trifluoromethyl)pyrimidin-2-yl group, 2-pyrazinyl group, 5,6-dimethylpyrazin-2-yl group, 3-phenylpyrazin-2-yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridin-4-yl group, 2-methylpyridin-5-yl group, 2-methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridin-5-yl group, 3-methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridin-3-yl group, 2,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group, 3-phenylpyridin-2-yl group, 4-phenylpyridin-2-yl group, 5-phenylpyridin-2-yl group, 6-phenylpyridin-2-yl group, 3,6-diphenylpyridin-2-yl group, 4,6-diphenylpyridin-2-yl group, 3,5-diphenylpyridin-2-yl group, 4,5,6-triphenylpyridin-2-yl group, 2-phenylpyridin-3-yl group, 4-phenylpyridin-3-yl group, 5-phenylpyridin-3-yl group, 6-phenylpyridin-3-yl group, 2,4-diphenylpyridin-3-yl group, 2,5-diphenylpyridin-3-yl group, 2,6-diphenylpyridin-3-yl group, 4,6-diphenylpyridin-3-yl group, 2,4,6-triphenylpyridin-3-yl group, 2,5,6-triphenylpyridin-3-yl group, 2-phenylpyridin-4-yl group, 3-phenylpyridin-4-yl group, 2,3-diphenylpyridin-4-yl group, 2,5-diphenylpyridin-4-yl group, 2,6-diphenylpyridin-4-yl group, 3,5-diphenylpyridin-4-yl group, 2,3,5,6-tetraphenylpyridin-4-yl group, 2,2'-bipyridin-6-yl group, 2,2'-bipyridin-5-yl group, 2,2'-bipyridin-4-yl group, 2,4'-bipyridin-5-yl group, 2,3'-bipyridin-5-yl group, 2,4'-bipyridin-3'-yl group, 2,2':6'2”-terpyridin-6-yl group, 2,2':6'2”-terpyridin-4'-yl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, quinoxalin-2-yl group, quinoxalin-5-yl group, quinoxalin-6-yl group, quinazolin-2-yl group, quinazolin-4-yl group, quinazolin-5-yl group, quinazolin-6-yl group, quinazolin-7-yl group, quinazolin-8-yl group, etc. are exemplified.,

[0040] [Regarding R] R is (iv) a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (v) an aromatic hydrocarbon group of a monocyclic, linked ring, or condensed ring having 6 to 30 carbon atoms, (vi) an aromatic heterocyclic group of a monocyclic, linked ring, or condensed ring having 4 to 30 carbon atoms, or (vii) The aromatic hydrocarbon group or aromatic heterocyclic group is a group substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms.

[0041] In the case of (vii), the carbon number of the substituent of the aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 4 to 30 carbon atoms is not included in the carbon number of the aromatic hydrocarbon group or aromatic heterocyclic group.

[0042] The monocyclic, linked-ring, or condensed-ring aromatic hydrocarbon group having 6 to 30 carbon atoms in (v) is not particularly limited. For example, a phenyl group, a naphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, a benzofluorenyl group, a pyrenyl group, a triphenylenyl group, a chrysenyl group, a perylenyl group, a fluoranthenyl group, an acenaphthylenyl group, a biphenylyl group, a terphenylyl group, a naphthylphenyl group, a triphenylene group, etc. may be mentioned. Here, the aromatic hydrocarbon group means a monocyclic ring without heteroatoms, a condensed ring without heteroatoms, or a linked ring formed by linking these (that is, a linked ring formed by linking rings without heteroatoms).

[0043] The monocyclic, linked ring, or condensed ring aromatic heterocyclic group having 4 to 30 carbon atoms in the above (vi) is not particularly limited, and examples thereof include a pyridyl group, a pyrazinyl group, a pyrimidyl group, a pyridazinyl group, a quinolyl group, an isoquinolyl group, a phenanthridyl group, a benzoquinolyl group, an acridinyl group, a thienyl group, a furyl group, a benzofuranyl group, a benzothienyl group, a dibenzofuranyl group, a dibenzothienyl group, a bipyridyl group, a terpyridinyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a phenanthrolinyl group, a phthalazinyl group, a thienyl group, a furyl group, a bithienyl group, a biferryl group, a benzothienyl group, a benzofuranyl group, a dibenzothienyl group, a dibenzofuranyl group, a phenyltriazolyl group, a diphenyltriazolyl group, and the like. Here, the aromatic heterocyclic group means a monocyclic ring containing a heteroatom, a condensed ring containing a heteroatom, or a linked ring in which these are linked (that is, rings containing heteroatoms are linked). That is, the aromatic heterocyclic group is a monocyclic ring containing a heteroatom, a condensed ring containing a heteroatom, a linked ring,

[0044] Examples of the aromatic hydrocarbon group or aromatic heterocyclic group in the above (vii) include groups in which the groups mentioned in (v) or (vi) are substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms.

[0045] The alkyl group having 1 to 10 carbon atoms in the above (iv) is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and the like.

[0046] The alkyloxy group having 1 to 10 carbon atoms in the above (iv) is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a t-butoxy group, and the like.

[0047] The acyl group having 1 to 10 carbon atoms in the above (iv) is not particularly limited, and examples thereof include a methanoyl group, an ethanoyl group, a propanoyl group, and a benzoyl group.

[0048] R is preferably a group selected from either (vi) or (vii) having no substituent in terms of a high glass transition temperature.

[0049] Specifically, R may be substituted with one or more groups selected from the group consisting of a phenyl group, a tolyl group, a pyridyl group, a methylpyridyl group, a dimethylpyridyl group, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, and is preferably a phenyl group, a naphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, a benzofluorenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a chrysenyl group, an acenaphthyl group, a pyrimidyl group, a pyrazyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a benzofuryl group, a benzothienyl group, a dibenzofuryl group, a dibenzothienyl group, a phenyltriazolyl group, and a diphenyltriazolyl group. More preferably, R is a phenyl group, a naphthyl group, a fluorenyl group, an anthryl group, a phenanthryl group, a benzofluorenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrimidyl group, a pyrazyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a benzofuryl group, a benzothienyl group, a dibenzofuryl group, a dibenzothienyl group, a biphenyl group, a phenyltriazolyl group, a diphenyltriazolyl group, or a pyridylphenyl group. A plurality of Rs may be the same or different.

[0050] [Regarding Ra to Re] Ra to Re are (a1) to (e1) a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a cyano group, an amino group, a nitro group, an acyl group having 1 to 10 carbon atoms, (a2) to (e2) an aromatic hydrocarbon group of a monocyclic, linked ring, or condensed ring having 6 to 30 carbon atoms, (a3) to (e3) are monocyclic, linked, or condensed aromatic heterocyclic groups having 4 to 30 carbon atoms, or (a4) to (e4) represent a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms.

[0051] Here, examples of the aromatic hydrocarbon group and aromatic heterocyclic group in Ra to Re are the same as those of the aromatic hydrocarbon group and aromatic heterocyclic group in R.

[0052] In one embodiment of the cyclic azine compound represented by formula (1-A), Ra is a phenyl group, a pyridyl group, or a group in which the phenyl group or pyridyl group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. In another embodiment of the cyclic azine compound represented by formula (1-A), Ra is a pyridyl group which may be substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms. Furthermore, in still another embodiment of the cyclic azine compound represented by formula (1-A), Ra is a hydrogen atom.

[0053] [Regarding n] n is an integer from 1 to 8. However, when Ra to Re are hydrogen atoms, n represents an integer from 2 to 8. It is more preferable that n is an integer from 1 to 4.

[0054] [Y 1 and Y 2 [Regarding] Y 1 and Y2 each independently represents a nitrogen atom or CH. Here, Y 1 and Y 2 at least one of which is a nitrogen atom. Y 1 is preferably a nitrogen atom. Y 1 and Y 2 are more preferably both nitrogen atoms.

[0055] [For each formula] However, in formulas (1-C) to (1-E), the 9-position and the 10-position of phenanthrene are different; R substituted at the 10-position of phenanthrene is a monocyclic or fused-ring aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group in which the monocyclic or fused-ring aromatic hydrocarbon group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms, and when the 9-position of phenanthrene is substituted with R, R substituted at the 9-position of the phenanthrene represents a group other than an unsubstituted phenyl group.

[0056] In formulas (1-A) and (1-B), the 9-position and the 10-position of phenanthrene may be different.

[0057] In formula (1-B), Rb is a monocyclic or fused-ring aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group in which the monocyclic or fused-ring aromatic hydrocarbon group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms, and when the 9-position of phenanthrene is substituted with R, R substituted at the 9-position of the phenanthrene may represent a group other than an unsubstituted phenyl group.

[0058] In formulas (1-B) to (1-E), the 9-position and the 10-position of phenanthrene are simultaneously a monocyclic or linked-ring aromatic hydrocarbon group having 6 to 30 carbon atoms, and the monocyclic or linked-ring aromatic hydrocarbon group may be unsubstituted or substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms.

[0059] [Specific examples of preferred compounds] Among the compounds represented by formula (1), specific examples of preferred compounds include compounds having the structures shown in the following formulas (1-1) to (1-87), but the cyclic azine compound (1) is not limited thereto.

[0060] [Chemical formula]

[0061] [Chemical formula]

[0062] [Chemical formula]

[0063] [Chemical formula]

[0064] [Chemical formula]

[0065] [Chemical formula]

[0066] [Chemistry]

[0067] [Chemistry]

[0068] Among these, the cyclic azine compound represented by any one of formulas (1-1) to (1-26), (1-48), and (1-85) is particularly preferred.

[0069] Next, a method for producing a cyclic azine compound according to another aspect of the present disclosure (hereinafter referred to as a method for producing a cyclic azine compound (1)) will be described. The cyclic azine compound (1) can be produced by the method shown in the following reaction route 1 or 2. That is, the method for producing the cyclic azine compound (1) includes subjecting a cyclic azine intermediate represented by formula (2) and a compound represented by formula (3) to a coupling reaction, or includes subjecting a cyclic azine intermediate represented by formula (4) and a compound represented by formula (5) to a coupling reaction. Any of the coupling reactions is preferably carried out in the presence of a palladium catalyst.

[0070] [Chemistry]

[0071] [Chemistry]

[0072] In formulas (2) to (5), Ar 1 , Ar 2 , R, n, Y 1 , and Y 2 are each defined as Ar 1 , Ar2 , R, n, Y 1 , and Y 2 are the same as defined; L represents a group corresponding to the phenanthrenyl group of the cyclic azine compound of formulas (1-A) to (1-E); X 1 and X 2 each independently represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom; M 1 and M 2 each independently represents ZnZ 1 , MgZ 2 , Sn(Z 3 )3, or B(OZ 4 )2; Z 1 and Z 2 each independently represents a chlorine atom, a bromine atom or an iodine atom; Z 3 is the same or different and represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Z 4 is the same or different and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group.

[0073] Also, when M 1 and M 2 represent B(OZ 4 )2, the two (OZ 4 ) groups may combine together to form a ring with the boron atom. Among these, B(OZ 4 )2 is preferred.

[0074] ZnZ 1 , MgZ 2 is not particularly limited, and examples include ZnCl, ZnBr, ZnI, MgCl, MgBr, MgI, etc. Sn(Z 3 )3 is not particularly limited, and examples include Sn(Me)3, Sn(Bu)3, etc. B(OZ 4)2 is not particularly limited, and examples thereof include B(OH)2, B(OMe)2, B(O i Pr)2, B(OBu)2, B(OPh)2, etc. Here, Me represents a methyl group, i Pr represents an isopropyl group, Bu represents a butyl group, and Ph represents a phenyl group. Further, when two (OZ 4 ) groups are integrated to form a ring together with a boron atom, examples of B(OZ 4 )2 are not particularly limited, and examples thereof include groups represented by the following (I) to (VI), and the group represented by (II) is preferable in terms of good yield.

[0075]

Chemical formula

[0076] Reaction route 1 involves subjecting the cyclic azine intermediate (2) and the compound (3) to a coupling reaction in the presence of a palladium catalyst as necessary to produce the cyclic azine compound (1). Reaction route 1 can obtain the target product in good yield by applying the reaction conditions of general coupling reactions such as the Suzuki-Miyaura reaction, Negishi reaction, Tamai-Kumada reaction, Stille reaction, etc. When applying the reaction conditions of the Suzuki-Miyaura reaction to reaction route 1, it is preferably carried out in the presence of a base.

[0077] The cyclic azine intermediate represented by formula (2) used in reaction route 1 can be synthesized, for example, according to Dyes Pigment. 2018, Vol. 157, pp. 377-384. Commercially available products may also be used. Examples of the cyclic azine intermediate represented by formula (2) include compounds having the structures shown in the following 2-1 to 2-15, but the present invention is not limited thereto. In formulas (2-1) to (2-15), X 1 has the same definition as described above.

[0078]

Chemical formula

[0079] X 1 Examples of the group represented by 1 include a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group, or an iodine atom. From the viewpoint of good yield of the cyclic azine compound (1), a chlorine atom is preferred.

[0080] The compound (3) used in Reaction Route 1 can be produced, for example, according to J. Org. Chem. 2015, Vol. 80, pp. 11706 - 11717. Commercially available products may also be used. Examples of the compound (3) include the following 3 - 1 to 3 - 21, but the present invention is not limited thereto. In the formulas (3 - 1) to (3 - 21), M 1 has the same definition as described above.

[0081]

Chemical formula

[0082]

Chemical formula

[0083] M 1 The group represented by 1 is not particularly limited, and examples thereof include ZnZ 1 , MgZ 2 , Sn(Z 3 )3, or two (OZ 4 ) groups may be integrated to form a ring together with a boron atom, such as B(OZ 4 )2. Among these, B(OZ 4 )2 is preferred.

[0084] The palladium catalyst that can be used in Reaction Route 1 is not particularly limited, and specifically, palladium salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, etc.; Complex compounds such as π-allyl palladium chloride dimer, palladium acetylacetonate, tris(dibenzylideneacetone) dipalladium, bis(dibenzylideneacetone) palladium, dichlorobis(acetonitrile) palladium, dichlorobis(benzonitrile) palladium; and, Palladium complexes having a tertiary phosphine as a ligand, such as dichlorobis(triphenylphosphine) palladium, tetrakis(triphenylphosphine) palladium, dichloro(1,1'-bis(diphenylphosphino) ferrocene) palladium, bis(tri-t-butylphosphine) palladium, bis(tricyclohexylphosphine) palladium, dichlorobis(tricyclohexylphosphine) palladium; are mentioned.

[0085] Palladium complexes having a tertiary phosphine as a ligand can also be prepared in the reaction system by adding a tertiary phosphine to a palladium salt or complex compound. Tertiary phosphines that can be used at this time include triphenylphosphine, trimethylphosphine, tributylphosphine, tri(t-butyl)phosphine, tricyclohexylphosphine, t-butyldiphenylphosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(diphenylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-(di-t-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, tri(2-furyl)phosphine, tri(o-tolyl)phosphine, tris(2,5-xylyl)phosphine, (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, and the like.

[0086] Among these, a palladium complex having a tertiary phosphine as a ligand is preferable in terms of good yield, and a palladium complex having 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl or triphenylphosphine as a ligand is more preferable.

[0087] The molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably in the range of 1:10 to 10:1, and more preferably in the range of 1:2 to 3:1 in terms of good yield. There is no limitation on the amount of the palladium catalyst used in Reaction Route 1, but in terms of good yield, the molar equivalent of the palladium catalyst is preferably in the range of 0.005 to 0.5 molar equivalent relative to the boron compound.

[0088] The base used in Reaction Route 1 is not particularly limited, and examples thereof include metal hydroxide salts such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; metal carbonate salts such as sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; metal acetate salts such as potassium acetate and sodium acetate; metal phosphate salts such as potassium phosphate and sodium phosphate; metal fluoride salts such as sodium fluoride, potassium fluoride, and cesium fluoride; metal alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium isopropoxide, and potassium tert-butoxide; and the like. Among them, metal carbonate salts and metal phosphate salts are preferable in terms of good reaction yield, and potassium carbonate or potassium phosphate is more preferable. There is no particular limitation on the amount of the base, but in terms of good reaction yield, the molar ratio of the base to the boron compound is preferably in the range of 1:2 to 10:1, and more preferably in the range of 1:1 to 4:1.

[0089] Reaction Route 1 can be carried out in a solvent. Examples of the solvent include water; ethers such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and tetralin; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; esters such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactone; amides such as N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP); ureas such as N,N,N’,N’-tetramethylurea (TMU) and N,N’-dimethylpropyleneurea (DMPU); and alcohols such as dimethyl sulfoxide (DMSO), methanol, ethanol, isopropyl alcohol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol. These can be used by mixing them in any ratio. There is no particular limitation on the amount of the solvent used. Among these, water, ether, amide, alcohol, or a mixed solvent thereof is preferable in terms of good reaction yield, and a mixed solvent of THF and water is more preferable.

[0090] Reaction Route 1 can be carried out at a temperature appropriately selected from 0°C to 200°C, and it is preferably carried out at a temperature appropriately selected from 40°C to 150°C in terms of good reaction yield. Reaction Route 1 can be obtained by performing ordinary treatment after the reaction is completed. If necessary, it may be purified by recrystallization, column chromatography, sublimation, preparative HPLC, or the like.

[0091] Subsequently, Reaction Route 2 will be described. Reaction Route 2 involves subjecting the cyclic azine intermediate represented by formula (4) and the compound represented by formula (5) to a coupling reaction in the presence of a palladium catalyst as necessary to produce the cyclic azine compound (1). In Reaction Route 2, by applying the reaction conditions of common coupling reactions such as the Suzuki-Miyaura reaction, Negishi reaction, Tamai-Kumada reaction, and Stille reaction, the target product can be obtained in good yield. When applying the reaction conditions of the Suzuki-Miyaura reaction to Reaction Route 2, it is preferably carried out in the presence of a base.

[0092] The cyclic azine intermediate represented by formula (4) used in Reaction Route 2 can be produced, for example, according to the method disclosed in Korean Patent Application Publication No. 2017 / 0049441. Examples of the cyclic azine intermediate represented by formula (4) include compounds having the structures shown in the following 4-1 to 4-24, but the present invention is not limited thereto. In formulas (4-1) to (4-24), X 2 has the same definition as described above.

[0093]

Chemical formula

[0094]

Chemical formula

[0095]

Chemical formula

[0096] X 2 The leaving group represented by is a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group, or an iodine atom. A chlorine atom or a bromine atom is preferred in terms of good yield of the cyclic azine compound (1).

[0097] The compound represented by the formula (5) used in Reaction Route 2 can be produced, for example, according to J. Org. Chem. 2017, Vol. 82, pp. 9258-9262. Also, it can be synthesized from the compound represented by the formula (7) using a reaction for synthesizing a general organometallic compound (for example, Angew. Chem. Int. Ed. 2007, Vol. 46, pp. 5359-5363), or a commercially available product may be used.

[0098] Examples of the compound represented by the formula (5) include compounds having the structures shown in 5-1 to 5-24 below, but the present invention is not limited thereto. In the formulas (5-1) to (5-24), M 2 has the same definition as described above.

[0099]

Chemical formula

[0100]

Chemical formula

[0101] Examples of the palladium catalyst, base, solvent, reaction temperature, and post-treatment (purification) that can be used in Reaction Route 2 are the same as those exemplified in Reaction Route 1, and the preferred configurations are also the same.

[0102] The cyclic azine compound (1) can be used, for example, in applications of organic electronic devices such as organic light-emitting diodes (OLEDs) and optoelectronic devices. Among these, the cyclic azine compound (1) is preferably used as a material for organic light-emitting diodes. When the cyclic azine compound (1) is used as a part of the components of an organic light-emitting diode, effects such as increased current efficiency and extended lifespan can be obtained. In particular, these effects are more pronounced when the cyclic azine compound (1) is used as an electron transport layer.

[0103] Hereinafter, the uses of the cyclic azine compound (1) will be described.

[0104] <Materials for organic electroluminescent devices, electron transport materials for organic electroluminescent devices> Although the cyclic azine compound (1) is not particularly limited, for example, it can be used as a material for an organic electroluminescent device. Further, the cyclic azine compound (1) can be used, for example, as an electron transport material for an organic electroluminescent device. That is, the material for an organic electroluminescent device according to one aspect of the present disclosure contains the cyclic azine compound (1). Further, the electron transport material for an organic electroluminescent device according to one aspect of the present disclosure contains the cyclic azine compound (1). The material for an organic electroluminescent device and the electron transport material for an organic electroluminescent device containing the cyclic azine compound (1) contribute to the production of an organic electroluminescent device excellent in durability and current efficiency.

[0105] <Organic electroluminescent device> The organic electroluminescent device according to one aspect of the present disclosure contains the cyclic azine compound (1). The configuration of the organic electroluminescent device is not particularly limited, and examples thereof include the configurations (a) to (f) shown below. (a): Anode / Light emitting layer / Cathode (b): Anode / Hole transport layer / Light emitting layer / Cathode (c): Anode / Light emitting layer / Electron transport layer / Cathode (d): Anode / Hole transport layer / Light emitting layer / Electron transport layer / Cathode (e): Anode / Hole injection layer / Hole transport layer / Light emitting layer / Electron transport layer / Electron injection layer / Cathode (f): Anode / Hole injection layer / Charge generation layer / Hole transport layer / Light emitting layer / Electron transport layer / Cathode.

[0106] Hereinafter, the organic electroluminescent device according to one aspect of the present disclosure will be described in more detail with reference to FIG. 1, taking the configuration (f) as an example. The organic electroluminescent device shown in FIG. 1 has a so-called bottom emission type device structure, but the organic electroluminescent device according to one aspect of the present disclosure is not limited to the bottom emission type device structure. That is, the organic electroluminescent device according to one aspect of the present disclosure may have other known device structures such as a top emission type. FIG. 1 is a schematic cross-sectional view showing an example of a stacked structure of an organic electroluminescent device including a cyclic azine compound according to one aspect of the present disclosure.

[0107] The organic electroluminescent device 100 includes a substrate 1, an anode 2, a hole injection layer 3, a charge generation layer 4, a hole transport layer 5, a light emitting layer 6, an electron transport layer 7, and a cathode 8 in this order. However, some of these layers may be omitted, and conversely, other layers may be added. For example, an electron injection layer may be provided between the electron transport layer 7 and the cathode 8, the charge generation layer 4 may be omitted, and the hole transport layer 5 may be directly provided on the hole injection layer 3. Further, for example, a single layer having functions of a plurality of layers, such as an electron injection / transport layer having functions of an electron injection layer and an electron transport layer in a single layer, may be provided instead of the plurality of layers. Furthermore, for example, a single-layer hole transport layer 5 and a single-layer electron transport layer 7 may each be composed of a plurality of layers.

[0108] [Layer containing cyclic azine compound (1)] The organic electroluminescent device includes the cyclic azine compound (1) in at least one layer selected from the group consisting of the light emitting layer and at least one layer between the light emitting layer and the cathode. Therefore, in the configuration example shown in FIG. 1, the organic electroluminescent device 100 includes the cyclic azine compound (1) in at least one layer selected from the group consisting of the light emitting layer 6 and the electron transport layer 7. In particular, it is preferable that the electron transport layer 7 contains the cyclic azine compound (1). The cyclic azine compound (1) may be contained in a plurality of layers included in the organic electroluminescent device, and when an electron injection layer is provided between the electron transport layer and the cathode, the electron injection layer may contain the cyclic azine compound (1). In the following, the organic electroluminescent device 100 in which the electron transport layer 7 contains the cyclic azine compound (1) will be described.

[0109] [Substrate 1] The substrate is not particularly limited, and examples thereof include a glass plate, a quartz plate, a plastic plate, etc. Further, in the case of a configuration in which light emission is extracted from the substrate 1 side, the substrate 1 is transparent to the wavelength of light. Examples of the plastic film having light transmissivity include films made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), etc.

[0110] [Anode 2] An anode 2 is provided on the substrate 1 (on the hole injection layer 3 side). In the case of an organic electroluminescent element having a configuration in which light emission is extracted through the anode, the anode is formed of a material that passes or substantially passes the light emission. The transparent material used for the anode is not particularly limited, and examples thereof include indium-tin oxide (ITO; Indium Tin Oxide), indium-zinc oxide (IZO; Indium Zinc Oxide), tin oxide, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, and metal sulfides such as zinc sulfide. In the case of an organic electroluminescent element having a configuration in which light is extracted only from the cathode side, the transmission characteristics of the anode are not important. Therefore, examples of the material used for the anode in this case include gold, iridium, molybdenum, palladium, platinum, etc. A buffer layer (electrode interface layer) may be provided on the anode.

[0111] [Hole injection layer 3, hole transport layer 5] Between the anode 2 and the light-emitting layer 6 described later, a hole injection layer 3, a charge generation layer 4 described later, and a hole transport layer 5 are provided in this order from the anode 2 side. The hole injection layer and the hole transport layer have a function of transmitting holes injected from the anode to the light-emitting layer. By interposing the hole injection layer and the hole transport layer between the anode and the light-emitting layer, more holes are injected into the light-emitting layer at a lower electric field. In addition, the hole injection layer and the hole transport layer also function as an electron blocking layer. That is, electrons injected from the cathode and transported from the electron injection layer and / or the electron transport layer to the light-emitting layer are suppressed from leaking into the hole injection layer and / or the hole transport layer by the electron barrier existing at the interface between the light-emitting layer and the hole injection layer and / or the hole transport layer. As a result, the electrons are accumulated at the interface in the light-emitting layer, resulting in effects such as improved light-emitting efficiency, and an organic electroluminescent element with excellent light-emitting performance can be obtained.

[0112] The materials for the hole injection layer and the hole transport layer have at least one of hole injection property, hole transport property, and electron blocking property. The materials for the hole injection layer and the hole transport layer may be either organic or inorganic.

[0113] Specific examples of the materials for the hole injection layer and the hole transport layer include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline-based copolymers, conductive polymer oligomers (especially thiophene oligomers), porphyrin compounds, aromatic tertiary amine compounds, styrylamine compounds, etc. Among these, porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds are preferred, and aromatic tertiary amine compounds are particularly preferred.

[0114] Specific examples of the aromatic tertiary amine compound and the styrylamine compound include N,N,N’,N’-tetraphenyl-4,4’-diaminophenyl, N,N’-diphenyl-N,N’-bis(3-methylphenyl)-[1,1’-biphenyl]-4,4’-diamine (TPD), 2,2-bis(4-di-p-tolylaminophenyl)propane, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N,N’,N’-tetra-p-tolyl-4,4’-diaminobiphenyl, 1,1-bis(4-di-p-tolylaminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenylmethane, N,N’-diphenyl-N,N’-di(4-methoxyphenyl)-4,4’-diaminobiphenyl, N,N,N’,N’-tetraphenyl-4,4’-diaminodiphenyl ether, 4,4’-bis(diphenylamino)quarterphenyl, N,N,N-tri(p-tolyl)amine, 4-(di-p-tolylamino)-4’-[4-(di-p-tolylamino)styryl]stilbene, 4-N,N-diphenylamino-(2-diphenylvinyl)benzene, 3-methoxy-4’-N,N-diphenylaminostilbene, N-phenylcarbazole, 4,4’-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD), 4,4’,4’’-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (MTDATA), and the like.

[0115] In addition, inorganic compounds such as p-type Si and p-type SiC can also be cited as an example of the material for the hole injection layer and the hole transport layer.

[0116] The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of a plurality of layers of the same composition or different compositions.

[0117] [Charge generation layer 4] A charge generation layer 4 may be provided between the hole injection layer 3 and the hole transport layer 5. Although there is no particular limitation on the material of the charge generation layer, for example, dipyrrolo[2,3-f:2’,3’-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN) can be mentioned. The charge generation layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of a plurality of layers of the same composition or different compositions.

[0118] [Light-emitting layer 6] A light-emitting layer 6 is provided between the hole transport layer 5 and the electron transport layer 7 described later. Examples of the material of the light-emitting layer include phosphorescent materials, fluorescent materials, and thermally activated delayed fluorescent materials. In the light-emitting layer, electron-hole pairs recombine, and as a result, light emission occurs.

[0119] The light-emitting layer may be composed of a single low-molecular material or a single polymer material, but more generally, it is composed of a host material doped with a guest compound. The light emission mainly occurs from the dopant and can have any color.

[0120] Examples of the host material include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, and an anthryl group. More specifically, DPVBi (4,4’-bis(2,2-diphenylvinyl)-1,1’-biphenyl), BCzVBi (4,4’-bis(9-ethyl-3-carbazolvinylene)1,1’-biphenyl), TBADN (2-t-butyl-9,10-di(2-naphthyl)anthracene), ADN (9,10-di(2-naphthyl)anthracene), CBP (4,4’-bis(carbazol-9-yl)biphenyl), CDBP (4,4’-bis(carbazol-9-yl)-2,2’-dimethylbiphenyl), 2-(9-phenylcarbazol-3-yl)-9-[4-(4-phenylphenylquinazolin-2-yl)carbazole, 9,10-bis(biphenyl)anthracene, etc. can be mentioned.

[0121] Examples of the fluorescent dopant include anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylene pyran compounds, thiopyran compounds, polymethine compounds, pyrylium, thiapyrylium compounds, fluorene derivatives, periflanthene derivatives, indenoperylene derivatives, bis(azinyl)amine boron compounds, bis(azinyl)methane compounds, carbostyryl compounds, and the like. The fluorescent dopant may be a combination of two or more selected from these.

[0122] Examples of the phosphorescent dopant include transition metal complexes such as iridium, platinum, palladium, osmium and the like.

[0123] Specific examples of the fluorescent dopant and the phosphorescent dopant include Alq3 (tris(8-hydroxyquinoline)aluminum), DPAVBi (4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl), perylene, bis[2-(4-n-hexylphenyl)quinoline](acetylacetonato)iridium(III), Ir(PPy)3 (tris(2-phenylpyridine)iridium(III)), and FIrPic (bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(III))), and the like.

[0124] Further, the light-emitting material is not limited to being contained only in the light-emitting layer. For example, the light-emitting material may be contained in a layer adjacent to the light-emitting layer (the hole transport layer 5 or the electron transport layer 7). Thereby, the light emission efficiency of the organic electroluminescent element can be further increased.

[0125] The light-emitting layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of a plurality of layers of the same composition or different compositions.

[0126] [Electron transport layer 7] An electron transport layer 7 is provided between the light-emitting layer 6 and the cathode 8 described later. The electron transport layer has a function of transmitting electrons injected from the cathode to the light-emitting layer. By interposing the electron transport layer between the cathode and the light-emitting layer, electrons are injected into the light-emitting layer at a lower electric field. As described above, the electron transport layer preferably contains the cyclic azine compound (1).

[0127] In addition to the cyclic azine compound (1), the electron transport layer may further contain a conventionally known electron transport material. Examples of the conventionally known electron transport materials include lithium 8-hydroxyquinolinate (Liq), zinc bis(8-hydroxyquinolinate), copper bis(8-hydroxyquinolinate), manganese bis(8-hydroxyquinolinate), aluminum tris(8-hydroxyquinolinate), aluminum tris(2-methyl-8-hydroxyquinolinate), gallium tris(8-hydroxyquinolinate), beryllium bis(10-hydroxybenzo[h]quinolinate), zinc bis(10-hydroxybenzo[h]quinolinate), gallium bis(2-methyl-8-quinolinato)chloride, gallium bis(2-methyl-8-quinolinato)(o-cresolato), aluminum bis(2-methyl-8-quinolinato)-1-naphtholate, or gallium bis(2-methyl-8-quinolinato)-2-naphtholate, 2-[3-(9-phenanthrenyl)-5-(3-pyridinyl)phenyl]-4,6-diphenyl-1,3,5-triazine, and 2-(4,’’-di-2-pyridinyl[1,1’:3’,1’’-terphenyl]-5-yl)-4,6-diphenyl-1,3,5-triazine, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinolato)-4-(phenylphenolato)aluminum), and beryllium bis(10-hydroxybenzo[h]quinolinate), etc.

[0128] The electron transport layer may have a single-layer structure composed of one or more materials, or a laminated structure composed of a plurality of layers of the same composition or different compositions.

[0129] When the electron transport layer has a two-layer structure with the first electron transport layer on the light-emitting layer side and the second electron transport layer on the cathode side, it is preferable that the second electron transport layer contains the cyclic azine compound (1).

[0130] [Cathode 8] A cathode 8 is provided on the electron transport layer 7. In the case of an organic electroluminescence device configured to extract only the light emitted through the anode, the cathode can be formed from any conductive material. Examples of the cathode material include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al2O3) mixture, indium, lithium / aluminum mixture, rare earth metals, and the like. A buffer layer (electrode interface layer) may be provided on the cathode (on the electron transport layer side).

[0131] [Formation method of each layer] Except for the electrodes (anode, cathode) described above, each layer can be formed by thinning the material of each layer (together with a material such as a binder resin and a solvent, if necessary) into a thin film by a known method such as vacuum evaporation, spin coating, casting, LB (Langmuir-Blodgett) method, or the like. There is no particular limitation on the film thickness of each layer, but it is usually about 5 nm to 5 μm. There is no particular limitation on the film thickness of each layer formed in this way, and it can be appropriately selected according to the situation, but it is usually in the range of 5 nm to 5 μm. The anode and the cathode can be formed by thinning the electrode material into a thin film by a method such as evaporation or sputtering. A pattern may be formed through a mask having a desired shape during evaporation or sputtering, or a pattern having a desired shape may be formed by photolithography after forming a thin film by evaporation or sputtering or the like. The film thickness of the anode and the cathode is preferably 1 μm or less, and more preferably 10 nm or more and 200 nm or less.

[0132] The organic electroluminescent device according to one aspect of the present disclosure may be used as a kind of lamp such as for lighting or an exposure light source, or may be used as a projection device of a type that projects an image or a display device (display) of a type that directly visualizes a still image or a moving image. When used as a display device for video playback, the driving method may be either a simple matrix (passive matrix) method or an active matrix method. Further, by using two or more kinds of the organic electroluminescent devices of this aspect having different emission colors, a full-color display device can be manufactured.

[0133] Note that the cyclic azine compound (1) can be synthesized by appropriately combining known reactions (for example, Suzuki-Miyaura cross-coupling reaction, etc.).

Examples

[0134] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not construed as being limited by these examples in any way.

[0135] 1 For the measurement of 1H-NMR, Bruker ASCEND 400 (400 MHz; manufactured by BRUKER) was used. 1 1H-NMR was measured using deuterated chloroform (CDCl3) as a measurement solvent and tetramethylsilane (TMS) as an internal standard substance. HPLC was performed using Shimadzu LC-2040C 3D.

[0136] The light emission characteristics of the organic electroluminescent device were evaluated by applying a direct current to the fabricated device at room temperature using a luminance meter (product name: BM-9, manufactured by Topcon Techno House Co., Ltd.). Note that in this specification, room temperature means 15°C to 30°C, particularly 25°C.

[0137] Synthesis Example - 1

Chemical formula

[0138] Under an argon atmosphere, 9-bromo-2-chloro-10-phenylphenanthrene (500 mg, 1.4 mmol) was dissolved in THF (10 mL). This solution was cooled to -78 °C, and a 1.64 M n-butyllithium-hexane solution (0.92 mL, 1.5 mmol) was added. After stirring at -78 °C for 30 minutes, a solution prepared by dissolving zinc chloride (222 mg, 1.6 mmol) in THF (5 mL) was added, and the mixture was further stirred at the same temperature for 30 minutes. After the reaction solution was warmed to room temperature, it was stirred for 30 minutes. To this, 2-chloro-4,6-diphenyl-1,3,5-triazine (400 mg, 1.5 mmol) and tetrakistriphenylphosphine palladium (78 mg, 70 μmol) were added, and the mixture was heated to reflux for 14 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure. Ethyl acetate and an aqueous sodium hydroxide solution were added to the residue, and the mixture was stirred for 15 minutes. The solid was collected by filtration and washed with methanol to obtain the target white solid of 2-(2-chloro-10-phenylphenanthren-9-yl)-4,6-diphenyl-1,3,5-triazine (yield 0.58 g, yield 82%).

[0139] 1 1H-NMR (CDCl3): δ 8.76 - 8.79 (m, 2H), 8.52 (d, J = 7.0 Hz, 4H), 7.73 (d, J = 7.8 Hz, 2H), 7.65 - 7.70 (m, 2H), 7.56 (m, 1H), 7.56 (d, J = 7.5 Hz, 2H), 7.49 (dd, J = 7.0, 1.4 Hz, 4H), 7.36 (d, J = 7.0 Hz, 2H), 7.24 (t, J = 6.0 Hz, 2H), 7.14 (dd, J = 7.4, 1.3 Hz, 1H).

[0140] Synthesis Example - 2

Chemical Structure

[0141] Under an argon atmosphere, 2-(2-chloro-10-phenylphenanthren-9-yl)-4,6-diphenyl-1,3,5-triazine (2.00 g, 3.8 mmol), 3-pyridylboronic acid (614 mg, 4.9 mmol), palladium acetate (43 mg, 0.19 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylphenyl (183 mg, 0.38 mmol) were added with THF (40 mL) and 2.0 M aqueous potassium phosphate solution (5.7 mL), and the mixture was stirred under heating under reflux for 18 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, and the residue was washed with water and methanol. The obtained crude product was suspended in xylene, heated to 150 °C, and then filtered while hot. After allowing the filtrate to cool, the resulting solid was filtered off. This solid was washed with methanol and then dried under reduced pressure to obtain the target white solid of 2,4-diphenyl-6-[10-phenyl-2-(3-pyridyl)phenanthren-9-yl]-1,3,5-triazine (yield 1.40 g, yield 63%).

[0142] 1 1H-NMR (CDCl3): δ 8.95 (d, J = 8.6 Hz, 1H), 8.85 - 8.87 (m, 2H), 8.57 (dd, J = 4.8, 1.5 Hz, 1H), 8.54 (d, J = 5.2 Hz, 4H), 7.96 (dd, J = 8.6, 1.9 Hz, 1H), 7.92 (s, 1H), 7.87 (dt, J = 8.0, 1.9 Hz, 1H), 7.76 (d, J = 8.6 Hz, 1H), 7.72 (d, J = 7.0 Hz, 1H), 7.55 - 7.59 (m, 3H), 7.50 (dd, J = 8.6, 1.2 Hz, 4H), 7.43 (dd, J = 7.6, 1.2 Hz, 2H), 7.34 (dd, J = 8.0, 4.8 Hz, 1H), 7.25 (t, J = 8.0 Hz, 2H), 7.14 (dd, J = 8.0, 1.2 Hz, 1H).

[0143] Synthesis Example - 3

Chemical Structure

[0144] Under an argon atmosphere, 2-(2-chloro-10-phenylphenanthren-9-yl)-4,6-diphenyl-1,3,5-triazine (1.30 g, 2.5 mmol), 9-phenanthreneboronic acid (675 mg, 3.0 mmol), palladium acetate (28 mg, 0.12 mmol), and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylphenyl (120 mg, 0.25 mmol) were suspended in THF (26 mL). To this suspension, 2 M aqueous potassium phosphate solution (3.8 mL) was sequentially added, and the mixture was stirred under heating under reflux for 18 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the resulting residue was washed with water and methanol to obtain a crude product. The obtained crude product was suspended in xylene, heated to 150 °C, and then filtered while hot. After allowing the filtrate to cool, the resulting solid was filtered off. By drying the solid under reduced pressure, a white solid of 2,4-diphenyl-6-(10-phenyl-[2,9′-biphenanthren]-9-yl)-1,3,5-triazine (yield 1.30 g, yield 78%) was obtained.

[0145] 1 1H-NMR (CDCl3): δ 8.97 (d, J = 8.5 Hz, 1H), 8.92 (d, J = 8.5 Hz, 1H), 8.76 (d, J = 8.2 Hz, 1H), 8.70 (d, J = 8.2 Hz, 1H), 8.54 (d, J = 8.0 Hz, 4H), 8.86 - 8.93 (m, 4H), 7.79 (d, J = 7.5 Hz, 1H), 7.75 (t, J = 7.5 Hz, 1H), 7.70 (s, 1H), 7.66 (dd, J = 8.5, 7.5 Hz, 2H), 7.47 - 7.61 (m, 9H), 7.43 (dd, J = 8.2, 1.2 Hz, 2H), 7.15 (t, J = 7.8 Hz, 2H), 7.01 (J = 7.5, 1.2 Hz, 1H).

[0146] Synthesis Example - 4

Chemical Structure

[0147] Under an argon atmosphere, 2-(2-chloro-10-phenylphenanthren-9-yl)-4,6-diphenyl-1,3,5-triazine (2.50 g, 4.8 mmol), biphenylboronic acid (1.23 g, 6.2 mmol), palladium acetate (32 mg, 0.14 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylphenyl (140 mg, 0.29 mmol) were suspended in THF (20 mL). To this suspension, 2.0 M aqueous potassium phosphate solution (7.2 mL) was sequentially added, and the mixture was stirred for 20 hours under heating under reflux. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration, washed with water and methanol to obtain a crude product. The crude product and 1 g of activated carbon were suspended in toluene and heated with stirring at 110 °C for 30 minutes. After stirring, filtration through celite was carried out, and the low-boiling components were distilled off under reduced pressure from the obtained solution. The obtained solid was washed with toluene to obtain a white solid of 2-(2-([1,1′-biphenyl]-4-yl)-10-phenylphenanthren-9-yl)-4,6-diphenyl-1,3,5-triazine (yield 1.59 g, yield 44%).

[0148] 1 1H-NMR (CDCl3): δ 8.93 (d, J = 8.7 Hz, 1H), 8.87 (d, J = 8.2 Hz, 1H), 8.54 (d, J = 7.0 Hz, 4H), 8.04 (dd, J = 8.6, 1.9 Hz, 1H), 7.97 (d, J = 1.8 Hz, 1H), 7.71 - 7.77 (m, 2H), 7.64 - 7.69 (m, 4H), 7.62 (dd, J = 8.5, 1.4 Hz, 2H), 7.53 - 7.59 (m, 1H), 7.56 (dd, J = 7.4, 2.4 Hz, 2H), 7.51 (dd, J = 6.2, 1.4 Hz, 3H), 7.43 - 7.48 (m, 5H), 7.36 (t, J = 5.4 Hz, 1H), 7.23 - 7.27 (m, 2H), 7.14 (t, J = 7.4 Hz, 1H).

[0149] Synthesis Example - 5

Chemical Structure

[0150] Under an argon atmosphere, 2-(2-chloro-10-phenylphenanthren-9-yl)-4,6-diphenyl-1,3,5-triazine (100 mg, 0.19 mmol), trifluoromethylphenylboronic acid (48 mg, 0.25 mmol), palladium acetate (2.2 mg, 9.6 μmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylphenyl (9.2 mg, 19 μmol) were suspended in THF (0.8 mL). To this suspension, 2.0 M aqueous potassium phosphate solution (0.3 mL) was sequentially added, and the mixture was stirred overnight under heating under reflux. After allowing to cool to room temperature, water and chloroform were added, and the organic layer was extracted. The organic layer was further washed with water and then saturated brine. Sodium sulfate was added to the extract and stirred at room temperature for a while, and then the desiccant was filtered off. The low-boiling components were distilled off under reduced pressure from the filtrate. The obtained crude product was purified by column chromatography (developing solution: chloroform / hexane) to obtain a white solid of 2,4-diphenyl-6-(10-phenyl-2-(4-(trifluoromethyl)phenyl)phenanthren-9-yl)-1,3,5-triazine (yield 88 mg, yield 73%).

[0151] 1 1H-NMR (CDCl3): δ 8.94 (d, J = 8.6 Hz, 1H), 8.87 (d, J = 8.6 Hz, 1H), 8.53 (d, J = 8.6 Hz, 4H), 7.98 (d, J = 8.6 Hz, 1H), 7.92 (s, 1H), 7.55 (dd, J = 12.8, 8.2 Hz, 2H), 7.65 - 7.70 (m, 4H), 7.58 (t, J = 7.4 Hz, 3H), 7.50 (t, J = 7.6 Hz, 4H), 7.43 (d, J = 6.9 Hz, 2H), 7.23 - 7.27 (m, 2H), 7.14 (t, J = 7.4 Hz, 1H).

[0152] Synthesis Example - 6

Chemical Structure

[0153] Under an argon atmosphere, 2-(2-chloro-10-phenylphenanthren-9-yl)-4,6-diphenyl-1,3,5-triazine (100 mg, 0.19 mmol), 4-t-butylphenylboronic acid (45 mg, 0.25 mmol), palladium acetate (2.2 mg, 9.6 μmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylphenyl (9.2 mg, 19 μmol) were suspended in THF (1.3 mL). To this suspension, 2.0 M aqueous potassium phosphate solution (290 μL) was added sequentially, and the mixture was stirred overnight under heating under reflux. After allowing to cool to room temperature, water and chloroform were added, and the organic layer was extracted. The organic layer was further washed with water and then saturated brine. Sodium sulfate was added to the extract and stirred at room temperature for a while, then the desiccant was filtered off, and the low-boiling components were distilled off under reduced pressure from the filtrate. The obtained crude product was purified by column chromatography (developing solution: chloroform / hexane) to obtain a white solid of 2-{2-[4-(tert-butyl)phenyl]-10-phenylphenanthren-9-yl}-4,6-diphenyl-1,3,5-triazine (yield 61 mg, yield 51%).

[0154] 1 1H-NMR (CDCl3): δ 8.88 (d, J = 8.6 Hz, 1H), 8.85 (d, J = 8.3 Hz, 1H), 8.53 (d, J = 8.6 Hz, 4H), 7.72 (dd, J = 16.1, 8.0 Hz, 2H), 7.41 - 7.58 (m, 14H), 7.20 - 7.24 (m, 3H), 7.12 (t, J = 6.2 Hz, 1H), 1.34 (s, 9H).

[0155] Synthesis Example - 7

Chemical Structure

[0156] Under an argon atmosphere, 2-(2-chloro-10-phenylphenanthren-9-yl)-4,6-diphenyl-1,3,5-triazine (100 mg, 0.19 mmol), 2-aminopyridine-5-boronic acid pinacol ester (55 mg, 0.25 mmol), palladium acetate (2 mg, 9.6 μmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylphenyl (9 mg, 19 μmol) were suspended in THF (1.3 mL). To this suspension, 2.0 M aqueous potassium phosphate solution (0.3 mL) was sequentially added, and the mixture was stirred overnight under heating under reflux. After allowing to cool to room temperature, water and chloroform were added, and the organic layer was extracted. The organic layer was further washed with water and then saturated brine. Sodium sulfate was added to the extract and stirred at room temperature for a while, then the desiccant was filtered off, and the low-boiling components were distilled off under reduced pressure from the filtrate. The obtained crude product was separated and purified by column chromatography (developing solution: chloroform / hexane) to obtain a white solid of 5-(9-(4,6-diphenyl-1,3,5-triazine-2-yl)-10-phenylphenanthren-2-yl)pyridin-2-amine (yield 51 mg, yield 46%).

[0157] 1 1H-NMR (CDCl3): δ 8.88 (d, J = 8.6 Hz, 1H), 8.84 (d, J = 8.3 Hz, 1H), 8.53 (d, J = 8.5 Hz, 4H), 8.32 (s, 1H), 7.89 (dd, J = 8.6, 1.9 Hz, 1H), 7.81 (s, 1H), 7.73 (t, J = 8.6 Hz, 2H), 7.66 (dd, J = 7.2, 1.2 Hz, 1H), 7.58 - 7.54 (m, 3H), 7.47 - 7.52 (m, 4H), 7.41 (d, J = 8.3 Hz, 2H), 7.23 - 7.21 (m, 2H), 7.13 (t, J = 5.4 Hz, 1H), 6.55 (d, J = 8.5 Hz, 1H), 4.48 (s, 2H).

[0158] Synthesis Example - 8

Chemical Structure

[0159] Under an argon atmosphere, 2-(2-chloro-10-phenylphenanthren-9-yl)-4,6-diphenyl-1,3,5-triazine (100 mg, 0.19 mmol), 2-thiopheneboronic acid pinacol ester (53 mg, 0.25 mmol), palladium acetate (2 mg, 9.6 μmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylphenyl (9 mg, 19 μmol) were suspended in THF (1.3 mL). To this suspension, 2.0 M aqueous potassium phosphate solution (290 μL) was added sequentially, and the mixture was stirred overnight under heating under reflux. After allowing to cool to room temperature, water and chloroform were added, and the organic layer was extracted. The organic layer was further washed with water and then saturated brine. Sodium sulfate was added to the extract and stirred at room temperature for a while, and then the desiccant was filtered off. The low-boiling components were distilled off under reduced pressure from the filtrate. The obtained crude product was separated and purified by column chromatography (developing solution: chloroform / hexane) to obtain a white solid of 2,4-diphenyl-6-(10-phenyl-2-(thiophen-2-yl)phenanthren-9-yl)-1,3,5-triazine (yield 93 mg, yield 86%).

[0160] 1 1H-NMR (CDCl3): δ 8.83 (d, J = 8.6 Hz, 1H), 8.82 (d, J = 8.2 Hz, 1H), 8.54 (d, J = 8.6 Hz, 4H), 7.98 (dd, J = 8.6, 1.9 Hz, 1H), 7.92 (s, 1H), 7.74 (d, J = 8.5 Hz, 1H), 7.70 (d, J = 8.2 Hz, 1H), 7.54 - 7.59 (m, 3H), 7.50 (dd, J = 8.5 Hz, 4H), 7.42 (d, J = 8.3 Hz, 2H), 7.23 - 7.29 (m, 4H), 7.16 (t, J = 7.5 Hz, 1H), 7.06 (dd, J = 5.0, 3.6 Hz, 1H).

[0161] Synthesis Reference Example - 1

Chemical Structure

[0162] Under an argon atmosphere, 2-(2-chloro-10-phenylphenanthren-9-yl)-4,6-diphenyl-1,3,5-triazine (7.9 g, 15 mmol), bis(pinacolato)diboron (4.6 g, 18 mmol), palladium(II) acetate (100 mg, 0.46 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylphenyl (0.44 mg, 0.91 mmol), potassium acetate (5.4 g, 55 mmol) were suspended in THF (150 mL) and stirred under heating under reflux for 18 hours. The low-boiling components were distilled off under reduced pressure from the reaction solution, and the resulting solid was washed with water, methanol and hexane, then dissolved in chloroform, activated carbon was added and stirred for 30 minutes. After removing the activated carbon by filtration through celite, the low-boiling components were distilled off under reduced pressure from the filtrate to obtain a white solid of 2,4-diphenyl-6-(10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenanthren-9-yl)-1,3,5-triazine (yield 5.6 g, yield 66%).

[0163] 1 1H-NMR (CDCl3): δ 8.88 (d, J = 8.4 Hz, 1H), 8.83 (d, J = 8.4 Hz, 1H), 8.52 (brd, J = 8.1 Hz, 4H), 8.20 (d, J = 0.8 Hz, 1H), 8.12 (dd, J = 8.4, 1.2 Hz, 1H), 7.74 (dd, J = 8.4, 0.8 Hz, 1H), 7.70 (ddd, J = 8.4, 7.0, 1.2 Hz, 1H), 7.60 - 7.46 (m, 7H), 7.40 (brd, J = 7.8 Hz, 2H), 7.23 (dd, J = 7.8, 7.5 Hz, 2H), 7.12 (brt, J = 7.5 Hz, 1H) 1.33 (s, 12H).

[0164] Synthesis Example - 9

Chemical Structure

[0165] Under an argon atmosphere, 2,4-diphenyl-6-(10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenanthren-9-yl)-1,3,5-triazine (5.6 g, 9.2 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.6 g, 9.7 mmol), and tetrakis(triphenylphosphine)palladium (320 mg, 0.28 mmol) were suspended in THF (90 mL). To this suspension, an aqueous solution of 2.0 M potassium carbonate (17 mL) was added, and the mixture was stirred under reflux for 18 hours. After allowing to cool to room temperature, the solid obtained by filtration was washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110 °C, activated carbon was added, and the mixture was filtered while hot using celite, and then allowed to stand. The precipitated solid was collected by filtration to obtain a white solid of 2,9-bis(4,6-diphenyl-1,3,5-triazin-2-yl)-10-phenylphenanthrene (yield 4.0 g, yield 61%).

[0166] 1 1H-NMR (CDCl3): δ 9.25 (d, J = 1.3 Hz, 1H), 9.05 (dd, J = 8.7, 1.5 Hz, 1H), 9.01 (d, J = 8.7 Hz, 1H), 8.94 (d, J = 8.3 Hz, 1H), 8.67 (brd, J = 7.7 Hz, 4H), 8.57 (brd, J = 7.7 Hz, 4H), 7.84 (brd, J = 8.3 Hz, 1H), 7.78 (brdd, J = 8.3, 7.1 Hz, 1H), 7.66 - 7.47 (m, 15H), 7.38 (dd, J = 8.0, 7.5 Hz, 2H), 7.31 (brt, J = 7.5 Hz, 1H).

[0167] Synthesis Reference Example - 2

Chemical Structure

[0168] Under an argon atmosphere, 9-biphenyl-2-chloro-10-phenylphenanthrene (2.48 g, 5.6 mmol), bis(pinacolato)diboron (1.70 g, 6.7 mmol), potassium acetate (1.66 g, 17 mmol), tris(dibenzylideneacetone)dipalladium (128 mg, 0.14 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylphenyl (267 mg, 0.56 mmol) were dissolved in THF (30 mL), and the mixture was heated to reflux for 16 hours. After cooling to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain the crude product. The crude product was purified by column chromatography (developing solution: hexane / chloroform) to obtain a white solid of 2-(9-([1,1′-biphenyl]-4-yl)-10-phenylphenanthren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (B-1) (yield 1.47 g, yield 49%).

[0169] 1 1H-NMR (CDCl3): δ 8.85 (d, J = 8.3 Hz, 1H), 8.80 (d, J = 8.9 Hz, 1H), 8.06 (dd, J = 7.3, 1 Hz, 2H), 7.59 - 7.69 (m, 2H), 7.67 (t, J = 8.2 Hz, 1H), 7.59 (s, 1H), 7.53 (m, 1H), 7.48 (d, J = 8.4 Hz, 2H), 7.43 (t, J = 7.3 Hz, 2H), 7.33 (t, J = 7.3 Hz, 1H), 7.18 - 7.23 (m, 7H), 1.31 (s, 12H).

[0170] Synthesis Reference Example - 3

Chemical Structure

[0171] Under an argon atmosphere, 10-biphenyl-3-chloro-9-phenylphenanthrene (1.90 g, 4.3 mmol), bis(pinacolato)diboron (1.30 g, 5.1 mmol), potassium acetate (1.27 g, 13 mmol), tris(dibenzylideneacetone)dipalladium (100 mg, 0.11 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylphenyl (200 mg, 0.42 mmol) were dissolved in THF (30 mL), and the mixture was heated under reflux for 9.5 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. The crude product was purified by column chromatography (developing solution: hexane / chloroform) to obtain a white solid (yield 1.45 g, yield 63%) of 2-(10-([1,1′-biphenyl]-4-yl)-9-phenylphenanthren-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (B-2).

[0172] 1 1H-NMR (CDCl3): δ 9.31 (s, 1H), 8.98 (d, J = 8.3 Hz, 1H), 7.88 (dd, J = 8.2, 1.0 Hz, 1H), 7.68 (t, J = 8.3 Hz, 1H), 7.63 - 7.60 (m, 3H), 7.57 (dd, J = 8.2, 1.0 Hz, 1H), 7.50 (dd, J = 8.3, 1.8 Hz, 2H), 7.49 (m, 1H), 7.43 (t, J = 7.3 Hz, 2H), 7.32 (t, J = 7.3 Hz, 1H), 7.17 - 7.25 (m, 7H), 1.43 (s, 12H).

[0173] Synthesis Example - 10

Chemical Structure

[0174] Under an argon atmosphere, 2,4-diphenyl-6-(2'-(phenylethynyl)-[1,1'-biphenyl]-4-yl)-1,3,5-triazine (12.4 g, 26 mmol), copper(II) bromide (17.6 g, 79 mmol), and potassium phosphate (2.72 g, 13 mmol) were suspended in nitromethane (240 mL) and stirred under heating under reflux for 2 days. After allowing to cool to room temperature, chloroform was added to the reaction solution, and the copper salt was removed by filtration through celite, and then the low-boiling components were distilled off under reduced pressure. Recrystallization from toluene of the obtained crude product gave a white solid of 2-(9-bromo-10-phenylphenanthren-2-yl)-4,6-diphenyl-1,3,5-triazine (yield 8.77 g, yield 61%).

[0175] 1 1H-NMR (CDCl3): 8.87 - 8.89 (m, 2H), 8.81 (d, J = 8.6 Hz, 1H), 8.77 - 8.80 (m, 1H), 8.61 (d, J = 7.0 Hz, 4H), 8.55 - 8.58 (m, 1H), 7.75 - 7.80 (m, 2H), 7.67 - 7.68 (m, 3H), 7.60 (t, J = 7.2 Hz, 2H), 7.48 - 7.55 (m, 6H).

[0176] Synthesis Example - 11

Chemical Structure

[0177] Under an argon atmosphere, 2-(9-bromo-10-phenylphenanthren-2-yl)-4,6-diphenyl-1,3,5-triazine (300 mg, 0.53 mmol), 2-thiopheneboronic acid (82 mg, 0.64 mmol), palladium acetate (12 mg, 53 μmol), tri(cyclohexyl)phosphine toluene solution (0.6 M, 180 μL), and 2.0 M aqueous potassium phosphate solution (800 μL) were suspended in dimethylformamide (2 mL), and the mixture was heated and stirred at 110 °C for 15 hours. After cooling to room temperature, separation was carried out by column chromatography and size exclusion chromatography to obtain a crude product. When this crude product was analyzed by HPLC, 2,4-diphenyl-6-(10-phenyl-9-(thiophen-2-yl)phenanthren-2-yl)-1,3,5-triazine was contained in the crude product in a yield of 23%.

[0178] 1 1H-NMR (CDCl3): δ 9.09 (s, 1H), 8.98 (m, 1H), 8.95 (d, J = 8.7 Hz, 1H), 8.88 (d, J = 8.7 Hz, 1H), 8.65 (d, J = 6.9 Hz, 4H), 7.88 (t, J = 8.2 Hz, 1H), 7.75 (t, J = 8.2 Hz, 1H), 7.53 - 7.65 (m, 7H), 7.44 - 7.48 (m, 3H), 7.37 - 7.39 (m, 2H), 7.31 (dd, J = 5.1, 1.2 Hz, 1H), 7.00 (dd, J = 5.1, 3.4 Hz, 1H), 6.96 (dd, J = 3.4, 1.2 Hz, 1H).

[0179] Synthesis Example - 12

Chemical Structure

[0180] Under an argon atmosphere, 2-(9-bromo-10-phenylphenanthren-2-yl)-4,6-diphenyl-1,3,5-triazine (300 mg, 0.53 mmol), benzofuran-2-boronic acid pinacol ester (103 mg, 0.64 mmol), palladium acetate (12 mg, 53 μmol), tris(cyclohexyl)phosphine toluene solution (0.6 M, 180 μL), and 2.0 M aqueous potassium phosphate solution (800 μL) were suspended in dimethylformamide (2 mL) and heated with stirring at 110 °C for 15 hours. After cooling to room temperature, separation was performed by wet column chromatography and size exclusion chromatography to obtain a crude product. When this crude product was analyzed by HPLC, 2-(9-(benzofuran-2-yl)-10-phenylphenanthren-2-yl)-4,6-diphenyl-1,3,5-triazine was contained in the crude product in a yield of 4%.

[0181] 1 1H-NMR (CDCl3): δ 9.18 (s, 1H), 9.02 (dd, J = 8.7, 1.7 Hz, 1H), 8.96 (d, J = 8.2 Hz, 1H), 8.89 (d, J = 8.2 Hz, 1H), 8.66 (d, J = 6.9 Hz, 4H), 7.81 (d, J = 8.2 Hz, 1H), 7.76 (t, J = 8.2 Hz, 1H), 7.55 - 7.65 (m, 7H), 7.49 - 7.54 (m, 3H), 7.43 - 7.47 (m, 4H), 7.29 (m, 1H), 7.22 (m, 1H), 6.56 (s, 1H).

[0182] Synthesis Example - 13

Chemical Structure

[0183] Under an argon atmosphere, 2-(9-bromo-10-phenylphenanthren-2-yl)-4,6-diphenyl-1,3,5-triazine (300 mg, 0.53 mmol), 2-phenylpyridine-5-boronic acid pinacol ester (179 mg, 0.64 mmol), palladium acetate (12 mg, 53 μmol), tricyclohexylphosphine toluene solution (0.6 M, 180 μL), and 2.0 M aqueous potassium phosphate solution (800 μL) were suspended in dimethylformamide (2 mL), and heated with stirring at 110 °C for 15 hours. After cooling to room temperature, separation was carried out by column chromatography and size exclusion chromatography to obtain a crude product. When this crude product was analyzed by HPLC, 2,4-diphenyl-6-(10-phenyl-9-(6-phenylpyridin-3-yl)phenanthren-2-yl)-1,3,5-triazine was contained in the crude product in a yield of 9%.

[0184] 1 1H-NMR (CDCl3): δ 9.11 (s, 1H), 8.96 - 9.00 (m, 2H), 8.92 (d, J = 8.2 Hz, 1H), 8.64 (d, J = 7.0 Hz, 4H), 8.04 (d, J = 7.1 Hz, 2H), 7.77 (t, J = 8.2 Hz, 1H), 7.31 - 7.72 (m, 19H).

[0185] Synthesis Example - 14

Chemical Structure

[0186] Under an argon atmosphere, 2-(9-bromo-10-phenylphenanthren-2-yl)-4,6-diphenyl-1,3,5-triazine (300 mg, 0.53 mmol), 1.2 molar equivalents of triphenylene boronic acid (173 mg, 0.64 mmol), palladium acetate (12 mg, 53 μmol), tri(cyclohexyl)phosphine toluene solution (0.6 M, 180 μL), and 2.0 M aqueous potassium phosphate solution (800 μL) were suspended in dimethylformamide (2 mL), and heated with stirring at 110 °C for 15 hours. After cooling to room temperature, separation was carried out by wet column chromatography to obtain a crude product. When this crude product was analyzed by HPLC, the crude purified product contained 2,4-diphenyl-6-(10-phenyl-9-(triphenylene-2-yl)phenanthren-2-yl)-1,3,5-triazine in a yield of 6%.

[0187] 1 1H-NMR (CDCl3): δ 9.17 (s, 1H), 9.02 (s, 2H), 8.95 (d, J = 8.0 Hz, 1H), 8.58 - 8.67 (m, 7H), 8.69 (d, J = 8.2 Hz, 2H), 8.59 (d, J = 7.9 Hz, 1H), 7.52 - 7.77 (m, 14H), 7.39 - 7.42 (m, 2H), 7.35 (t, J = 6.8 Hz, 1H), 7.28 - 7.30 (m, 2H).

[0188] Synthesis Reference Example - 4

Chemical Structure

[0189] Under an argon atmosphere, 3-(2-chloro-10-phenylphenanthren-9-yl)pyridine (874 mg, 2.4 mmol), bis(pinacolato)diboron (728 mg, 2.9 mmol), potassium acetate (1.66 g, 17 mmol), tris(dibenzylideneacetone)dipalladium (128 mg, 60 μmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylphenyl (267 mg, 0.24 mmol) were dissolved in THF (10 mL), and the mixture was heated under reflux for 14 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. The obtained crude product was purified by wet column chromatography (developing solution: hexane / chloroform) to obtain a white solid of 3-(10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenanthren-9-yl)pyridine (yield 731 mg, yield 67%).

[0190] 1 1H-NMR (CDCl3): δ 8.86 (d, J = 8.2 Hz, 1H), 8.80 (d, J = 8.2 Hz, 1H), 6.44 (d, J = 6.5 Hz, 1H), 8.42 (s, 1H), 8.08 (d, J = 8.3 Hz, 1H), 8.05 (s, 1H), 7.69 (t, J = 8.3 Hz, 1H), 7.53 (dt, J = 8.2, 1.1 Hz, 1H), 7.44 - 7.48 (m, 2H), 7.12 - 7.28 (m, 6H), 1.31 (s, 12H).

[0191] Synthesis Example - 15

Chemical Structure

[0192] Under an argon atmosphere, 3-(10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenanthren-9-yl)pyridine (100 mg, 0.22 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (70 mg, 0.26 mmol), tetrakistriphenylphosphine palladium (25 mg, 22 μmol), and 2.0 M aqueous potassium phosphate solution (330 μL) were suspended in 1,4-dioxane (1 mL), and the mixture was heated with stirring for 12 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. The obtained crude product was purified by column chromatography (developing solution: ethyl acetate / chloroform) to obtain a white solid of 2,4-diphenyl-6-(10-phenyl-9-(pyridin-3-yl)phenanthren-2-yl)-1,3,5-triazine (yield 71 mg, yield 58%).

[0193] 1 1H-NMR (CDCl3): δ 9.11 (s, 1H), 8.99 - 9.02 (m, 2H), 8.93 (d, J = 8.2 Hz, 1H), 8.64 - 8.67 (m, 4H), 8.54 (m, 1H), 8.51 (dd, J = 4.9, 1.7 Hz, 1H), 7.77 (t, J = 8.3 Hz, 1H), 7.52 - 7.63 (m, 10H), 7.40 - 7.42 (m, 3H), 7.28 - 7.33 (m, 2H).

[0194] Synthesis Example - 16

Chemical Structure

[0195] Under an argon atmosphere, 3-(10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenanthren-9-yl)pyridine (100 mg, 0.22 mmol), 2,4-di([1,1'-biphenyl]-4-yl)-6-chloro-1,3,5-triazine (110 mg, 0.26 mmol), tetrakistriphenylphosphine palladium (25 mg, 22 μmol), and 2.0 M aqueous potassium phosphate solution (330 μL) were suspended in 1,4-dioxane (1 mL), and the mixture was heated and stirred for 12 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. The obtained crude product was purified by column chromatography (developing solution: ethyl acetate / chloroform) to obtain a white solid of 2,4-di([1,1'-biphenyl]-4-yl)-6-(10-phenyl-9-(pyridin-3-yl)phenanthren-2-yl)-1,3,5-triazine (yield 130 mg, yield 83%).

[0196] 1 1H-NMR (CDCl3): δ 9.12 (s, 1H), 8.97 - 9.03 (m, 2H), 8.93 (d, J = 8.3 Hz, 1H), 8.71 (d, J = 7.8 Hz, 4H), 8.54 (s, 1H), 8.51 (dd, J = 4.9, 1.7 Hz, 1H), 7.76 (m, 5H), 7.71 (d, J = 7.4 Hz, 4H), 7.56 - 7.62 (m, 3H), 7.51 (t, J = 7.2 Hz, 4H), 7.40 - 7.44 (m, 5H), 7.28 - 7.35 (m, 2H), 7.24 - 7.27 (m, 1H).

[0197] Synthesis Example - 17

Chemical Structure

[0198] Under an argon atmosphere, 3-(10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenanthren-9-yl)pyridine (100 mg, 0.22 mmol), 2,4-bis(4-(t-butyl)phenyl)-6-chloro-1,3,5-triazine (100 mg, 0.26 mmol), tetrakistriphenylphosphine palladium (25 mg, 22 μmol), and 2.0 M aqueous potassium phosphate solution (330 μL) were suspended in 1,4-dioxane (1 mL), and heated with stirring for 12 hours. After cooling to room temperature, water and methanol were added, and the precipitated solid was collected by filtration, washed with water and methanol to obtain a crude product. The obtained crude product was purified by column chromatography (developing solution: ethyl acetate / chloroform) to obtain a white solid of 2,4-bis(4-(t-butyl)phenyl)-6-(10-phenyl-9-(pyridin-3-yl)phenanthren-2-yl)-1,3,5-triazine (yield 91 mg, yield 61%).

[0199] 1 1H-NMR (CDCl3): δ 9.08 (s, 1H), 8.98 - 9.01 (m, 2H), 8.93 (d, J = 8.2 Hz, 1H), 8.54 - 8.57 (m, 1H), 8.55 (d, J = 8.6 Hz, 4H), 8.51 (dd, J = 5.0, 1.7 Hz, 1H), 7.77 (t, J = 6.6 Hz, 1H), 7.57 - 7.61 (m, 3H), 7.55 (d, J = 8.6 Hz, 4H), 7.40 - 7.44 (m, 3H), 7.31 - 7.33 (m, 2H), 7.27 - 7.30 (m, 1H), 1.41 (s, 18H).

[0200] Synthesis Example - 18

Chemical Structure

[0201] Under an argon atmosphere, 3-(10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenanthren-9-yl)pyridine (100 mg, 0.22 mmol), 2-chloro-4,6-bis(4-methoxyphenyl)-1,3,5-triazine (86 mg, 0.26 mmol), tetrakistriphenylphosphine palladium (25 mg, 22 μmol), and 2.0 M aqueous potassium phosphate solution (330 μL) were suspended in 1,4-dioxane (1 mL), and heated with stirring for 12 hours. After cooling to room temperature, water and methanol were added, and the precipitated solid was collected by filtration, washed with water and methanol to obtain a crude product. The obtained crude product was purified by column chromatography (developing solution: ethyl acetate / chloroform) to obtain a white solid of 2,4-bis(4-methoxyphenyl)-6-(10-phenyl-9-(pyridin-3-yl)phenanthren-2-yl)-1,3,5-triazine (yield 95 mg, yield 70%).

[0202] 1 1H-NMR (CDCl3): δ 9.06 (s, 1H), 8.96 (m, 2H), 8.92 (d, J = 8.3 Hz, 1H), 8.58 (d, J = 8.8 Hz, 4H), 8.55 (s, 1H), 8.52 (dd, J = 4.9, 1.6 Hz, 1H), 7.77 (t, J = 8.0 Hz, 1H), 7.56 - 7.63 (m, 3H), 7.40 - 7.43 (m, 3H), 7.29 - 7.34 (m, 2H), 7.25 (m, 1H), 7.03 (d, J = 8.8 Hz, 4H), 3.94 (s, 6H).

[0203] Synthesis Example - 19

Chemical Structure

[0204] Under an argon atmosphere, 3-(10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenanthren-9-yl)pyridine (100 mg, 0.22 mmol), 2-chloro-4,6-bis(4-(neopentylthio)phenyl)-1,3,5-triazine (116 mg, 0.26 mmol), tetrakistriphenylphosphine palladium (25 mg, 22 μmol), and 2.0 M aqueous potassium phosphate solution (330 μL) were suspended in 1,4-dioxane (1 mL), and the mixture was heated and stirred for 12 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. The obtained crude product was purified by column chromatography (developing solution: ethyl acetate / chloroform) to obtain a white solid of 2,4-bis(4-(neopentylthio)phenyl)-6-(10-phenyl-9-(pyridin-3-yl)phenanthren-2-yl)-1,3,5-triazine (yield 107 mg, yield 64%).

[0205] 1 1H-NMR (CDCl3): δ 9.05 (s, 1H), 8.96 (m, 2H), 8.92 (d, J = 8.3 Hz, 1H), 8.54 (s, 1H), 8.52 (m, 1H), 8.50 (d, J = 8.5 Hz, 4H), 7.76 (t, J = 8.3 Hz, 1H), 7.62 - 7.51 (m, 3H), 7.43 - 7.40 (m, 3H), 7.42 (d, J = 8.5 Hz, 4H), 7.32 - 7.24 (m, 3H), 3.00 (s, 4H), 1.11 (s, 18H).

[0206] Synthesis Example - 20

Chemical Structure

[0207] Under an argon atmosphere, 3-(10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenanthren-9-yl)pyridine (100 mg, 0.22 mmol), 4-chloro-2,6-diphenylpyrimidine (70 mg, 0.26 mmol), tetrakistriphenylphosphine palladium (25 mg, 22 μmol), and 2.0 M aqueous potassium phosphate solution (330 μL) were suspended in 1,4-dioxane (1 mL), and the mixture was heated with stirring for 12 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain a crude product. The obtained crude product was purified by column chromatography (developing solution: ethyl acetate / chloroform) to obtain a white solid of 2,4-biphenyl-6-(10-phenyl-9-(pyridin-3-yl)phenanthren-2-yl)pyrimidine (yield 105 mg, yield 85%).

[0208] 1 1H-NMR (CDCl3): δ 8.97 (d, J = 8.8 Hz, 1H), 8.90 (d, J = 8.2 Hz, 1H), 8.68 (s, 1H), 8.58 - 8.54 (m, 3H), 8.52 (s, 1H), 8.50 (d, J = 2.8 Hz, 1H), 8.22 - 8.25 (m, 2H), 7.97 (s, 1H), 7.76 (t, J = 8.2 Hz, 1H), 7.54 - 7.61 (m, 6H), 7.50 - 7.52 (m, 3H), 7.35 - 7.41 (m, 3H), 7.22 - 7.31 (m, 3H).

[0209] Synthesis Example - 21

Chemical Structure

[0210] Under an argon atmosphere, 3-(10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenanthren-9-yl)pyridine (100 mg, 0.22 mmol), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (67 mg, 0.19 mmol), tetrakistriphenylphosphine palladium (19 mg, 16 μmol), and 2.0 M aqueous potassium phosphate solution (240 μL) were suspended in 1,4-dioxane (700 μL), and the mixture was heated with stirring for 12 hours. After allowing to cool to room temperature, water and methanol were added, and the precipitated solid was collected by filtration, washed with water and methanol to obtain a crude product. The obtained crude product was purified by column chromatography (developing solution: ethyl acetate / chloroform) to obtain a white solid of 2-([1,1'-biphenyl]-4-yl)-4-phenyl-6-(10-phenyl-9-(pyridin-3-yl)phenanthren-2-yl)-1,3,5-triazine (yield 67 mg, yield 65%).

[0211] 1 1H-NMR (CDCl3): δ 9.10 (s, 1H), 9.00 (d, J = 8.7 Hz, 1H), 8.96 (d, J = 8.7 Hz, 1H), 8.91 (d, J = 8.2 Hz, 1H), 8.69 (d, J = 8.4 Hz, 2H), 8.65 (d, J = 8.4 Hz, 2H), 8.54 (s, 1H), 8.50 (d, J = 3.7 Hz, 1H), 7.74 (m, 1H), 7.75 (d, J = 8.4 Hz, 2H), 7.71 (d, J = 8.4 Hz, 2H), 7.62 - 7.49 (m, 4H), 7.53 (d, J = 8.2 Hz, 2H), 7.50 (d, J = 7.7 Hz, 2H), 7.40 - 7.44 (m, 4H), 7.23 - 7.33 (m, 3H).

[0212] Synthesis Reference Example - 5

Chemical Structure

[0213] Under an argon atmosphere, 4-bromo-3-iodophenol (16 g, 52 mmol), dichlorobis(triphenylphosphine)palladium (0.70 g, 1.0 mmol), and copper(I) iodide (0.38 g, 2.0 mmol) were stirred in triethylamine (100 mL) at room temperature for 15 minutes. Phenylacetylene (6.3 mL, 57 mmol) was added to the reaction solution, and the mixture was stirred at room temperature for 18 hours. The low-boiling components were distilled off under reduced pressure from the reaction solution, and after quenching with 28% aqueous ammonia solution, the mixture was extracted with chloroform. The extract was washed with 1 M aqueous hydrochloric acid and saturated brine, and then the low-boiling components were distilled off under reduced pressure from the extract to obtain 4-bromo-3-(2-phenylethynyl)phenol (10 g, 71%).

[0214] 1 H-NMR(CDCl3):δ7.57(m,2H),7.45(d,J=8.6Hz,1H),7.36(m,3H),7.04(d,J=3.0Hz,1H),6.71(dd,J=8.6,3.0Hz,1H),4.90(brs,1H).

[0215] Synthesis Reference Example - 6

Chemical Structure

[0216] Under an argon atmosphere, 4-bromo-3-(2-phenylethynyl)phenol (10 g, 37 mmol), 4-chlorophenylboronic acid (6.3 g, 40 mmol), and dichlorobis(triphenylphosphine)palladium (0.51 g, 0.73 mmol) were suspended in THF (370 mL). 2.0 M aqueous potassium carbonate solution (37 mL, 74 mmol) was added to this suspension, and the mixture was stirred at 80 °C for 18 hours. The low-boiling components were distilled off under reduced pressure from the reaction solution, and after extraction with chloroform, the extract was dried over sodium sulfate and then the desiccant was removed by filtration. The low-boiling components were distilled off under reduced pressure from the obtained filtrate to obtain 4'-chloro-2-(2-phenylethynyl)-1,1'-biphenyl-4-ol (9.5 g, 81%).

[0217] 1H-NMR(CDCl3): δ 7.56 (broad doublet, J = 8.4 Hz, 2H), 7.40 (broad doublet, J = 8.4 Hz, 2H), 7.37 - 7.29 (multiplet, 5H), 7.26 (doublet, J = 8.2 Hz, 1H), 7.11 (doublet, J = 2.6 Hz, 1H), 6.89 (doublet of doublets, J = 8.2, 2.6 Hz, 1H), 5.03 (broad singlet, 1H).

[0218] Synthesis Reference Example - 7

Chem.

[0219] 4'-Chloro-2-(2-phenylethynyl)-1,1'-biphenyl-4-ol (2.6 g, 8.5 mmol) was dissolved in chloroform (20 mL), trifluoroacetic acid (20 mL) was added, and the mixture was stirred at room temperature for 17 hours. The low-boiling components were distilled off under reduced pressure from the reaction solution, and the resulting oily substance was purified by column chromatography (developing solvent: hexane:chloroform:ethyl acetate = 10:1:1) to obtain 7-chloro-9-phenylphenanthren-2-ol (1.6 g, 61%).

[0220] 1 H-NMR(CDCl3): δ 8.60 (doublet, J = 2.2 Hz, 1H), 8.52 (doublet, J = 9.7 Hz, 1H), 7.79 (doublet, J = 8.8 Hz, 1H), 7.56 - 7.43 (multiplet, 5H), 7.50 (singlet, 1H), 7.40 (doublet of doublets, J = 8.8, 2.2 Hz, 1H), 7.25 - 7.22 (multiplet, 2H).

[0221] Synthesis Reference Example - 8

Chem.

[0222] 7-Chloro-9-phenylphenanthren-2-ol (0.70 g, 2.3 mmol) was dissolved in chloroform (25 mL), and anhydrous trifluoromethanesulfonic acid (0.77 mL, 4.6 mmol) and pyridine (0.74 mL, 9.2 mmol) were added at 0 °C, followed by stirring at room temperature for 18 h. The reaction solution was quenched with 1 M aqueous hydrochloric acid and then extracted with chloroform. The extract was washed with saturated aqueous sodium hydrogen carbonate and dried over sodium sulfate, and then the desiccant was removed by filtration. The low-boiling components were distilled off under reduced pressure from the obtained filtrate to give 7-chloro-9-phenylphenanthren-2-yl trifluoromethanesulfonate (0.95 g, 95%).

[0223] 1 1H-NMR (CDCl3): δ 8.71 (d, J = 9.2 Hz, 1H), 8.68 (d, J = 2.1 Hz, 1H), 7.88 (d, J = 8.8 Hz, 1H), 7.79 (d, J = 2.5 Hz, 1H), 7.67 (s, 1H), 7.61 - 7.46 (m, 7H).

[0224] Synthesis Reference Example - 9

Chemical Structure

[0225] Under an argon atmosphere, 7-chloro-9-phenylphenanthren-2-yl trifluoromethanesulfonate (2.6 g, 6.0 mmol), phenylboronic acid (0.79 g, 6.5 mmol), and dichlorobis(triphenylphosphine)palladium (0.13 g, 0.18 mmol) were suspended in THF (60 mL). To this suspension, 2.0 M aqueous potassium carbonate solution (6.0 mL, 12 mmol) was added, and the mixture was stirred at 80 °C for 17 h. The low-boiling components were distilled off under reduced pressure from the reaction solution, and after extraction with chloroform, the extract was dried over sodium sulfate and the desiccant was removed by filtration. The low-boiling components were distilled off under reduced pressure from the obtained filtrate to give a crude product of 2-chloro-7,10-diphenylphenanthrene (2.2 g). Under an argon atmosphere, this crude product, bis(pinacolato)diboron (1.8 g, 7.2 mmol), palladium acetate (40 mg, 0.18 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (0.17 g, 0.36 mmol), and potassium acetate (2.1 g, 22 mmol) were suspended in THF (60 mL) and stirred at 80 °C for 16 hours. The low-boiling components were distilled off under reduced pressure from the reaction solution, and after extraction with chloroform, the extract was dried over sodium sulfate and the desiccant was removed by filtration. After distilling off the low-boiling components under reduced pressure from the obtained filtrate, the obtained solid was washed with methanol to obtain 2-(7,10-diphenylphenanthren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.1 g, 77%).

[0226] 1 1H-NMR (CDCl3): δ 9.28 (brs, 1H), 8.94 (brd, J = 8.7 Hz, 1H), 8.10 (d, J = 2.0 Hz, 1H), 7.96 - 7.88 (m, 3H), 7.81 - 7.75 (m, 3H), 7.60 - 7.44 (m, 7H), 7.40あ (brt, J = 7.4 Hz, 1H), 1.43 (s, 12H).

[0227] Synthesis Example - 22

Chemical Structure

[0228] Under an argon atmosphere, 2-(4-biphenyl)-4-chloro-6-phenyl-1,3,5-triazine (1.6 g, 4.6 mmol), 2-(7,10-diphenylphenanthren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.0 g, 4.4 mmol), and dichlorobis(triphenylphosphine)palladium (0.15 g, 0.13 mmol) were suspended in THF (40 mL). To this suspension, an aqueous 2.0 M potassium carbonate solution (8.0 mL, 16 mmol) was added, and the mixture was stirred at 80 °C for 18 hours. After allowing to cool to room temperature, water and hexane were added to the reaction mixture, and the precipitated solid was collected by filtration and then washed with water, methanol, and hexane. The obtained solid was dissolved in toluene heated to 110 °C, activated carbon was added, and the mixture was filtered while hot using celite. After standing, the precipitated solid was collected by filtration to obtain 2-(4-biphenyl)-4-(7,10-diphenylphenanthren-2-yl)-6-phenyl-1,3,5-triazine (1.9 g, 68%).

[0229] 1 1H-NMR (CDCl3): δ 10.3 (brs, 1H), 9.09 (d, J = 8.5 Hz, 1H), 8.95 - 8.86 (m, 5H), 8.16 (brs, 1H), 8.13 (d, J = 8.5 Hz, 1H), 8.08 (brd, J = 9.0 Hz, 1H), 7.88 (s, 1H), 7.87 (d, J = 8.5 Hz, 2H), 7.82 (brd, J = 8.0 Hz, 2H), 7.75 (brd, J = 8.0 Hz, 2H), 7.68 - 7.48 (m, 12H), 7.43 (m, 2H).

[0230] Next, the device evaluation will be described. The structural formula and abbreviation of the compound used for device evaluation are shown below.

[0231]

Chemical formula

[0232] Device Example - 1 (see Figure 2) (Preparation of Substrate 1 and Anode 2) As a substrate having an anode on its surface, a glass substrate with an ITO transparent electrode in which a 2-mm-wide indium tin oxide (ITO) film (film thickness: 110 nm) was patterned in a stripe shape was prepared. Next, after washing this substrate with isopropyl alcohol, surface treatment was performed by ozone ultraviolet cleaning.

[0233] (Preparation for vacuum evaporation) On the substrate subjected to surface treatment after washing, vacuum evaporation of each layer was performed by the vacuum evaporation method to form each layer by lamination. First, the glass substrate was introduced into the vacuum evaporation chamber and the pressure was reduced to 1.0×10 -4 Pa. Then, fabrication was carried out according to the film formation conditions of each layer in the following order.

[0234] (Fabrication of hole injection layer 3) Sublimation-purified HIL was deposited at a rate of 0.15 nm / second to a thickness of 55 nm to fabricate a hole injection layer.

[0235] (Fabrication of charge generation layer 4) Sublimation-purified HAT was deposited at a rate of 0.05 nm / second to a thickness of 5 nm to fabricate a charge generation layer.

[0236] (Fabrication of first hole transport layer 51) HTL-1 was deposited at a rate of 0.15 nm / second to a thickness of 10 nm to fabricate a first hole transport layer.

[0237] (Fabrication of second hole transport layer 52) HTL-2 was deposited at a rate of 0.15 nm / second to a thickness of 10 nm to fabricate a second hole transport layer.

[0238] (Fabrication of light-emitting layer 6) EML-1 and EML-2 were deposited at a rate of 0.18 nm / second to a thickness of 25 nm at a ratio of 95:5 (mass ratio) to fabricate a light-emitting layer.

[0239] (Fabrication of first electron transport layer 71) ETL-1 was deposited at a rate of 0.15 nm / second to a thickness of 5 nm to fabricate a first electron transport layer 7.

[0240] (Fabrication of the second electron transport layer 72) 2,4-Diphenyl-6-[10-phenyl-2-(3-pyridyl)phenanthren-9-yl]-1,3,5-triazine (Compound 1-1) synthesized in Synthesis Example-2 and Liq were formed into a film with a thickness of 25 nm at a ratio of 50:50 (mass ratio) to fabricate the second electron transport layer 71. The film formation rate was 0.15 nm / second.

[0241] (Fabrication of the cathode 8) Finally, a metal mask was arranged so as to be perpendicular to the ITO stripe on the substrate, and the cathode 8 was formed into a film. The cathode was formed into a film with a thickness of 80 nm and 20 nm in this order with silver / magnesium (mass ratio 1 / 10) and silver, respectively, to form a two-layer structure. The film formation rate of silver / magnesium was 0.5 nm / second, and the film formation rate of silver was 0.2 nm / second.

[0242] As described above, an organic electroluminescent element 100 having a light-emitting area of 4 mm as shown in FIG. 2 was fabricated. The film thickness of each layer was measured with a stylus type film thickness gauge (DEKTAK, manufactured by Bruker). 2 In addition, the element was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. The sealing was performed using a glass sealing cap and a film-forming substrate (element) with a bisphenol F type epoxy resin (manufactured by Nagase ChemteX).

[0243] Furthermore, a direct current was applied to the organic electroluminescent element fabricated as described above, and the light-emitting characteristics were evaluated using a luminance meter (product name: BM-9, manufactured by Topcon Techno House). As the light-emitting characteristics, the current efficiency (cd / A) when a current density of 10 mA / cm

[0244] was passed was measured, and the element life (h) during continuous lighting was measured. The element life (h) in Table 1 was measured by measuring the luminance decay time during continuous lighting when the fabricated element was driven at an initial luminance of 1000 cd / m 2 and the luminance (cd / m 2 was measured. 2The time required until [[ID=]] decreases by 15% was measured. The current efficiency and the device lifetime are relative values with the results in Device Reference Example 1 described later as the reference value (100). The obtained measurement results are shown in Table 1.

[0245] Device Example - 2 In Device Example - 1, an organic electroluminescent device was fabricated and evaluated in the same manner as in Device Example - 1, except that 2,4 - diphenyl - 6-(10 - phenyl - [2,9'-biphenanthrene]-9 - yl)-1,3,5 - triazine (Compound 1 - 2) synthesized in Synthesis Example - 3 was used instead of Compound 1 - 1. The obtained measurement results are shown in Table 1.

[0246] Device Reference Example - 1 In Device Example - 1, an organic electroluminescent device was fabricated and evaluated in the same manner as in Device Example - 1, except that 2 - [5-(9 - phenanthryl)-3-(3 - pyridyl)phenyl]-4,6 - diphenyl - 1,3,5 - triazine (ETL - 2) described in Patent Document 1 was used instead of Compound 1 - 1. The obtained measurement results are shown in Table 1.

[0247]

Table 1

[0248] The cyclic azine compound according to one aspect of the present disclosure is extremely excellent in the heat resistance of the film quality, and an organic electroluminescent device excellent in current efficiency can be provided by using the compound.

[0249] In addition, the cyclic azine compound according to one aspect of the present disclosure has good thermal stability during sublimation purification, so it is excellent in the operability of sublimation purification, and a material with few impurities that cause device deterioration of the organic electroluminescent device can be provided. Further, the cyclic azine compound according to one aspect of the present disclosure is excellent in the stability of the vapor deposition film, so an organic electroluminescent device with a long lifetime can be provided.

[0250] In addition, the thin film composed of the cyclic azine compound according to one aspect of the present disclosure is excellent in electron transport ability, hole blocking ability, redox resistance, water resistance, oxygen resistance, electron injection characteristics, etc., and thus is useful as a material for organic electroluminescent elements, and is useful as an electron transport material, a hole blocking material, a light-emitting host material, etc. In particular, it is useful when used as an electron transport material.

Explanation of reference numerals

[0251] 1 Substrate 2 Anode 3 Hole injection layer 4 Charge generation layer 5 Hole transport layer 6 Light-emitting layer 7 Electron transport layer 8 Cathode 51 First hole transport layer 52 Second hole transport layer 71 First electron transport layer 72 Second electron transport layer 100 Organic electroluminescent element

Claims

1. A cyclic azine compound represented by formula (1-A): 【Chemical 1】 In the formula,[[]]END]] Ar １ and Ar ２ are each independently represents a phenyl group, a biphenylyl group, or a naphthyl group; R is (v) a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, (vi) a monocyclic, linked, or condensed aromatic heterocyclic group having 4 to 30 carbon atoms, or (vii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms, and the R is located at the 2-position of phenanthrene; Ra is (a2) a phenyl group, or (a4) a group in which the phenyl group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, and a halogenated alkyl group having 1 to 3 carbon atoms; n represents 1, Y １ and Y ２ represents a nitrogen atom.

2. A cyclic azine compound represented by formula (1-C): [Chemical Formula 3] In the formula,[[]]END]] Ar １ and Ar ２ are each independently represents a phenyl group or a biphenylyl group; R is (v) a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, (vi) a monocyclic, linked, or condensed aromatic heterocyclic group having 4 to 30 carbon atoms, or (vii) a group in which the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic heterocyclic group having 4 to 30 carbon atoms, provided that when Rc is a monocyclic group having 6 to 30 carbon atoms substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, and a halogenated alkyl group having 1 to 3 carbon atoms, and the 9-position of phenanthrene is substituted with R, the R substituted at the 9-position of the phenanthrene represents a group other than an unsubstituted phenyl group; Rc is (c2) a phenyl group, or (c4) a group in which the phenyl group is substituted with one or more groups selected from the group consisting of a fluorine atom, an alkyl group having 1 to 10 carbon atoms, and a halogenated alkyl group having 1 to 3 carbon atoms; n represents 1, provided that the 9-position and the 10-position of phenanthrene are different; Y １ and Y ２ each independently represents a nitrogen atom.

3. A cyclic azine compound represented by any one of formulas (1-1) to (1-7), (1-10), (1-12) to (1-19), or (1-24). 【Chemical Formula 6】 【Chemical Formula 7】 [Chemical Formula 8]

4. A material for an organic electroluminescent device, comprising the cyclic azine compound according to any one of Claims 1 to 3.

5. An organic electroluminescent device, comprising the cyclic azine compound according to any one of Claims 1 to 3.

6. A method for producing a cyclic azine compound represented by formula (1), comprising: coupling a compound represented by formula (2) and a compound represented by formula (3) in the presence of a metal catalyst, wherein the cyclic azine compound represented by formula (1) is the cyclic azine compound according to any one of Claims 1 to 3: 【Chemical Formula 9】 In the formulas, Ar １ , Ar ２ , R, n, Y １ and Y ２ has the same meaning as formula (1-A) or (1-C); L represents a group corresponding to the phenanthrenyl group of the cyclic azine compound of formula (1-A) or (1-C); X １ represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom; M １ represents ZnZ １ , MgZ ２ , Sn(Z ３ ), ３ or B(OZ ４ ); ２ ; Z １ and Z ２ each independently represents a chlorine atom, a bromine atom or an iodine atom; Z ３ is the same or different and represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Z ４ is the same as or different from and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group; However, when M １ represents B(OZ ４ ), ２ the two (OZ ４ groups may together form a ring with the boron atom.

7. A method for producing a cyclic azine compound represented by formula (1), comprising: coupling a compound represented by formula (4) and a compound represented by formula (5) in the presence of a metal catalyst, wherein the cyclic azine compound represented by formula (1) is the cyclic azine compound according to any one of Claims 1 to 3: 【Chemical Formula 10】 In the formulas, Ar １ 、 Ar ２ 、 R, n, Y １ and Y ２ are synonymous with formula (1-A) or (1-C); L represents a group corresponding to the phenanthrenyl group of the cyclic azine compound of formula (1-A) or (1-C); X ２ represents a chlorine atom, a bromine atom, a trifluoromethanesulfonyloxy group or an iodine atom.; M ２ represents ZnZ １ , MgZ ２ , Sn(Z ３ ), ３ or B(OZ ４ ); ２ ; Z １ and Z ２ each independently represents a chlorine atom, a bromine atom or an iodine atom; Z ３ is the same or different and represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Z ４ is the same as or different from and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group; However, when M ２ represents B(OZ ４ ), ２ the two (OZ ４ groups may combine together with the boron atom to form a ring.

Images