JP2011063584A - Triazine derivative, method for producing the same and organic electroluminescent element comprising the same as constituent component - Google Patents

Abstract

（式中、Ａｒ^１は、置換されていてもよい芳香族炭化水素基を表す。Ａｒ^２はフェニル基、ピリジル基又はピリミジル基を表す。Ａｒ^３は、置換されていてもよい２〜４環からなる芳香族炭化水素基を表す。Ｚは、炭素原子又は窒素原子を表す。Ｘは、フェニレン基又はピリジレン基を表す。ｐは、０から２の整数を表す。ｐが２のとき、Ｘは同一又は相異なっていてもよい。）で示される環状アジン誘導体。これを構成成分とする有機電界発光素子。
【選択図】なしProvided is a cyclic azine derivative which has a high heat resistance while reducing a driving voltage by being used as an electron transport material in an organic electroluminescence device.
SOLUTION: General formula (1)

(In the formula, Ar ¹ represents an optionally substituted aromatic hydrocarbon group. Ar ² represents a phenyl group, a pyridyl group or a pyrimidyl group. Ar ³ represents an optionally substituted 2 to 4 ring. Z represents a carbon atom or a nitrogen atom, X represents a phenylene group or a pyridylene group, p represents an integer of 0 to 2. When p is 2, X represents X May be the same or different.). An organic electroluminescent element comprising this as a constituent component.
[Selection figure] None

Description

  The present invention relates to a cyclic azine derivative having 2 to 4 aromatic hydrocarbon groups, a method for producing the same, and an organic electroluminescent device containing the same. More specifically, the present invention relates to a cyclic azine derivative having a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and a fluorenyl group, which is useful as a constituent component of an organic electroluminescence device, and a method for producing the same, and these are used in at least one layer of an organic compound layer. The present invention relates to a low voltage and high heat resistance organic electroluminescent device.

  An organic electroluminescent element is formed by sandwiching a light-emitting layer containing a light-emitting material between a hole transport layer and an electron transport layer, and further attaching an anode and a cathode to the outside, and recombination of holes and electrons injected into the light-emitting layer. It is an element that utilizes light emission (fluorescence or phosphorescence) when the generated excitons are deactivated, and is applied to displays and the like.

  Patent Document 1 discloses an example in which a 1,3,5-triazine derivative is used for an organic electroluminescent device, but these do not have a polycyclic aromatic group and are different from the cyclic azine derivative of the present invention. .

  Examples in which 1,3,5-triazine derivatives having a polycyclic aromatic group are used in organic electroluminescent devices are disclosed in Patent Documents 2 and 3, but these triazine derivatives are sterically hindered by polycyclic aromatic groups. It is limited to those that cause structural isomerism, and is different from the cyclic azine derivative of the present invention. In addition, both patent documents have no description regarding the glass transition temperature (Tg) and electron mobility of the compound.

  Further, Compound 6-13 described in Patent Document 4 refers to a compound having 1,3,5-triazine and a pyrenyl group, but there is no specific example, and it relates to Tg and mobility. There is no description.

JP 2008-280330 A JP 2001-143869 A JP 2004-22334 A Japanese Patent Laid-Open No. 2004-2297

  The conventional organic electroluminescent device has a high driving voltage for obtaining sufficient light emission, and the heat generated by the high driving voltage promotes the decomposition of the organic electroluminescent material, thereby causing the life of the device to be shortened.

  The reason why a high driving voltage is required is that the electron mobility of the material constituting the organic electroluminescent element, particularly the electron transport material, is low. Further, the heat resistance of the material is important for improving the durability of the element, and the constituent material is required to exhibit a high Tg. Therefore, the electron transport material needs to have a high mobility and a high Tg, but none of these conventional compounds satisfy the high Tg and the high electron mobility.

  As a result of intensive studies to solve the above problems, the present inventors have found that the cyclic azine derivative (1) of the present invention in which a polycyclic aromatic group is introduced into a cyclic azine skeleton having a high electron mobility has a high Tg. It was found that an amorphous thin film can be formed by any of vacuum deposition and spin coating. In addition, the present inventors have found that organic electroluminescent devices using these as an electron transport layer can achieve higher heat resistance, lower driving voltage of the device, and longer life compared to general-purpose organic electroluminescent devices, and completed the present invention. It came to do.

  That is, the present invention relates to the general formula (1)

(In the formula, Ar ¹ represents an optionally substituted aromatic hydrocarbon group. Ar ² represents a phenyl group, a pyridyl group or a pyrimidyl group. Ar ³ represents an optionally substituted 2 to 4 ring. X represents an phenylene group or a pyridylene group, p represents an integer of 0 to 2. When p is 2, X may be the same or different. Represents a carbon atom or a nitrogen atom).

  The present invention also provides a general formula (2)

(In the formula, Ar ¹ represents an optionally substituted aromatic hydrocarbon group. Ar ³ represents an optionally substituted aromatic hydrocarbon group having 2 to 4 rings. Z represents a carbon atom. Or a nitrogen atom, Y ¹ represents a chlorine atom, a bromine atom, or an iodine atom), and the general formula (3)

(In the formula, Ar ² represents a phenyl group, a pyridyl group or a pyrimidyl group. X represents a phenylene group or a pyridylene group. P represents an integer of 0 to 2. When p is 2, X is the same or M may represent ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B (OR ⁴ ) ₂ , provided that R ¹ and R ² are each independently a chlorine atom, bromine atom or Represents an iodine atom, R ³ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and B (OR ⁴ ) ₂ two R ⁴ may be the same or different. Furthermore, the two R ⁴ with a compound represented by the also possible.) to form a ring containing an oxygen atom and a boron atom together, optionally Is the presence of a palladium catalyst in the presence of a base. Characterized in that in a coupling reaction, the general formula (1)

(In the formula, Ar ¹ represents an optionally substituted aromatic hydrocarbon group. Ar ² represents a phenyl group, a pyridyl group or a pyrimidyl group. Ar ³ represents an optionally substituted 2 to 4 ring. X represents an phenylene group or a pyridylene group, p represents an integer of 0 to 2. When p is 2, X may be the same or different. Represents a carbon atom or a nitrogen atom).

  The present invention also provides a general formula (2)

(Wherein, Ar ¹ is .Z the .Ar ³ representing the optionally substituted aromatic hydrocarbon group representing an aromatic hydrocarbon group consisting of two to four rings which may optionally be substituted, carbon atoms Or Y ¹ represents a chlorine atom, a bromine atom or an iodine atom), and a compound represented by the general formula (4):

(In the formula, Ar ³ represents an optionally substituted aromatic hydrocarbon group having 2 to 4 rings. M represents ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B (OR ⁴ ) _2. Wherein R ¹ and R ² each independently represent a chlorine atom, a bromine atom or an iodine atom, R ³ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ⁴ represents a hydrogen atom, represents an alkyl group or a phenyl group having a carbon number of 1 to ^4, B (oR 4) 2 two R ⁴ ₂ may be the same or different. Furthermore, the two R ⁴ oxygen atoms and the boron atom together And a compound represented by the general formula (5):

(In the formula, Ar ¹ represents an optionally substituted aromatic hydrocarbon group. Z represents a carbon atom or a nitrogen atom. Y ¹ and Y ² are each independently a chlorine atom, a bromine atom or an iodine atom. A cyclic azine derivative represented by the general formula (1), wherein the compound represented by formula (1) is produced by a coupling reaction in the presence of a palladium catalyst, optionally in the presence of a base. It is related with the manufacturing method.

  Furthermore, this invention relates to the organic electroluminescent element characterized by using the cyclic azine derivative shown by General formula (1) as a structural component.

  Hereinafter, the present invention will be described in detail.

Examples of the optionally substituted aromatic hydrocarbon group represented by Ar ¹ include an optionally substituted phenyl group or an optionally substituted naphthyl group.

Examples of the optionally substituted phenyl group represented by Ar ¹ include a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 4-trifluoromethylphenyl group, and 3-trifluoromethyl. Phenyl group, 2-trifluoromethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2, 4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl group, 3,5-dipropylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,4-diisopropylphenyl group, 3,5-di Isopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl group, 2-tert-butylphenyl group, 3-tert- Phenyl substituted with an alkyl group having 1 to 4 carbon atoms such as butylphenyl group, 4-tert-butylphenyl group, 2,4-di-tert-butylphenyl group, 3,5-di-tert-butylphenyl group 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 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-trifluoromethyl Biphenyl-4-yl group, 3-trifluoromethylbiphenyl-4-yl group, 2'-trifluoromethylbiphenyl-4-yl group, 4'-trifluoromethylbiphenyl-4-yl group, 6-trifluoromethyl Biff Enyl-3-yl group, 5-trifluoromethylbiphenyl-3-yl group, 2'-trifluoromethylbiphenyl-3-yl group, 4'-trifluoromethylbiphenyl-3-yl group, 5-trifluoromethyl Biphenyl-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 Ru-4-yl group, 4′-propylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-tripropylbiphenyl-4-yl group, 6-propylbiphenyl-3-yl group, 4′-propyl Biphenyl-3-yl group, 5-propylbiphenyl-2-yl group, 4′-propylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-tripropylbiphenyl-2-yl group, 3-isopropylbiphenyl -4-yl group, 4′-isopropylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-triisopropylbiphenyl-4-yl group, 6-isopropylbiphenyl-3-yl group, 4′-isopropylbiphenyl -3-yl group, 5-isopropylbiphenyl-2-yl group, 4'-isopropylbiphenyl-2-yl group, 2 ', 4', 6'-triisopropylbiphenyl-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-tert-butylbiphenyl- 4-yl group, 4′-tert-butylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-tri-tert-butylbiphenyl-4-yl group, 6-tert-butylbiphenyl-3-yl group 4′-tert-butylbiphenyl-3-yl group, 5-tert-butylbiphenyl-2-yl group, 4′-tert-butylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-tri- tert-Butylbiphenyl-2-yl And a phenyl group substituted in the phenyl group and the like. A phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a 4-butylphenyl group, a 4-tert-butylphenyl group, a biphenyl-4-group, in terms of good performance as a material for an organic electroluminescent element An yl group, a biphenyl-3-yl group, and a biphenyl-2-yl group are desirable, and a phenyl group and a biphenyl-3-yl group are more desirable in terms of a good reaction yield.

Examples of the naphthyl group which may be substituted represented by Ar ^1, 1-naphthyl, 2-other-naphthyl group, 4-methyl-naphthalen-1-yl group, 4-trifluoromethyl-1-yl Group, 4-ethylnaphthalen-1-yl group, 4-propylnaphthalen-1-yl group, 4-butylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalene-1 -Yl group, 5-trifluoromethylnaphthalen-1-yl group, 5-ethylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group, 5-butylnaphthalen-1-yl group, 5-tert- Butylnaphthalen-1-yl group, 6-methylnaphthalen-2-yl group, 6-trifluoromethylnaphthalen-2-yl group, 6-ethylnaphthalen-2-yl group, 6-propylnaphthalen-2-yl group, 6-butylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalen-2-yl group, 7-trifluoromethylnaphthalene-2 1 carbon number such as -yl group, 7-ethylnaphthalen-2-yl group, 7-propylnaphthalen-2-yl group, 7-butylnaphthalen-2-yl group, and 7-tert-butylnaphthalen-2-yl group A naphthyl group substituted by ~ 4 alkyl groups. 1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group in terms of good performance as a material for organic electroluminescent elements 5-tert-butylnaphthalen-1-yl group, 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalen-2-yl group or A 7-tert-butylnaphthalen-2-yl group is desirable, and a 1-naphthyl group is more desirable in terms of easy synthesis.

Ar ² represents a phenyl group, a pyridyl group or a pyrimidyl group.

Examples of the aromatic hydrocarbon group having 2 to 4 rings which may be substituted represented by Ar ³ include an optionally substituted naphthyl group, an optionally substituted anthryl group, and an optionally substituted ring. Examples thereof include a phenanthryl group, an optionally substituted fluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted pyrenyl group, and an optionally substituted triphenylenyl group.

Examples of the optionally substituted naphthyl group represented by Ar ³ include 1-naphthyl group, 2-naphthyl group, 4-methylnaphthalen-1-yl group, and 4-trifluoromethylnaphthalen-1-yl group. 4-ethylnaphthalen-1-yl group, 4-propylnaphthalen-1-yl group, 4-butylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalene-1- Yl group, 5-trifluoromethylnaphthalen-1-yl group, 5-ethylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group, 5-butylnaphthalen-1-yl group, 5-tert-butyl Naphthalen-1-yl group, 6-methylnaphthalen-2-yl group, 6-trifluoromethylnaphthalen-2-yl group, 6-ethylnaphthalen-2-yl group, 6- Propylnaphthalen-2-yl group, 6-butylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalen-2-yl group, 7-trifluoromethylnaphthalen-2-yl Group, 7-ethylnaphthalen-2-yl group, 7-propylnaphthalen-2-yl group, 7-butylnaphthalen-2-yl group, 7-tert-butylnaphthalen-2-yl group and the like. And a naphthyl group substituted with an alkyl group. 1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group in terms of good performance as a material for organic electroluminescent elements 5-tert-butylnaphthalen-1-yl group, 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalen-2-yl group or A 7-tert-butylnaphthalen-2-yl group is desirable, and a 1-naphthyl group is more desirable in terms of easy synthesis.

Examples of the optionally substituted anthryl group represented by Ar ³ include 1-anthryl group, 2-anthryl group, 9-anthryl group, 2-methylanthracen-1-yl group, 3-methylanthracene-1 -Yl group, 4-methylanthracen-1-yl group, 9-methylanthracen-1-yl group, 10-methylanthracen-1-yl group, 2-phenylanthracen-1-yl group, 3-phenylanthracene-1 -Yl group, 4-phenylanthracen-1-yl group, 5-phenylanthracen-1-yl group, 6-phenylanthracen-1-yl group, 7-phenylanthracen-1-yl group, 8-phenylanthracene-1 -Yl group, 9-phenylanthracen-1-yl group, 10-phenylanthracen-1-yl group, 1-methylanthracene- 2-yl group, 3-methylanthracen-2-yl group, 4-methylanthracen-2-yl group, 9-methylanthracen-2-yl group, 10-methylanthracen-2-yl group, 1-phenylanthracene- 2-yl group, 3-phenylanthracen-2-yl group, 4-phenylanthracen-2-yl group, 5-phenylanthracen-2-yl group, 6-phenylanthracen-2-yl group, 7-phenylanthracene- 2-yl group, 8-phenylanthracen-2-yl group, 9-phenylanthracen-2-yl group, 10-phenylanthracen-2-yl group, 2-methylanthracen-9-yl group, 3-methylanthracene- 9-yl group, 4-methylanthracen-9-yl group, 10-methylanthracen-9-yl group, 2-phenylant Sen-9-yl group, 3-phenylanthracen-9-yl group, 4-phenylanthracen-9-yl group, 5-phenylanthracen-9-yl group, 6-phenylanthracen-9-yl group, 7-phenyl Anthryl group substituted with an alkyl group having 1 to 4 carbon atoms or phenyl group, such as anthracen-9-yl group, 8-phenylanthracen-9-yl group, 10-phenylanthracen-9-yl group, and the like, and organic A 1-anthryl group, a 2-anthryl group, a 9-anthryl group, and a 10-phenylanthracen-9-yl group are preferable from the viewpoint of good performance as a material for an electroluminescent element, and a 9-anthryl group is easy to synthesize. Is more preferable.

Examples of the optionally substituted phenanthryl group represented by Ar ³ include 1-phenanthryl group, 2-phentolyl group, 3-phenanthryl group, 4-phenanthryl group, 2-phenylphenanthren-1-yl group, 3 -Phenylphenanthren-1-yl group, 4-phenylphenanthren-1-yl group, 9-phenylphenanthren-1-yl group, 1-phenylphenanthren-2-yl group, 3-phenylphenanthren-2-yl group, 4 -Phenylphenanthren-2-yl group, 9-phenylphenanthren-2-yl group, 1-phenylphenanthren-3-yl group, 2-phenylphenanthren-3-yl group, 4-phenylphenanthren-3-yl group, 9 -Phenylphenanthren-3-yl group, 1-phenylphenanthrene-4-i Group, 2-phenylphenanthren-4-yl group, 3-phenylphenanthren-4-yl group, 9-phenylphenanthren-4-yl group, 9-phenanthryl group, 1-phenylphenanthren-9-yl group, 2- A phenanthryl group substituted with an alkyl group having 1 to 4 carbon atoms or a phenyl group, such as a phenylphenanthren-9-yl group, a 3-phenylphenanthrene-9-yl group, and a 4-phenylphenanthrene-9-yl group; A 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group are preferable in terms of good performance as a material for an organic electroluminescent device, and 9-phenanthryl in terms of easy synthesis. Groups are more preferred.

The optionally substituted fluorenyl group represented by Ar ³ includes 9,9-dimethylfluoren-1-yl group, 9,9-dimethylfluoren-2-yl group, and 9,9-dimethylfluorene-3- Yl group, 9,9-dimethylfluoren-4-yl group, 9,9-diphenylfluoren-1-yl group, 9,9-diphenylfluoren-2-yl group, 9,9-diphenylfluoren-3-yl group , 9,9-diphenylfluoren-4-yl group and the like, a fluorenyl group substituted with an alkyl group having 1 to 4 carbon atoms or a phenyl group, and the performance as a material for an organic electroluminescent element is good. , 9-dimethylfluoren-2-yl group, 9,9-dimethylfluoren-3-yl group and 9,9-diphenylfluoren-2-yl group are preferred, A 9-dimethylfluoren-2-yl group is more preferred.

The optionally substituted benzofluorenyl group represented by Ar ^3, 9,9-dimethyl-benzo [a] fluoren-3-yl group, 9,9-dimethyl-benzo [a] fluoren-4-yl A group, 9,9-dimethylbenzo [a] fluoren-5-yl group, 9,9-dimethylbenzo [a] fluoren-6-yl group, 9,9-dimethylbenzo [a] fluoren-7-yl group, 9,9-dimethylbenzo [a] fluoren-8-yl group, 9,9-dimethylbenzo [b] fluoren-1-yl group, 9,9-dimethylbenzo [b] fluoren-4-yl group, 9-dimethylbenzo [b] fluoren-5-yl group, 9,9-dimethylbenzo [b] fluoren-6-yl group, 9,9-dimethylbenzo [b] fluoren-7-yl group, 9,9- Dimethylbenzo [b] Fluoren-8-yl group, 9,9-dimethylbenzo [c] fluoren-1-yl group, 9,9-dimethylbenzo [c] fluoren-2-yl group, 9,9-dimethylbenzo [c] fluorene- 5-yl group, 9,9-dimethylbenzo [c] fluoren-6-yl group, 9,9-dimethylbenzo [c] fluoren-7-yl group, 9,9-dimethylbenzo [c] fluorene-8- Yl group, 9,9-diphenylbenzo [a] fluoren-3-yl group, 9,9-diphenylbenzo [a] fluoren-4-yl group, 9,9-diphenylbenzo [a] fluoren-5-yl group 9,9-diphenylbenzo [a] fluoren-6-yl group, 9,9-diphenylbenzo [a] fluoren-7-yl group, 9,9-diphenylbenzo [a] fluoren-8-yl group, 9 , 9 Diphenylbenzo [b] fluoren-1-yl group, 9,9-diphenylbenzo [b] fluoren-4-yl group, 9,9-diphenylbenzo [b] fluoren-5-yl group, 9,9-diphenylbenzo [B] Fluoren-6-yl group, 9,9-diphenylbenzo [b] fluoren-7-yl group, 9,9-diphenylbenzo [b] fluoren-8-yl group, 9,9-diphenylbenzo [c Fluoren-1-yl group, 9,9-diphenylbenzo [c] fluoren-2-yl group, 9,9-diphenylbenzo [c] fluoren-5-yl group, 9,9-diphenylbenzo [c] fluorene Alkyl having 1 to 4 carbon atoms such as -6-yl group, 9,9-diphenylbenzo [c] fluoren-7-yl group, 9,9-diphenylbenzo [c] fluoren-8-yl group Alternatively, a benzofluorenyl group substituted with a phenyl group may be mentioned, and a 9,9-dimethylbenzo [a] fluoren-6-yl group, 9,9- Dimethylbenzo [a] fluoren-7-yl group, 9,9-dimethylbenzo [b] fluoren-6-yl group, 9,9-dimethylbenzo [b] fluoren-7-yl group, 9,9-dimethylbenzo [C] A fluoren-2-yl group, a 9,9-dimethylbenzo [c] fluoren-6-yl group, and a 9,9-dimethylbenzo [c] fluoren-7-yl group are preferable and are easy to synthesize. A 9,9-dimethylbenzo [c] fluoren-2-yl group is more preferred.

Examples of the optionally substituted pyrenyl group represented by Ar ³ include 1-pyrenyl group, 6-phenylpyren-1-yl group, 7-phenylpyren-1-yl group, and 8-phenylpyren-1-yl. Group, 2-pyrenyl group, 6-phenylpyren-2-yl group, 7-phenylpyren-2-yl group, 8-phenylpyren-2-yl group, etc., and performance as a material for organic electroluminescent elements However, a 1-pyrenyl group and a 2-pyrenyl group are preferable, and a 2-pyrenyl group is more preferable in terms of easy synthesis.

Examples of the optionally substituted triphenylenyl group represented by Ar ³ include a 1-triphenylenyl group and a 2-triphenylenyl group.

  X represents a phenylene group or a pyridylene group.

  The compound represented by the general formula (3) can be produced, for example, by using a method disclosed in JP 2008-280330 A (0061) to (0076). Examples of the compound (3) include the following (I) to (LXXIX), but the present invention is not limited to these.

  The compound represented by the general formula (4) can be produced, for example, using the method disclosed in JP-A No. 2001-335516 (0047) to (0082).

Examples of ZnR ¹ and MgR ² represented by M include ZnCl, ZnBr, ZnI, MgCl, MgBr, and MgI. Examples of Sn (R ³ ) ₃ represented by M include Sn (Me) ₃ and Sn (Bu) ₃ .

Examples of B (OR ⁴ ) ₂ represented by M include B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , and B (OBu) ₂ . Examples of B (OR ⁴ ) ₂ in the case where two R ⁴ are combined to form a ring containing an oxygen atom and a boron atom include groups represented by the following (LXXX) to (LXXXV): A group represented by (LXXXI) is desirable because it can be exemplified and the yield is good.

  Next, the manufacturing method of this invention is demonstrated. The cyclic azine derivative (1) of the present invention has the following reaction formula:

(In the formula, Ar ¹ represents an optionally substituted aromatic hydrocarbon group. Ar ² represents a phenyl group, a pyridyl group or a pyrimidyl group. Ar ³ consists of 2 to 4 rings which may be substituted. Represents an aromatic hydrocarbon group, Z represents a carbon atom or a nitrogen atom, X represents a phenylene group or a pyridylene group, p represents an integer of 0 to 2, and when p is 2, X is the same Y ¹ represents a chlorine atom, a bromine atom, or an iodine atom, and M represents ZnR ¹ , MgR ² , Sn (R ³ ) ₃ , or B (OR ⁴ ) ₂ . R ¹ and R ² each independently represent a chlorine atom, a bromine atom or an iodine atom, R ³ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ⁴ represents a hydrogen atom, and 1 to 4 carbon atoms. Represents an alkyl group or a phenyl group of B (OR ⁴ ) ₂ The two R ⁴ groups may be the same or different, and the two R ⁴ groups may include an oxygen atom and a boron atom to form a ring. it can.

  “Step 1” is a method for obtaining the cyclic azine derivative (1) of the present invention by reacting the compound (2) with the compound (3) in the presence of a palladium catalyst, optionally in the presence of a base. -By applying reaction conditions for general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the desired product can be obtained in good yield.

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

  A palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or a complex compound. The tertiary phosphine that can be used at this time is triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5. -Bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) Biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1 ′ -Bis (diphenylphosphino) Erocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (±) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl And 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl. Triphenylphosphine is preferable because it is easily available and the reaction yield is good. The molar ratio between the tertiary phosphine and the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 in terms of good reaction yield.

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

  The molar ratio of the compound (2) and the compound (3) used in “Step 1” is preferably 1: 2 to 5: 1, and more preferably 1: 2 to 2: 1 in terms of a good yield.

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

  “Step 1” can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably performed at 40 ° C. to 80 ° C. in terms of a good yield.

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

  In addition, the compound (2) used in the production of the cyclic azine derivative (1) of the present invention has the following reaction formula:

(In the formula, Ar ¹ represents an optionally substituted aromatic hydrocarbon group. Ar ³ represents an optionally substituted aromatic hydrocarbon group composed of 2 to 4 rings. Z represents a carbon atom or Y ¹ and Y ² each independently represent a chlorine atom, a bromine atom, or an iodine atom, and M represents ZnR ¹ , MgR ² , Sn (R ³ ) ₃ , B (OR ⁴ ) ₂ . Provided that R ¹ and R ² each independently represent a chlorine atom, a bromine atom or an iodine atom, R ³ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁴ represents a hydrogen atom or carbon number. 1 from an alkyl group or a phenyl group ^4, B (oR 4) 2 two R ⁴ ₂ may be the same or different. Furthermore, the two R ⁴ contain an oxygen atom and a boron atom together Can also form a ring.) Door can be.

  In “Step 2”, the compound (5) is reacted with the compound (4) in the presence of a base and in the presence of a palladium catalyst in some cases to produce the compound (2) used for the production of the cyclic azine derivative (1) of the present invention. The target product can be obtained in good yield by applying reaction conditions of general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc. it can. Examples of the palladium catalyst that can be used in "Step 2" include the same palladium salts or complex compounds exemplified in "Step 1". Among these, a palladium complex having a tertiary phosphine as a ligand is more preferable in terms of a good reaction yield, is easily available, and a palladium complex having triphenylphosphine as a ligand in terms of a good reaction yield. Particularly preferred.

  A palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or a complex compound. Examples of the tertiary phosphine that can be used at this time include the same tertiary phosphines as exemplified in “Step 1”. Triphenylphosphine is preferable because it is easily available and the reaction yield is good. The molar ratio between the tertiary phosphine and the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 in terms of good reaction yield.

  As the base that can be used in “Step 2”, the same bases as those exemplified in “Step 1” can be exemplified, and potassium carbonate is preferable in terms of a good yield. The molar ratio of base to compound (4) is preferably 1: 1 to 10: 1, and more preferably 2: 1 to 3: 1 in terms of good yield.

  The molar ratio of compound (5) to compound (4) used in “Step 2” is preferably 1: 2 to 5: 1, and more preferably 1: 2 to 2: 1 in terms of good yield.

  Examples of the solvent that can be used in “Step 2” include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene, diethyl ether, ethanol, methanol, and xylene, and these may be used in appropriate combination. It is desirable to use a mixed solvent of toluene and ethanol in terms of good yield.

  “Step 2” can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably performed at 40 ° C. to 80 ° C. in terms of a good yield.

  Compound (2) can be obtained by carrying out a normal treatment after completion of “Step 2”. If necessary, it may be purified by recrystallization, column chromatography, sublimation or the like, but it can also be subjected to “Step 1” without isolation.

Although there is no restriction | limiting in particular in the manufacturing method of the thin film for organic electroluminescent elements which consists of cyclic azine derivative | guide_body (1) of this invention, The film-forming by a vacuum evaporation method is possible. Film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The vacuum degree of the vacuum chamber when forming a film by the vacuum evaporation method is determined by taking into account the manufacturing tact time and manufacturing cost of manufacturing the organic electroluminescence device, and commonly used diffusion pumps, turbo molecular pumps, cryopumps, etc. 1 × 10 ⁻² to 1 × 10 ⁻⁵ Pa which can be reached by the above is desirable. The deposition rate is preferably 0.005 to 1.0 nm / second, depending on the thickness of the film to be formed. In addition, since the cyclic azine derivative (1) has high solubility in chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, tetrahydrofuran or the like, a spin coating method using a general-purpose apparatus, an inkjet method, Film formation by a casting method or a dip method is also possible.

  The thin film comprising the cyclic azine derivative (1) of the present invention has high surface smoothness, amorphousness, heat resistance, electron transport ability, hole blocking ability, redox resistance, water resistance, oxygen resistance, electron injection characteristics, and the like. Therefore, it is useful as a material for an organic electroluminescence device, and can be used as an electron transport material, a hole blocking material, a light emitting host material, and the like. Further, since it is a wide band gap compound, it can be applied not only to conventional fluorescent device applications but also to phosphorescent devices. Therefore, the thin film comprising the cyclic azine derivative (1) of the present invention is expected to be used as a constituent component of the organic electroluminescence device.

It is sectional drawing of the organic electroluminescent element produced by embodiment (element evaluation).

EXAMPLES Hereinafter, although an experimental example, a test example, and a reference example are given and this invention is demonstrated further in detail, this invention is not limited to these.
Experimental example-1

Under an argon stream, 9-phenanthreneboronic acid (1.91 g, 8.56 mmol), 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (4.00 g, 8. 56 mmol) and tetrakis (triphenylphosphine) palladium (98.9 mg, 0.086 mmol) were suspended in a mixed solvent of toluene (320 mL) and ethanol (40 mL), and the temperature was raised to 60 ° C. To this, 1M aqueous K ₂ CO ₃ solution (25.7 mL, 25.7 mmol) was slowly added dropwise, followed by stirring for 4 hours. After cooling to room temperature, 4- (2-pyridyl) phenylboronic acid (2.56 g, 12.8 mmol) and 1M K ₂ CO ₃ (25.7 mL, 25.7 mmol) were added, and the temperature was raised to 70 ° C. And stirred for 12 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2), and the desired product 4,6-diphenyl-2- [5- (9-phenanthryl) -4 ′-(2 A white solid (yield 3.91 g, yield 64%) of -pyridyl) biphenyl-3-yl] -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.31 (d, J = 7.00 Hz, 1H), 7.58-7.65 (m, 8H), 7.70 (t, J = 7.0 Hz, 1H), 7.76 (t, J = 7.0 Hz, 2H), 7.82-7.87 (m, 2H), 7.93 (s, 1H), 7.99 (d, J = 8.5 Hz, 2H), 8.02 (d , J = 8.2 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H), 8.12 (s, 1H), 8.23 (d, J = 8.4 Hz, 2H), 8 .78 (d, J = 8.2 Hz, 1H), 8.82 (d, J = 8.1 Hz, 4H), 8.89 (d, J = 8.2 Hz, 1H), 8.98 (s, 1H), 9.21 (s, 1H).
The obtained compound had a Tg of 133 ° C.
Experimental example-2

9- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) anthracene (0.98 g, 3.21 mmol), 2- (3,5-dibromophenyl) under argon flow ) -4,6-diphenyl-1,3,5-triazine (1.50 g, 3.21 mmol), tetrakis (triphenylphosphine) palladium (37.1 mg, 0.032 mmol) in toluene (100 mL) and ethanol (20 mL) ) And the mixture was heated to 60 ° C. A 1M aqueous K ₂ CO ₃ solution (9.63 mL, 9.63 mmol) was slowly added dropwise thereto, followed by stirring for 3 hours. After cooling to room temperature, 4- (2-pyridyl) phenylboronic acid (0.96 g, 4.82 mmol) and 1M K ₂ CO ₃ (6.42 mL, 6.42 mmol) were added, and the temperature was raised to 60 ° C. And stirred for 17 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The resulting crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2) to obtain the desired 2- [5- (9-anthryl) -4 ′-(2-pyridyl) biphenyl-3. -Il] -4,6-diphenyl-1,3,5-triazine was obtained as a white solid (yield 0.68 g, yield 33%).

_{^{1 H-NMR (CDCl 3)}} : δ. 7.34 (brs, 1H), 7.44 (t, J = 7.6 Hz, 2H), 7.53-7.64 (m, 9H), 7.85-7.88 (m, 4H), 8.01 (d, J = 7.6 Hz, 2H), 8.03 (s, 1H), 8.16 (d, J = 8.5 Hz, 2H) 8.23 (d, J = 8.3 Hz, 2H), 8.64 (s, 1H), 8.79 (d, J = 5.6 Hz, 4H), 8.89 (s, 1H), 9.31 (s, 1H).
Experimental Example-3

Under an argon stream, 1-naphthaleneboronic acid (0.37 g, 2.14 mmol), 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (1.00 g, 2. 14 mmol), tetrakis (triphenylphosphine) palladium (24.7 mg, 0.021 mmol) was suspended in a mixed solvent of toluene (80 mL) and ethanol (10 mL), and the temperature was raised to 60 ° C. A 1M aqueous K ₂ CO ₃ solution (8.56 mL, 8.56 mmol) was slowly added dropwise thereto, followed by stirring for 3 hours. After cooling to room temperature, 4- (2-pyridyl) phenylboronic acid (0.64 g, 3.21 mmol) was added, and then the mixture was heated to 70 ° C. and stirred for 3 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2) to obtain the desired 4,6-diphenyl-2- [5- (1-naphthyl) -4 ′-(2 A white solid (yield 0.61 g, yield 49%) of -pyridyl) biphenyl-3-yl] -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.32 (t, J = 6.5 Hz, 1H), 7.53 (t, J = 6.9 Hz, 1H), 7.57-7.68 (m, 10H), 7.83-7.87 (M, 2H), 7.98 (d, J = 8.4 Hz, 2H), 8.00-8.05 (m, 2H), 8.07 (s, 1H), 8.23 (d, J = 6.7 Hz, 2H), 7.79 (d, J = 6.5 Hz, 1H), 8.82 (d, J = 8.5 Hz, 4H), 8.93 (s, 1H), 9.18. (S, 1H).
The Tg of the obtained compound was 107 ° C.
Experimental Example-4

Under an argon stream, 1-pyreneboronic acid (0.53 g, 2.14 mmol), 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (1.00 g, 2.14 mmol) ), Tetrakis (triphenylphosphine) palladium (24.7 mg, 0.0214 mmol) was suspended in a mixed solvent of toluene (80 mL) and ethanol (10 mL), and the temperature was raised to 60 ° C. A 1M aqueous K ₂ CO ₃ solution (8.56 mL, 8.56 mmol) was slowly added dropwise thereto, followed by stirring for 3 hours. After cooling to room temperature, 4- (2-pyridyl) phenylboronic acid (0.64 g, 3.21 mmol) was added, and then the mixture was heated to 70 ° C. and stirred for 3 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2) to obtain the desired 4,6-diphenyl-2- [5- (1-pyrenyl) -4 ′-(2 A white solid (yield 0.37 g, yield 26%) of -pyridyl) biphenyl-3-yl] -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.35 (brs, 1H), 7.57-7.65 (m, 6H), 7.86-7.91 (m, 2H), 8.03 (d, J = 8.4 Hz, 2H), 8.08 (t, J = 7.6 Hz, 1H), 8.13 (d, J = 9.3 Hz, 1H), 8.18-8.29 (m, 8H), 8.33 (d, J = 9.3 Hz, 1 H), 8.37 (d, J = 7.8 Hz, 1 H), 8.80 (d, J = 4.8 Hz, 1 H), 8.83 (d, J = 7.9 Hz, 4H), 9.07 (s, 1H), 9.23 (s, 1H).
Experimental example-5

9-phenanthreneboronic acid (0.54 g, 2.42 mmol), 4,6-bis (biphenyl-3-yl) -2- (3,5-dibromophenyl) -1,3,5-triazine under argon flow (1.50 g, 2.42 mmol) and tetrakis (triphenylphosphine) palladium (56.0 mg, 0.048 mmol) were suspended in a mixed solvent of toluene (150 mL) and ethanol (20 mL), and the temperature was raised to 60 ° C. A 1M aqueous K ₂ CO ₃ solution (7.26 mL, 7.26 mmol) was slowly added dropwise thereto, followed by stirring for 3 hours. After cooling to room temperature, 4- (2-pyridyl) phenylboronic acid (0.72 g, 3.63 mmol) and 1M K ₂ CO ₃ (7.26 mL, 7.26 mmol) were added, and the temperature was raised to 60 ° C. And stirred for 4 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2) to obtain the desired 4,6-bis (biphenyl-3-yl) -2- [5- (9-phenanthryl). ) -4 ′-(2-pyridyl) biphenyl-3-yl] -1,3,5-triazine was obtained as a white solid (yield 1.1 g, yield 58%).

_{^{1 H-NMR (CDCl 3)}} : δ. 7.34 (brs, 1H), 7.43 (t, J = 7.4 Hz, 2H), 7.52 (t, J = 7.4 Hz, 4H), 7.66 (t, J = 8.1 Hz) , 1H), 7.68 (t, J = 7.7 Hz, 2H), 7.70 (t, J = 7.7 Hz, 1H), 7.74-7.78 (m, 2H), 7.76. (D, J = 8.4 Hz, 4H), 7.87 (d, J = 7.6 Hz, 4H), 7.94 (s, 1H), 8.00 (d, J = 8.4 Hz, 2H) , 8.01 (d, J = 7.7 Hz, 1H), 8.12 (t, J = 7.4 Hz, 1H), 8.14 (s, 1H), 8.23 (d, J = 8. 3 Hz, 2H), 8.80 (d, J = 7.8 Hz, 1H), 8.80 (d, J = 7.8 Hz, 2H), 8.82 (d, J = 8.3 Hz, 1H), 8.88 (d, J = 8.3 Hz, 1 ), 9.01 (s, 1H), 9.05 (s, 2H), 9.21 (s, 1H).
The Tg of the obtained compound was 119 ° C.
Experimental example-6

Under an argon stream, 9-phenanthreneboronic acid (0.71 g, 3.21 mmol), 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (1.50 g, 3.21). 21 mmol) and tetrakis (triphenylphosphine) palladium (37.0 mg, 0.0321 mmol) were suspended in a mixed solvent of toluene (120 mL) and ethanol (15 mL), and the temperature was raised to 60 ° C. A 1 M aqueous solution of K ₂ CO ₃ (9.63 mL, 9.63 mmol) was slowly added dropwise thereto, followed by stirring for 6 hours. After cooling to room temperature, 3-pyridineboronic acid (0.59 g, 4.82 mmol) and 1M K ₂ CO ₃ (9.63 mL, 9.63 mmol) were added, and then the mixture was warmed to 60 ° C. and stirred for 18 hours. . The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2), and 4,6-diphenyl-2- [5- (9-phenanthryl) -3- (3- A white solid (yield 0.87 g, yield 48%) of pyridyl) phenyl] -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.59-7.67 (m, 8H), 7.72 (t, J = 7.0 Hz, 1H), 7.76-7.80 (m, 2H), 7.90 (s, 1H), 7.90 (brt, J = 6.5 Hz, 1H), 7.96 (d, J = 8.1 Hz, 1H), 8.02 (d, J = 7.1 Hz, 1H), 8.05 (s , 1H), 8.60 (d, J = 8.0 Hz, 1H), 8.80 (d, J = 7.0 Hz, 4H), 8.83 (d, J = 8.4 Hz, 1H), 8 .89 (d, J = 8.3 Hz, 1H), 9.13 (d, J = 5.4 Hz, 1H), 9.14 (s, 1H), 9.22 (s, 1H).
Experimental example-7

Under an argon stream, 9-phenanthreneboronic acid (0.71 g, 3.21 mmol), 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (1.50 g, 3.21). 21 mmol) and tetrakis (triphenylphosphine) palladium (37.0 mg, 0.0321 mmol) were suspended in a mixed solvent of toluene (120 mL) and ethanol (15 mL), and the temperature was raised to 60 ° C. A 1 M aqueous solution of K ₂ CO ₃ (9.63 mL, 9.63 mmol) was slowly added dropwise thereto, followed by stirring for 8 hours. After cooling to room temperature, 3- (3-pyridyl) phenylboronic acid (0.59 g, 4.82 mmol) and 1M K ₂ CO ₃ (9.63 mL, 9.63 mmol) were added, and the temperature was raised to 60 ° C. And stirred for 18 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2), and 4,6-diphenyl-2- [5- (9-phenanthryl) -3 ′-(3 A white solid (yield 0.86 g, yield 42%) of -pyridyl) biphenyl-3-yl] -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.57-7.66 (m, 7H), 7.69-7.72 (m, 2H), 7.44-7.81 (m, 3H), 7.81 (dd, J = 8.0) , 5.4 Hz, 1H), 7.92 (s, 1H), 8.02 (t, J = 7.80 Hz, 4H), 8.07 (s, 1H), 8.46 (d, J = 8 .1 Hz, 1H), 8.72 (d, J = 5.3 Hz, 1H), 8.81 (d, J = 7.0 Hz, 4H), 8.82 (d, J = 8.2 Hz, 1H) , 8.88 (d, J = 8.2 Hz, 1H), 9.02 (s, 1H), 9.06 (s, 1H), 9.14 (s, 1H).
The Tg of the obtained compound was 112 ° C.
Experimental Example-8

Under an argon stream, 9-phenanthreneboronic acid (0.43 g, 1.93 mmol), 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (0.90 g, 1. 93 mmol) and tetrakis (triphenylphosphine) palladium (22.3 mg, 0.0193 mmol) were suspended in a mixed solvent of toluene (75 mL) and ethanol (10 mL), and the temperature was raised to 60 ° C. A 1M aqueous K ₂ CO ₃ solution (5.78 mL, 5.78 mmol) was slowly added dropwise thereto, followed by stirring for 7 hours. After cooling to room temperature, 3- (6-phenyl) pyridine boronic acid (0.57 g, 2.89 mmol) and 1M of _{K 2 CO 3 (5.78mL, 5.78mmol} ) was heated to 70 ° C. after the addition of And stirred for 14 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2), and 4,6-diphenyl-2- [5- (9-phenanthryl) -1- (6- A white solid (yield 0.73 g, yield 59%) of the synthesis of phenylpyridin-3-yl) phenyl-3-yl] -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.50 (t, J = 6.8 Hz, 1H), 7.55-7.66 (m, 9H), 7.71 (t, J = 6.8 Hz, 1H), 7.77 (t, J = 7.0 Hz, 2H), 7.93 (s, 1H), 7.95 (d, J = 8.2 Hz, 1H), 8.02 (d, J = 7.8 Hz, 1H), 8.05 (D, J = 8.3 Hz, 1H), 8.10 (s, 1H), 8.14 (d, J = 7.2 Hz, 2H), 8.24 (d, J = 7.0 Hz, 1H) , 8.82 (d, J = 6.9 Hz, 4H), 8.85 (d, J = 8.2 Hz, 1H), 8.89 (d, J = 8.2 Hz, 1H), 9.03 ( s, 1H), 9.22 (s, 1H), 9.26 (s, 1H).
Tg of the obtained compound was 127 degreeC.
Experimental example-9

Under an argon stream, 9-phenanthreneboronic acid (0.714 g, 3.22 mmol), 2- (3,5-dibromophenyl) -4,6-diphenylpyrimidine (1.50 g, 3.22 mmol), tetrakis (triphenyl) Phosphine) palladium (37.2 mg, 0.0322 mmol) was suspended in a mixed solvent of toluene (120 mL) and ethanol (15 mL), and the temperature was raised to 50 ° C. A 1 M aqueous solution of K ₂ CO ₃ (9.66 mL, 9.66 mmol) was slowly added dropwise thereto, followed by stirring for 18 hours. After cooling to room temperature, 4- (2-pyridyl) heated phenylboronic acid (0.961 g, 4.83 mmol) and 1M of aqueous _K 2 CO ₃ (9.66mL, 9.66mmol) in 60 ° C. after the addition of And stirred for 4 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2), and the desired product 4,6-diphenyl-2- [5- (9-phenanthryl) -4 ′-(2 A white solid (-pyridyl) biphenyl-3-yl] -pyrimidine (yield 1.28 g, 62% yield) was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.25 (t, J = 4.9 Hz, 1H), 7.53-7.58 (m, 6H), 7.60 (d, J = 7.5 Hz, 1H), 7.66 (t, J = 7.0 Hz, 1H), 7.12 (t, J = 8.2 Hz, 2H), 7.62-7.83 (m, 2H), 7.90 (s, 1H), 7.95-8. 0.00 (m, 4H), 8.07 (d, J = 8.1 Hz, 1H), 8.09 (s, 1H), 8.17 (d, J = 8.5 Hz, 1H), 8.30 −8.32 (m, 4H), 8.73 (d, J = 5.0 Hz, 1H), 8.79 (d, J = 8.3 Hz, 1H), 8.84 (d, J = 8. 2Hz, 1H), 8.90 (s, 1H), 9.14 (s, 1H).
Experimental example-10

Under an argon stream, 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (8.00 g, 17.1 mmol), 9-phenanthreneboronic acid (3.80 g, 17. 1 mmol) and tetrakis (triphenylphosphine) palladium (198 mg, 0.171 mmol) were suspended in a mixed solvent of toluene (600 mL) and ethanol (80 mL), and the temperature was raised to 50 ° C. A 1 M aqueous solution of K ₂ CO ₃ (51.4 mL, 51.4 mmol) was slowly added dropwise thereto, followed by stirring for 15 hours. After cooling the reaction mixture to room temperature, low-boiling components were distilled off under reduced pressure, and inorganic substances were removed by column chromatography (developing solvent hexane: chloroform = 1: 1), whereby 4,6-diphenyl-2- [5 A mixture (9.59 g) containing-(9-phenanthryl) -3-bromophenyl] -1,3,5-triazine was obtained. Under a stream of argon, the resulting mixture containing 4,6-diphenyl-2- [5- (9-phenanthryl) -3-bromophenyl] -1,3,5-triazine (2.00 g), bispinacolatodi Boron (1.35 g, 5.31 mmol), potassium acetate (1.04 g, 10.6 mmol) and dichlorobistriphenylphosphine palladium (128 mg, 0.142 mmol) were suspended in tetrahydrofuran (70 mL) and stirred at 70 ° C. for 5 hours. did. After cooling the reaction mixture to room temperature, low-boiling components were distilled off under reduced pressure, and inorganic substances were removed by column chromatography (developing solvent hexane: chloroform = 1: 1), whereby 4,6-diphenyl-2- [5 -(9-phenanthryl) -3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -1,3,5-triazine-containing mixture (1.50 g ) The resulting 4,6-diphenyl-2- [5- (9-phenanthryl) -3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) was obtained under an argon stream. Phenyl] -1,3,5-triazine-containing mixture (0.50 g), 6-bromo-2,2′bipyridine (288 mg, 1.22 mmol), tetrakis (triphenylphosphine) palladium (47.3 mg,. 0409 mmol) was suspended in toluene (25 mL). 2M Na ₂ CO ₃ aqueous solution (10 mL, 20 mmol) was added thereto, and the mixture was stirred at 90 ° C. for 15 hours. After cooling the reaction mixture to room temperature, the organic layer was distilled off under reduced pressure to obtain a crude product. This was purified by column chromatography (developing solvent hexane: chloroform = 1: 2), and the desired 2- [3- (2,2′-bipyridin-6-yl) -5- (9-phenanthryl) phenyl]- 4,6-diphenyl-1,3,5-triazine (0.46 g) was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.38 (brs, 1H), 7.59-7.66 (m, 7H), 7.73 (t, J = 7.7 Hz, 1H), 7.75-7.78 (m, 2H), 7.89 (brs, 1H), 7.96 (s, 1H), 8.02-8.11 (m, 5H), 8.55 (brs, 1H), 8.66 (s, 1H), 8 .76 (brd, J = 7.9 Hz, 2H), 8.84 (d, J = 7.7 Hz, 2H), 8.85 (d, J = 7.8 Hz, 4H), 8.90 (d, J = 8.4 Hz, 1H), 9.04 (s, 1H), 9.71 (s, 1H).
The Tg of the obtained compound was 122 ° C.
Experimental example-11

Under an argon stream, 9-phenanthreneboronic acid (143 mg, 0.644 mmol), 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (300 mg, 0.644 mmol), tetrakis (Triphenylphosphine) palladium (7.44 mg, 0.00644 mmol) was suspended in a mixed solvent of toluene (24 mL) and ethanol (3 mL), and the temperature was raised to 60 ° C. A 1M aqueous K ₂ CO ₃ solution (1.93 mL, 1.93 mmol) was slowly added dropwise thereto, followed by stirring for 3 hours. After cooling to room temperature, 2- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] pyrimidine (0.961 g, 4.83 mmol) and 1M K ₂ CO ₃ aqueous solution (9.66 mL, 9.66 mmol) was added, and then the mixture was heated to 70 ° C. and stirred for 19 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2), and the desired product 4,6-diphenyl-2- [5- (9-phenanthryl) -4 ′-(2 A white solid (yield 214 mg, yield 52%) of -pyrimidyl) biphenyl-3-yl] -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.22 (t, J = 4.8 Hz, 1H), 7.54-7.63 (m, 7H), 7.67 (t, J = 7.4 Hz, 1H) ), 7.73 (t, J = 7.6 Hz, 2H), 7.90 (s, 1H), 7.96-7.99 (m, 3H), 8.03 (d, J = 8.4 Hz) , 1H), 8.10 (s, 1H), 8.62 (d, J = 8.7 Hz, 2H), 8.79 (d, J = 8.3 Hz, 2H), 8.79 (d, J = 8.0 Hz, 2H), 8.79-8.80 (m, 1H), 8.85 (d, J = 4.9 Hz, 2H), 8.84-8.86 (m, 1H) 95 (s, 1H), 9.19 (s, 1H).
Experimental example-12

Under an argon stream, 2-phenanthreneboronic acid (77.6 mg, 0.167 mmol), 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (37 mg, 0.167 mmol) Tetrakis (triphenylphosphine) palladium (5.78 mg, 0.0050 mmol) was suspended in a mixed solvent of toluene (7 mL) and ethanol (0.8 mL), and the temperature was raised to 50 ° C. A 1 M aqueous K ₂ CO ₃ solution (0.50 mL, 0.50 mmol) was slowly added dropwise thereto, followed by stirring for 2 hours. After cooling to room temperature, 4- (2-pyridyl) phenylboronic acid (49.8 mg, 0.25 mmol) and 1M K ₂ CO ₃ (0.50 mL, 0.50 mmol) were added, and the temperature was raised to 60 ° C. And stirred for 17 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The resulting crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2) to obtain the desired 4,6-diphenyl-2- [5- (2-phenanthryl) -4 ′-(2 A white solid (yield 30 mg, yield 28%) of -pyridyl) biphenyl-3-yl] -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.26-7.30 (m, 1H), 7.52-7.66 (m, 7H), 7.69-7.72 (m, 1H), 7.77-7.85 (m, 3H) ), 7.89 (d, J = 8.9 Hz, 1H), 7.95 (t, J = 7.1 Hz, 1H), 7.96 (d, J = 8.5 Hz, 2H), 8.11 (D, J = 8.5 Hz, 2H), 8.20 (d, J = 8.6 Hz, 2H), 8.24 (s, 1H), 8.29 (s, 1H), 8.74-8 .76 (m, 2H), 8.81 (d, J = Hz, 2H), 8.82 (d, J = Hz, 2H), 8.84 (d, J = 8.8 Hz, 1H), 9 .06 (s, 1H), 9.12 (s, 1H).
Experimental Example-13

9-phenanthreneboronic acid (5.00 g, 10.7 mmol), 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (2.38 g, 10. 7 mmol) and tetrakis (triphenylphosphine) palladium (124 mg, 0.107 mmol) were suspended in a mixed solvent of toluene (400 mL) and ethanol (50 mL), and the temperature was raised to 50 ° C. A 1M aqueous K ₂ CO ₃ solution (32.1 mL, 32.1 mmol) was slowly added dropwise thereto, followed by stirring for 3 hours. After cooling to room temperature, 3- (2-pyridyl) phenylboronic acid (3.19 g, 10.7 mmol) and 1 M aqueous K ₂ CO ₃ solution (32.1 mL, 32.1 mmol) were added, and then the temperature was raised to 60 ° C. And stirred for 15 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2) to obtain 4,6-diphenyl-2- [5- (9-phenanthryl) -3 ′-(2 A white solid (yield 2.50 g, 37% yield) of -pyridyl) biphenyl-3-yl] -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.53-7.62 (m, 8H), 7.67 (t, J = 7.7 Hz, 2H), 7.23 (t, J = 8.2 Hz, 1H), 7.78 (t, J = 7.9 Hz, 1H), 7.84 (d, J = 7.9 Hz, 1H), 7.90 (s, 1H), 7.90 (d, J = 8.4 Hz, 1H), 7.98 (D, J = 7.8 Hz, 1H), 8.03 (d, J = 8.2 Hz, 1H), 8.06 (d, J = 7.8 Hz, 1H), 8.11 (s, 1H) , 8.42 (s, 1H), 8.72 (d, J = 4.9 Hz, 1H), 8.79 (d, J = 8.3 Hz, 2H), 8.79 (d, J = 8. 2 Hz, 2H), 8.79 (m, 2H), 8.85 (d, J = 8.2 Hz, 1H), 8.95 (s, 1H), 9.17 (s, 1H).
The resulting compound had a Tg of 115 ° C.
Experimental example-14

Under an argon stream, 9,9-dimethyl-2-fluoreneboronic acid (0.95 g, 4 mmol), 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (1. 87 g, 4 mmol) and tetrakis (triphenylphosphine) palladium (46.2 mg, 0.04 mmol) were suspended in a mixed solvent of toluene (150 mL) and ethanol (20 mL), and the temperature was raised to 50 ° C. A 1 M aqueous K ₂ CO ₃ solution (12 mL, 12 mmol) was slowly added dropwise thereto, followed by stirring for 18 hours. After cooling to room temperature, 4- (2-pyridyl) was stirred phenylboronic acid (1.19 g, 6 mmol) and 1M of _K 2 _CO 3 (12 mL, 12 mmol) was heated to 60 ° C. After adding 2 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2), and the desired product 2- [5- (9,9-dimethylfluoren-2-yl) -4 ′-( A white solid (yield 1.61 g, yield 61.5%) of 2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ. 1.63 (s, 6H), 7.31 (dd, J = 7.0, 4.8, 1H), 7.38-7.44 (m, 2H), 7.52 (d, J = 6) .5, H), 7.60-7.68 (m, 6H), 7.81-7.88 (m, 5H), 7.93 (d, J = 7.8, 1H), 7.98. (D, J = 8.5, 2H), 8.17 (s, H), 8.23 (d, J = 8.5, 2H), 8.78 (d, J = 4.8, 1H) , 8.85 (d, J = 8.1, 4H), 9.07 (s, 2H).
The Tg of the obtained compound was 118 ° C.
Experimental example-15

Under an argon stream, 9,9-dimethyl-2-fluoreneboronic acid (0.71 g, 3 mmol), 2- (3,5-dibromophenyl) -4,6-diphenylpyrimidine (1.4 g, 3 mmol), tetrakis ( Triphenylphosphine) palladium (34.7 mg, 0.03 mmol) was suspended in a mixed solvent of toluene (115 mL) and ethanol (15 mL), and the temperature was raised to 50 ° C. A 1M aqueous K ₂ CO ₃ solution (9 mL, 9 mmol) was slowly added dropwise thereto, followed by stirring for 18 hours. After cooling to room temperature, 4- (2-pyridyl) phenylboronic acid (0.896 g, 4.5 mmol) and 1M K ₂ CO ₃ (9 mL, 9 mmol) were added, and the temperature was raised to 60 ° C. to 3.5 Stir for hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2), and the desired product 2- [5- (9,9-dimethylfluoren-2-yl) -4 ′-( A white solid (2-pyridyl) biphenyl-3-yl] -4,6-diphenylpyrimidine (yield 0.85 g, yield 43.3%) was obtained.

¹ H-NMR (CDCl ₃ ): δ. 1.63 (s, 6H), 7.30 (d, J = 5.7 Hz, 1H), 7.34-7.42 (m, 2H), 7.52 (d, J = 6.6 Hz, 1H) ), 7.59-7.64 (m, 6H), 7.82-7.92 (m, 6H), 7.98 (d, J = 8.4 Hz, 2H), 8.10 (d, J = 6.8 Hz, 2H), 8.21 (d, J = 8.4 Hz, 2H), 8.37 (d, J = 6.3 Hz, 4H), 8.78 (d, J = 4.8 Hz, 1H), 9.04 (s, 2H).
Experimental example-16

Under an argon stream, 9,9-dimethyl-2-benzo [c] fluoreneboronic acid (185 mg, 0.644 mmol), 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5- Triazine (300 mg, 0.644 mmol) and tetrakis (triphenylphosphine) palladium (7.44 mg, 0.00644 mmol) were suspended in a mixed solvent of toluene (24 mL) and ethanol (3 mL), and the temperature was raised to 50 ° C. A 1M aqueous K ₂ CO ₃ solution (1.93 mL, 1.93 mmol) was slowly added dropwise thereto, and the mixture was stirred for 3 hours, heated to 80 ° C., and further stirred for 3 hours. After cooling to room temperature, 4- (2-pyridyl) phenylboronic acid (256 mg, 1.29 mmol) and 1M K ₂ CO ₃ (2.90 mL, 2.90 mmol) were added, and the temperature was raised to 80 ° C. Stir for hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2) to obtain the desired 2- [5- (9,9-dimethylbenzo [c] fluoren-2-yl)- A white solid (yield 172 mg, yield 38.0%) of 4 ′-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ. 1.63 (s, 6H), 7.25-7.29 (m, 1H), 7.42 (t, J = 7.4 Hz, 1H), 7.49-7.64 (m, 9H), 7.69-7.73 (m, 1H), 7.74 (s, 1H), 7.79 (t, J = 8.1 Hz, 1H), 7.83 (d, J = 7.7 Hz, 1H) ), 7.97 (d, J = 8.7 Hz, 2H), 8.08 (s, 1H), 8.11 (d, J = 7.8 Hz, 1H), 8.20 (d, J = 8) .6 Hz, 2H), 8.43 (d, J = 7.8 Hz, 1H), 8.75 (d, J = 4.9 Hz, 1H), 8.79 (d, J = 8.3 Hz, 2H) , 8.80 (d, J = 8.1 Hz, 2H), 8.91 (d, J = 8.5 Hz, 1H), 8.94 (s, 1H), 9.18 (s, 1H).
Experimental Example-17

Under an argon stream, 9-phenanthreneboronic acid (0.538 g, 2.42 mmol), 2- (3,5-dibromophenyl) -4,6-di-p-tolyl-1,3,5-triazine (1. 20 g, 2.42 mmol) and tetrakis (triphenylphosphine) palladium (28.0 mg, 0.0242 mmol) were suspended in a mixed solvent of toluene (90 mL) and ethanol (10 mL), and the temperature was raised to 50 ° C. A 1M aqueous K ₂ CO ₃ solution (7.26 mL, 7.26 mmol) was slowly added dropwise thereto, followed by stirring for 3 hours. After cooling to room temperature, 4- (2-pyridyl) phenylboronic acid (0.722 g, 3.63 mmol) and 1M aqueous K2CO3 solution (7.26 mL, 7.26 mmol) were added, and then the temperature was raised to 60 ° C. and 15 Stir for hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The resulting crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 1: 2) to obtain the desired 4,6-di-p-tolyl-2- [5- (9-phenanthryl) -4. A white solid (yield 0.680 g, yield 42%) of '-(2-pyridyl) biphenyl-3-yl] -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ. 2.47 (s, 6H), 7.25-7.28 (m, 1H), 7.35 (d, J = 8.0 Hz, 4H), 7.60 (t, J = 7.7 Hz, 1H) ), 7.67 (t, J = 7.4 Hz, 1H), 7.73 (t, J = 7.4 Hz, 1H), 7.73 (t, J = 7.4 Hz, 1H), 7.79. (T, J = 7.8 Hz, 1H), 7.83 (d, J = 7.8 Hz, 1H), 7.90 (s, 1H), 7.95 (d, J = 8.4 Hz, 2H) 7.98 (d, J = 8.0 Hz, 1H), 8.04 (d, J = 7.9 Hz, 1H), 8.07 (s, 1H), 8.18 (d, J = 8. 5 Hz, 2H), 8.66 (d, J = 8.1 Hz, 4H), 8.74 (d, J = 5.0 Hz, 1H), 8.79 (d, J = 8.4 Hz, 1H), 8.85 (d, J = 8.0 Hz, 1H) 8.92 (s, 1H), 9.16 (s, 1H).
Reference Example-1

  Under an argon stream, 9-phenanthreneboronic acid (0.71 g, 3.21 mmol), 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (1.50 g, 3.21). 21 mmol) and tetrakis (triphenylphosphine) palladium (37.0 mg, 0.0321 mmol) were suspended in a mixed solvent of toluene (120 mL) and ethanol (15 mL), heated to 60 ° C. and stirred for 12 hours. The reaction mixture was cooled to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained crude product was purified by silica gel chromatography (developing solvent hexane: chloroform = 2: 1) to obtain the desired 4,6-diphenyl-2- [5- (9-phenanthryl) -3-bromophenyl]. A white solid of -1,3,5-triazine (yield 0.54 g, yield 30%) was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.57-7.76 (m, 10H), 7.82 (s, 1H), 7.93-7.89 (m, 3H), 8.78 (d, J = 8.0 Hz, 4H), 8.80 (d, J = 8.2 Hz, 1H), 8.85 (d, J = 8.2 Hz, 1H), 8.90 (s, 1H), 9.02 (s, 1H).
Comparative Example-1
2- [4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl-5′-yl] -4,6-di-p-tolyl-1,3 , 5-Triazine Tg Measurement

2- [4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl-5′-yl] -4, which is a compound described in Patent Document 1. As a result of thermal analysis of 6-di-p-tolyl-1,3,5-triazine, Tg was 108 ° C.
Test Example-1
Preparation of an organic electroluminescent device comprising 4,6-diphenyl-2- [5- (9-phenanthryl) -4 ′-(2-pyridyl) biphenyl-3-yl] -1,3,5-triazine as a constituent component And Performance Evaluation A glass substrate with an ITO transparent electrode in which an indium tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used as the substrate. The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm ² as shown in FIG.
First, the glass substrate was introduced into a vacuum evaporation tank and the pressure was reduced to 1.0 × 10 ⁻⁴ Pa. Thereafter, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4 and an electron transport layer 5 are sequentially formed as an organic compound layer on the glass substrate indicated by 1 in FIG. Filmed. As the hole injection layer 2, sublimation-purified phthalocyanine copper (II) was vacuum-deposited with a film thickness of 25 nm. As the hole transport layer 3, N, N′-bis (1-naphthyl) -N, N′-diphenyl-4,4′-biphenyl (NPD) was vacuum-deposited with a film thickness of 45 nm. As the light emitting layer 4, 4,4′-bis (2,2′-diphenylvinyl) -1,1′-diphenyl (DPVBi) and 4,4′-bis {2- [4- (N, N-diphenyl) are used. Amino) phenyl] vinyl} biphenyl (DPAVBi) was vacuum deposited with a thickness of 40 nm at a ratio of 99: 1 wt%. As the electron transport layer 5, 4,6-diphenyl-2- [5- (9-phenanthryl) -4 ′-(2-pyridyl) biphenyl-3-yl] -1,3, obtained in Experimental Example 1 was used. 5-Triazine was vacuum deposited with a thickness of 20 nm. Each organic material was formed into a film by a resistance heating method, and the heated compound was vacuum-deposited at a film formation rate of 0.3 to 0.5 nm / second. Finally, a metal mask was disposed so as to be orthogonal to the ITO stripe, and the cathode layer 6 was formed. The cathode layer 6 was made into a two-layer structure by vacuum-depositing lithium fluoride and aluminum with thicknesses of 0.5 nm and 100 nm, respectively. Each film thickness was measured with a stylus type film thickness meter (DEKTAK). Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

A direct current was applied to the produced organic electroluminescent element, and the measured value of the produced element was evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As measured values of the device produced and produced, voltage (V) and current efficiency (cd / A) when a current density of 20 mA / cm ^{2 was} passed were measured. The measured values of the fabricated element were 5.3 V and 10.5 cd / A. The luminance half time of this element was 155 hours.
Test example-2
An organic electroluminescent element was produced in the same manner as in Test Example 1 except that the light emitting layer 4 of Test Example 1 was changed to Alq ₃ having a film thickness of 40 nm. The measured values of the fabricated device were a voltage of 5.2 V and a current efficiency of 2.5 cd / A when a current density of 20 mA / cm ² was passed. The luminance half time of this device was 2015 hours.
Test Example-3
An organic electroluminescent element was produced in the same manner as in Test Example-1, except that the electron transport layer 5 of Test Example 1 was changed to Alq ₃ having a thickness of 20 nm. The measured values of the fabricated element were a voltage of 6.9 V and a current efficiency of 6.1 cd / A when a current density of 20 mA / cm ² was passed. The luminance half time of this device was 53 hours.
Test Example-4
An organic electroluminescent device was produced in the same manner as in Test Example-2 except that the electron transport layer 5 of Test Example-2 was changed to Alq ₃ having a thickness of 20 nm. The measured values of the fabricated element were 5.4 V when the current density was 20 mA / cm ² and 4.3 cd / A. The luminance half time of this device was 1785 hours.
Test Example-5
The electron transport layer 5 of Test Example 1 was converted to 4,6-diphenyl-2- [5- (1-naphthyl) -4 ′-(2-pyridyl) biphenyl-3-yl] -1,3, having a thickness of 20 nm. An organic electroluminescent element was produced in the same manner as in Test Example 1 except that 5-triazine was used. The measured values of the fabricated element were 6.0 V when the current density was 20 mA / cm ² and the current efficiency was 11.1 cd / A. The luminance half time of this element was 113 hours.
Test Example-6
Except for changing the electron transport layer 5 of Test Example 1 to 2- [5- (9-phenanthryl) -3 ′-(3-pyridyl) biphenyl-3-yl] -1,3,5-triazine having a thickness of 20 nm. Produced an organic electroluminescent device in the same manner as in Test Example-1. Measurements of the manufactured device, the voltage upon applying a current density of 20 mA / cm ² is 6.1 V, the current efficiency was 11.5 cd / A. The luminance half time of this element was 117 hours.
Test Example-7
The electron transport layer 5 of Test Example 1 was converted to 2- [3- (2,2′-bipyridin-6-yl) -5- (9-phenanthryl) phenyl] -4,6-diphenyl-1, having a thickness of 20 nm. An organic electroluminescent element was produced in the same manner as in Test Example 1 except that 3,5-triazine was used. The measured values of the manufactured element were 5.3 V and current efficiency of 8.0 cd / A when a current density of 20 mA / cm ² was passed.
Test Example-8
The electron transport layer 5 of Test Example 1 was converted into a 20-nm-thick 4,6-diphenyl-2- [5- (9-phenanthryl) -3 ′-(2-pyridyl) biphenyl-3-yl] -1,3. An organic electroluminescent element was produced in the same manner as in Test Example 1 except that 5-triazine was used. The measured values of the fabricated element were 6.6 V when the current density was 20 mA / cm ² and 9.7 cd / A.
Test Example-9
In Test Example 1, the hole injection layer 2 was 10 nm phthalocyanine copper (II), and the hole transport layer 3 was 30 nm N, N′-bis (1-naphthyl) -N, N′-diphenyl-4,4 '-Biphenyl (NPD), the light-emitting layer 4 is formed with 30 nm of 4,4'-bis (9H-carbazol-9-yl) biphenyl (CBP) and tris (2-phenylpyridinate) iridium (III) (Ir (PPy ₃ ) is a layer with a ratio of 94: 6 wt%, and the electron transport layer 5 is 5 nm of bis (2-methyl-8-quinolinolate) -4- (phenylphenolate) aluminum (BAlq) and 45 nm of 2- [5 A layer in which-(9,9-dimethylfluoren-2-yl) -4 '-(2-pyridyl) biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine was sequentially formed was used. . Other than this, an organic electroluminescent element was prepared by the same method as in Test Example 1, and the optical characteristics were evaluated. The measured values of the fabricated element were a voltage of 7.7 V and a current efficiency of 29.2 cd / A when a current density of 20 mA / cm ² was passed.
Test Example-10
In Test Example -9, except that the electron transport layer 5 to 5nm bis (2-methyl-8-quinolinolato) -4- (phenylphenolate) aluminum (BAlq) and 45 nm Alq ₃ of the same manner as in Test Example -9 The organic electroluminescent device was prepared by the method described above, and the optical characteristics were evaluated. The measured values of the fabricated element were 9.0 V when the current density was 20 mA / cm ² , and the current efficiency was 26.7 cd / A.

  As described above, it has been found that, when the cyclic azine derivative of the present invention is used in an organic electroluminescence device, low voltage and high efficiency and a long life can be achieved.

  The present invention provides a cyclic azine derivative having a novel structure that enables low voltage driving and high heat resistance of an element by using it as an electron transport layer of an organic electroluminescent element, and further reduces the voltage using the compound. An organic electroluminescent device provided is provided.

1. 1. Glass substrate with ITO transparent electrode 2. hole injection layer Hole transport layer 4. Light emitting layer 5. Electron transport layer 6. Cathode layer

Claims (8)

General formula (1)

(Wherein, Ar ¹ is, .Ar ² representing the optionally substituted aromatic hydrocarbon group is a phenyl group, .Ar ³ representing a pyridyl group or a pyrimidyl group, a substituted 2-4 may be ring Z represents a carbon atom or a nitrogen atom, X represents a phenylene group or a pyridylene group, p represents an integer of 0 to 2. When p is 2, X represents X May be the same or different.). The cyclic azine derivative according to claim 1, wherein Ar ¹ is an optionally substituted phenyl group. Ar ³ is an optionally substituted naphthyl group, an optionally substituted anthryl group, an optionally substituted phenanthryl group, an optionally substituted pyrenyl group, an optionally substituted fluorenyl group or a substituted The cyclic azine derivative according to claim 1 or 2, which is a triphenylenyl group which may be present. General formula (2)

(In the formula, Ar ¹ represents an optionally substituted aromatic hydrocarbon group. Ar ³ represents an optionally substituted aromatic hydrocarbon group having 2 to 4 rings. Z represents a carbon atom. Or a nitrogen atom, Y ¹ represents a chlorine atom, a bromine atom, or an iodine atom), and the general formula (3)

(.X representing wherein, Ar ² is a phenyl group, a pyridyl group or pyrimidyl group, .p showing a phenylene group or pyridylene group, when .p is 2 represents an integer of 0 to 2, X is the same or M may represent ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B (OR ⁴ ) ₂ , provided that R ¹ and R ² are each independently a chlorine atom, bromine atom or Represents an iodine atom, R ³ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and B (OR ⁴ ) ₂ The two R ⁴ groups may be the same or different, and the two R ⁴ groups may include an oxygen atom and a boron atom to form a ring. Is the presence of a palladium catalyst in the presence of a base. Characterized in that in a coupling reaction, the general formula (1)

(In the formula, Ar ¹ represents an optionally substituted aromatic hydrocarbon group. Ar ² represents a phenyl group, a pyridyl group or a pyrimidyl group. Ar ³ represents an optionally substituted 2 to 4 ring. Z represents a carbon atom or a nitrogen atom, X represents a phenylene group or a pyridylene group, p represents an integer of 0 to 2. When p is 2, X represents X May be the same or different from each other.). General formula (2)

(In the formula, Ar ¹ represents an optionally substituted aromatic hydrocarbon group. Ar ³ represents an optionally substituted aromatic hydrocarbon group having 2 to 4 rings. Z represents a carbon atom. Or Y ¹ represents a chlorine atom, a bromine atom or an iodine atom), and a compound represented by the general formula (4):

(In the formula, Ar ³ represents an optionally substituted aromatic hydrocarbon group having 2 to 4 rings. M represents ZnR ¹ , MgR ² , Sn (R ³ ) ₃ or B (OR ⁴ ) _2. Wherein R ¹ and R ² each independently represent a chlorine atom, a bromine atom or an iodine atom, R ³ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ⁴ represents a hydrogen atom, Represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and two R ⁴ groups of B (OR ⁴ ) ₂ may be the same or different, and the two R ⁴ groups together are an oxygen atom and a boron atom. And a compound represented by the general formula (5):

(In the formula, Ar ¹ represents an optionally substituted aromatic hydrocarbon group. Z represents a carbon atom or a nitrogen atom. Y ¹ and Y ² are each independently a chlorine atom, a bromine atom or an iodine atom. 5. The method for producing a cyclic azine derivative according to claim 4, wherein the compound is represented by a coupling reaction in the presence of a palladium catalyst, optionally in the presence of a base. .   The method for producing a cyclic azine derivative according to claim 4 or 5, wherein the palladium catalyst is a palladium catalyst having a tertiary phosphine as a ligand.   The method for producing a cyclic azine derivative according to any one of claims 4 to 6, wherein the palladium catalyst is a palladium catalyst having triphenylphosphine as a ligand. General formula (1)

(In the formula, Ar ¹ represents an optionally substituted aromatic hydrocarbon group. Ar ² represents a phenyl group, a pyridyl group or a pyrimidyl group. Ar ³ represents an optionally substituted 2 to 4 ring. Z represents a carbon atom or a nitrogen atom, X represents a phenylene group or a pyridylene group, p represents an integer of 0 to 2. When p is 2, X represents X May be the same or different from each other.) An organic electroluminescent device comprising a cyclic azine derivative represented by

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