JP2016033115A - N-triazylphenazine compound, method for producing the same, and use therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electron transport material which can be used for a large-sized display, an illumination and others, is excellent in drive voltage and element luminous efficiency, and also has excellent life properties.SOLUTION: The N-triazylphenazine compound obtained by, for example, the following reaction formula, enables a positive hole and an electron to be efficiently injected and transported to a light emitting layer for recoupling, and therefore is useful as an organic electroluminescent element.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an N-triazylphenazine compound, a production method thereof, and an organic electroluminescent device using the compound.

  The organic electroluminescent element has a structure in which a light emitting layer containing a light emitting material is sandwiched between a hole transport layer and an electron transport layer, and an anode and a cathode are attached to the outside, and holes injected into the light emitting layer and It is a self-emitting element that utilizes a light emission phenomenon (fluorescence or phosphorescence) when excitons generated by electron recombination are deactivated. Since it is a self-luminous type, it is excellent in visibility, and since it is a completely solid element, it is easy to handle and manufacture. In addition, since it is a thin film type device, it is attracting attention from the viewpoints of space saving and portability, and is applied to displays, lighting, and the like. At present, the organic electroluminescence device has begun to be used for commercial purposes. However, further improvement in light emission efficiency, reduction in driving voltage, and longer life are required for energy saving.

  In order to achieve high efficiency, low voltage drive, and long life of the organic electroluminescent device, it is necessary to efficiently inject and transport holes and electrons to the light emitting layer and recombine them. In this regard, improvement of each material constituting the organic electroluminescent element, particularly an electron transporting material, has been demanded.

  Patent Document 1 discloses an N-triazylphenazine compound as a light emitting material of an organic electroluminescent element. When these materials are used as an electron transport material, the voltage of the device is greatly increased and the light emission efficiency is low, so that it cannot be used for the electron transport material.

  Patent Document 2 discloses an electron transport layer host material capable of obtaining an organic EL element having a low driving voltage and an element using the same. However, when this material is used as an electron transport material, the device has a high driving voltage, and the light emission efficiency of the device is low, so that it cannot be used as an electron transport material.

WO2013 / 172255 WO2012 / 015274

  Organic electroluminescent devices are used in various display devices, and more efficient light emission is required for practical use of large displays and lighting. An object of the present invention is to provide an electron transporting material that is superior in driving voltage and light emitting efficiency of the device and also has excellent life characteristics as compared with conventionally known electron transporting materials for organic electroluminescence devices.

  As a result of intensive studies to solve the above-described problems, the present inventors have found that an organic electroluminescent device using the N-triazylphenazine compound shown in the present invention as an electron transporting layer transports a conventionally known material by electron transport. As compared with the organic electroluminescent element used for the layer, it was found that the driving voltage is low, the luminous efficiency is improved, and the life is long, and the present invention has been completed.

  That is, the present invention relates to an N-triazylphenazine compound represented by the following general formula (1) (hereinafter also referred to as “compound (1)”), a production method thereof, and an application thereof.

（式中、
Ａｒ^１およびＡｒ^２は、各々独立に、炭素数６〜１２の芳香族炭化水素基（メチル基、メトキシ基、ピリジル基、ピリミジル基、フッ素原子、または炭素数２〜１０のアルキル基、アルコキシ基、アルコキシアルキル基、エステル基、もしくはエステルアルキル基で置換されていてもよい）を表す。
Ａｒ^３は、連結及び／又は縮環していてもよい炭素数１０〜２６の芳香族炭化水素基または連結及び／又は縮環していてもよい炭素数８〜２５の含窒素へテロ芳香族基（これらの基は、メチル基、メトキシ基、フッ素原子、または炭素数２〜１０のアルキル基、アルコキシ基、アルコキシアルキル基、エステル基もしくはエステルアルキル基で置換されていてもよい）を表す。
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、各々独立に、水素原子、メチル基、メトキシ基、フェニル基、フッ素原子、または炭素数２〜１０のアルキル基、アルコキシ基、アルコキシアルキル基、エステル基もしくはエステルアルキル基を表す。
また、式中の各水素原子は各々独立に重水素原子であってもよい。）

(Where
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 12 carbon atoms (methyl group, methoxy group, pyridyl group, pyrimidyl group, fluorine atom, alkyl group having 2 to 10 carbon atoms, alkoxy group) , May be substituted with an alkoxyalkyl group, an ester group, or an ester alkyl group.
Ar ³ is an aromatic hydrocarbon group having 10 to 26 carbon atoms which may be linked and / or condensed, or a nitrogen-containing heteroaromatic group having 8 to 25 carbon atoms which may be linked and / or condensed. Represents a group (these groups may be substituted with a methyl group, a methoxy group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group).
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a methyl group, a methoxy group, a phenyl group, a fluorine atom, or a carbon number of 2 to 10 Represents an alkyl group, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.
In addition, each hydrogen atom in the formula may independently be a deuterium atom. )

  Since the compound (1) of the present invention has good charge injection and transport properties, it is useful as a material for organic electroluminescence devices, and can be used as an electron transport material and a light emitting host material. The organic electroluminescent device having an electron transport layer containing the compound (1) of the present invention is superior in organic EL device using a general-purpose electron transport material, has a low driving voltage, excellent luminous efficiency, and has a long lifetime. .

  The compound (1) of the present invention is capable of organic electroluminescence by simultaneously reducing the gap between singlet energy and triplet energy (Example 2: 0.12 eV, Gaussian TD-DFT calculation) and good electron injection properties. Achieved high device efficiency.

The cross-sectional schematic diagram of the organic electroluminescent element produced by Test example-1 etc. is represented.

  Hereinafter, the present invention will be described in detail.

Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 12 carbon atoms (methyl group, methoxy group, pyridyl group, pyrimidyl group, fluorine atom, alkyl group having 2 to 10 carbon atoms, alkoxy group) , May be substituted with an alkoxyalkyl group, an ester group or an ester alkyl group).

  Although it does not specifically limit as a C6-C12 aromatic hydrocarbon group, For example, a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenyl group, 3-biphenyl group, or 4- Biphenyl group etc. are mentioned.

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

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

Although it does not specifically limit as a C2-C10 alkyl group, an alkoxy group, an alkoxyalkyl group, ester group, or ester alkyl group, For example, an ethyl group (-Et), n-propyl group (n- Pr), i-propyl group (i-Pr), n-butyl group (n-Bu), t-butyl group (t-Bu), pentyl (-Pent), hexyl group (-Hex), heptyl group (- Hept), octyl group (—Oct) (above, an alkyl group having 2 to 10 carbon atoms), ethoxy group, n-propyloxy group, i-propyloxy group, n-butyloxy group, t-butyloxy group, pentyloxy group Hexyloxy group, heptyloxy group, octyloxy group (above, alkoxy group having 2 to 10 carbon atoms), methoxymethyl group, methoxyethyl group, methoxypropiyl Group, methoxybutyl group, methoxyhexyl group, methoxyheptyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, pentyloxypropyl group (above, C2-C10 alkoxyalkyl group), methyl ester Group, ethyl ester group, n-propyl ester group, i-propyl ester group, n-butyl ester group, t-butyl ester group, pentyl ester group, hexyl ester group, heptyl ester group (above, having 2 to 10 carbon atoms) ester _{group), - CH 2 COOMe, -CH} 2 COOEt, -CH 2 COO (n-Pr), - CH 2 COO (i-Pr), - CH 2 COO (n-Bu), - CH 2 COO (t _{-Bu), - CH 2 COOHex,} -CH 2 CH 2 CH 2 COOMe, -CH 2 CH _{2 CH 2 COOEt, -CH 2 CH} 2 CH 2 COO (n-Pr), - CH 2 CH 2 CH 2 COO (i-Pr), - CH 2 CH 2 CH 2 COO (n-Bu), - CH 2 CH ₂ CH ₂ COO (t-Bu), -Hex-COOMe (above, ester alkyl group having 2 to 10 carbon atoms) and the like.

The substituent represented by Ar ¹ and Ar ² is not particularly limited, and examples thereof include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, and 2,3-dimethyl. Phenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2-ethylphenyl group, 3 -Ethylphenyl group, 4-ethylphenyl group, 2-ethyl-3-methylphenyl group, 2-ethyl-4-methylphenyl group, 2-ethyl-5-methylphenyl group, 2-ethyl-6-methylphenyl group 3-ethyl-2-methylphenyl group, 3-ethyl-4-methylphenyl group, 3-ethyl-5-methylphenyl group, 3-ethyl-6-methylphenyl group, -Ethyl-2-methylphenyl group, 4-ethyl-3-methylphenyl group, 2-hexylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 4-hexyl-2-methylphenyl group, 4-hexyl -3-ethylphenyl group, 4-hexyloxy-2-propylphenyl group, 4-hexyloxy-3-butylphenyl group, 3-ethoxyethyl-5-methylphenyl group, 3-ethoxyethyl-6-methylphenyl group 2-methyl ester phenyl group, 3-methyl ester phenyl group, 4-methyl ester phenyl group, 2-hexyl ester phenyl group, 3-hexyl ester phenyl group, 4-hexyl ester phenyl group, 2- (2-pyridyl) ) Phenyl group, 3- (2-pyridyl) phenyl group, 4- (2-pyridyl) phenyl group, 3, 5-bis (2-pyridyl) phenyl group, 2- (3-pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 3,5-bis (3-pyridyl) ) Phenyl group, 2- (4-pyridyl) phenyl group, 3- (4-pyridyl) phenyl group, 4- (4-pyridyl) phenyl group, 3,5-bis (4-pyridyl) phenyl group, 2- ( 2-pyrimidyl) phenyl group, 3- (2-pyrimidyl) phenyl group, 4- (2-pyrimidyl) phenyl group, 2- (4-pyrimidyl) phenyl group, 3- (4-pyrimidyl) phenyl group, 4- ( 4-pyrimidyl) phenyl group, 2- (5-pyrimidyl) phenyl group, 3- (5-pyrimidyl) phenyl group, 4- (5-pyrimidyl) phenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4 − Fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, perfluorophenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 3-methylnaphthalen-1-yl group, 4-methylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 6-methylnaphthalen-1-yl group, 1-methylnaphthalen-2-yl group, 3-methylnaphthalen-2-yl group, 4-methylnaphthalen-2-yl group, 5-methylnaphthalen-2-yl group, 6-methylnaphthalen-2-yl group, 2-hexylnaphthalen-1-yl group, 3-hexyloxynaphthalen-1-yl group, 4-methoxyethylnaphthalen-1-yl group, 5-hexyl Ester naphthalen-1-yl group, 6-pentoxynaphthalen-1-yl group, 1-methoxyethylnaphthalen-2-yl group, 3-pentylnaphthalen-2-yl group, 4-pentoxynaphthalen-2-yl group 5-methoxyethylnaphthalen-2-yl group, 6-butylnaphthalen-2-yl group, 3- (2-pyridyl) naphthalen-1-yl group, 4- (2-pyridyl) naphthalen-1-yl group, 3- (3-pyridyl) naphthalen-1-yl group, 4- (3-pyridyl) naphthalen-1-yl group, 3- (4-pyridyl) naphthalen-1-yl group, 4- (4-pyridyl) naphthalene -1-yl group, 4- (2-pyridyl) naphthalen-2-yl group, 6- (2-pyridyl) naphthalen-2-yl group, 7- (2-pyridyl) naphthalen-2-yl group, 4- (3 -Pyridyl) naphthalen-2-yl group, 6- (3-pyridyl) naphthalen-2-yl group, 7- (3-pyridyl) naphthalen-2-yl group, 4- (4-pyridyl) naphthalen-2-yl Group, 6- (4-pyridyl) naphthalen-2-yl group, 7- (4-pyridyl) naphthalen-2-yl group, 3- (2-pyrimidyl) naphthalen-1-yl group, 4- (2-pyrimidyl) ) Naphthalen-1-yl group, 3- (4-pyrimidyl) naphthalen-1-yl group, 4- (4-pyrimidyl) naphthalen-1-yl group, 3- (5-pyrimidyl) naphthalen-1-yl group, 4- (5-pyrimidyl) naphthalen-1-yl group, 4- (2-pyrimidyl) naphthalen-2-yl group, 6- (2-pyrimidyl) naphthalen-2-yl group, 7- (2-pyrimidyl) naphthalene -2-yl 4- (4-pyrimidyl) naphthalen-2-yl group, 6- (4-pyrimidyl) naphthalen-2-yl group, 7- (4-pyrimidyl) naphthalen-2-yl group, 4- (5-pyrimidyl) Naphthalen-2-yl group, 6- (5-pyrimidyl) naphthalen-2-yl group, 7- (5-pyrimidyl) naphthalen-2-yl group, 2-fluoronaphthalen-1-yl group, 3-fluoronaphthalene- 1-yl group, 4-fluoronaphthalen-1-yl group, 5-fluoronaphthalen-1-yl group, 6-fluoronaphthalen-1-yl group, 1-fluoronaphthalen-2-yl group, 3-fluoronaphthalene- 2-yl group, 4-fluoronaphthalen-2-yl group, 5-fluoronaphthalen-2-yl group, 6-fluoronaphthalen-2-yl group, perfluoronaphthalene-1 Yl group, perfluoronaphthalen-2-yl group, 3-biphenyl group, 4-biphenyl group, 2-methylbiphenyl-3-yl group, 4-methylbiphenyl-3-yl group, 5-methylbiphenyl-3-yl Group, 6-methylbiphenyl-3-yl group, 2'-methylbiphenyl-3-yl group, 3'-methylbiphenyl-3-yl group, 4'-methylbiphenyl-3-yl group, 2,6-dimethyl group Biphenyl-3-yl group, 2 ′, 6′-dimethylbiphenyl-3-yl group, 2-methylbiphenyl-4-yl group, 3-methylbiphenyl-4-yl group, 2′-methylbiphenyl-4-yl Group, 3'-methylbiphenyl-4-yl group, 4'-methylbiphenyl-4-yl group, 2,6-dimethylbiphenyl-4-yl group, 2 ', 6'-dimethylbiphenyl-4-yl group, 2-hexyl Biphenyl-3-yl group, 4-hexyloxybiphenyl-3-yl group, 5-ethoxyethylbiphenyl-3-yl group, 6-hexyl ester biphenyl-3-yl group, 2'-pentylbiphenyl-3-yl group 3'-pentyloxybiphenyl-3-yl group, 4'-propyloxymethylbiphenyl-3-yl group, 2-butylbiphenyl-4-yl group, 3-butoxybiphenyl-4-yl group, 2'-ethoxy Methyl biphenyl-4-yl group, 3′-butyl ester biphenyl-4-yl group, 4′-pentylbiphenyl-4-yl group, 3 ′-(2-pyridyl) biphenyl-3-yl group, 3 ′-( 3-pyridyl) biphenyl-3-yl group, 3 ′-(4-pyridyl) biphenyl-3-yl group, 4 ′-(2-pyridyl) biphenyl-3-yl group, 4 ′-(3-pyridyl) B) Biphenyl-3-yl group, 4 ′-(4-pyridyl) biphenyl-3-yl group, 3 ′-(2-pyridyl) biphenyl-4-yl group, 3 ′-(3-pyridyl) biphenyl-4 -Yl group, 3 '-(4-pyridyl) biphenyl-4-yl group, 4'-(2-pyridyl) biphenyl-4-yl group, 4 '-(3-pyridyl) biphenyl-4-yl group, 4 '-(4-pyridyl) biphenyl-4-yl group, 3'-(2-pyrimidyl) biphenyl-3-yl group, 3 '-(4-pyrimidyl) biphenyl-3-yl group, 3'-(5- Pyrimidyl) biphenyl-3-yl group, 4 ′-(2-pyrimidyl) biphenyl-3-yl group, 4 ′-(4-pyrimidyl) biphenyl-3-yl group, 4 ′-(5-pyrimidyl) biphenyl-3 -Yl group, 3 '-(2-pyrimidyl) biphenyl-4-yl group 3 ′-(4-pyrimidyl) biphenyl-4-yl group, 3 ′-(5-pyrimidyl) biphenyl-4-yl group, 4 ′-(2-pyrimidyl) biphenyl-4-yl group, 4 ′-( 4-pyrimidyl) biphenyl-4-yl group, 4 ′-(5-pyrimidyl) biphenyl-4-yl group, 2-fluorobiphenyl-3-yl group, 4-fluorobiphenyl-3-yl group, 5-fluorobiphenyl -3-yl group, 6-fluorobiphenyl-3-yl group, 2'-fluorobiphenyl-3-yl group, 3'-fluorobiphenyl-3-yl group, 4'-fluorobiphenyl-3-yl group, 2 2,6-difluorobiphenyl-3-yl group, 2 ', 6'-difluorobiphenyl-3-yl group, 2-fluorobiphenyl-4-yl group, 3-fluorobiphenyl-4-yl group, 2'-fluorobiphe Ru-4-yl group, 3′-fluorobiphenyl-4-yl group, 4′-fluorobiphenyl-4-yl group, 2,6-difluorobiphenyl-4-yl group, 2 ′, 6′-difluorobiphenyl- 4-yl group etc. are mentioned.

Ar ¹ and Ar ² are each independently a phenyl group, a naphthyl group, or a biphenyl group (these groups are a methyl group, a methoxy group, a pyridyl group, a pyrimidyl group) in terms of good performance as an organic electroluminescent element material. Or may be substituted with a fluorine atom).

Further, Ar ¹ and Ar ² are each independently a phenyl group, a biphenyl group, a naphthyl group, a pyridylphenyl group, or a pyrimidylphenyl group (these groups are substituted with a methyl group, a methoxy group, or a fluorine atom) It is preferable that it may be.

Further, Ar ¹ and Ar ² are each independently a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 1-naphthyl group, 2-naphthyl group, 3-biphenyl group, 4 -Biphenyl group, 2,6-dimethylbiphenyl-3-yl group, 2,6-dimethylbiphenyl-4-yl group, 2 ', 6'-dimethylbiphenyl-3-yl group, 2', 6'-dimethylbiphenyl -4-yl group, 3- (2-pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 3- (4-pyridyl) phenyl group, 4- (2-pyridyl) phenyl group, 4- (3 -Pyridyl) phenyl group, 4- (4-pyridyl) phenyl group, 3- (2-pyrimidyl) phenyl group, or 4- (2-pyrimidyl) phenyl group is more preferable.

  Of these substituents, each independently a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-biphenyl group, 4-biphenyl group, 1-naphthyl group, or It is more preferably a 2-naphthyl group.

Ar ³ is an aromatic hydrocarbon group having 10 to 26 carbon atoms which may be linked and / or condensed, or a nitrogen-containing heteroaromatic group having 8 to 25 carbon atoms which may be linked and / or condensed. Represents a group (these groups may be substituted with a methyl group, a methoxy group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group).

Alkyl group, an alkoxy group in the 2 to 10 carbon atoms, an alkoxyalkyl group, for an ester group or ester group, can be exemplified the same as the substituents shown by Ar ¹ and Ar ^2.

  Although it does not specifically limit as said C10-C26 aromatic hydrocarbon group which may be connected and / or condensed, The substitution represented by following (A1)-(A116) A group can be exemplified (* represents a connecting part).

上記の、連結及び／又は縮環していてもよい炭素数８〜２５の含窒素へテロ芳香族基は、連結及び／又は置換していてもよい炭素数１０〜２６の芳香族炭化水素基において少なくとも一つの炭化原子（又は炭化水素）が窒素原子に交換されたものを表し、次の（Ｂ１）〜（Ｂ５１０）で表される置換基を例示することができる（＊は連結部を表す）。

The above-mentioned nitrogen-containing heteroaromatic group having 8 to 25 carbon atoms which may be linked and / or condensed is an aromatic hydrocarbon group having 10 to 26 carbon atoms which may be linked and / or substituted. In which at least one carbon atom (or hydrocarbon) is replaced with a nitrogen atom, and the following substituents represented by (B1) to (B510) can be exemplified (* represents a connecting part). ).

Ａｒ^３は、有機電界発光素子材料として性能が良い点で、連結および／または縮環していてもよい炭素数１０〜２２芳香族炭化水素基または連結および／または縮環していてもよい炭素数８〜２１の含窒素へテロ芳香族基（これらの基は、メチル基、メトキシ基、フッ素原子、または炭素数２〜１０のアルキル基、もしくは炭素数２〜１０のアルコキシで置換されていてもよい）であることが好ましい。

Ar ³ is a C10-22 aromatic hydrocarbon group that may be linked and / or condensed, or a carbon that may be linked and / or condensed, in terms of good performance as an organic electroluminescent device material. A nitrogen-containing heteroaromatic group having 8 to 21 (these groups are substituted with a methyl group, a methoxy group, a fluorine atom, an alkyl group having 2 to 10 carbon atoms, or an alkoxy group having 2 to 10 carbon atoms) It is also preferable.

  About the C10-22 aromatic hydrocarbon group which may be linked and / or condensed, and the nitrogen-containing heteroaromatic group having 8 to 21 carbon atoms which may be linked and / or condensed Are the substituents enumerated in (A1) to (A116) and (B1) to (B510), respectively, and those having a suitable carbon number are listed as examples.

Furthermore, Ar ³ is a naphthyl group, anthracyl group, phenanthryl group, pyrenyl group, fluoryl group, triphenylene group, fluoranthryl group, imidazolyl group, indolyl group, carbazolyl group, carbolyl group in terms of good performance as an organic electroluminescent element material. , Quinolyl group, isoquinolyl group, naphthyridyl group, quinoxalyl group, quinazolyl group, phenanthridyl group, acridyl group, phenanthroyl group, benzoquinolyl group, benzoisoquinolyl group, benzonaphthylyl group, benzoquinoxalyl group, and benzoquinazolyl group An aromatic group selected from the group consisting of: naphthyl, anthracyl, phenanthryl, pyrenyl, fluoryl, triphenylene, fluoranthryl, imidazolyl, indolyl, carbazolyl, carbolyl Group, quinolyl group, isoquinolyl group, naphthyridyl group, quinoxalyl group, quinazolyl group, phenanthridyl group, acridyl group, phenanthroyl group, benzoquinolyl group, benzoisoquinolyl group, benzonaphthylyl group, benzoquinoxalyl group, benzoquinazolyl group , A phenyl group, a pyridyl group, and an aromatic group having 8 to 20 carbon atoms formed by linking two or more groups selected from the group consisting of a pyrimidyl group (these groups are a methyl group, a methoxy group, a fluorine atom, or More preferably, it may be substituted with an alkyl group having 2 to 10 carbon atoms or an alkoxy group having 2 to 10 carbon atoms.

As for Ar ³ , an aromatic group having 8 to 26 carbon atoms consisting of only a 6-membered ring in which 2 to 5 benzene rings and / or pyridine rings and / or pyrimidine rings are connected and / or condensed in terms of excellent synthesis. It is preferably a group (which may be substituted with a methyl group, a methoxy group, a fluorine atom, an alkyl group having 2 to 10 carbon atoms, or an alkoxy group having 2 to 10 carbon atoms).

  Furthermore, an aromatic group having 8 to 22 carbon atoms consisting of only a 6-membered ring in which 2 to 4 benzene rings and / or pyridine rings and / or pyrimidine rings are linked and / or condensed, these groups are methyl, methoxy More preferably a group, a fluorine atom, an alkyl group having 2 to 10 carbon atoms, or an alkoxy group having 2 to 10 carbon atoms).

  The preferred substituents are (A1) to (A13), (A16), (A18), (A20) to (A33), (A35) to (A46), (A49) to (A56), (A62). , (A66), (A67), (A70) to (A76), (A81), (A82), (A85), (A88) to (A97), (B1) to (B7), (B10), ( B11), (B13), (B15) to (B76), (B79) to (B89), (B94), (B95), (B100), (B101), (B106) to (B146), (B154) -(B244), (B251)-(B260), (B265)-(B288), (B293)-(B394), (B396)-(B398), (B400), (B401), (B403)-( B405), (B407) to (B 13), (B415) ~ (B432), (B436), (B437), (B445) ~ (B467), (B471) ~ (B495) are preferred.

  Of these substituents, (A1) to (A12), (A16), (A18), (A20) to (A33), (A42) to (A46), (A50) to (A55), ( A66), (A67), (A70), (A73)-(A76), (A81), (A82), (A88)-(A97), (B1)-(B7), (B10), (B11) , (B13), (B15) to (B57), (B60), (B62), (B63), (B65), (B67), (B68), (B70), (B72), (B73), ( B75), (B79)-(B81), (B88), (B89), (B94), (B95), (B100), (B101), (B108)-(B146), (B154)-(B236) , (B251) to (B260), (B265) to (B288), B293)-(B296), (B305), (B306), (B309)-(B332), (B348)-(B376), (B383)-(B394), (B396)-(B398), (B400) , (B401), (B403), (B404), (B407) to (B409), (B411) to (B413), (B415) to (B432), (B436), (B437), (B445) to (B445) ( B467), (B478) to (B482), and (B488) to (B491) are more preferable.

  In addition, an aromatic group consisting of only a 6-membered ring in which 2 to 5 benzene rings and / or pyridine rings and / or pyrimidine rings are connected and / or condensed, benzene ring and / or pyridine ring and / or pyrimidine ring are 2 The aromatic group consisting of four linked and / or condensed six-membered rings is not particularly limited, but the above-mentioned (A1) to (A10), (A13), (A16) to (A93) ), (A96), (A97), (A102) to (A116), (B1) to (B7), (B16) to (B430), (B445) to (B510). Groups can be exemplified.

As for Ar ³ , among the above substituents, an aromatic hydrocarbon group composed of only a 6-membered ring having 8 to 18 carbon atoms which may be linked and / or condensed, or a linked and / or condensed ring A nitrogen-containing heteroaromatic group composed of only a 6-membered ring having 8 to 18 carbon atoms (these groups are a methyl group, a methoxy group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms) Or may be substituted with an alkoxy group having 2 to 10 carbon atoms). For example, naphthyl group, biphenyl group, naphthylphenyl group, phenylnaphthyl group, anthracyl group, phenanthryl group, pyrenyl group, triphenylene Group, fluoranthryl group, pyridyl-phenyl group, phenyl-pyridyl group, diphenyl-pyridyl group, dipyridyl-phenyl group, pyridyl-biphenyl Group, pyridyl-naphthyl group, naphthyl-pyridyl group, pyridyl-anthracyl group, anthracyl-pyridyl group, pyridyl-phenanthryl group, phenanthryl-pyridyl group, quinolyl group, isoquinolyl group, phenyl-quinolyl group, quinolyl-phenyl group, phenyl- An isoquinolyl group or an isoquinolyl-phenyl group (these groups may be substituted with a methyl group, a methoxy group, a fluorine atom, an alkyl group having 2 to 10 carbon atoms, or an alkoxy group having 2 to 10 carbon atoms) Is mentioned.

As for Ar ³ , among the above-mentioned substituents, a nitrogen-containing heteroaromatic group composed of only a 6-membered ring having 8 to 18 carbon atoms which may be linked and / or condensed (these groups are More preferably a methyl group, a methoxy group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, or an alkoxy group having 2 to 10 carbon atoms), for example, a pyridyl-phenyl group, Phenyl-pyridyl group, diphenylpyridyl group, dipyridyl-phenyl group, pyridyl-biphenyl group, quinolyl group, isoquinolyl group, phenyl-quinolyl group, quinolyl-phenyl group, phenyl-isoquinolyl group, or isoquinolyl-phenyl group (these groups are , Methyl group, methoxy group, fluorine atom, alkyl group having 2 to 10 carbon atoms, or alcohol having 2 to 10 carbon atoms And may be substituted with a xy group).

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a methyl group, a methoxy group, a phenyl group, a fluorine atom, or a carbon number of 2 to 10 Represents an alkyl group, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.

Examples of the alkyl group having 2 to 10 carbon atoms, alkoxy group, alkoxyalkyl group, ester group or ester alkyl group include the same substituents as those exemplified for Ar ¹ and Ar ² .

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a methyl group, in terms of good performance as a compound organic electroluminescent device material, It is preferably a methoxy group, a phenyl group or a fluorine atom, more preferably each independently a hydrogen atom, a methyl group or a phenyl group, and more preferably a hydrogen atom.

  Moreover, each hydrogen atom in General formula (1) may be a deuterium atom each independently.

  Although it does not specifically limit about general formula (1), It can illustrate by following (C1)-(C483).

次に、本発明の化合物（１）の製造方法について説明する。

Next, the manufacturing method of the compound (1) of this invention is demonstrated.

  Compound (1) of the present invention has the following reaction formula:

（式（１）、（２）および（３）中、Ｍ^１は脱離基を表し、その他の各記号については前記と同じ定義である。）
で示される方法で製造することができる。

(In formulas (1), (2) and (3), M ¹ represents a leaving group, and other symbols are as defined above.)
It can be manufactured by the method shown in

  That is, the compound represented by the general formula (1) is produced by coupling the compound represented by the general formula (2) and the compound represented by the general formula (3) in the presence of a metal catalyst. .

  The compound represented by the general formula (2) is referred to as compound (2). The same applies to compound (3).

The compound (3), although the above (A1) ~ (A116) and (B1) ~ (B510) in the * can be exemplified compound was changed to ^{M 1,} the present invention is not limited thereto . Here, M ¹ represents a leaving group.

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

  “Step 1” is a step of synthesizing compound (1).

  Compound (1) is synthesized by reacting compound (2) and compound (3) in the presence of a metal catalyst.

The leaving group represented by M ¹ in the compound (3) is not particularly limited, and examples thereof include a chlorine group, a bromine group, an iodine group, a trifluoromethylsulfonyloxy (OTf) group, and a methanesulfonyloxy group. And chloromethanesulfonyloxy group and p-toluenesulfonyloxy group.

  Examples of the metal catalyst that can be used in “Step 1” include a palladium catalyst, a nickel catalyst, and a copper catalyst.

  The palladium catalyst that can be used in “Step 1” is not particularly limited. For example, a salt such as palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, or tertiary phosphine is used as a ligand. The palladium complex which has as can be illustrated. Furthermore, π-allyl palladium chloride dimer, palladium acetylacetonate, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and dichloro [1,1′-bis (diphenylphosphine). Fino) ferrocene] complex compounds such as palladium. Among these, a palladium complex having a tertiary phosphine as a ligand is preferable in terms of a good reaction yield.

  A palladium complex having a tertiary phosphine as a ligand can 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 in this case is not particularly limited. For example, 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) ferrocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (±) -2,2′-bis (diphenylphosphine) Fino) -1,1′-binaphthyl, 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl and the like. 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl is preferred because it is easily available and the reaction yield is good.

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

  The nickel catalyst that can be used in “Step 1” is not particularly limited. For example, [1,1′-bis (diphenylphosphino) ferrocene] nickel (II) dichloride, [1,2-bis]. (Diphenylphosphino) ethane] nickel (II) dichloride, [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride, [1,1′-bis (diphenylphosphino) propane] nickel (II) Dichloride, 1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride, [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride, and the like.

Further, the nickel catalyst is obtained by adding the above-mentioned tertiary phosphine to a nickel salt or complex compound,
It can also be prepared in a reaction system.

  The nickel salt or complex compound is not particularly limited. For example, nickel fluoride, nickel chloride, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel perchlorate, nickel formate, nickel oxalate And nickel acetate, nickel benzoate, nickel acetylacetonate and the like.

  The molar ratio of the tertiary phosphine and the nickel 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 a copper catalyst that can be used in “Step 1”, a copper powder or a copper salt prepared in a reaction system with a copper salt and a ligand can be used.

  Although it does not specifically limit as a copper salt, For example, copper oxide, copper fluoride, copper chloride, copper bromide, copper iodide, copper sulfate, copper nitrate, copper formate, copper oxalate, copper acetate, etc. It can be illustrated.

  Examples of the ligand include the above-mentioned tertiary phosphine, 1,10-phenanthroline, trans-1,2-cyclohexanediamine and the like.

  In "Step 1", a base can be used as necessary. The base is not particularly limited. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, tripotassium phosphate, sodium phosphate, sodium fluoride, fluoride Examples thereof include potassium and cesium fluoride, and potassium carbonate and tripotassium phosphate are desirable in terms of good yield. The molar ratio of base to compound (3) is preferably 1: 2 to 10: 1, and more preferably 1: 1 to 3: 1 in terms of good yield.

  In “Step 1”, a solvent can be used as necessary, and it is preferable to use a solvent in terms of reaction control. The solvent that can be used in “Step 1” is not particularly limited, and examples thereof include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethyl ether, ethanol, methanol, and xylene. These may be used in appropriate combination. It is desirable to use xylene in terms of a good yield.

  “Step 1” can be performed at a temperature appropriately selected from 0 ° C. to 180 ° C., and is more preferably performed at 80 ° C. to 150 ° C. in terms of a good yield.

  Compound (1) can be obtained by carrying out a usual treatment (separation operation or the like) performed by those skilled in the art after completion of “Step 1”. Furthermore, you may refine | purify by recrystallization, column chromatography, sublimation, etc. as needed.

  Further, the compound (2) of the present invention has the following reaction formula:

（式（２）、（４）および（５）中、Ｍ^２は脱離基を表し、その他の各記号については前記と同じ定義である。）
で示される方法で製造することができる。

(In formulas (2), (4) and (5), M ² represents a leaving group, and the other symbols have the same definitions as above.)
It can be manufactured by the method shown in

  That is, the compound represented by the general formula (2) is produced by coupling the compound represented by the general formula (4) and the compound represented by the general formula (5) in the presence of a metal catalyst. . “Step 2” means a step of synthesizing compound (2).

  About the metal catalyst, the same thing as what was shown at process 1 can be used.

Moreover, the reaction conditions of step 2 is the same as Step 1, M ² may be exemplified the same substituents as M ^1.

  The N-triazylphenazine compound represented by the general formula (1) of the present application is suitably used as a material for an organic electroluminescent element.

  Furthermore, the N-triazylphenazine compound represented by the general formula (1) of the present application is suitably used as an electron transport material or an electron injection material for an organic electroluminescence device.

Although there is no limitation in particular in the manufacturing method of the thin film for organic electroluminescent elements containing the N-triazyl phenazine compound shown by General formula (1) of this invention, The film-forming by a vacuum evaporation method is mentioned as a preferable example. it can. 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 such that the production tact time for producing the organic electroluminescent element is short and the production cost is superior, so that commonly used diffusion pumps, turbo molecular pumps, cryogenic pumps are used. About 1 × 10 ⁻² to 1 × 10 ⁻⁶ Pa which can be reached by a pump or the like is preferable, and more preferably 1 × 10 ⁻³ to 10 ⁻⁶ Pa. The deposition rate is preferably 0.005 to 10 nm / second, more preferably 0.01 to 1 nm / second, although it depends on the thickness of the film to be formed. Moreover, the thin film for organic electroluminescent elements which consists of an N-triazyl phenazine compound shown by General formula (1) can also be manufactured also by a solution coating method. For example, the N-triazylphenazine compound represented by the general formula (1) is dissolved in an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, or tetrahydrofuran, and a general-purpose apparatus is used. Film formation by a spin coat method, an ink jet method, a cast method, a dip method, or the like is also possible.

  A typical structure of the organic electroluminescence device that can obtain the effects of the present invention includes a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode.

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

  The organic electroluminescent device is typically placed on a substrate, and the anode or cathode can be in contact with the substrate. The electrode in contact with the substrate is called the lower electrode for convenience. Generally, the lower electrode is an anode, but the organic electroluminescence device of the present invention is not limited to such a form. The substrate may be light transmissive or opaque, depending on the intended emission direction. Light transmission properties are desirable for viewing electroluminescent emission through a substrate. Transparent glass or plastic is generally employed as such a substrate. The substrate may be a composite structure including multiple material layers.

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

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

  The hole transport layer of the organic electroluminescent device preferably contains one or more hole transport compounds such as aromatic tertiary amines. Aromatic tertiary amine means that the compound contains one or more trivalent nitrogen atoms, the trivalent nitrogen atoms being bonded only to carbon atoms, one or more of these carbon atoms being An aromatic ring is formed. Specifically, the aromatic tertiary amine can be an arylamine, such as a monoarylamine, diarylamine, triarylamine, or a polymeric arylamine.

  An aromatic tertiary amine having one or more amine groups can be used as the hole transport material. Furthermore, a polymeric hole transport material can be used. For example, poly (N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline, or the like can be used. For example, NPD (N, N′-bis (naphthalen-1-yl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine), α-NPD (N, N′-di) (1-naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine), TPBi (1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) ) Benzene) or TPD (N, N′-bis (3-methylphenyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine).

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

  The light emitting layer of the organic electroluminescent element contains a phosphorescent material or a fluorescent material, and in this case, light emission occurs as a result of recombination of electron-hole pairs in this region. The emissive layer may consist of a single material including both small molecules and polymers, but more commonly consists of a host material doped with a guest compound, in which case the emission is mainly from the dopant. Occurs and can have any color.

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

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

  Examples of useful fluorescent dopants include anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine and quinacridone, dicyanomethylenepyran compounds, thiopyran compounds, polymethine compounds, pyrylium or thiapyrylium compounds, fluorene derivatives, perifanthene derivatives, indeno Examples include perylene derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, and carbostyryl compounds.

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

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

  The thin film forming material used for forming the electron transport layer of the organic electroluminescence device of the present invention is an N-triazylphenazine compound represented by the general formula (1) of the present application. Note that the electron transporting layer may contain another electron transporting material, and examples of the electron transporting material include alkali metal complexes, alkaline earth metal complexes, and earth metal complexes. Desirable alkali metal complexes, alkaline earth metal complexes, and earth metal complexes include, for example, 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinato) zinc, and bis (8-hydroxyquinolinate). Copper, bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, Bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolate) gallium, bis (2-methyl-8-quinolina) G) -1-naphthoquinone Trad aluminum or bis (2-methyl-8-quinolinato) -2-naphthoquinone Trad gallium, and the like.

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

In the organic electroluminescence device of the present invention, an electron injection layer may be provided for the purpose of improving electron injection properties and improving device characteristics (for example, light emission efficiency, constant voltage driving, or high durability). Preferred compounds for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, or anthrone. Etc. In addition, the metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO _x , AlO _x , SiN _x , SiON, Various oxides such as AlON, GeO _X , LiO _X , LiON, TiO _X , TiON, TaO _X , TaON, TaN _X , C (the above X represents an integer), nitrides, and oxynitrides Inorganic compounds can also be used.

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

  EXAMPLES Hereinafter, although an experiment example and a test example are given and this invention is demonstrated further in detail, this invention is limited to these and is not interpreted.

  Experimental Example-1 (Example)

アルゴン気流下、１−クロロ−３，５−ジフェニルトリアジン ３．１２ｇ（１１．７ｍｍｏｌ）、ジヒドロフェナジン ３．０３ｇ（１６．７ｍｍｏｌ）、酢酸パラジウム ７４．８ｍｇ（０．３３ｍｍｏｌ）、１Ｍ−トリ（ｔｅｒｔ−ブチル）ホスフィンヘキサン溶液 １．０ｍＬ（０．０９６ｍｍｏｌ）、１８−クラウン−６−エーテル ８８０ｍｇ（３．３３ｍｍｏｌ）および炭酸カリウム ４．６０ｇ（３３．３ｍｍｏｌ）をキシレン １１１ｍＬに溶解し、１５０℃で１４時間加熱撹拌した。室温まで放冷後、クロロホルムおよび水を加えて分液抽出を行い、有機層をあつめて減圧留去した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒クロロホルム：ヘキサン＝３：２）で精製することで、目的の５−（３，５−ジフェニルトリアジン−２−イル）−１０Ｈ−ジヒドロフェナジンの薄黄粉末（収量２．１１ｇ，収率４４％）を得た。

Under an argon stream, 3.12 g (11.7 mmol) of 1-chloro-3,5-diphenyltriazine, 3.03 g (16.7 mmol) of dihydrophenazine, 74.8 mg (0.33 mmol) of palladium acetate, 1M-tri (tert -Butyl) phosphine hexane solution 1.0 mL (0.096 mmol), 18-crown-6-ether 880 mg (3.33 mmol) and potassium carbonate 4.60 g (33.3 mmol) were dissolved in xylene 111 mL, Stir for hours. After cooling to room temperature, chloroform and water were added for liquid separation extraction, and the organic layer was collected and evaporated under reduced pressure. The obtained crude product was purified by silica gel chromatography (developing solvent chloroform: hexane = 3: 2), so that the target 5- (3,5-diphenyltriazin-2-yl) -10H-dihydrophenazine was diluted. A yellow powder (yield 2.11 g, yield 44%) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 6.98 (d, J = 7.8 Hz, 2H), 7.09 (t, J = 7.7 Hz, 2H), 7.18 (t, J = 7.6 Hz, 2H), 7.55-7.59 (m, 4H), 7.61-7.66 (m, 2H), 7.82 (d, J = 8.0 Hz, 2H), 8.44 (d, J = 6.9 Hz, 4H), 8.97 (s, 1H).
Experimental Example-2 (Example)

アルゴン気流下、５−（３，５−ジフェニルトリアジン−２−イル）−１０Ｈ−ジヒドロフェナジン ７００ｍｇ（１．６９ｍｍｏｌ）、１−クロロ−３，５−ビス（２−ピリジル）ベンゼン ４９７ｍｇ（１．８６ｍｍｏｌ）、酢酸パラジウム ７．５９ｍｇ（０．０３３８ｍｍｏｌ）、１Ｍ−トリ（ｔｅｒｔ−ブチル）ホスフィンヘキサン溶液 ９６μＬ（０．０９６ｍｍｏｌ）、１８−クラウン−６−エーテル ８９．０ｍｇ（０．３３８ｍｍｏｌ）および炭酸カリウム ４６７ｍｇ（３．３８ｍｍｏｌ）をキシレン １１．０ｍＬに溶解し、１５０℃で１４時間加熱撹拌した。室温まで放冷後、クロロホルムおよび水を加えて分液抽出を行い、有機層をあつめて減圧留去した。得られた粗生成物をシリカゲルクロマトグラフィー（展開溶媒クロロホルム）で精製することで、目的の５−（３，５−ジフェニルトリアジン−２−イル）−１０−{３，５−ビス（２−ピリジル）フェニル}ジヒドロフェナジン（化合物 Ｃ８４）の薄黄粉末（収量８７８ｍｇ，収率８１％）を得た。

Under an argon stream, 700 mg (1.69 mmol) of 5- (3,5-diphenyltriazin-2-yl) -10H-dihydrophenazine, 497 mg (1.86 mmol) of 1-chloro-3,5-bis (2-pyridyl) benzene ), Palladium acetate 7.59 mg (0.0338 mmol), 1 M-tri (tert-butyl) phosphine hexane solution 96 μL (0.096 mmol), 18-crown-6-ether 89.0 mg (0.338 mmol) and potassium carbonate 467 mg (3.38 mmol) was dissolved in 11.0 mL of xylene and heated and stirred at 150 ° C. for 14 hours. After cooling to room temperature, chloroform and water were added for liquid separation extraction, and the organic layer was collected and evaporated under reduced pressure. By purifying the obtained crude product by silica gel chromatography (developing solvent chloroform), the desired 5- (3,5-diphenyltriazin-2-yl) -10- {3,5-bis (2-pyridyl) was obtained. ) Phenyl} dihydrophenazine (Compound C84) was obtained as a pale yellow powder (Yield 878 mg, Yield 81%).

¹ H-NMR (CDCl ₃ ), δ (ppm): 6.61 (d, J = 8.3 Hz, 2H), 7.07 (t, J = 8.4 Hz, 2H), 7.17 (t, J = 7.6 Hz, 2H), 7.26-7.47 (m, 2H), 7.47-7.56 (m, 6H), 7.79 (t, J = 7.8 Hz, 2H), 7.88 (d, J = 8.1 Hz, 2H), 7.95 (d, J = 7.8 Hz, 2H), 8.14 (S, 2H), 8.55 (d, J = 6.6 Hz) , 4H), 8.72 (d, J = 4.5 Hz, 2H), 8.94 (s, 1H).
Experimental Example-3 (Example)

アルゴン気流下、５−（３，５−ジフェニルトリアジン−２−イル）−１０Ｈ−ジヒドロフェナジン ７００ｍｇ（１．６９ｍｍｏｌ）、１−クロロ−３−（２−ピリジル）ベンゼン ４３６ｍｇ（１．８６ｍｍｏｌ）、酢酸パラジウム ７．５９ｍｇ（０．０３３８ｍｍｏｌ）、１Ｍ−トリ（ｔｅｒｔ−ブチル）ホスフィンヘキサン溶液 ９６μＬ（０．０９６ｍｍｏｌ）、１８−クラウン−６−エーテル ８９．０ｍｇ（０．３３８ｍｍｏｌ）および炭酸カリウム ４６７ｍｇ（３．３８ｍｍｏｌ）をキシレン １１．０ｍＬに溶解し、１５０℃で１４時間加熱撹拌した。室温まで放冷後、メタノールを加えてろ過し、水、メタノール、ヘキサンで固体洗浄した。得られた固体をクロロホルムで再結晶することで、目的の５−（３，５−ジフェニルトリアジン−２−イル）−１０−{３−（２−ピリジル）フェニル}ジヒドロフェナジン（化合物 Ｃ６９）の薄黄粉末（収量６２５ｍｇ，収率６５％）を得た。

Under argon stream, 5- (3,5-diphenyltriazin-2-yl) -10H-dihydrophenazine 700 mg (1.69 mmol), 1-chloro-3- (2-pyridyl) benzene 436 mg (1.86 mmol), acetic acid Palladium 7.59 mg (0.0338 mmol), 1M-tri (tert-butyl) phosphine hexane solution 96 μL (0.096 mmol), 18-crown-6-ether 89.0 mg (0.338 mmol) and potassium carbonate 467 mg (3. 38 mmol) was dissolved in 11.0 mL of xylene and stirred at 150 ° C. for 14 hours. After cooling to room temperature, methanol was added and the mixture was filtered and washed with water, methanol and hexane. The obtained solid was recrystallized from chloroform, so that the target 5- (3,5-diphenyltriazin-2-yl) -10- {3- (2-pyridyl) phenyl} dihydrophenazine (compound C69) was diluted. A yellow powder (yield 625 mg, yield 65%) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 6.50 (d, J = 8.2 Hz, 2H), 7.06 (t, J = 8.4 Hz, 2H), 7.16 (t, J = 7.7 Hz, 2H), 7.47-7.56 (m, 8H), 7.73-7.77 (m, 3H), 7.94 (d, J = 8.0 Hz, 2H), 8.02 (s, 1H), 8.25 (d, J = 7.9 Hz, 1H), 8.53-8.56 (m, 4H), 8.69 (s, 1H).
Experimental Example-4 (Example)

アルゴン気流下、５−（３，５−ジフェニルトリアジン−２−イル）−１０Ｈ−ジヒドロフェナジン ７００ｍｇ（１．６９ｍｍｏｌ）、８−ブロモキノリン ３０５ｍｇ（１．８６ｍｍｏｌ）、酢酸パラジウム ７．５９ｍｇ（０．０３３８ｍｍｏｌ）、１Ｍ−トリ（ｔｅｒｔ−ブチル）ホスフィンヘキサン溶液 ９６μＬ（０．０９６ｍｍｏｌ）、１８−クラウン−６−エーテル ８９．０ｍｇ（０．３３８ｍｍｏｌ）および炭酸カリウム ４６７ｍｇ（３．３８ｍｍｏｌ）をキシレン １１．０ｍＬに溶解し、１５０℃で１４時間加熱撹拌した。室温まで放冷後、メタノールを加えてろ過し、水、メタノールで固体洗浄した。得られた固体をトルエンで再結晶することで、目的の５−（３，５−ジフェニルトリアジン−２−イル）−１０−（８−キノリル）ジヒドロフェナジン（化合物 Ｃ３５）の薄黄粉末（収量６４９ｍｇ，収率７１％）を得た。

Under an argon stream, 700 mg (1.69 mmol) of 5- (3,5-diphenyltriazin-2-yl) -10H-dihydrophenazine, 305 mg (1.86 mmol) of 8-bromoquinoline, 7.59 mg (0.0338 mmol) of palladium acetate ) 1M-tri (tert-butyl) phosphine hexane solution 96 μL (0.096 mmol), 18-crown-6-ether 89.0 mg (0.338 mmol) and potassium carbonate 467 mg (3.38 mmol) in 11.0 mL of xylene It melt | dissolved and it heat-stirred at 150 degreeC for 14 hours. After cooling to room temperature, methanol was added and the mixture was filtered and washed with water and methanol. The obtained solid was recrystallized from toluene to give a light yellow powder (yield: 649 mg) of the desired 5- (3,5-diphenyltriazin-2-yl) -10- (8-quinolyl) dihydrophenazine (Compound C35). Yield 71%).

¹ H-NMR (CDCl ₃ ), δ (ppm): 6.06 (d, J = 7.5 Hz, 2H), 6.89 (t, J = 8.0 Hz, 2H), 7.10 (t, J = 7.5 Hz, 2H), 7.44-7.56 (m, 7H), 7.70 (t, J = 7.0 Hz, 1H), 7.88 (d, J = 6.6 Hz, 1H) ), 7.97 (d, J = 8.0 Hz, 2H), 8.01 (d, J = 8.9 Hz, 1H), 8.31 (d, J = 7.5 Hz, 1H), 8.57 (D, J = 7.1 Hz, 4H), 8.81 (s, 1H).
Test Example-1 (Example)
Preparation and evaluation of the organic electroluminescent element were performed as follows. As the substrate, a glass substrate with an ITO transparent electrode in which an indium tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface-treated by oxygen plasma cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum evaporation method, and an organic electroluminescence device having a light-emitting area of 4 mm ² as shown in FIG.

First, the said glass substrate was introduce | transduced in the vacuum evaporation tank and it pressure-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 HIL was vacuum-deposited with a film thickness of 65 nm.
As the hole transport layer 3, HAT and HTL were vacuum-deposited with a thickness of 5 nm and 10 nm, respectively.
As the light emitting layer 4, EML-1 and EML-2 were vacuum-deposited by the film thickness of 25 nm in the ratio of 954: 46 (mass%).
As the electron transport layer 5, 5- (3,5-diphenyltriazin-2-yl) -10- {3,5-bis (2-pyridyl) phenyl} dihydrophenazine synthesized in Experimental Example-2 of the present invention is used. Vacuum deposition was performed with a film thickness of 30 nm.
Finally, a metal mask was disposed so as to be orthogonal to the ITO stripe, and the cathode layer 6 was formed. As the cathode layer 6, Liq, silver magnesium, and silver were vacuum-deposited with a thickness of 0.5 nm, 80 nm, and 20 nm, respectively, to form a three-layer structure.

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

  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. The structural formulas and abbreviations of the compounds used are shown below.

作製した有機電界発光素子に直流電流を印加し、ＴＯＰＣＯＮ社製のＬＵＭＩＮＡＮＣＥ ＭＥＴＥＲ（ＢＭ−９）の輝度計を用いて発光特性を評価した。発光特性として、電流密度１０ｍＡ／ｃｍ^２を流した時の電圧（Ｖ）、輝度（ｃｄ／ｍ^２）、電流効率（ｃｄ／Ａ）、電力効率（ｌｍ／Ｗ）を測定した。測定結果を表１に示す。なお、素子の駆動電圧は４．００Ｖであった。

A direct current was applied to the produced organic electroluminescence device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As light emission characteristics, voltage (V), luminance (cd / m ² ), current efficiency (cd / A), and power efficiency (lm / W) when a current density of 10 mA / cm ² was passed were measured. The measurement results are shown in Table 1. The drive voltage of the element was 4.00V.

Test Example-2 (Example)
Experimental Example 3 was changed to 5- (3,5-diphenyltriazin-2-yl) -10- {3,5-bis (2-pyridyl) phenyl} dihydrophenazine in the electron transport layer 5 of Test Example-1. Organic electroluminescence in the same manner as in Test Example 1 except that 5- (3,5-diphenyltriazin-2-yl) -10- {3- (2-pyridyl) phenyl} dihydrophenazine obtained in Step 1 was used. An element was fabricated and evaluated in the same manner as in Test Example-1. The measurement results are shown in Table 1. The drive voltage of the element was 4.08V.

Test Example-3 (Example)
Experimental Example 4 was changed to 5- (3,5-diphenyltriazin-2-yl) -10- {3,5-bis (2-pyridyl) phenyl} dihydrophenazine in the electron transport layer 5 of Test Example-1. An organic electroluminescent device was produced in the same manner as in Test Example 1 except that 5- (3,5-diphenyltriazin-2-yl) -10- (8-quinolyl) dihydrophenazine obtained in Step 1 was used. Evaluation was performed in the same manner as in Test Example-1. The measurement results are shown in Table 1. The drive voltage of the element was 4.94V.

Reference Example-1
Instead of 5- (3,5-diphenyltriazin-2-yl) -10- {3,5-bis (2-pyridyl) phenyl} dihydrophenazine in the electron transport layer 5 of Test Example 1, patent number WO2008129999 2,4-diphenyl-6- [4,4 ″ -di (2-pyridyl) -1,1 ′: 3 ′, 1 ″ -terphenyl-5′-yl] -1,3,5 -The organic electroluminescent element which vacuum-deposited triazine (represented by a following formula) was produced and measured similarly to Test Example-1. The measurement results are shown in Table 1.

  The thin film comprising the compound (1) of the present invention exhibits high thin film stability, heat resistance, electron transport properties, hole blocking ability, redox resistance, water resistance, oxygen resistance, electron injection properties, etc. Especially as a material of an electroluminescent element, it can use suitably as an electron transport material. The compound (1) of the present invention has a wide energy gap and triplet energy, and can be used in combination with a fluorescent or phosphorescent organic electroluminescent material. Therefore, it can be applied to various elements such as a single color display element, a three primary color display element, and a white element for illumination use. Moreover, the compound (1) of this invention can be used for a light emission host layer other than an electron carrying layer from the characteristic. Moreover, it can be used even if it mixes or laminates with another compound as an electron carrying layer. Furthermore, this compound has high solubility, and can be used for coating elements in addition to vapor deposition. From these effects, these elements are expected to have significant effects such as suppression of battery consumption by reducing power consumption, improvement of product life by extending life, and reduction of burden on the drive circuit.

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

Claims (13)

An N-triazylphenazine compound represented by the general formula (1).

(Where
Ar ¹ and Ar ² are each independently an aromatic hydrocarbon group having 6 to 12 carbon atoms (methyl group, methoxy group, pyridyl group, pyrimidyl group, fluorine atom, alkyl group having 2 to 10 carbon atoms, alkoxy group) , May be substituted with an alkoxyalkyl group, an ester group, or an ester alkyl group.
Ar ³ is an aromatic hydrocarbon group having 10 to 26 carbon atoms which may be linked and / or condensed, or a nitrogen-containing heteroaromatic group having 8 to 25 carbon atoms which may be linked and / or condensed. Represents a group (these groups may be substituted with a methyl group, a methoxy group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group).
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a methyl group, a methoxy group, a phenyl group, a fluorine atom, or a carbon number of 2 to 10 Represents an alkyl group, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.
In addition, each hydrogen atom in the formula may independently be a deuterium atom. ) Ar ³ is a C10-22 aromatic hydrocarbon group which may be linked and / or condensed, or a nitrogen-containing heteroaromatic group having 8 to 21 carbon atoms which may be linked and / or condensed. 2. These groups may be substituted with a methyl group, a methoxy group, a fluorine atom, an alkyl group having 2 to 10 carbon atoms, or an alkoxy group having 2 to 10 carbon atoms. N-triazylphenazine compounds. Ar ³ is an aromatic group having 8 to 26 carbon atoms composed of only a 6-membered ring in which 2 to 5 benzene rings and / or pyridine rings and / or pyrimidine rings are connected and / or condensed (these groups are methyl The N-triazylphenazine compound according to claim 1, which may be substituted with a group, a methoxy group, a fluorine atom, an alkyl group having 2 to 10 carbon atoms, or an alkoxy group having 2 to 10 carbon atoms. Ar ³ is an aromatic group having 8 to 22 carbon atoms composed of a 6-membered ring formed by connecting and / or condensing 2 to 4 benzene rings and / or pyridine rings and / or pyrimidine rings (these groups are methyl N-triazylphenazine compound according to claim 1 or 3, which may be substituted with a group, a methoxy group, a fluorine atom, an alkyl group having 2 to 10 carbon atoms, or an alkoxy group having 2 to 10 carbon atoms. . R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a methyl group, a methoxy group, a phenyl group, or a fluorine atom, 5. The N-triazylphenazine compound according to any one of 4 above. R < ¹ >, R < ² >, R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ >, R < ⁷ > and R < ⁸ > are hydrogen atoms, The N-triazylphenazine compound as described in any one of Claims 1-5. Ar ¹ and Ar ² are each independently a phenyl group, a naphthyl group, or a biphenyl group (these groups may be substituted with a methyl group, a methoxy group, a pyridyl group, a pyrimidyl group, or a fluorine atom). The N-triazylphenazine compound according to any one of claims 1 to 6. Ar ¹ and Ar ² are phenyl groups, The N-triazylphenazine compound according to any one of claims 1 to 7. The N-triazyl according to claim 1, wherein a compound represented by the following general formula (2) and a compound represented by the following general formula (3) are subjected to a coupling reaction in the presence of a metal catalyst. A method for producing a phenazine compound.

(Ar ¹ , Ar ² , Ar ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , m in the general formulas (1), (2), (3) And n are the same as defined in general formula (1), and M ¹ represents a leaving group.)   The organic electroluminescent element material containing the N-triazyl phenazine compound of Claims 1-8.   A light emitting layer host material, electron injection material or electron transport material comprising the N-triazylphenazine compound according to claim 1.   An electron injection material or an electron transport material comprising the N-triazylphenazine compound according to claim 1. An N-triazylphenazine compound represented by the general formula (2) according to claim 9.

(In the formula, Ar ¹ , Ar ² , Ar ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , m, n, and M ¹ are the same as described above. )

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