JP2023107430A - Adamantane compound, and element comprising the same - Google Patents

Abstract

To provide a novel adamantane compound and further provide an organic electroluminescent device having excellent heat resistance, and excellent longevity or luminous efficiency.SOLUTION: The present invention provides an adamantane compound represented by the general formula (1), where Ar1 is a C6-24 aromatic hydrocarbon group; Ar2 is a single bond or a C6-24 aromatic hydrocarbon group; Ar3 is a C6-24 aromatic hydrocarbon group; Ad is a 1-adamantyl group or 2-adamantyl group; a, b and d each represent 1 or 2, and c is 0 or 1, where a+b+c=3; Z1, Z2 and Z3 independently represent a nitrogen atom or C-H.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a novel adamantyl group-containing cyclic azine compound and an organic electroluminescence device containing the same.

Conventional organic electroluminescent devices have a higher driving voltage than inorganic light emitting diodes, have lower luminance and luminous efficiency, and have a significantly shorter device life, and have not been put to practical use. Although recent organic electroluminescence devices have been gradually improved, materials with even better luminous efficiency characteristics, driving voltage characteristics, and long life characteristics are in demand. Furthermore, high heat resistance may be required depending on the application such as in-vehicle use, and the material is required to have a high glass transition temperature (Tg).

Adamantane compounds disclosed in Patent Document 1 and triazine compounds disclosed in Patent Document 2 are examples of electron transport materials with excellent long life for organic electroluminescent devices. Further, Patent Documents 3 to 7 disclose compounds having an adamantyl group for organic electroluminescence devices. However, further improvements have been desired in terms of the heat resistance of the material and the voltage, lifetime and luminous efficiency of the organic electroluminescence device using the material.

JP 2015-34159 A Japanese Patent Application Laid-Open No. 2007-314503 Chinese Patent Application Publication No. 112661709 Korean Patent Publication No. 10-2021-0062458 Chinese Patent Application Publication No. 111662241 Chinese Patent Application Publication No. 111646951 Chinese Patent Application Publication No. 111961038

One aspect of the present invention is to provide a new adamantane compound, and another aspect is directed to providing an organic electroluminescence device that is excellent in heat resistance, long life or luminous efficiency.

式中、
Ａｒ^１は、炭素数６～２４の芳香族炭化水素基を表す；
Ａｒ^２は、単結合または炭素数６～２４の芳香族炭化水素基を表す；
Ａｒ^３は、炭素数６～２４の芳香族炭化水素基を表す；
Ａｒ^１、芳香族炭化水素基である場合のＡｒ^２、およびＡｒ^３は、それぞれ、単数若しくは複数のフェニル基、ナフチル基、フェナントリル基、アントリル基、トリフェニレニル基、テルフェニル基、メチル基、ｔｅｒｔ－ブチル基、フルオロ基、および重水素の群から選択される１つ以上の置換基で置換されており、または無置換である；
Ａｄは、１－アダマンチル基または２－アダマンチル基を表す；
ａは、１または２を表す；
ｂは、１または２を表す；
ｃは、０または１を表す；
ｄは、１または２を表す；
ただし、ａ＋ｂ＋ｃ＝３である；
Ｚ^１、Ｚ^２およびＺ^３は各々独立に窒素原子またはＣ－Ｈを表す。
＜態様２＞
Ｚ^１、Ｚ^２およびＺ^３のうち、２つ以上が窒素原子である、態様１に記載のアダマンタン化合物。
＜態様３＞
Ｚ^１、Ｚ^２およびＺ^３のうち、２つが窒素原子であり、１つがＣ－Ｈである、態様１または２に記載のアダマンタン化合物。
＜態様４＞
Ａｒ^２が、炭素数６～２４の芳香族炭化水素基である、態様１～３のいずれか一項に記載のアダマンタン化合物。
＜態様５＞
Ａｒ^２が、フェニル基で置換されていてもよいフェニレン基またはビフェニリレン基である、態様４に記載のアダマンタン化合物。
＜態様６＞
Ａｒ^２が、フェニル基で置換されていてもよい１，４－フェニレン基または４，４’－ビフェニリレン基である、態様４に記載のアダマンタン化合物。
＜態様７＞
Ａｒ^２が、無置換である、態様４に記載のアダマンタン化合物。
＜態様８＞
Ａｒ^１が、炭素数１２～１６の芳香族炭化水素基である、態様１～７のいずれか一項に記載のアダマンタン化合物。
＜態様９＞
Ａｒ^１が、４－ビフェニリル基、まはた４－ナフチルフェニル基である、態様１～７のいずれか一項に記載のアダマンタン化合物。
＜態様１０＞
Ａｒ^１およびＡｒ^３が、各々独立に、フェニル基またはナフチル基で置換されていてもよいフェニル基である、態様１～７のいずれか一項に記載のアダマンタン化合物。
＜態様１１＞
Ａｒ^１およびＡｒ^３が、無置換である、態様１～９のいずれか一項に記載のアダマンタン化合物。
＜態様１２＞
一般式（１－１）で表される、態様１に記載のアダマンタン化合物：
式中、
Ｒ^１は、単結合、水素原子、または炭素数６～１８の芳香族炭化水素基を表す；
Ｒ^２は、水素原子または炭素数６～１８の芳香族炭化水素基を表す；
Ｒ^３は、単結合または炭素数６～１８の芳香族炭化水素基を表す；
Ｒ^１およびＲ^２のいずれかまたは両方が、炭素数６～１８の芳香族炭化水素基である；
Ｒ^１、Ｒ^２、およびＲ^３は、それぞれ、芳香族炭化水素基である場合、単数若しくは複数のフェニル基、ナフチル基、フェナントリル基、アントリル基、トリフェニレニル基、テルフェニル基、メチル基、ｔｅｒｔ－ブチル基、フルオロ基、および重水素の群から選択される１つ以上の置換基で置換されており、または無置換である；
Ａｄは、１－アダマンチル基または２－アダマンチル基を表す；
ｅは、０、１または２を表す；
ｆは、１または２を表す；
Ｚ^１、Ｚ^２およびＺ^３は、各々独立に、窒素原子またはＣ－Ｈを表し、Ｚ^１、Ｚ^２およびＺ^３のうち２つ以上が、窒素原子である。
＜態様１３＞
Ｒ^１、Ｒ^２およびＲ^３に関して、前記芳香族炭化水素基の炭素数が、６～１２である、態様１２に記載のアダマンタン化合物。
＜態様１４＞
Ｒ^１、Ｒ^２およびＲ^３は、それぞれ、芳香族炭化水素基である場合、無置換である、態様１２または１３に記載のアダマンタン化合物。
＜態様１５＞
ｅ＝０である、態様１２～１４のいずれか一項に記載のアダマンタン化合物。
＜態様１６＞
Ｒ^１が、フェニル基またはナフチル基であり、
Ｒ^２が、水素原子またはフェニル基である、
態様１５に記載のアダマンタン化合物。
＜態様１７＞
Ｒ^３が、単結合またはフェニレン基である、態様１５または１６に記載のアダマンタン化合物。
＜態様１８＞
一般式（１）で表されるアダマンタン化合物を含有する有機電界発光素子：

式中、
Ａｒ^１は、炭素数６～２４の芳香族炭化水素基を表す；
Ａｒ^２は、単結合または炭素数６～２４の芳香族炭化水素基を表す；
Ａｒ^３は、炭素数６～２４の芳香族炭化水素基を表す；
Ａｒ^１、芳香族炭化水素基である場合のＡｒ^２、およびＡｒ^３は、それぞれ、単数若しくは複数のフェニル基、ナフチル基、フェナントリル基、アントリル基、トリフェニレニル基、ビフェニリル基、テルフェニル基、メチル基、ｔｅｒｔ－ブチル基、フルオロ基、または重水素の群から選択される１つ以上の置換基で置換されており、または無置換である；
Ａｄは１－アダマンチル基または２－アダマンチル基を表す；
ａは、１または２を表す；
ｂは、１または２を表す；
ｃは、０または１を表す；
ｄは、１または２を表す；
ただし、ａ＋ｂ＋ｃ＝３である；
Ｚ^１、Ｚ^２およびＺ^３は各々独立に窒素原子またはＣ－Ｈを表す。
＜態様１９＞
前記一般式（１）で表されるアダマンタン化合物を含有する層が電子輸送層である、態様１８に記載の有機電界発光素子。
＜態様２０＞
前記一般式（１）で表されるアダマンタン化合物がドープされている、態様１８または１９に記載の有機電界発光素子。
＜態様２１＞
前記ドープがＬｉｑである、態様２０に記載の有機電界発光素子。 The invention according to the present disclosure includes the following aspects.
<Aspect 1>
Adamantane compound represented by the general formula (1):

During the ceremony,
Ar ¹ represents an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ² represents a single bond or an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ³ represents an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ¹ , Ar ² when it is an aromatic hydrocarbon group, and Ar ³ are each one or more of a phenyl group, naphthyl group, phenanthryl group, anthryl group, triphenylenyl group, terphenyl group, methyl group, tert- substituted or unsubstituted with one or more substituents selected from the group of butyl, fluoro, and deuterium;
Ad represents a 1-adamantyl group or a 2-adamantyl group;
a represents 1 or 2;
b represents 1 or 2;
c represents 0 or 1;
d represents 1 or 2;
with the proviso that a+b+c=3;
Z ¹ , Z ² and Z ³ each independently represent a nitrogen atom or C—H.
<Aspect 2>
The adamantane compound according to aspect 1, wherein two or more of Z ¹ , Z ² and Z ³ are nitrogen atoms.
<Aspect 3>
The adamantane compound according to aspect 1 or ² , wherein two of Z ¹ , Z ² and Z 3 are nitrogen atoms and one is CH.
<Aspect 4>
The adamantane compound according to any one of aspects 1-3, wherein Ar ² is an aromatic hydrocarbon group having 6 to 24 carbon atoms.
<Aspect 5>
5. The adamantane compound according to aspect 4, wherein Ar ² is a phenylene or biphenylylene group optionally substituted with a phenyl group.
<Aspect 6>
The adamantane compound according to aspect 4, wherein Ar ² is a 1,4-phenylene group or a 4,4'-biphenylylene group optionally substituted with a phenyl group.
<Aspect 7>
The adamantane compound according to aspect 4, wherein Ar ² is unsubstituted.
<Aspect 8>
The adamantane compound according to any one of aspects 1-7, wherein Ar ¹ is an aromatic hydrocarbon group having 12 to 16 carbon atoms.
<Aspect 9>
The adamantane compound according to any one of aspects 1-7, wherein Ar ¹ is a 4-biphenylyl group or a 4-naphthylphenyl group.
<Aspect 10>
The adamantane compound according to any one of aspects 1-7, wherein Ar ¹ and Ar ³ are each independently a phenyl group optionally substituted with a phenyl group or a naphthyl group.
<Aspect 11>
10. The adamantane compound according to any one of aspects 1-9, wherein Ar ¹ and Ar ³ are unsubstituted.
<Aspect 12>
The adamantane compound according to aspect 1, represented by the general formula (1-1):
During the ceremony,
R ¹ represents a single bond, a hydrogen atom, or an aromatic hydrocarbon group having 6 to 18 carbon atoms;
R ² represents a hydrogen atom or an aromatic hydrocarbon group having 6 to 18 carbon atoms;
R ³ represents a single bond or an aromatic hydrocarbon group having 6 to 18 carbon atoms;
either or both of R ¹ and R ² are aromatic hydrocarbon groups having 6 to 18 carbon atoms;
When each of R ¹ , R ² and R ³ is an aromatic hydrocarbon group, one or more phenyl groups, naphthyl groups, phenanthryl groups, anthryl groups, triphenylenyl groups, terphenyl groups, methyl groups, tert- substituted or unsubstituted with one or more substituents selected from the group of butyl, fluoro, and deuterium;
Ad represents a 1-adamantyl group or a 2-adamantyl group;
e represents 0, 1 or 2;
f represents 1 or 2;
Z ¹ , Z ² and Z ³ each independently represent a nitrogen atom or CH, and two or more of Z ¹ , Z ² and Z ³ are nitrogen atoms.
<Aspect 13>
13. The adamantane compound according to aspect 12, wherein for R ¹ , R ² and R ³ , the aromatic hydrocarbon group has 6 to 12 carbon atoms.
<Aspect 14>
14. The adamantane compound according to aspects 12 or 13, wherein R ¹ , R ² and R ³ are each unsubstituted when they are aromatic hydrocarbon groups.
<Aspect 15>
The adamantane compound according to any one of aspects 12-14, wherein e=0.
<Aspect 16>
R ¹ is a phenyl group or a naphthyl group,
R ² is a hydrogen atom or a phenyl group,
An adamantane compound according to aspect 15.
<Aspect 17>
17. The adamantane compound according to aspects 15 or 16, wherein ^R3 is a single bond or a phenylene group.
<Aspect 18>
An organic electroluminescent device containing an adamantane compound represented by formula (1):

During the ceremony,
Ar ¹ represents an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ² represents a single bond or an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ³ represents an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ¹ , Ar ² when it is an aromatic hydrocarbon group, and Ar ³ are each one or more of a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a triphenylenyl group, a biphenylyl group, a terphenyl group, and a methyl group. , substituted with one or more substituents selected from the group of tert-butyl group, fluoro group, or deuterium, or unsubstituted;
Ad represents a 1-adamantyl group or a 2-adamantyl group;
a represents 1 or 2;
b represents 1 or 2;
c represents 0 or 1;
d represents 1 or 2;
with the proviso that a+b+c=3;
Z ¹ , Z ² and Z ³ each independently represent a nitrogen atom or C—H.
<Aspect 19>
19. The organic electroluminescence device according to aspect 18, wherein the layer containing the adamantane compound represented by formula (1) is an electron transport layer.
<Aspect 20>
20. The organic electroluminescence device according to aspect 18 or 19, which is doped with the adamantane compound represented by formula (1).
<Aspect 21>
21. The organic electroluminescent device according to aspect 20, wherein said dope is Liq.

One aspect of the present invention can provide a novel adamantane compound, and another aspect can provide an electron-transporting material excellent in heat resistance, long life and/or luminous efficiency.

FIG. 1 is a schematic cross-sectional view of a preferred embodiment of an organic electric field element containing an adamantane compound, which is one aspect of the present invention. FIG. 2 is a schematic cross-sectional view of an organic electroluminescence device according to Device Example 1 of the present invention.

Hereinafter, embodiments of the present invention will be described in detail.

One aspect of the present invention is an adamantane compound represented by the above general formula (1) (hereinafter also referred to as “adamantane compound (1)” or simply “compound (1)”), and an organic electric field containing it It relates to a light emitting device.

<Adamantane compound represented by general formula (1)>
The adamantane compound, which is one embodiment of the present invention, is represented by general formula (1).

式中、
Ａｒ^１は、炭素数６～２４の芳香族炭化水素基を表す；
Ａｒ^２は、単結合または炭素数６～２４の芳香族炭化水素基を表す；
Ａｒ^３は、炭素数６～２４の芳香族炭化水素基を表す；
Ａｒ^１、芳香族炭化水素基である場合のＡｒ^２、およびＡｒ^３は、それぞれ、単数若しくは複数のフェニル基、ナフチル基、フェナントリル基、アントリル基、トリフェニレニル基、テルフェニル基、メチル基、ｔｅｒｔ－ブチル基、フルオロ基、および重水素の群から選択される１つ以上の置換基で置換されており、または無置換である；
Ａｄは、１－アダマンチル基または２－アダマンチル基を表す；
ａは、１または２を表す；
ｂは、１または２を表す；
ｃは、０または１を表す；
ｄは、１または２を表す；
ただし、ａ＋ｂ＋ｃ＝３である；
Ｚ^１、Ｚ^２およびＺ^３は各々独立に窒素原子またはＣ－Ｈを表す。

During the ceremony,
Ar ¹ represents an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ² represents a single bond or an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ³ represents an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ¹ , Ar ² when it is an aromatic hydrocarbon group, and Ar ³ are each one or more of a phenyl group, naphthyl group, phenanthryl group, anthryl group, triphenylenyl group, terphenyl group, methyl group, tert- substituted or unsubstituted with one or more substituents selected from the group of butyl, fluoro, and deuterium;
Ad represents a 1-adamantyl group or a 2-adamantyl group;
a represents 1 or 2;
b represents 1 or 2;
c represents 0 or 1;
d represents 1 or 2;
with the proviso that a+b+c=3;
Z ¹ , Z ² and Z ³ each independently represent a nitrogen atom or C—H.

The adamantane compound represented by formula (1) according to the embodiment of the present invention has high amorphous properties, a high glass transition temperature relative to the molecular weight, high luminous efficiency, long life, and low voltage electroluminescent device characteristics have Without intending to be limited by theory, this is believed to be due to having an adamantyl group with large steric hindrance and a donor property.

The Tg of the adamantane compound represented by formula (1) according to the embodiment of the present invention is preferably 110°C or higher, more preferably 130°C or higher. Adamantane compounds having a relatively high Tg are particularly advantageous in organic electroluminescent device applications that require high heat resistance. This Tg is measured using a DSC (Differential scanning calorimetry) device under an atmosphere of 23° C. and 50% RH.

<<Ar ¹ , Ar ² and Ar ³ >>
Ar ² represents a single bond or an aromatic hydrocarbon group having 6 to 24 carbon atoms. Ar ¹ and Ar ³ each independently represent an aromatic hydrocarbon group having 6 to 24 carbon atoms.

The "aromatic hydrocarbon group" is a hydrocarbon group containing a benzene ring, and has, for example, a ring structure (single ring or condensed ring) or a structure in which multiple ring structures are bonded with single bonds.

The aromatic hydrocarbon group having 6 to 24 carbon atoms in Ar ¹ and Ar ³ is not particularly limited, but a phenyl group, biphenylyl group, terphenyl group, naphthyl group, phenanthryl group, anthryl group, pyrenyl group, Preferred examples include a triphenylenyl group, a chrysenyl group, a fluoranthenyl group, an acenaphthylenyl group, a fluorenyl group, a benzofluorenyl group and the like.

Regarding Ar ² , the aromatic hydrocarbon group having 6 to 24 carbon atoms is not particularly limited, but a phenylene group, a biphenylylene group, a terphenylylene group, a naphthylene group, a phenanthenediyl group, anthracenediyl group, a pyrenediyl group, a tri Preferred examples include a renifendiyl group, a chrysenediyl group, a fluoranthenediyl group, an acenaphthylenediyl group, a fluorenediyl group, and a benzofluorenediyl group. Particularly preferably, for Ar ² , the C 6-24 aromatic hydrocarbon group is a (preferably unsubstituted) phenylene group or a biphenylylene group.

Ar ¹ , Ar ² when it is an aromatic hydrocarbon group, and Ar ³ are each one or more of a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a triphenylenyl group, a biphenylyl group, a terphenyl group, and a methyl group. , a tert-butyl group, a fluoro group, and deuterium, or may be unsubstituted.

It is particularly preferred that Ar ¹ , Ar ² and Ar ³ are unsubstituted.

Ar ² is preferably an aromatic hydrocarbon group having 6 to 24 carbon atoms. Particularly preferably, Ar ² is a phenyl group-substituted or unsubstituted (preferably unsubstituted) phenylene group or biphenylylene group, still more preferably Ar ² is a phenyl group-substituted or or an unsubstituted (preferably unsubstituted) 1,4-phenylene group or 4,4'-biphenylylene group.

Ar ¹ is preferably an unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, more preferably an aromatic hydrocarbon group having 12 to 16 carbon atoms. Ar ¹ may be a phenyl group substituted with a phenyl group or a naphthyl group. Ar ¹ is particularly preferably a 4-biphenylyl group or a 4-naphthylphenyl group, most preferably a 4-biphenylyl group, in terms of excellent performance.

Ar ³ is preferably an unsubstituted aromatic hydrocarbon group having 6 to 24 carbon atoms, more preferably an aromatic hydrocarbon group having 12 to 16 carbon atoms. Ar ³ may be a phenyl group substituted with a phenyl group or a naphthyl group. Ar ³ is preferably an unsubstituted phenyl group, a biphenylyl group, a naphthyl group, a phenyl group substituted with a naphthyl group, a phenanthryl group, an anthryl group, or a phenyl group substituted with an anthryl group. or an unsubstituted biphenylyl group.

<<a, b, c and d>>
a represents 1 or 2, b represents 1 or 2, c represents 0 or 1, and d represents 1 or 2, respectively. However, a+b+c=3. preferably a=b=c=1

<<Z ¹ , Z ² and Z ³ >>
Z ¹ , Z ² and Z ³ each independently represent a nitrogen atom or C—H. At least two of Z ¹ , Z ² and Z ³ are preferably nitrogen atoms. More preferably, two are nitrogen atoms and one is CH.

<Preferred example of the adamantane compound represented by the general formula (1)>
Examples of the adamantane compound represented by the general formula (1) include compounds represented by the following (A1) to (A34). “Ad ¹ ” represents a 1-adamantyl group, and “Ad ² ” represents a 2-adamantyl group.

Ar ² is not particularly limited, but examples thereof include (B1) to (B47) below.

Ar ¹ — and Ar ³ — are not particularly limited, but examples thereof include (C1) to (C71) below.

In the compound (1) of the present application, Ar ² represented by (B1) to (B47), Ar ¹ represented by (C1) to (C71), and Preferred examples include compounds in which Ar ³ represented by (C1) to (C71) are combined.
Further preferred examples of the compound (1) of the present application include the following (D1)-(D232). “Ad ¹ ” represents a 1-adamantyl group, and “Ad ² ” represents a 2-adamantyl group.

All of the exemplified compounds have a Tg of 100° C. or higher.

Among the adamantane compounds represented by the above general formula (1), the adamantane compounds represented by the following general formula (1-1) are particularly preferred:

In formula (1-1),
R ¹ represents a single bond, a hydrogen atom, or an aromatic hydrocarbon group having 6 to 18 carbon atoms;
R ² represents a hydrogen atom or an aromatic hydrocarbon group having 6 to 18 carbon atoms;
R ³ represents a single bond or an aromatic hydrocarbon group having 6 to 18 carbon atoms;
either or both of R ¹ and R ² are aromatic hydrocarbon groups having 6 to 18 carbon atoms;
When each of R ¹ , R ² and R ³ is an aromatic hydrocarbon group, one or more phenyl groups, naphthyl groups, phenanthryl groups, anthryl groups, triphenylenyl groups, terphenyl groups, methyl groups, tert- substituted or unsubstituted with one or more substituents selected from the group of butyl, fluoro, and deuterium;
Ad represents a 1-adamantyl group or a 2-adamantyl group;
e represents 0, 1 or 2;
f represents 1 or 2;
Z ¹ , Z ² and Z ³ each independently represent a nitrogen atom or CH, and two or more of Z ¹ , Z ² and Z ³ are nitrogen atoms.

The adamantane compound represented by the above general formula (1-1) is an aromatic ring having Z ¹ , Z ² and Z ³ (especially a heteroaromatic ring such as triazine or pyrimidine) and three benzene rings are bonded to it. and R ¹ to R ³ are attached to these three benzene rings at the para positions, respectively.

An adamantane compound having such a structure is particularly useful as a material for an organic electroluminescent device (especially a material for an electron transport layer), and by using this compound, luminous efficiency characteristics, driving voltage characteristics, and long life characteristics It is possible to obtain an organic electroluminescence device that is particularly excellent in

In the adamantane compound represented by the general formula (1-1), at least one of R ¹ to R ³ is an aromatic hydrocarbon group having 6 to 18 carbon atoms. That is, the adamantane compound represented by the above general formula (1-1) is a benzene ring bonded to an aromatic ring having Z ¹ , Z ² and Z ³ (especially a heteroaromatic ring such as triazine or pyrimidine) has an aromatic hydrocarbon ring attached at the para position to

While not intending to be bound by theory, aromatics attached para to a benzene ring attached to an aromatic ring having Z ¹ , Z ² , and Z ³ (especially heteroaromatic rings such as triazines or pyrimidines) When it has a tribal hydrocarbon ring, the LUMO distributed around the aromatic ring with Z ¹ , Z ² , and Z ³ (especially triazine or pyrimidine) is broadened, resulting in compound mobility (electron transfer degree) is expected to improve.

Here, conventionally, when an organic electroluminescent device is produced using a compound having such a structure, good performance may not be obtained (see, for example, compound ETL-2 described in Examples of the present application). Although not intended to be limited by theory, when a compound having such a molecular structure is used as a material for a layer (e.g., an electron transport layer) constituting an organic electroluminescent device, the energy barrier between layers in the device increases. As a result, it is believed that the efficiency of the organic electroluminescent device is reduced.

In contrast, the adamantane compound represented by the general formula (1-1) according to the present invention exhibits excellent mobility, and the organic electroluminescent device produced using this compound has a particularly high efficiency. indicates The adamantane compound represented by the above general formula (1-1) is bound at the para position to the benzene ring bound to the aromatic ring (especially triazine or pyrimidine) having Z ¹ , Z ² and Z ³ In addition to the aromatic hydrocarbon ring, it further has an adamantyl group, which is believed to enable an organic electroluminescent device with particularly high performance in addition to excellent mobility.

Although not intended to be limited by theory, in the adamantane compound of the general formula (1-1) according to the present invention, the sterically bulky adamantyl group is exciton deactivation at the interface with the adjacent layer in the device. is thought to be suppressed. Specifically, for example, when an intermediate such as an exciplex is generated by the interaction between the light-emitting layer and the electron-transporting layer, the energy of the exciton is deactivated, which may cause a decrease in light-emitting efficiency. It is believed that high adamantyl groups can suppress the formation of such exciplexes.

Examples of R ¹ and R ³ when e=1 or 2 include (B1) to (B47) above, respectively. Examples of R ¹ and R ² when e=0 include (C1) to (C71) above.

When e=1 or 2, R ¹ can represent a single bond or an aromatic hydrocarbon group of 6-18 carbon atoms. When e=0, R ¹ can represent a hydrogen atom or an aromatic hydrocarbon group of 6-18 carbon atoms.

Regarding R ¹ , R ² and R ³ , the aromatic hydrocarbon group preferably has 6 to 12 carbon atoms (particularly 6 to 10 carbon atoms).

When each of R ¹ , R ² and R ³ is an aromatic hydrocarbon group, it is preferably unsubstituted.

e is preferably 0 (e=0). When e=0, R ¹ is preferably a phenyl group or a naphthyl group, R ² is preferably a hydrogen atom or a phenyl group, and/or R ³ is a single bond or a phenylene group is preferred.

When e=0, general formula (1-1) is represented by general formula (1-10) below.

The adamantane compound represented by general formula (1-1) is particularly preferably an adamantane compound represented by general formula (1-11), (1-12) or (1-13) below.

<Method for Producing Adamantane Compound Represented by Formula (1)>
The adamantane compound (1) according to the embodiment of the present invention can be produced, for example, by cross-coupling reactions shown in Reaction Schemes 1 to 3 below.

In reaction formulas 1 to 3, X represents F, Cl, Br, I, OTf, or a group having F, Cl, Br, I or OTf as a partial structure. M represents a metallic or organometallic group that is effective in coupling reactions, such as Li, Na, B(OR ¹¹ ) ₂ , MgBr, MgCl, ZnCl, ZnBr, ZnCl, Zn(tmeda), Sn(n-Bu) ₃ , SiMe ₃ and the like.

Here, R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and two R ¹¹ may be the same or different. Also, two OR ¹¹ and the boron atom may form a ring. That is, examples of B(OR ¹¹ ) ₂ include the following (I) to (VI).

The reaction conditions for the cross-coupling reaction can be prepared using the methods described in, for example, JP-A-2015-34159 and WO2019/191454.

<Organic Electroluminescent Device Containing Adamantane Compound Represented by Formula (1)>
Hereinafter, an organic electroluminescent device (hereinafter sometimes simply referred to as an organic electroluminescent device) containing the adamantane compound (1) according to the present disclosure will be described.

An organic electroluminescent device according to one aspect of the present invention contains the adamantane compound (1) according to the present disclosure, and particularly has a layer containing the adamantane compound (1) according to the present disclosure.

The configuration of the organic electroluminescent device is not particularly limited, but includes, for example, configurations (i) to (v) shown below.

(i): anode/light emitting layer/cathode (ii): anode/hole transport layer/light emitting layer/cathode (iii): anode/light emitting layer/electron transport layer/cathode (iv): anode/hole transport layer/ Light emitting layer/electron transport layer/cathode (v): anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode

The adamantane compound (1) according to the present disclosure may be contained in any of the above layers, but in terms of excellent light emitting properties of the organic electroluminescent device, the group consisting of the layer between the light emitting layer and the cathode It is preferably contained in one or more selected layers. Therefore, in the configurations shown in (i) to (v) above, the adamantane compound (1) is preferably contained in one or more layers selected from the group consisting of the electron transport layer and the electron injection layer.

Hereinafter, the organic electroluminescence device according to one aspect of the present invention will be described in more detail with reference to FIG. 1, taking the configuration (v) above as an example.

The organic electroluminescent device shown in FIG. 1 has a so-called bottom emission type device configuration, but the organic electroluminescent device according to one aspect of the present invention is not limited to the bottom emission type device configuration. do not have. That is, the organic electroluminescence device according to one aspect of the present invention may have other known device configurations such as top emission type.

The organic electroluminescence device 100 shown in FIG. 1 includes a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode 8 in this order. Prepare. However, some of these layers may be omitted, or conversely, other layers may be added. For example, a hole-blocking layer may be provided between the light-emitting layer 5 and the electron-transporting layer 6, the hole-injecting layer 3 may be omitted, and the hole-transporting layer 4 may be provided directly on the anode 2. good too.

Further, a single layer having the functions of a plurality of layers, such as an electron injection/transport layer having both the function of an electron injection layer and the function of an electron transport layer in a single layer. It may be a configuration provided instead of. Furthermore, for example, the single-layer hole transport layer 4 and the single-layer electron transport layer 6 may each consist of a plurality of layers.

<Layer containing adamantane compound (1)>
In the configuration example shown in FIG. 1, the organic electroluminescent device 100 contains the adamantane compound (1) in one or more layers selected from the group consisting of the light emitting layer 5, the electron transport layer 6 and the electron injection layer . In particular, the electron transport layer 6 preferably contains the adamantane compound (1). The adamantane compound (1) may be contained in multiple layers of the organic electroluminescence device.

In addition, the organic electroluminescence device 100 in which the electron transport layer 6 contains the adamantane compound (1) will be described below.

[Substrate 1]
Examples of the substrate 1 include a glass plate, a quartz plate, a plastic plate, and a plastic film. Among these, a glass plate, a quartz plate, and a transparent plastic film are preferable.

Examples of light-transmitting plastic films include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC ), cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like.
In addition, in the case of the configuration in which light emission is extracted from the substrate 1 side, the substrate 1 is transparent to the wavelength of light.

[Anode 2]
An anode 2 is provided on the substrate 1 (on the hole injection layer 3 side).
Materials for the anode include metals, alloys, electrically conductive compounds, and mixtures thereof having a large work function (for example, 4 eV or more). Specific examples of materials for the anode include metals such as Au; conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ and ZnO.
For organic electroluminescent devices configured such that emitted light is extracted through the anode, the anode is formed of a conductive transparent material that is transparent or substantially transparent to the emitted light.

[Hole injection layer 3, hole transport layer 4]
A hole injection layer 3 and a hole transport layer 4 are provided in this order from the anode 2 side between the anode 2 and a light emitting layer 5 to be described later.

The hole-injecting layer and the hole-transporting layer have a function of transferring holes injected from the anode to the light-emitting layer, and the hole-injecting layer and the hole-transporting layer are interposed between the anode and the light-emitting layer. causes more holes to be injected into the light-emitting layer at lower electric fields.

Moreover, the hole injection layer and the hole transport layer also function as electron blocking layers. 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 blocked by the electron barrier present at the interface between the light emitting layer and the hole injection layer and/or the hole transport layer. , the leakage to the hole injection layer and/or the hole transport layer is suppressed. As a result, the electrons are accumulated at the interface in the light-emitting layer, resulting in an effect such as an improvement in light-emitting efficiency, and an organic electroluminescence device having excellent light-emitting performance can be obtained.

Materials for the hole injection layer and the hole transport layer have at least one of hole injection, hole transport, and electron barrier properties. Materials for the hole injection layer and the hole transport layer may be either organic or inorganic.

Specific examples of materials for the hole injection layer and hole transport layer include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, and amino-substituted chalcone. derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers (especially thiophene oligomers), porphyrin compounds, aromatic tertiary amine compounds, styryl Examples include amine compounds.

Among these, porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds are preferred, and aromatic tertiary amine compounds are particularly preferred, from the viewpoint of good performance of the organic electroluminescent device.

Specific examples of aromatic tertiary amine compounds and styrylamine compounds include N,N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N'- Bis(m-tolyl)-[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-tolylamino phenyl)-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)quadriphenyl , 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-diphenylaminostilbenzene, N-phenylcarbazole, 4,4'-bis[N-(1-naphthyl)-N-phenylamino] biphenyl (NPD), 4,4′,4″-tris[N-(m-tolyl)-N-phenylamino]triphenylamine (MTDATA) and the like.

Inorganic compounds such as p-type-Si and p-type-SiC can also be cited as examples of the material for the hole injection layer and the material for the hole transport layer.
The hole injection layer and the hole transport layer may have a single structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.

[Light emitting layer 5]
A light-emitting layer 5 is provided between the hole-transporting layer 4 and an electron-transporting layer 6, which will be described later.
Materials for the light-emitting layer include phosphorescent light-emitting materials, fluorescent light-emitting materials, and thermally activated delayed fluorescent light-emitting materials. In the light-emitting layer, electron-hole pairs recombine, resulting in light emission.

The emissive layer may consist of a single small molecule material or a single polymeric material, but more commonly consists of a host material doped with a guest compound. Emission comes primarily from dopants and can have any color.

Host materials include, for example, compounds having a biphenylyl 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-carbazovinylene) 1, 1′-biphenyl), TBADN (2-tert-butyl-9,10-di(2-naphthyl)anthracene), ADN (9,10-di(2-naphthyl)anthracene), CBP (4,4′-bis (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 and the like can be mentioned.

Examples of fluorescent dopants include anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compounds, thiopyran compounds, polymethine compounds, pyrylium, thiapyrylium compounds, fluorene derivatives, periflanthene derivatives, and indenoperylenes. derivatives, bis(azinyl)amine boron compounds, bis(azinyl)methane compounds, carbostyril compounds, boron compounds, cyclic amine compounds and the like. The fluorescent dopant may be a combination of two or more selected from these.

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

Specific examples of fluorescent dopants and phosphorescent dopants include Alq ₃ (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.

Moreover, the luminescent material is not limited to being contained only in the luminescent layer. For example, the light-emitting material may be contained in a layer adjacent to the light-emitting layer (hole-transporting layer 4 or electron-transporting layer 6). This can further increase the luminous efficiency of the organic electroluminescence device.

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 having the same composition or different compositions.

[Electron transport layer 6]
An electron transport layer 6 is provided between the light emitting layer 5 and an electron injection layer 7 which will be described later.
The electron transport layer has a function of transmitting electrons injected from the cathode to the light emitting layer. By interposing an electron-transporting layer between the cathode and the light-emitting layer, electrons are injected into the light-emitting layer at a lower electric field.

The electron transport layer preferably contains the adamantane compound (1) according to the present disclosure. In addition to the adamantane compound (1), the electron transport layer may further contain one or more selected from conventionally known electron transport materials.

When the adamantane compound (1) is not contained in the electron-transporting layer but is contained in another layer, one or more selected from conventionally known electron-transporting materials can be used as the electron-transporting material constituting the electron-transporting layer. can be done.

Conventionally known electron-transporting materials include alkali metal complexes, alkaline earth metal complexes, earth metal complexes, and the like. Alkali metal complexes, alkaline earth metal complexes, and earth metal complexes include, for example, 8-hydroxyquinolinatolithium (Liq), bis(8-hydroxyquinolinato)zinc, and bis(8-hydroxyquinolinato)copper. , bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis (10-hydroxybenzo[h]quinolinate) beryllium, bis(10-hydroxybenzo[h]quinolinate)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinate)(o -cresolato)gallium, bis(2-methyl-8-quinolinato)-1-naphtholatoaluminum, bis(2-methyl-8-quinolinato)-2-naphtholatogallium, and the like.

The electron-transporting 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 having the same composition or different compositions.

In the organic electroluminescent device according to this aspect, an electron injection layer may be provided for the purpose of improving electron injection properties and improving device characteristics (e.g., luminous efficiency, low voltage drive, or high durability).

[Electron injection layer 7]
An electron injection layer 7 is provided between the electron transport layer 6 and a cathode 8 which will be described later.
The electron injection layer has a function of transferring electrons injected from the cathode to the light emitting layer. By interposing an electron injection layer between the cathode and the light emitting layer, electrons are injected into the light emitting layer at a lower electric field.

Materials for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, frelenylidenemethane, anthraquinodimethane, anthrone, and Liq. Organic compounds such as (8-hydroxyquinolinolato-lithium) can be mentioned. Furthermore, SiO ₂ , AlO, SiN, SiON, AlON, GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, LiF, Li, Na, Ca, Mg, CsF, CaCO ₃ , C, Yb, etc. Inorganic compounds such as oxides, fluorides, nitrides and oxynitrides are also included.

[Cathode 8]
A cathode 8 is provided on the electron injection layer 7 .
In the case of an organic electroluminescence device configured so that only light emitted through the anode is taken out, the cathode can be made of any conductive material.

Materials for the cathode include, for example, metals with a small work function (hereinafter also referred to as electron-injecting metals), alloys, electrically conductive compounds, and mixtures thereof. Here, a metal with a small work function is, for example, a metal of 4 eV or less.

Specific examples of cathode materials include sodium, sodium-potassium alloys, magnesium, lithium, magnesium/copper mixtures, magnesium/silver mixtures, magnesium/aluminum mixtures, magnesium/indium mixtures, aluminum/aluminum oxide (Al ₂ O ₃ ). mixtures, indium, lithium/aluminum mixtures, rare earth metals, and the like.

Among these, mixtures of electron-injecting metals and second metals, which are stable metals with a larger work function value, such as magnesium/silver mixtures, magnesium /aluminum mixtures, magnesium/ _indium mixtures, aluminum/aluminum oxide ( _Al2O3 ) mixtures, lithium/aluminum mixtures, etc. are preferred.

[Method of Forming Each Layer]
Each layer except for the electrodes (anode, cathode) described above is formed by thinning by a known method such as a vacuum deposition method, a spin coating method, a casting method, or a LB (Langmuir-Blodgett method) method. be able to. The material for each layer may be used alone, or if necessary, it may be used together with a material such as a binder resin and a solvent.

The thickness of each layer thus formed is not particularly limited and can be appropriately selected depending on the situation, but is usually in the range of 5 nm to 5 μm.

The anode and cathode can be formed by thinning an electrode material by a method such as vapor deposition or sputtering. A pattern may be formed through a mask of a desired shape during vapor deposition or sputtering, or a pattern of a desired shape may be formed by photolithography after forming a thin film by vapor deposition, sputtering, or the like.

The film thickness of the anode and cathode is preferably 1 μm or less, more preferably 10 nm or more and 200 nm or less.

When forming a layer (particularly, an electron-transporting layer) containing adamantane compound (1), it may be used in combination with the conventionally known electron-transporting material. Therefore, for example, the adamantane compound (1) and a conventionally known electron-transporting material may be co-deposited, or a layer of a conventionally known electron-transporting material may be laminated on the layer of the adamantane compound (1).

The organic electroluminescence element may be used as a kind of lamp for illumination or as a light source for exposure, a projection device for projecting an image onto a screen or the like, or a display for directly viewing a still image or a moving image. You may use it as a device (display). When the organic electroluminescence element is used as a display device for reproducing moving images, the drive system may be a simple matrix (passive matrix) system or an active matrix system. Further, by using two or more kinds of organic electroluminescent elements having different emission colors, it is possible to produce a full-color display device.

The adamantane compound (1) according to the present disclosure, particularly when used as an electron-transporting layer, can provide an organic electroluminescence device that is significantly superior in luminous efficiency and low-voltage characteristics compared to conventionally known adamantane compounds. . Furthermore, the adamantane compound (1) has a high amorphous property due to its sterically hindered skeleton, and has high film quality stability. Therefore, effects such as improvement in drive stability of the organic electroluminescence device and improvement in luminous efficiency are expected. In addition, the adamantane compound (1) has high chemical stability due to its characteristic skeleton, and can contribute to the extension of the life of the organic electroluminescence device.

The adamantane compound (1) according to the present disclosure is particularly a triazine compound that can achieve high levels of low-voltage drive, high efficiency and long life of the device by using it as an electron transport layer of an organic electroluminescent device. can be provided. Furthermore, it is possible to provide an organic electroluminescence device using the adamantane compound (1), which can be driven at a low voltage, has high efficiency, and has a long life.

EXAMPLES Preferred embodiments of the present invention will be described in more detail below with reference to examples and comparative examples, but the present invention should not be construed as being limited thereto.

[ ¹ H-NMR measurement]
Bruker ASCEND HD (400 MHz; manufactured by BRUKER) was used for ¹ H-NMR measurement. ¹ H-NMR was measured using deuterated chloroform (CDCl ₃ ) as a measurement solvent and tetramethylsilane (TMS) as an internal standard substance. Commercially available reagents were used.

[FDMS measurement]
FDMS measurement was performed using M-80B manufactured by Hitachi, Ltd.

[DSC measurement (glass transition temperature, crystallization temperature)]
The glass transition temperature (Tg) and crystallization temperature (Tc) were measured using a DSC (Differential scanning calorimetry) device DSC7020 (manufactured by Hitachi High-Tech Science). Aluminum oxide (Al ₂ O ₃ ) was used as a reference in the DSC measurement, and the sample was 10 mg.

As a pretreatment for the measurement, the temperature was raised from 30° C. to the melting point or higher at a rate of 10° C./min to melt the sample, and then the sample was brought into contact with dry ice for rapid cooling. Subsequently, the temperature of the pretreated sample was increased from 30° C. at a rate of 10° C./min, and the glass transition temperature and crystallization temperature were measured.

<Synthesis example>
<<Synthesis Example-1>>

Under an argon atmosphere, 4-(1-adamantyl)phenyl triflate (150.0 g, 416.2 mmol), bis(neopentyl glycolate) diboron (103.4 g, 457.8 mmol), potassium acetate (122.5 g, 1248.8 mmol). 6 mmol) and palladium acetate (1.87 g, 8.32 mmol) were suspended in THF (1340 mL) and heated under reflux for 17 hours. After cooling the resulting reaction mixture to room temperature, the reaction residue was removed by filtration. The resulting filtrate was concentrated to dryness and purified by silica gel chromatography (developing solvent: toluene) to give the target 5,5-dimethyl-2-[4-(1-adamantyl)phenyl]-1,3, 2-Dioxaborinane was obtained (85.0 g, 63% yield).
¹ H NMR (CDCl ₃ ) δ 1.01 (s, 6H), 1.56 (s, 4H), 1.77 (brs, 6H), 1.92 (brs, 6H), 2.09 (brs, 3H) , 7.36 (d, J=8.4 Hz, 2H), 7.75 (d, J=8.4 Hz, 2H).

<<Synthesis Example-2>>

Under an argon atmosphere, 2,4-dichloro-6-phenyl-1,3,5-triazine (10.0 g, 33.1 mmol), 4-chlorophenylboronic acid (5.69 g, 36.4 mmol), and tetrakis (tri Phenylphosphine)palladium (765 mg, 0.662 mmol) was suspended in THF (330 mL). After adding 2.0 M aqueous potassium carbonate solution (49.6 mL) to this suspension, the mixture was heated under reflux for 12 hours. After allowing to cool, water and methanol were added to the reaction mixture. The resulting solid was collected by filtration and purified by recrystallization from toluene to obtain the target 2-(4-biphenylyl)-4-chloro-6-(4-chlorophenyl)1,3,5-triazine ( 12.5 g, 40% yield).
¹ H NMR (CDCl ₃ ) δ 7.43 (t, J = 7.3 Hz, 1 H), 7.49 (d, J = 7.8 Hz, 2 H), 7.54 (d, J = 8.7 Hz, 2 H) , 7.69 (dd, J=8.5, 1.5 Hz, 2H), 7.79 (d, J=8.6 Hz, 2H), 8.60 (d, J=8.7 Hz, 2H), 8.69 (d, J=8.5Hz, 2H).

<<Synthesis Example-3>>

アルゴン雰囲気下、２－（４－ビフェニリル）－４－クロロ－６－（４－クロロフェニル）１，３，５－トリアジン（５．００ｇ，１３．２ｍｍｏｌ）、５，５－ジメチル－２－［４－（１－アダマンチル）フェニル］－１，３，２－ジオキサボリナン（４．２９ｇ，１３．２ｍｍｏｌ）、およびテトラキス（トリフェニルホスフィン）パラジウム（３０６ｍｇ，０．２６４ｍｍｏｌ）をトルエン（１３２ｍＬ）に懸濁した。この懸濁液に、２．０Ｍ－リン酸カリウム水溶液（１９．８ｍＬ）を加えた後、２１時間加熱還流した。放冷後、反応混合物に水およびメタノールを加えた。生じた固体をろ取し、トルエンによる再結晶によって精製することで、目的の２－（４－アダマンチルフェニル）－４－（４－ビフェニリル）－６－（４－クロロフェニル）－１，３，５－トリアジンを得た（６．２ｇ、収率８５％）。
^１ＨＮＭＲ（ＣＤＣｌ_３）δ１．８２（ｂｒｓ，６Ｈ），２．０１（ｂｒｓ，６Ｈ），２．１５（ｂｒｓ，３Ｈ），７．４２（ｔ，Ｊ＝７．２Ｈｚ，１Ｈ），７．４９－７．５３（ｍ，２Ｈ），７．５５（ｄ，Ｊ＝８．９Ｈｚ，２Ｈ），７．５８（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），７．７１（ｄｄ，Ｊ＝８．３，１．２Ｈｚ，２Ｈ），７．８１（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ）．

Under an argon atmosphere, 2-(4-biphenylyl)-4-chloro-6-(4-chlorophenyl)1,3,5-triazine (5.00 g, 13.2 mmol), 5,5-dimethyl-2-[4 -(1-adamantyl)phenyl]-1,3,2-dioxaborinane (4.29 g, 13.2 mmol) and tetrakis(triphenylphosphine) palladium (306 mg, 0.264 mmol) were suspended in toluene (132 mL). . After adding 2.0 M aqueous potassium phosphate solution (19.8 mL) to this suspension, the mixture was heated under reflux for 21 hours. After allowing to cool, water and methanol were added to the reaction mixture. The resulting solid was collected by filtration and purified by recrystallization from toluene to give the target 2-(4-adamantylphenyl)-4-(4-biphenylyl)-6-(4-chlorophenyl)-1,3,5 -triazine (6.2 g, 85% yield).
¹ H NMR (CDCl ₃ ) δ 1.82 (brs, 6H), 2.01 (brs, 6H), 2.15 (brs, 3H), 7.42 (t, J = 7.2 Hz, 1H), 7. 49-7.53 (m, 2H), 7.55 (d, J = 8.9Hz, 2H), 7.58 (d, J = 8.6Hz, 2H), 7.71 (dd, J = 8 .3, 1.2 Hz, 2H), 7.81 (d, J=8.6 Hz, 2H).

<<Synthesis Example-4 (D158)>>

アルゴン雰囲気下、２－（４－アダマンチルフェニル）－４－（４－ビフェニリル）－６－（４－クロロフェニル）－１，３，５－トリアジン（３．００ｇ，５．４１ｍｍｏｌ）、５，５－ジメチル－２－［４－（１－アダマンチル）フェニル］－１，３，２－ジオキサボリナン（１．９３ｇ，５．９６ｍｍｏｌ）、酢酸パラジウム（２４．３ｍｇ，０．１０８ｍｍｏｌ）および２－ジシクロへキシルホスフィノ－２’，４’,６’－トリイソプロピルビフェニル（１０３ｍｇ，０．２１７ｍｍｏｌ）をテトラヒドロフラン（５４ｍＬ）に懸濁した。この懸濁液に、２．０Ｍ－リン酸カリウム水溶液（８．１ｍＬ）を加えた後、２０時間加熱還流した。放冷後、反応混合物に水およびメタノールを加えた。生じた固体をろ取し、トルエンによる再結晶によって精製することで、目的の２－（４’－アダマンチルビフェニル－４－イル）－４－（４－アダマンチルフェニル）－６－（４－ビフェニリル）－１，３，５－トリアジン（化合物Ｄ１５８）を得た（２．８５ｇ、収率７２％）。
^１ＨＮＭＲ（ＣＤＣｌ_３）δ１．８４（ｂｒｓ，１２Ｈ），２．０２（ｂｒｓ，６Ｈ），２．０４（ｂｒｓ，６Ｈ），２．１７（ｂｒｓ，６Ｈ），７．４４（ｔ，Ｊ＝７．３Ｈｚ，１Ｈ），７．５１－７．５５（ｍ，４Ｈ），７．６１（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．７２（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．７５（ｄ，Ｊ＝７．２Ｈｚ，２Ｈ），７．８４（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ），８．７６（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．８７（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），８．８９（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ）．

Under an argon atmosphere, 2-(4-adamantylphenyl)-4-(4-biphenylyl)-6-(4-chlorophenyl)-1,3,5-triazine (3.00 g, 5.41 mmol), 5,5- Dimethyl-2-[4-(1-adamantyl)phenyl]-1,3,2-dioxaborinane (1.93 g, 5.96 mmol), palladium acetate (24.3 mg, 0.108 mmol) and 2-dicyclohexylphosphino- 2′,4′,6′-Triisopropylbiphenyl (103 mg, 0.217 mmol) was suspended in tetrahydrofuran (54 mL). After adding 2.0 M aqueous potassium phosphate solution (8.1 mL) to this suspension, the mixture was heated under reflux for 20 hours. After allowing to cool, water and methanol were added to the reaction mixture. The resulting solid was collected by filtration and purified by recrystallization from toluene to give the target 2-(4'-adamantylbiphenyl-4-yl)-4-(4-adamantylphenyl)-6-(4-biphenylyl) -1,3,5-triazine (Compound D158) was obtained (2.85 g, 72% yield).
¹ H NMR (CDCl ₃ ) δ 1.84 (brs, 12H), 2.02 (brs, 6H), 2.04 (brs, 6H), 2.17 (brs, 6H), 7.44 (t, J = 7.3Hz, 1H), 7.51-7.55 (m, 4H), 7.61 (d, J = 8.5Hz, 2H), 7.72 (d, J = 8.5Hz, 2H), 7.75 (d, J = 7.2Hz, 2H), 7.84 (d, J = 8.0Hz, 4H), 8.76 (d, J = 8.6Hz, 2H), 8.87 (d , J=8.3 Hz, 2H), 8.89 (d, J=8.4 Hz, 2H).

<<Synthesis Example-5 (D9)>>

アルゴン雰囲気下、２－（４－アダマンチルフェニル）－４－（４－ビフェニリル）－６－（４－クロロフェニル）－１，３，５－トリアジン（２．５０ｇ，４．５１ｍｍｏｌ）、１－ナフタレンボロン酸（０．８５ｇ，４．９６ｍｍｏｌ）、酢酸パラジウム（２０．３ｍｇ，０．０９０ｍｍｏｌ）および２－ジシクロへキシルホスフィノ－２’，４’,６’－トリイソプロピルビフェニル（８６．０ｍｇ，０．１８１ｍｍｏｌ）をテトラヒドロフラン（４５ｍＬ）に懸濁した。この懸濁液に、２．０Ｍ－リン酸カリウム水溶液（６．８ｍＬ）を加えた後、２０時間加熱還流した。放冷後、反応混合物に水およびメタノールを加えた。生じた固体をろ取し、トルエンによる再結晶によって精製することで、目的の２－（４－アダマンチルフェニル）－４－（４－ビフェニリル）－６－｛４－（１－ナフチル）フェニル｝－１，３，５－トリアジン（化合物Ｄ９）を得た（１．８５ｇ、収率６４％）。
^１ＨＮＭＲ（ＣＤＣｌ_３）δ１．８５（ｂｒｓ，６Ｈ），２．０４（ｂｒｓ，６Ｈ），２．１８（ｂｒｓ，３Ｈ），７．４３－７．６４（ｍ，９Ｈ），７．７４－７．７７（ｍ，４Ｈ），７．８５（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．９４－８．０２（ｍ，３Ｈ），８．７８（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），８．９１（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），８．９４（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ）．

2-(4-adamantylphenyl)-4-(4-biphenylyl)-6-(4-chlorophenyl)-1,3,5-triazine (2.50 g, 4.51 mmol), 1-naphthalene boron under argon atmosphere acid (0.85 g, 4.96 mmol), palladium acetate (20.3 mg, 0.090 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (86.0 mg, 0.181 mmol) was suspended in tetrahydrofuran (45 mL). After adding 2.0 M aqueous potassium phosphate solution (6.8 mL) to this suspension, the mixture was heated under reflux for 20 hours. After allowing to cool, water and methanol were added to the reaction mixture. The resulting solid was collected by filtration and purified by recrystallization from toluene to give the target 2-(4-adamantylphenyl)-4-(4-biphenylyl)-6-{4-(1-naphthyl)phenyl}- 1,3,5-Triazine (compound D9) was obtained (1.85 g, 64% yield).
¹ H NMR (CDCl ₃ ) δ 1.85 (brs, 6H), 2.04 (brs, 6H), 2.18 (brs, 3H), 7.43-7.64 (m, 9H), 7.74- 7.77 (m, 4H), 7.85 (d, J = 8.4Hz, 2H), 7.94-8.02 (m, 3H), 8.78 (d, J = 8.7Hz, 2H) ), 8.91 (d, J=8.4 Hz, 2H), 8.94 (d, J=8.4 Hz, 2H).

Compound D9 had a Tg of 144° C. and no Tc was detected.

<<Synthesis Example-6>>

アルゴン雰囲気下、２－（４－アダマンチルフェニル）－４－（４－ビフェニリル）－６－（４－クロロフェニル）－１，３，５－トリアジン（５．００ｇ，９．０２ｍｍｏｌ）、ビス（ピナコラト）ジボロン（２．７５ｇ，１０．８ｍｍｏｌ）、酢酸パラジウム（４０．５ｍｇ、０．１８ｍｍｏｌ）、２－ジシクロへキシルホスフィノ－２’，４’,６’－トリイソプロピルビフェニル（１７２ｍｇ、０．３６１ｍｍｏｌ）、酢酸カリウム（２．６６ｇ、２７．１ｍｍｏｌ）をＴＨＦ（９０ｍＬ）に懸濁し、１７時間加熱還流した。得られた反応混合物を室温まで冷却したのち、ろ過によって反応残渣を取り除いた。得られたろ液を濃縮乾固させ、シリカゲルクロマトグラフィー（展開溶媒：トルエンとヘキサンの混合溶媒）により精製することにより、目的の２－（４－アダマンチルフェニル）－４－（４－ビフェニリル）－６－［４－（４，４，５，５－テトラメチル）－１，３，２－ジオキサボロラン－２－イル］－１，３，５－トリアジンを得た（４．１９ｇ、収率７２％）。
^１ＨＮＭＲ（ＣＤＣｌ_３）δ１．４０（ｓ，１２Ｈ），１．８２（ｂｒｓ，６Ｈ），２．０１（ｂｒｓ，６Ｈ），２．１２（ｂｒｓ，３Ｈ），７．４２（ｔ，Ｊ＝７．５Ｈｚ，１Ｈ），７．５１（ｔ，Ｊ＝７．５Ｈｚ，２Ｈ），７．５９（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），７．７２（ｄｄ，Ｊ＝８．５，１．４Ｈｚ，２Ｈ），７．８２（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），８．０１（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），８．７２（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．７７（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ），８．８５（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ）．

2-(4-adamantylphenyl)-4-(4-biphenylyl)-6-(4-chlorophenyl)-1,3,5-triazine (5.00 g, 9.02 mmol), bis(pinacolato) under argon atmosphere Diboron (2.75 g, 10.8 mmol), palladium acetate (40.5 mg, 0.18 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (172 mg, 0.361 mmol), acetic acid Potassium (2.66 g, 27.1 mmol) was suspended in THF (90 mL) and heated to reflux for 17 hours. After cooling the resulting reaction mixture to room temperature, the reaction residue was removed by filtration. The resulting filtrate was concentrated to dryness and purified by silica gel chromatography (developing solvent: mixed solvent of toluene and hexane) to give the target 2-(4-adamantylphenyl)-4-(4-biphenylyl)-6. -[4-(4,4,5,5-tetramethyl)-1,3,2-dioxaborolan-2-yl]-1,3,5-triazine was obtained (4.19 g, 72% yield). .
¹ H NMR (CDCl ₃ ) δ 1.40 (s, 12H), 1.82 (brs, 6H), 2.01 (brs, 6H), 2.12 (brs, 3H), 7.42 (t, J = 7.5Hz, 1H), 7.51 (t, J = 7.5Hz, 2H), 7.59 (d, J = 8.7Hz, 2H), 7.72 (dd, J = 8.5, 1 .4Hz, 2H), 7.82 (d, J = 8.3Hz, 2H), 8.01 (d, J = 8.3Hz, 2H), 8.72 (d, J = 8.5Hz, 2H) , 8.77 (d, J=8.1 Hz, 2H), 8.85 (d, J=8.4 Hz, 2H).

<<Synthesis Example-7 (D8)>>

アルゴン雰囲気下、２－（４－アダマンチルフェニル）－４－（４－ビフェニリル）－６－［４－（４，４，５，５－テトラメチル）－１，３，２－ジオキサボロラン－２－イル］－１，３，５－トリアジン（２．００ｇ，３．１０ｍｍｏｌ）、２－ブロモナフタレン（０．７７ｇ、３．７２ｍｍｏｌ）、酢酸パラジウム（１３．９ｍｇ，０．０６２ｍｍｏｌ）および２－ジシクロへキシルホスフィノ－２’，４’,６’－トリイソプロピルビフェニル（５９．１ｍｇ，０．１２４ｍｍｏｌ）をテトラヒドロフラン（３１ｍＬ）に懸濁した。この懸濁液に、２．０Ｍ－リン酸カリウム水溶液（４．６ｍＬ）を加えた後、２０時間加熱還流した。放冷後、反応混合物に水およびメタノールを加えた。生じた固体をろ取し、トルエンによる再結晶によって精製することで、目的の２－（４－アダマンチルフェニル）－４－（４－ビフェニリル）－６－｛４－（２－ナフチル）フェニル｝－１，３，５－トリアジン（化合物Ｄ８）を得た（１．２０ｇ、収率６４％）。
^１ＨＮＭＲ（ＣＤＣｌ_３）δ１．８３（ｂｒｓ，６Ｈ），２．０２（ｂｒｓ，６Ｈ），２．１６（ｂｒｓ，３Ｈ），７．４２（ｔ，Ｊ＝７．２Ｈｚ，１Ｈ），７．５０－７．５７（ｍ，４Ｈ），７．６０（ｄ，＝８．８Ｈｚ，２Ｈ），７．７３（ｄ，Ｊ＝７．６Ｈｚ，２Ｈ），７．８３（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．８５－８．００（ｍ，６Ｈ），８．１８（ｂｒｓ，１Ｈ），７．４５（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），８．８８（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．９１（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ）．

Under an argon atmosphere, 2-(4-adamantylphenyl)-4-(4-biphenylyl)-6-[4-(4,4,5,5-tetramethyl)-1,3,2-dioxaborolan-2-yl ]-1,3,5-triazine (2.00 g, 3.10 mmol), 2-bromonaphthalene (0.77 g, 3.72 mmol), palladium acetate (13.9 mg, 0.062 mmol) and 2-dicyclohexylphosphino -2',4',6'-Triisopropylbiphenyl (59.1 mg, 0.124 mmol) was suspended in tetrahydrofuran (31 mL). After adding 2.0 M aqueous potassium phosphate solution (4.6 mL) to this suspension, the mixture was heated under reflux for 20 hours. After allowing to cool, water and methanol were added to the reaction mixture. The resulting solid was collected by filtration and purified by recrystallization from toluene to give the target 2-(4-adamantylphenyl)-4-(4-biphenylyl)-6-{4-(2-naphthyl)phenyl}- 1,3,5-triazine (compound D8) was obtained (1.20 g, 64% yield).
¹ H NMR (CDCl ₃ ) δ 1.83 (brs, 6H), 2.02 (brs, 6H), 2.16 (brs, 3H), 7.42 (t, J = 7.2 Hz, 1H), 7. 50-7.57 (m, 4H), 7.60 (d, = 8.8Hz, 2H), 7.73 (d, J = 7.6Hz, 2H), 7.83 (d, J = 8. 5Hz, 2H), 7.85-8.00 (m, 6H), 8.18 (brs, 1H), 7.45 (d, J = 8.7Hz, 2H), 8.88 (d, J = 8.6 Hz, 2H), 8.91 (d, J=8.7 Hz, 2H).

Compound D8 had a Tg of 139° C. and no Tc was detected.

<<Synthesis Example-8 (D81)>>

アルゴン雰囲気下、２－（ビフェニル－4－イル）－４－（４－ブロモフェニル）－６－フェニル－１，３，５－トリアジン（１３．０ｇ，２８．０ｍｍｏｌ）、５，５－ジメチル－２－［４－（１－アダマンチル）フェニル］－１，３，２－ジオキサボリナン（９．９９ｇ，３０．８ｍｍｏｌ）、およびテトラキストリフェニルホスフィンパラジウム（６４７ｍｇ，０．５６０ｍｍｏｌ）をテトラヒドロフラン（２８０ｍＬ）に懸濁した。この懸濁液に、２．０Ｍ－リン酸カリウム水溶液（４２．０ｍＬ）を加えた後、１８時間加熱還流した。放冷後、反応混合物に水およびメタノールを加えた。生じた固体をろ取し、トルエンによる再結晶によって精製することで、目的の２－（４’－アダマンチルビフェニル－４－イル）－４－（４－ビフェニリル）－６－フェニル－１，３，５－トリアジン（化合物Ｄ８１）を得た（５．２０ｇ、収率３１％）。
^１ＨＮＭＲ（ＣＤＣｌ_３）δ１．８４（ｂｒｓ，６Ｈ），２．１２（ｂｒｓ，６Ｈ），２．１７（ｂｒｓ，３Ｈ），７．４５（ｔ，Ｊ＝７．２Ｈｚ，１Ｈ），７．５２－７．５５（ｍ，４Ｈ），７．６０－７．６６（ｍ，３Ｈ），７．７２（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．７５（ｄｄ，Ｊ＝８．５，１．４Ｈｚ，２Ｈ），７．８５（ｄ，Ｊ＝８．０Ｈｚ，４Ｈ
），８．８４（ｄｄ，Ｊ＝８．０，１．９Ｈｚ，２Ｈ），８．８８（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．８９（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ）．

Under an argon atmosphere, 2-(biphenyl-4-yl)-4-(4-bromophenyl)-6-phenyl-1,3,5-triazine (13.0 g, 28.0 mmol), 5,5-dimethyl- 2-[4-(1-adamantyl)phenyl]-1,3,2-dioxaborinane (9.99 g, 30.8 mmol) and tetrakistriphenylphosphine palladium (647 mg, 0.560 mmol) were suspended in tetrahydrofuran (280 mL). muddy. After adding 2.0 M aqueous potassium phosphate solution (42.0 mL) to this suspension, the mixture was heated under reflux for 18 hours. After allowing to cool, water and methanol were added to the reaction mixture. The resulting solid was collected by filtration and purified by recrystallization from toluene to give the target 2-(4'-adamantylbiphenyl-4-yl)-4-(4-biphenylyl)-6-phenyl-1,3, 5-triazine (compound D81) was obtained (5.20 g, 31% yield).
¹ H NMR (CDCl ₃ ) δ 1.84 (brs, 6H), 2.12 (brs, 6H), 2.17 (brs, 3H), 7.45 (t, J = 7.2 Hz, 1H), 7. 52-7.55 (m, 4H), 7.60-7.66 (m, 3H), 7.72 (d, J=8.4Hz, 2H), 7.75 (dd, J=8.5 , 1.4Hz, 2H), 7.85 (d, J = 8.0Hz, 4H
), 8.84 (dd, J = 8.0, 1.9 Hz, 2H), 8.88 (d, J = 8.5 Hz, 2H), 8.89 (d, J = 8.5 Hz, 2H) .

Compound D81 had a Tg of 132° C. and no Tc was detected.

<<Synthesis Example-9 (D1)>>

アルゴン雰囲気下、２－（ビフェニル－4－イル）－４－クロロ－６－フェニル－１，３，５－トリアジン（１６．０ｇ，４６．５ｍｍｏｌ）、５，５－ジメチル－２－［４－（１－アダマンチル）フェニル］－１，３，２－ジオキサボリナン（１６．６ｇ，５１．２ｍｍｏｌ）、およびテトラキストリフェニルホスフィンパラジウム（１．０８ｇ，０．９３１ｍｍｏｌ）をテトラヒドロフラン（４６５ｍＬ）に懸濁した。この懸濁液に、２．０Ｍ－リン酸カリウム水溶液（６９．８ｍＬ）を加えた後、１６時間加熱還流した。放冷後、反応混合物に水およびメタノールを加えた。生じた固体をろ取し、トルエンによる再結晶によって精製することで、目的の２－（４－アダマンチルフェニル）－４－（４－ビフェニリル）－６－フェニル－１，３，５－トリアジン（化合物Ｄ１）を得た（１９．５ｇ、収率８１％）。
^１ＨＮＭＲ（ＣＤＣｌ_３）δ１．８５（ｂｒｓ，６Ｈ），２．０４（ｂｒｓ，６Ｈ），２．１８（ｂｒｓ，３Ｈ），７．４４（ｔ，ｄ＝７．２Ｈｚ，１Ｈ），７，５３（ｔ，ｄ＝７．５Ｈｚ，２Ｈ），７．５９－７．６５（ｍ，５Ｈ），７．７４（ｄｄ，Ｊ＝８．５，１．３Ｈｚ，２Ｈ），７．８３（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．７５（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），８．８２（ｄｄ，Ｊ＝８．０，１．８Ｈｚ，２Ｈ），８．８７（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ）．

Under an argon atmosphere, 2-(biphenyl-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (16.0 g, 46.5 mmol), 5,5-dimethyl-2-[4- (1-Adamantyl)phenyl]-1,3,2-dioxaborinane (16.6 g, 51.2 mmol) and tetrakistriphenylphosphine palladium (1.08 g, 0.931 mmol) were suspended in tetrahydrofuran (465 mL). After adding 2.0 M aqueous potassium phosphate solution (69.8 mL) to this suspension, the mixture was heated under reflux for 16 hours. After allowing to cool, water and methanol were added to the reaction mixture. The resulting solid was collected by filtration and purified by recrystallization from toluene to give the desired 2-(4-adamantylphenyl)-4-(4-biphenylyl)-6-phenyl-1,3,5-triazine (compound D1) was obtained (19.5 g, 81% yield).
¹ H NMR (CDCl ₃ ) δ 1.85 (brs, 6H), 2.04 (brs, 6H), 2.18 (brs, 3H), 7.44 (t, d = 7.2 Hz, 1H), 7, 53 (t, d = 7.5Hz, 2H), 7.59-7.65 (m, 5H), 7.74 (dd, J = 8.5, 1.3Hz, 2H), 7.83 (d , J = 8.6 Hz, 2H), 8.75 (d, J = 8.7 Hz, 2H), 8.82 (dd, J = 8.0, 1.8 Hz, 2H), 8.87 (d, J=8.6Hz, 2H).

<<Synthesis Example-10 (D87)>>

合成実施例－８と同様な方法で２－（４’－アダマンチルビフェニル－４－イル）－４，６－ビス（４－ビフェニリル）－１，３，５－トリアジン（化合物Ｄ８７）を得た。^１ＨＮＭＲ（ＣＤＣｌ_３）δ１．８４（ｂｒｓ，６Ｈ），２．０２（ｂｒｓ，６Ｈ），２．１７（ｂｒｓ，３Ｈ），７．４５（ｔ，Ｊ＝７．５Ｈｚ，２Ｈ），７．５２－７．５６（ｍ，６Ｈ），７．７２（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），７．７５（ｄｄ，Ｊ＝８．３，１．３Ｈｚ，４Ｈ），７．８４－７．８６（ｍ，６Ｈ），８．８８－８．９１（ｍ，６Ｈ）．

2-(4'-adamantylbiphenyl-4-yl)-4,6-bis(4-biphenylyl)-1,3,5-triazine (Compound D87) was obtained in the same manner as in Synthesis Example-8. ¹ H NMR (CDCl ₃ ) δ 1.84 (brs, 6H), 2.02 (brs, 6H), 2.17 (brs, 3H), 7.45 (t, J = 7.5 Hz, 2H), 7. 52-7.56 (m, 6H), 7.72 (d, J=8.6Hz, 2H), 7.75 (dd, J=8.3, 1.3Hz, 4H), 7.84-7 .86 (m, 6H), 8.88-8.91 (m, 6H).

Compound D87 had a Tg of 155° C. and no Tc was detected.

<<Synthesis Example-11 (D175)>>

アルゴン雰囲気下、２－（４－クロロフェニル）－４，６ビス（４－ビフェニリル）ピリミジン（２．００ｇ，４．０４ｍｍｏｌ）、５，５－ジメチル－２－［４－（１－アダマンチル）フェニル］－１，３，２－ジオキサボリナン（１．３１ｇ，４．０４ｍｍｏｌ）、酢酸パラジウム（１８．１ｍｇ、０．０８１ｍｍｏｌ）および２－ジシクロへキシルホスフィノ－２’，４’,６’－トリイソプロピルビフェニル（７７．０ｍｇ，０．１６２ｍｍｏｌ）をテトラヒドロフラン（４０ｍＬ）に懸濁した。この懸濁液に、２．０Ｍ－リン酸カリウム水溶液（６．１ｍＬ）を加えた後、１９時間加熱還流した。放冷後、反応混合物に水およびメタノールを加えた。生じた固体をろ取し、トルエンによる再結晶によって精製することで、目的の２－（４’－アダマンチルビフェニル－４－イル）－４，６－ビス（４－ビフェニリル）ピリミジン（Ｄ１７５）を得た（２．４５ｇ、収率９０％）。
^１ＨＮＭＲ（ＣＤＣｌ_３）δ１．８３（ｂｒｓ，６Ｈ），２．０２（ｂｒｓ，６Ｈ），２．１６（ｂｒｓ，３Ｈ），７．４４（ｔ，ｄ＝７．２Ｈｚ，２Ｈ），７．５１－７．５５（ｍ，６Ｈ），７．７１－７．７５（ｍ，６Ｈ），７．８２－７．８５（ｍ，６Ｈ），８．１３（ｓ，１Ｈ），８．４４（ｄ，Ｊ＝８．６Ｈｚ，４Ｈ），８．８４（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ）．

2-(4-chlorophenyl)-4,6 bis(4-biphenylyl)pyrimidine (2.00 g, 4.04 mmol), 5,5-dimethyl-2-[4-(1-adamantyl)phenyl] under argon atmosphere -1,3,2-dioxaborinane (1.31 g, 4.04 mmol), palladium acetate (18.1 mg, 0.081 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (77 .0 mg, 0.162 mmol) was suspended in tetrahydrofuran (40 mL). After adding 2.0 M aqueous potassium phosphate solution (6.1 mL) to this suspension, the mixture was heated under reflux for 19 hours. After allowing to cool, water and methanol were added to the reaction mixture. The resulting solid was collected by filtration and purified by recrystallization from toluene to obtain the target 2-(4'-adamantylbiphenyl-4-yl)-4,6-bis(4-biphenylyl)pyrimidine (D175). (2.45 g, 90% yield).
¹ H NMR (CDCl ₃ ) δ 1.83 (brs, 6H), 2.02 (brs, 6H), 2.16 (brs, 3H), 7.44 (t, d = 7.2 Hz, 2H), 7. 51-7.55 (m, 6H), 7.71-7.75 (m, 6H), 7.82-7.85 (m, 6H), 8.13 (s, 1H), 8.44 ( d, J=8.6 Hz, 4H), 8.84 (d, J=8.4 Hz, 2H).

<<Synthesis Example-12 (D7)>>

アルゴン雰囲気下、２，４－ビス（ビフェニル－4－イル）－６－クロロ－１，３，５－トリアジン（９．００ｇ，２１．４ｍｍｏｌ）、５，５－ジメチル－２－［４－（１－アダマンチル）フェニル］－１，３，２－ジオキサボリナン（７．７ｇ，２３．６ｍｍｏｌ）、およびテトラキストリフェニルホスフィンパラジウム（４９．５ｍｇ，０．４２９ｍｍｏｌ）をテトラヒドロフラン（２１４ｍＬ）に懸濁した。この懸濁液に、２．０Ｍ－リン酸カリウム水溶液（３２．２ｍＬ）を加えた後、２３時間加熱還流した。放冷後、反応混合物に水およびメタノールを加えた。生じた固体をろ取し、トルエンによる再結晶によって精製することで、目的の２－（４－アダマンチルフェニル）－４，６－ビス（４－ビフェニリル）－１，３，５－トリアジン（化合物Ｄ７）を得た（９．８ｇ、収率７７％）。
^１ＨＮＭＲ（ＣＤＣｌ_３）δ１．８５（ｂｒｓ，６Ｈ），２．０４（ｂｒｓ，６Ｈ），２．１８（ｂｒｓ，３Ｈ），７．４４（ｔ，Ｊ＝７．５Ｈｚ，２Ｈ），７．５４（ｔ，Ｊ＝７．８Ｈｚ，４Ｈ），７．６２（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），７．７５（ｄ，Ｊ＝７．３Ｈｚ，４Ｈ），７．８５（ｄ，Ｊ＝８．６Ｈｚ，４Ｈ），８．７６（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．８９（ｄ，Ｊ＝８．５Ｈｚ，４Ｈ）．

Under an argon atmosphere, 2,4-bis(biphenyl-4-yl)-6-chloro-1,3,5-triazine (9.00 g, 21.4 mmol), 5,5-dimethyl-2-[4-( 1-Adamantyl)phenyl]-1,3,2-dioxaborinane (7.7 g, 23.6 mmol) and tetrakistriphenylphosphine palladium (49.5 mg, 0.429 mmol) were suspended in tetrahydrofuran (214 mL). After adding 2.0 M aqueous potassium phosphate solution (32.2 mL) to this suspension, the mixture was heated under reflux for 23 hours. After allowing to cool, water and methanol were added to the reaction mixture. The resulting solid was collected by filtration and purified by recrystallization from toluene to give the desired 2-(4-adamantylphenyl)-4,6-bis(4-biphenylyl)-1,3,5-triazine (compound D7 ) was obtained (9.8 g, 77% yield).
¹ H NMR (CDCl ₃ ) δ 1.85 (brs, 6H), 2.04 (brs, 6H), 2.18 (brs, 3H), 7.44 (t, J = 7.5 Hz, 2H), 7. 54 (t, J = 7.8 Hz, 4H), 7.62 (d, J = 8.7 Hz, 2H), 7.75 (d, J = 7.3 Hz, 4H), 7.85 (d, J = 8.6 Hz, 4H), 8.76 (d, J = 8.6 Hz, 2H), 8.89 (d, J = 8.5 Hz, 4H).

Compound D7 had a Tg of 131° C. and no Tc was detected.

<<Synthesis Example 13 (ETL1)>>
ETL1 was synthesized by the method described in Example 8 described in JP-A-2015-34159. The obtained compound had a Tg of 102°C and a Tc of 176°C.

<<Synthesis Example-14>>
ETL2 was synthesized by the method described in Example 22 of JP-A-2007-314503. The obtained compound had a Tg of 124°C and a Tc of 174°C.

From the above results, compounds D9, D8, D81, D87, and D7 were confirmed to have higher Tg than ETL1 and ETL2. Furthermore, since no crystallization peak is detected in these compounds, formation of a film structure having a high amorphous property can be expected during vapor deposition. It is presumed that the development of longevity and longevity was expressed.

<Examples of Organic Electroluminescence Devices>
An organic electroluminescence device was produced and its performance was evaluated. The materials used were refined by sublimation.

<Device Example-1>

An organic electroluminescence device 100 containing compound D158 was produced as follows (see FIG. 2).

(Preparation of substrate 1 and anode 2)
As a substrate 1 having an anode 2 on its surface, a glass substrate with an ITO transparent electrode, in which an indium-tin oxide (ITO) film (thickness: 110 nm) with a width of 2 mm was patterned in stripes, was prepared. Then, after washing the substrate with isopropyl alcohol, the surface was treated by ozone ultraviolet washing.

(Preparation for vacuum deposition)
Each layer was vacuum-deposited on the surface-treated substrate after cleaning by a vacuum deposition method to laminate each layer.

First, the glass substrate was introduced into a vacuum deposition tank, and the pressure was reduced to 1.0×10 ⁻⁴ Pa. Then, each layer was produced in the following order according to the film forming conditions of each layer. In addition, each organic material was formed into a film by a resistance heating method.

(Preparation of hole injection layer 3)
N-[1,1′-biphenyl]-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluoren-2-amine and 1,2,3-Tris[(4-cyano-2,3,5,6-tetrafluorophenyl)methylene]cyclopropane was deposited at a ratio of 99:1 (mass ratio) to a thickness of 10 nm to form a hole injection layer. 3 was produced. The deposition rate was 0.1 nm/sec.

(Preparation of first hole transport layer 41)
N-[1,1′-biphenyl]-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluoren-2-amine A film having a thickness of 85 nm was formed at a rate of 0.2 nm/sec to produce the first hole transport layer 41 .

(Preparation of second hole transport layer 42)
A film of N-phenyl-N-(9,9-diphenylfluoren-2-yl)-N-(1,1'-biphenyl-4-yl)amine was formed to a thickness of 5 nm at a rate of 0.15 nm/sec, and a second A hole transport layer 42 was produced.

(Preparation of light-emitting layer 5)
3-(10-phenyl-9-anthryl)-dibenzofuran and 2,7-bis[N,N-di-(4-tertbutylphenyl)]amino-bisbenzofurano-9,9′-spirofluorene at 95 A film having a thickness of 20 nm was formed at a ratio of :5 (mass ratio) to prepare a light-emitting layer 5 . The deposition rate was 0.1 nm/sec.

(Preparation of hole blocking layer 9)
2-[3′-(9,9-dimethyl-9H-fluoren-2-yl)[1,1′-biphenyl]-3-yl]-4,6-diphenyl-1,3,5-triazine A film of 6 nm was formed at a rate of 0.05 nm/sec to prepare a hole blocking layer 9 .

(Preparation of electron transport layer 6)
2-(4′-adamantylbiphenyl-4-yl)-4-(4-adamantylphenyl)-6-(4-biphenylyl)-1,3,5-triazine (Compound D158) synthesized in Synthesis Example-4 and 8-hydroxyquinolinolato-lithium (hereinafter referred to as Liq) were deposited at a ratio of 50:50 (mass ratio) to a thickness of 25 nm to prepare an electron transport layer 6 . The deposition rate was 0.15 nm/sec.

(Preparation of electron injection layer 7)
Yb was deposited to a thickness of 1 nm at a rate of 0.02 nm/sec to prepare the electron injection layer 7 .

(Preparation of cathode 8)
Finally, a metal mask was placed perpendicular to the ITO stripes (anode 2) on the substrate 1, and a cathode 8 was formed. The cathode was formed by depositing silver/magnesium (mass ratio 1/10) and silver in this order to 80 nm and 20 nm, respectively, to form a two-layer structure. The deposition rate of silver/magnesium was 0.5 nm/second, and the deposition rate of silver was 0.2 nm/second.

As described above, an organic electroluminescence device 100 having a light emitting area of 4 mm ² as shown in FIG. 2 was produced. Each film thickness was measured with a stylus film thickness meter (DEKTAK, manufactured by Bruker).

Further, this device was sealed in a nitrogen atmosphere glove box with an oxygen and water concentration of 1 ppm or less. Sealing was performed by using a bisphenol F type epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).

<Device Example-2>
In Device Example-1, 2-(4′-adamantylbiphenyl-4-yl)-4-(4-adamantylphenyl)-6-(4-biphenylyl)-1,3,5-triazine was added to the electron transport layer 6 (Compound D158) and Liq at a ratio of 50:50 (mass ratio) instead of forming a 25 nm film (film formation rate 0.15 nm / sec), 2-(4-adamantylphenyl) synthesized in Synthesis Example-5 -4-(4-biphenylyl)-6-{4-(1-naphthyl)phenyl}-1,3,5-triazine (compound D9) and Liq at a ratio of 50:50 (mass ratio) to form a 25 nm film ( An organic electroluminescence device was produced in the same manner as in Device Example-1, except that the film formation rate was 0.15 nm/sec.

<Device Example-3>
In Device Example-1, 2-(4′-adamantylbiphenyl-4-yl)-4-(4-adamantylphenyl)-6-(4-biphenylyl)-1,3,5-triazine was added to the electron transport layer 6 (Compound D158) and Liq at a ratio of 50:50 (mass ratio) instead of forming a 25 nm film (film formation rate 0.15 nm / sec), 2-(4-adamantylphenyl) synthesized in Synthesis Example-7 -4-(4-biphenylyl)-6-{4-(2-naphthyl)phenyl}-1,3,5-triazine (compound D8) and Liq at a ratio of 50:50 (mass ratio) to form a 25 nm film ( An organic electroluminescence device was produced in the same manner as in Device Example-1, except that the film formation rate was 0.15 nm/sec.

<Device Example-4>
In Device Example-1, 2-(4′-adamantylbiphenyl-4-yl)-4-(4-adamantylphenyl)-6-(4-biphenylyl)-1,3,5-triazine was added to the electron transport layer 6 (Compound D158) and Liq at a ratio of 50:50 (mass ratio) instead of forming a 25 nm film (film formation rate 0.15 nm / sec), 2-(4'-adamantylbiphenyl synthesized in Synthesis Example-8 -4-yl)-4-(4-biphenylyl)-6-phenyl-1,3,5-triazine (compound D81) and Liq at a ratio of 50:50 (mass ratio) to form a 25 nm film (film formation rate: 0 An organic electroluminescence device was produced in the same manner as in Device Example-1, except that the emission was 0.15 nm/sec).

<Device Example-5>
In Device Example-1, 2-(4′-adamantylbiphenyl-4-yl)-4-(4-adamantylphenyl)-6-(4-biphenylyl)-1,3,5-triazine was added to the electron transport layer 6 (Compound D158) and Liq at a ratio of 50:50 (mass ratio) instead of forming a 25 nm film (film formation rate 0.15 nm / sec), 2-(4-adamantylphenyl) synthesized in Synthesis Example-9 -4-(4-biphenylyl)-6-phenyl-1,3,5-triazine (compound D1) and Liq at a ratio of 50:50 (mass ratio) to form a 25 nm film (film formation rate: 0.15 nm/sec) An organic electroluminescence device was produced in the same manner as in Device Example-1, except that

<Device Example-6>
In Device Example-1, 2-(4′-adamantylbiphenyl-4-yl)-4-(4-adamantylphenyl)-6-(4-biphenylyl)-1,3,5-triazine was added to the electron transport layer 6 (Compound D158) and Liq at a ratio of 50:50 (mass ratio) instead of forming a 25 nm film (film formation rate 0.15 nm / sec), 2-(4'-adamantylbiphenyl synthesized in Synthesis Example-10 -4-yl)-4,6-bis(4-biphenylyl)-1,3,5-triazine (Compound D87) and Liq were deposited at a ratio of 50:50 (mass ratio) to a thickness of 25 nm (deposition rate: 0.00). An organic electroluminescence device was produced in the same manner as in Device Example-1, except that the emission was 15 nm/sec.

<Device Example-7>
In Device Example-1, 2-(4′-adamantylbiphenyl-4-yl)-4-(4-adamantylphenyl)-6-(4-biphenylyl)-1,3,5-triazine was added to the electron transport layer 6 (Compound D158) and Liq at a ratio of 50:50 (mass ratio) instead of forming a 25 nm film (film formation rate 0.15 nm / sec), 2-(4-adamantylphenyl) synthesized in Synthesis Example-12 -4,6-bis(4-biphenylyl)-1,3,5-triazine (compound D7) and Liq were deposited at a ratio of 50:50 (mass ratio) to form a 25 nm film (film formation rate: 0.15 nm/sec). An organic electroluminescence device was produced in the same manner as in Device Example-1 except for the above.

<Device Example-8>
In Device Example-1, 2-(4′-adamantylbiphenyl-4-yl)-4-(4-adamantylphenyl)-6-(4-biphenylyl)-1,3,5-triazine was added to the electron transport layer 6 (Compound D158) and Liq at a ratio of 50:50 (mass ratio) instead of forming a 25 nm film (film formation rate 0.15 nm / sec), 2-(4'-adamantylbiphenyl synthesized in Synthesis Example-11 -4-yl)-4,6-bis(4-biphenylyl)pyrimidine (compound D175) and Liq were deposited at a ratio of 50:50 (mass ratio) to form a 25 nm film (film formation rate: 0.15 nm/sec). , an organic electroluminescence device was produced in the same manner as in Device Example-1.

<Element Comparative Example-1>
In Device Example-1, the electron transport layer 6 contains 2-(4′-adamantylbiphenyl-4-yl)-4-(4-adamantylphenyl)-6-(4-biphenylyl)-1,3,5- Instead of forming a 25 nm film of triazine (compound D158) and Liq at a ratio of 50:50 (mass ratio) (film formation rate: 0.15 nm/sec), ETL-2 synthesized in Synthesis Example-14 and Liq were deposited at 50: An organic electroluminescence device was produced in the same manner as in Device Example-1, except that a 25 nm film was formed at a ratio of 50 (mass ratio) (film formation rate: 0.15 nm/sec).

<Evaluation of organic EL element>
A direct current was applied to the produced organic electroluminescence device, and the luminescence characteristics were evaluated using a luminance meter, LUMINANCE METER (BM-9) manufactured by TOPCON.

As light emission characteristics, the voltage (V) and power efficiency (lm/A) when a current density of 10 mA/cm ² was applied were measured, and the life of the element during continuous lighting was measured. The device life was measured by measuring the luminance decay time during continuous lighting when the device was driven at an initial luminance of 1000 cd/m ² , and measuring the time required for the luminance (cd/m ² ) to decrease by 5%. The values of voltage, power efficiency, and life are expressed as relative values when the value of device comparative example 1 is set to 100. Table 1 shows the results. The measurement was performed in an atmosphere of 23°C and 50% RH. A smaller value of voltage is better, and a higher value of efficiency and life is better.

From Table 1, compared with Device Comparative Example 1, the organic electroluminescent devices according to Device Examples 1 to 8 using the adamantane compound (1) according to the embodiment of the present invention have voltage, current efficiency and device life. It can be seen that these characteristics are improved.

<EOD evaluation>
Electron mobility is an important factor in improving the performance of organic electroluminescent devices. For example, the higher the electron mobility in the electron-transporting layer, the more electrons can be injected into the light-emitting layer, which can contribute to higher efficiency and lower voltage of the device. Therefore, in order to examine the mobility (electron mobility) of the above compound, an EOD (Electron Only Device) was manufactured and evaluated.

Specifically, EODs (Device Examples 11 to 18 and Device Comparative Example 11) were manufactured using the above compounds. An EOD using the compound ETL1 according to Synthesis Example 13 was also produced (Device Example 19).

The voltage (V) at a specific current was measured for each EOD produced. The smaller the voltage (EOD voltage), the higher the electron mobility of the compound. The value of voltage is expressed as a relative value when the value of device example 19 is set to 100.

More detailed manufacturing and evaluation procedures are shown below.

Using each of the compounds (target compounds) shown in Table 2 below, an EOD having the following device configuration was produced by vapor-depositing each layer on an ITO substrate in order, starting with Ag:
ITO/Ag (thickness: 10 nm)/Liq (thickness: 1 nm)/target compound: Liq=50:50 (thickness: 70 nm)/Yb (thickness: 1 nm)/AgMg (80 nm)
In this EOD, Ag/Liq deposited on ITO blocks the flow of holes.

For each EOD produced, the voltage (EOD voltage) was measured when a current density of 10 mA/cm ² was applied. The results are shown in Table 2 below.

As can be seen in Table 2, Device Examples 11-18 all exhibited lower EOD voltages than Device Example 19. This result shows that the compounds according to Device Examples 11-18 have higher electron mobilities than the compound according to Device Example 19. Compounds according to Element Examples 11-18 are attached at the para position to the benzene ring attached to the aromatic ring (particularly heteroaromatic rings such as triazines or pyrimidines) having Z ¹ , Z ² and Z ³ has an aromatic hydrocarbon ring. While not intending to be bound by theory, it is believed that such a structure broadened the LUMO of the compound and exhibited higher electron mobility compared to the compound of Device Example 19, which did not have such a structure. Conceivable.

This is also confirmed from a comparison between Device Example 19 and Device Comparative Example 11. That is, the compound (ETL2) of Element Comparative Example 11 also has an aromatic hydrocarbon ring (benzene ring) bonded at the para position to the benzene ring bonded to the aromatic ring having Z ¹ , Z ² and Z ³ and showed relatively high electron mobility.

According to the results in Table 2, the compound ETL2 has a higher electron mobility than the compounds according to the examples. However, according to the results in Table 1, the organic electroluminescence device fabricated using this compound ETL2 exhibited performance inferior to that of the compounds according to the examples. The reason for this is that structures with para-conjugated aromatic hydrocarbon rings, while providing high electron mobility, create deep LUMO energy levels and cause increased resistance at adjacent layer interfaces in the device. There is urination. Although not intending to be limited by theory, it is believed that the organic electroluminescent device manufactured using the compound ETL2 is greatly affected by this increase in resistance, and sufficient performance of the organic electroluminescent device cannot be obtained.

In contrast, the compounds of the present disclosure according to Device Examples 1-8 in Table 1, unlike compound ETL2, have terminal adamantyl groups, which result in deep LUMO energy levels. It is believed that the above disadvantages have been avoided or compensated for. Although not intended to be limited by theory, in the compounds according to Device Examples 1 to 8, the sterically bulky adamantyl group may suppress the deactivation of excitons at the interface between adjacent layers in the device. be. More specifically, for example, when an intermediate such as an exciplex is generated by the interaction between the light-emitting layer and the electron-transporting layer, the exciton energy is deactivated, which may cause a decrease in luminous efficiency. , the bulky adamantyl group is thought to work advantageously in suppressing the formation of such exciplexes.

It can be seen that the adamantane compound (1) according to the embodiment of the present invention is a novel adamantane compound that is highly amorphous and has excellent heat resistance. Therefore, it has good thermal stability during sublimation purification, so that it has excellent operability in sublimation purification and can provide a material with few impurities.

Moreover, the adamantane compound (1) according to another embodiment of the present invention is used as an electron transport material for organic electroluminescence devices, which is excellent in low driving voltage. Furthermore, according to the present invention, it is possible to provide an organic electroluminescence device that is excellent in power consumption.

Furthermore, the adamantane compound (1) according to another embodiment of the present invention can provide a long-life organic electroluminescence device due to excellent stability of the deposited film.

And the thin film composed of the adamantane compound (1) according to another embodiment of the present invention is excellent in electron transport ability, hole blocking ability, oxidation-reduction resistance, water resistance, oxygen resistance, electron injection characteristics, etc., so that organic electroluminescence It is useful as a material for devices, and particularly useful as an electron transporting material, a hole blocking material, a light emitting host material, and the like. Moreover, since the adamantane compound (1) according to the embodiment of the present invention is a wide bandgap compound, it can be suitably used not only for fluorescent devices but also for phosphorescent devices.

1. glass substrate2. Anode 3 . hole injection layer4. hole transport layer 41 . first hole transport layer 42 . Second hole transport layer 5 . light-emitting layer 9 . hole blocking layer6. electron transport layer7. electron injection layer8. cathode 100 . organic electroluminescent element

Claims (21)

Adamantane compound represented by the general formula (1):

During the ceremony,
Ar ¹ represents an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ² represents a single bond or an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ³ represents an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ¹ , Ar ² when it is an aromatic hydrocarbon group, and Ar ³ are each one or more of a phenyl group, naphthyl group, phenanthryl group, anthryl group, triphenylenyl group, terphenyl group, methyl group, tert- substituted or unsubstituted with one or more substituents selected from the group of butyl, fluoro, and deuterium;
Ad represents a 1-adamantyl group or a 2-adamantyl group;
a represents 1 or 2;
b represents 1 or 2;
c represents 0 or 1;
d represents 1 or 2;
with the proviso that a+b+c=3;
Z ¹ , Z ² and Z ³ each independently represent a nitrogen atom or C—H. 2. The adamantane compound of claim ¹ , wherein two or more of Z1, ^Z2 and ^Z3 are nitrogen atoms. 3. The adamantane compound according to claim ¹ or ² , wherein two of Z ¹ , Z 2 and Z 3 are nitrogen atoms and one is CH. The adamantane compound according to any one of claims 1 to 3, wherein Ar ² is an aromatic hydrocarbon group having 6 to 24 carbon atoms. 5. The adamantane compound according to claim 4, wherein ^Ar2 is a phenylene group or biphenylylene group optionally substituted with a phenyl group. 5. The adamantane compound according to claim 4, wherein Ar ² is a 1,4-phenylene group or a 4,4'-biphenylylene group optionally substituted with a phenyl group. 5. The adamantane compound of claim 4, wherein ^Ar2 is unsubstituted. The adamantane compound according to any one of claims 1 to 7, wherein Ar ¹ is an aromatic hydrocarbon group having 12 to 16 carbon atoms. The adamantane compound according to any one of claims 1 to 7, wherein Ar ¹ is a 4-biphenylyl group or a 4-naphthylphenyl group. The adamantane compound according to any one of claims 1 to 7, wherein Ar ¹ and Ar ³ are each independently a phenyl group optionally substituted with a phenyl group or a naphthyl group. The adamantane compound of any one of claims 1-9, wherein Ar ¹ and Ar ³ are unsubstituted. The adamantane compound according to claim 1, represented by the general formula (1-1):

During the ceremony,
R ¹ represents a single bond, a hydrogen atom, or an aromatic hydrocarbon group having 6 to 18 carbon atoms;
R ² represents a hydrogen atom or an aromatic hydrocarbon group having 6 to 18 carbon atoms;
R ³ represents a single bond or an aromatic hydrocarbon group having 6 to 18 carbon atoms;
either or both of R ¹ and R ² are aromatic hydrocarbon groups having 6 to 18 carbon atoms;
When each of R ¹ , R ² and R ³ is an aromatic hydrocarbon group, one or more phenyl groups, naphthyl groups, phenanthryl groups, anthryl groups, triphenylenyl groups, terphenyl groups, methyl groups, tert- substituted or unsubstituted with one or more substituents selected from the group of butyl, fluoro, and deuterium;
Ad represents a 1-adamantyl group or a 2-adamantyl group;
e represents 0, 1 or 2;
f represents 1 or 2;
Z ¹ , Z ² and Z ³ each independently represent a nitrogen atom or CH, and two or more of Z ¹ , Z ² and Z ³ are nitrogen atoms. The adamantane compound according to claim 12, wherein the aromatic hydrocarbon group has 6 to 12 carbon atoms for R ¹ , R ² and R ³ . 14. The adamantane compound of claim 12 or 13, wherein ^R1 , ^R2 and ^R3 are each unsubstituted when they are aromatic hydrocarbon groups. The adamantane compound according to any one of claims 12-14, wherein e=0. R ¹ is a phenyl group or a naphthyl group,
R ² is a hydrogen atom or a phenyl group,
16. The adamantane compound of claim 15. 17. The adamantane compound of claim 15 or 16, wherein ^R3 is a single bond or a phenylene group. An organic electroluminescent device containing an adamantane compound represented by formula (1):

During the ceremony,
Ar ¹ represents an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ² represents a single bond or an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ³ represents an aromatic hydrocarbon group having 6 to 24 carbon atoms;
Ar ¹ , Ar ² when it is an aromatic hydrocarbon group, and Ar ³ are each one or more of a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a triphenylenyl group, a biphenylyl group, a terphenyl group, and a methyl group. , tert-butyl group, fluoro group, or deuterium, substituted with one or more substituents, or unsubstituted;
Ad represents a 1-adamantyl group or a 2-adamantyl group;
a represents 1 or 2;
b represents 1 or 2;
c represents 0 or 1;
d represents 1 or 2;
with the proviso that a+b+c=3;
Z ¹ , Z ² and Z ³ each independently represent a nitrogen atom or C—H. 19. The organic electroluminescence device according to claim 18, wherein the layer containing the adamantane compound represented by formula (1) is an electron transport layer. 20. The organic electroluminescence device according to claim 18, wherein the adamantane compound represented by formula (1) is doped. 21. The organic electroluminescent device according to claim 20, wherein said dope is Liq.

Images