JP2019202943A - Phenyltriazole compound phenyltriazole metal complex and light emitter - Google Patents

Abstract

To provide a novel phenyltriazole compound, a phenyltriazole metal complex having the phenyltriazole compound as a ligand, and a light emitter having long life and capable of emitting blue phosphorescent by using the phenyltriazole metal complex.SOLUTION: There is provided a phenyltriazole metal complex represented by the formula (A). Rto Rare hydrogen atom, alkyl group, or a heterocycle represented by the formula (2), at least one of Rto Ris heterocycle represented by the formula (2). Yto Yare CR or N, at least one of Yto Yis N, Xto Xis CR, N or NR, Xis C or N, M is Ir, Pt, Au or Rh, m is 0, 1 or 2, n is 1, 2 or 3, R, Rto Rare hydrogen atom, halogen atom, alkyl group, alkyl group substituted by halogen atom, alkyloxy group or aryl group.SELECTED DRAWING: None

Description

  The present invention relates to a phenyltriazole compound, a phenyltriazole metal complex, and a light emitting device.

  As a light-emitting material used for a light-emitting layer of an organic electroluminescence element (hereinafter sometimes referred to as “light-emitting element”), a metal complex that emits light from a triplet excited state (hereinafter sometimes referred to as “phosphorescence”). Is known to provide higher luminous efficiency than fluorescent materials that emit light from a singlet excited state. Examples of blue light-emitting metal complexes that exhibit phosphorescence include metal complexes in which a ligand is bonded to a transition metal such as Ir, Pt, Au, and Rh (Patent Documents 1 and 2), 3-phenyl-1,2,4, and the like. -Metal complexes having a triazole derivative as a ligand (Patent Documents 3 and 4) are known.

International Publication No. 2002/015645 International Publication No. 2007/097153 International Publication No. 2013/151989 JP 2013-147450 A

  However, a conventional light emitting device using a blue light emitting metal complex exhibiting phosphorescence has a problem that its device life is short.

  The problem to be solved by the present invention is a novel phenyltriazole compound, a phenyltriazole metal complex having this phenyltriazole compound as a ligand, and a long-lived blue phosphorescent light emission using this phenyltriazole metal complex An object of the present invention is to provide a light emitting element that can be used.

The present invention includes the following aspects.
[1] A phenyltriazole compound represented by the following formula (1).

（Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅは、それぞれ独立して、水素原子、アルキル基又は下記式（２）で表される複素環であり、Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅのうち少なくとも一つは下記式（２）で表される複素環である。

(R ^A , R ^B , R ^C , R ^D and R ^E are each independently a hydrogen atom, an alkyl group or a heterocyclic ring represented by the following formula (2), and R ^A , R ^B , R ^C , R ^D and R ^E are each a heterocyclic ring represented by the following formula (2).

（Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅは、それぞれ独立して、ＣＲ又はＮであり、Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅのうち、少なくとも一つはＮであり、Ｒは水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。＊は結合部位を表す。）

(Y ^A , Y ^B , Y ^C , Y ^D and Y ^E are each independently CR or N, and at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N R is a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group, and * represents a bonding site.

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group. )

[2] The phenyltriazole compound according to [1], wherein R ^A and R ^E are alkyl groups.
[3] The phenyltriazole compound according to the above [1] or [2], wherein R ^B , R ^C or R ^D is a heterocyclic ring represented by the formula (2).

[4] A phenyltriazole metal complex represented by the following formula (A).

（Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅは、それぞれ独立して、水素原子、アルキル基又は下記式（２）で表される複素環であり、Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅのうち少なくとも一つは下記式（２）で表される複素環である。

(R ^A , R ^B , R ^C , R ^D and R ^E are each independently a hydrogen atom, an alkyl group or a heterocyclic ring represented by the following formula (2), and R ^A , R ^B , R ^C , R ^D and R ^E are each a heterocyclic ring represented by the following formula (2).

（Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅは、それぞれ独立して、ＣＲ又はＮであり、Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅのうち、少なくとも一つはＮであり、Ｒは水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。＊は結合部位を表す。）

(Y ^A , Y ^B , Y ^C , Y ^D and Y ^E are each independently CR or N, and at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N R is a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group, and * represents a bonding site.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group, or an alkyl group substituted with a halogen atom. , An alkyloxy group or an aryl group. X ¹ , X ² and X ³ are each independently CR, N or NR ¹⁰ , X ⁴ is C or N, and R and R ¹⁰ are each independently a hydrogen atom, a halogen atom, An alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group, or an aryl group. M is Ir, Pt, Au or Rh, m is 0, 1 or 2, and n is 1, 2 or 3. However, when M is Ir or Rh, m + n = 3, when M is Pt, m + n = 2, and when M is Au, m + n = 1. )

[5] The phenyltriazole metal complex according to [4], wherein R ^A and R ^E are alkyl groups.
[6] The phenyltriazole metal complex according to the above [4] or [5], wherein R ^B , R ^C or R ^D is a heterocyclic ring represented by the formula (2).

[7] An anode, a cathode, and a layer containing the phenyltriazole metal complex according to any one of [4] to [6] provided between the anode and the cathode. Light emitting element.

  Since the phenyltriazole compound of the present invention has an electron-attracting heterocyclic ring in addition to the ring coordinated to the metal, the electron injecting property and electron resistance can be improved and blue light emission can be maintained. Accordingly, the phenyltriazole metal complex having the phenyltriazole compound as a ligand is useful for the production of a light emitting device that promotes recombination of electrons and holes and can emit blue phosphorescence with a long lifetime.

It is sectional drawing which shows typically one Embodiment of the light emitting element of this invention.

<< Phenyltriazole compound >>
The phenyltriazole compound of the present invention is represented by the following formula (1).

In formula (1), R ^A , R ^B , R ^C , R ^D and R ^E are each independently a hydrogen atom, an alkyl group or a heterocycle represented by the following formula (2), and R ^A , At least one of R ^B , R ^C , R ^D and R ^E is a heterocyclic ring represented by the following formula (2). R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group.

Y ^A , Y ^B , Y ^C , Y ^D and Y ^E are each independently CR or N, and at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N. R is a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group, or an aryl group. * Represents a binding site.

As the alkyl group represented by R ^A , R ^B , R ^C , R ^D , R ^E , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R, linear, branched or cyclic Either is acceptable. Carbon number of a linear and branched alkyl group becomes like this. Preferably it is 1-30, More preferably, it is 1-12, Most preferably, it is 1-4. Moreover, carbon number in a cyclic alkyl group becomes like this. Preferably it is 3-30, More preferably, it is 3-12, Most preferably, it is 3-10. The alkyl group may have a substituent, but the carbon number of the substituent is not included in the above carbon number.

Examples of the alkyl group include methyl group, ethyl group, propyl group, iso-propyl group, butyl group, iso-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, Examples include 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group and the like. , Methyl group, ethyl group, propyl group, iso-propyl group, butyl group, iso-butyl group and tert-butyl group are preferable. R ¹ is preferably an alkyl group.

Substituted with halogen atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R, and halogen atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R Examples of the halogen atom of the alkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

The alkyloxy group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R may be linear, branched or cyclic. The carbon number of the linear and branched alkyloxy groups is preferably 1-30, more preferably 1-12, and particularly preferably 1-4. Moreover, carbon number of a cyclic | annular alkyloxy group becomes like this. Preferably it is 3-30, More preferably, it is 3-12, Most preferably, it is 3-10. The alkyloxy group may have a substituent, but the number of carbons of the substituent is not included in the above number of carbons.

  Examples of the alkyloxy group include a methyloxy group, an ethyloxy group, a propyloxy group, an iso-propyloxy group, a butyloxy group, an iso-butyloxy group, a tert-butyloxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group. , Heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethyloxy group, pentafluoroethyloxy group, perfluorobutyloxy Group, perfluorohexyloxy group, perfluorooctyloxy group, methyloxymethyloxy group, 2-methyloxyethyloxy group, etc., methyloxy group, ethyloxy group, propyloxy group, iso-propioxy Oxy group, butyloxy group, iso- butyloxy, tert- butyloxy groups are preferred.

The aryl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R has a carbon number of usually 6 to 60, preferably 7 to 48. The aryl group may have a substituent, but the carbon number of the substituent is not included in the above carbon number.

  Examples of the aryl group include a phenyl group and a C1-C12 alkyloxyphenyl group ("C1-C12 alkyloxy" means that the alkyloxy moiety has 1 to 12 carbon atoms. The same applies hereinafter. ), C1-C12 alkylphenyl group ("C1-C12 alkyl" means that the alkyl moiety has 1 to 12 carbon atoms. The same shall apply hereinafter), 1-naphthyl group, 2-naphthyl. Group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, pentafluorophenyl group and the like, and C1-C12 alkyloxyphenyl group, C1-C12 alkylphenyl group are preferable. Here, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. Examples of the aromatic hydrocarbon include those having a condensed ring and those in which two or more selected from independent benzene rings and / or condensed rings are bonded directly or via a group such as vinylene.

  The above-mentioned C1-C12 alkyl is a C1-C12 alkyl, and is the same as that described and exemplified for the alkyl group. Thus, for example, the C1-C12 alkyloxy in the group includes methyloxy, ethyloxy, propyloxy, iso-propyloxy, butyloxy, iso-butyloxy, tert-butyloxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, Examples include octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like. In addition, as the C1-C12 alkylphenyl in the above group, methylphenyl, ethylphenyl, dimethylphenyl, propylphenyl, mesityl, methylethylphenyl, iso-propylphenyl, butylphenyl, iso-butylphenyl, tert-butylphenyl, pentyl Examples thereof include phenyl, isoamylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl and the like. The same applies hereinafter.

The heterocycle represented by the formula (2) is preferably an aromatic ring. Of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E , one of the ortho positions of N is preferably CR ¹¹ (R ¹¹ is an alkyl group), and the ortho position of N is It is preferably CR ¹¹ and CR ¹² (R ¹¹ is an alkyl group, and R ¹² is a hydrogen atom or an alkyl group). Of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E , at least one of the ortho positions of N is CR ¹¹ , so that unwanted coordination to the transition metal during complex synthesis can be suppressed. R ¹¹ is more preferably a linear or branched alkyl group having 1 to 4 carbon atoms. R ¹² is more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

  Examples of the heterocyclic ring represented by the formula (2) include, but are not limited to, the heterocyclic rings represented by the following formulas (2-1) to (2-6).

  Examples of the heterocyclic ring represented by the formula (2-1) include heterocyclic rings represented by the following formulas (2-1-1) to (2-1-2). Examples of the heterocycle represented by the formula (2-2-1) to the formula (2-2-4) include the heterocycle represented by the formula (2-3). Examples of the ring include, but are not limited to, heterocyclic rings represented by the following formulas (2-3-1) to (2-3-2).

  Examples of the heterocyclic ring represented by the formula (2-4) include heterocyclic rings represented by the following formulas (2-4-1) to (2-4-2), and the formula (2-5) Examples of the heterocycle represented by the formula (2-5-1) to the formula (2-5-2) include the heterocycle represented by the formula (2-6). Examples of the ring include, but are not limited to, heterocyclic rings represented by the following formulas (2-6-1) to (2-6-2).

In the formula (1), R ^A and R ^E are preferably alkyl groups. When R ^A and R ^E are alkyl groups, the planarity between the benzene ring having these alkyl groups and the triazole ring can be reduced, the conjugation relationship can be broken, and blue emission can be maintained. As the alkyl group for R ^A and R ^E, a linear or branched alkyl group having 1 to 4 carbon atoms is more preferable.

In formula (1), R ^B , R ^C or R ^D is preferably a heterocyclic ring represented by the formula (2). As the heterocyclic ring represented by the formula (2) as R ^B , R ^C or R ^D , the heterocyclic ring represented by the formula (2-1) to the formula (2-6), -1) to a heterocyclic ring represented by formula (2-6-2).

  Examples of the phenyltriazole compound represented by the formula (1) include, but are not limited to, phenyltriazole compounds represented by the following formulas (1-1) to (1-10).

  Specific examples of the phenyltriazole compound represented by the formula (1) include, but are not limited to, the following formulas (1-101) to (1-128).

<Method for producing phenyltriazole compound>
The phenyltriazole compound represented by the formula (1) can be synthesized by, for example, reaction formulas of the formula (3-1) to the formula (3-9).

（Ｒ^ａ、Ｒ^ｂ、Ｒ^ｄ及びＲ^ｅは、それぞれ独立して、水素原子又はアルキル基であり、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅは、それぞれ独立して、ＣＲ又はＮであり、Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅのうち、少なくとも一つはＮであり、Ｒは水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。以下、式（３−２）及び式（３−２）において同じ。）

(R ^a , R ^b , R ^d and R ^e are each independently a hydrogen atom or an alkyl group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom. , A halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group, Y ^A , Y ^B , Y ^C , Y ^D and Y ^E are each independently CR or N And at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N, and R is a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, or an alkyloxy group. Or an aryl group, hereinafter the same in formula (3-2) and formula (3-2).)

（Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃ、Ｒ^ｄ及びＲ^ｅは、それぞれ独立して、水素原子又はアルキル基であり、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅは、それぞれ独立して、ＣＲ又はＮであり、Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅのうち、少なくとも一つはＮであり、Ｒは水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。以下、式（３−５）及び式（３−６）において同じ。）

(R ^a , R ^b , R ^c , R ^d and R ^e are each independently a hydrogen atom or an alkyl group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently , A hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group, or an aryl group Y ^A , Y ^B , Y ^C , Y ^D, and Y ^E are each independently CR Or N, and at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N, and R is a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, (It is an alkyloxy group or an aryl group. The same applies to the following formulas (3-5) and (3-6).)

（Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃ、Ｒ^ｄ及びＲ^ｅは、それぞれ独立して、水素原子又はアルキル基であり、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅは、それぞれ独立して、ＣＲ又はＮであり、Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅのうち、少なくとも一つはＮであり、Ｒは水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。以下、式（３−８）及び式（３−９）において同じ。）

(R ^a , R ^b , R ^c , R ^d and R ^e are each independently a hydrogen atom or an alkyl group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently , A hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group, or an aryl group Y ^A , Y ^B , Y ^C , Y ^D, and Y ^E are each independently CR Or N, and at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N, and R is a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, (It is an alkyloxy group or an aryl group. The same applies to the following formulas (3-8) and (3-9).)

  The raw material compounds used in the reactions of formula (3-1) to formula (3-9) can be synthesized by the reaction formula of the following formula (3-10).

（Ｒ^ａ’、Ｒ^ｂ’、Ｒ^ｃ’、Ｒ^ｄ’及びＲ^ｅ’は、それぞれ独立して、水素原子、アルキル基又はハロゲン原子であり、Ｒ^ａ’、Ｒ^ｂ’、Ｒ^ｃ’、Ｒ^ｄ’及びＲ^ｅ’のうち少なくとも一つはハロゲン原子である。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。）

(R ^a ′, R ^b ′, R ^c ′, R ^d ′ and R ^e ′ are each independently a hydrogen atom, an alkyl group or a halogen atom, and R ^a ′, R ^b ′, R ^c ′, At least one of R ^d ′ and R ^e ′ is a halogen atom, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group or a halogen atom. An alkyl group, an alkyloxy group or an aryl group substituted with

<< Phenyltriazole metal complex >>
The phenyltriazole metal complex of the present invention is represented by the following formula (A).

（Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅは、それぞれ独立して、水素原子、アルキル基又は下記式（２）で表される複素環であり、Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅのうち少なくとも一つは下記式（２）で表される複素環である。

(R ^A , R ^B , R ^C , R ^D and R ^E are each independently a hydrogen atom, an alkyl group or a heterocyclic ring represented by the following formula (2), and R ^A , R ^B , R ^C , R ^D and R ^E are each a heterocyclic ring represented by the following formula (2).

（Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅは、それぞれ独立して、ＣＲ又はＮであり、Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅのうち、少なくとも一つはＮであり、Ｒは水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。＊は結合部位を表す。）

(Y ^A , Y ^B , Y ^C , Y ^D and Y ^E are each independently CR or N, and at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N R is a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group, and * represents a bonding site.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group, or an alkyl group substituted with a halogen atom. , An alkyloxy group or an aryl group. X ¹ , X ² and X ³ are each independently CR, N or NR ¹⁰ , X ⁴ is C or N, and R and R ¹⁰ are each independently a hydrogen atom, a halogen atom, An alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group, or an aryl group. M is Ir, Pt, Au or Rh, m is 0, 1 or 2, and n is 1, 2 or 3. However, when M is Ir or Rh, m + n = 3, when M is Pt, m + n = 2, and when M is Au, m + n = 1. )

  When n is 3, it is preferable that the three ligands in the formula (A) are the same ligand (that is, one kind of ligand). When n is 2, the two ligands in the formula (A) are preferably the same ligand (that is, one kind of ligand). When m is 2, the two ligands in the formula (A) are preferably the same ligand (that is, one kind of ligand).

  Of the phenyltriazole metal complexes represented by the formula (A), n ligands are the phenyltriazole compounds. Of the phenyltriazole metal complex represented by the formula (A), m ligands are represented by the following formula (4).

（Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立して、ＣＲ、Ｎ又はＮＲ^１０であり、Ｘ^４はＣ又はＮであり、Ｒ及びＲ^１０は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。）

(R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group. X ¹ , X ² and X ³ are each independently CR, N or NR ¹⁰ , X ⁴ is C or N, and R and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group, a halogen atom, (It is an alkyl group, an alkyloxy group or an aryl group substituted with an atom.)

  Examples of the ligand represented by the formula (4) include ligands represented by the following formulas (4-1) to (4-4).

（Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。Ｒは、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基であり、複数のＲは、同じであっても異なっていてもよい。）

(R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group. R is a hydrogen atom. An atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group, and a plurality of R may be the same or different.)

  As the ligand represented by formula (4-1) to formula (4-4), a ligand represented by formula (4-1-0) to formula (4-4-0) shown below is preferable. .

（Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。Ｒは、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。）

(R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group. R is a hydrogen atom. An atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group, or an aryl group.)

  Examples of the ligand represented by the following formula (4-1-0) to formula (4-4-0) include those represented by the following formula (4-1-1) to formula (4-4-1). Ligands to be used.

  Among the phenyltriazole metal complexes represented by the formula (A), the complex in which the transition metal M is Ir is a homoleptic complex represented by the following formula (5-1) (m = 0, n = 3). The heteroleptic complex represented by the following formula (5-2) (m = 1, n = 2) and the heteroleptic complex represented by the following formula (5-3) (m = 2, n = 1) Is mentioned.

（Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅは、それぞれ独立して、水素原子、アルキル基又は式（２）で表される複素環であり、Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅのうち少なくとも一つは式（２）で表される複素環である。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。以下、同じ。）

(R ^A , R ^B , R ^C , R ^D and R ^E are each independently a hydrogen atom, an alkyl group or a heterocyclic ring represented by the formula (2), and R ^A , R ^B , R ^C , At least one of R ^D and R ^E is a heterocyclic ring represented by the formula (2): R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or a halogen atom. An alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group, or an aryl group. The same shall apply hereinafter.)

（Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅは、それぞれ独立して、水素原子、アルキル基又は式（２）で表される複素環であり、Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅのうち少なくとも一つは式（２）で表される複素環である。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立して、ＣＲ、Ｎ又はＮＲ^１０であり、Ｘ^４はＣ又はＮであり、Ｒ及びＲ^１０は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。以下、同じ。）

(R ^A , R ^B , R ^C , R ^D and R ^E are each independently a hydrogen atom, an alkyl group or a heterocyclic ring represented by the formula (2), and R ^A , R ^B , R ^C , At least one of R ^D and R ^E is a heterocyclic ring represented by the formula (2): R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ Are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group, and X ¹ , X ² and X ³ are each independently CR , N or NR ¹⁰ , X ⁴ is C or N, and R and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or An aryl group. The same applies hereinafter.)

  Examples of the homoleptic complex represented by the formula (5-1) include homoleptic complexes represented by the following formulas (5-1-1) to (5-1-10). It is not limited to these.

  Examples of the heteroleptic complex represented by the formula (5-2) include heteroleptic complexes represented by the following formulas (5-2-1) to (5-2-10). It is not limited to these.

  Examples of the heteroleptic complex represented by the formula (5-3) include heteroleptic complexes represented by the following formulas (5-3-1) to (5-3-10). It is not limited to these.

  Among the phenyltriazole metal complexes represented by the formula (A), the complex in which the transition metal M is Pt is a homoleptic complex represented by the following formula (5-4) (m = 0, n = 2). And a heteroleptic complex (m = 1, n = 1) represented by the following formula (5-5).

  Examples of the homoleptic complex represented by the formula (5-4) include homoleptic complexes represented by the following formulas (5-4-1) to (5-4-10). It is not limited to these.

  Examples of the heteroleptic complex represented by the formula (5-5) include heteroleptic complexes represented by the following formulas (5-5-1) to (5-5-10). It is not limited to these.

  Among the phenyltriazole metal complexes represented by the formula (A), the complex in which the transition metal M is Au is a phenyltriazole complex (m = 0, n = 1) represented by the following formula (5-6). Can be mentioned.

  Examples of the phenyltriazole complex represented by the formula (5-6) include phenyltriazole complexes represented by the following formulas (5-6-1) to (5-6-10). Not limited.

  The phenyltriazole metal complex represented by the formula (A) in which the transition metal M is Rh includes a homoleptic complex (m = 0, n = 3) represented by the following formula (5-7), A heteroleptic complex represented by (5-8) (m = 1, n = 2) and a heteroleptic complex represented by the following formula (5-9) (m = 2, n = 1). .

  Examples of the homoleptic complex represented by the formula (5-7) include homoleptic complexes represented by the following formulas (5-7-1) to (5-7-10). It is not limited to these.

  Examples of the heteroleptic complex represented by the formula (5-8) include heteroleptic complexes represented by the following formulas (5-8-1) to (5-8-10). It is not limited to these.

  Examples of the heteroleptic complex represented by the formula (5-9) include heteroleptic complexes represented by the following formulas (5-9-1) to (5-9-10). It is not limited to these.

<< Method for Producing Phenyltriazole Metal Complex >>
A method for producing the phenyltriazole metal complex represented by the formula (A) will be described.

  When n is 1, 2 or 3, and m = 0, the phenyltriazole metal complex (homoleptic complex) represented by the formula (A) can be synthesized, for example, according to the following reaction formula: it can.

（Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅは、それぞれ独立して、水素原子、アルキル基又は下記式（２）で表される複素環であり、Ｒ^Ａ、Ｒ^Ｂ、Ｒ^Ｃ、Ｒ^Ｄ及びＲ^Ｅのうち少なくとも一つは下記式（２）で表される複素環である。

(R ^A , R ^B , R ^C , R ^D and R ^E are each independently a hydrogen atom, an alkyl group or a heterocyclic ring represented by the following formula (2), and R ^A , R ^B , R ^C , R ^D and R ^E are each a heterocyclic ring represented by the following formula (2).

（Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅは、それぞれ独立して、ＣＲ又はＮであり、Ｙ^Ａ、Ｙ^Ｂ、Ｙ^Ｃ、Ｙ^Ｄ及びＹ^Ｅのうち、少なくとも一つはＮであり、Ｒは水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。＊は結合部位を表す。）

(Y ^A , Y ^B , Y ^C , Y ^D and Y ^E are each independently CR or N, and at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N R is a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group, and * represents a bonding site.

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group. M is Ir, Pt, Au or Rh, and n is 1, 2 or 3. However, when M is Ir or Rh, n = 3, when M is Pt, n = 2, and when M is Au, n = 1. Tf represents a trifluoromethylsulfonyl group. same as below. )

Inorganic metal source may be a hydrate of _MCl n · nH ₂ O, it may be the anhydride of MCl _n, may be an anhydride of K _{2 MCl n +} 2. However, M is Ir, Pt, Au, or Rh. When M is Ir or Rh, n = 3. When M is Pt, n = 2. When M is Au, n = 1. is there.

  When M is Ir or Rh, and m = 2 and n = 1, the phenyltriazole metal complex (heteroleptic complex) represented by the formula (A) is synthesized, for example, according to the following reaction formula be able to.

（Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立して、ＣＲ、Ｎ又はＮＲ^１０であり、Ｘ^４はＣ又はＮであり、Ｒ及びＲ^１０は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、ハロゲン原子で置換されたアルキル基、アルキルオキシ基又はアリール基である。ＭはＩｒ又はＲｈである。）

(R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group. X ¹ , X ² and X ³ are each independently CR, N or NR ¹⁰ , X ⁴ is C or N, and R and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group, a halogen atom, (It is an alkyl group, an alkyloxy group or an aryl group substituted with an atom. M is Ir or Rh.)

When M is Ir or Rh and m = 2 and n = 1, the inorganic metal raw material may be a hydrate of MCl ₃ .nH ₂ O or an anhydride of MCl ₃ , K ₂ MCl ₅ anhydride. However, M is Ir or Rh.

  When M is Ir or Rh, and m = 1 and n = 2, the phenyltriazole metal complex (heteroleptic complex) represented by the formula (A) is synthesized, for example, according to the following reaction formula be able to.

When M is Ir or Rh and m = 1 and n = 2, the inorganic metal raw material may be a hydrate of MCl ₃ .nH ₂ O or an anhydride of MCl ₃ , K ₂ MCl ₅ anhydride.

  When M is Pt, and m = 1 and n = 1, the phenyltriazole metal complex (heteroleptic complex) represented by the formula (A) can be synthesized according to the following reaction formula, for example. it can.

（ＭはＰｔである。）

(M is Pt.)

The inorganic metal raw material may be a hydrate of PtCl ₂ · nH ₂ O, an anhydride of PtCl _{2, or} an anhydride of K ₂ PtCl ₄ .

<< Light Emitting Element >>
The light-emitting element of the present invention includes an anode, a cathode, and a layer containing the phenyltriazole metal complex provided between the anode and the cathode.

  FIG. 1 is a cross-sectional view schematically showing one embodiment of a light emitting device of the present invention. In the light-emitting element 1 of FIG. 1, an anode 20, a hole injection layer 30, a hole transport layer 40, a light-emitting layer 50, an electron transport layer 60, an electron injection layer 70, and a cathode 80 are laminated on a substrate 10 in this order. The light emitting layer 50 includes the phenyltriazole metal complex.

  In the light emitting device of the present invention, the light emitting layer can inject holes from the anode, hole injection layer or hole transport layer when an electric field is applied, and inject electrons from the cathode, electron injection layer or electron transport layer. It has a function to move the injected charges (electrons and holes) by the force of an electric field, a function to recombine electrons and holes, and a function to connect this to light emission. Since the phenyltriazole has an electron-withdrawing heterocyclic ring in addition to the ring coordinated to the metal, it can enhance electron injection property and electron resistance, thereby making this phenyltriazole compound a ligand. The layer containing a phenyltriazole metal complex promotes recombination of electrons and holes, and can provide a light-emitting element with high emission efficiency and a long element lifetime. The light emitting layer may contain a host material using the phenyltriazole metal complex as a guest material. As the host material, a known material can be appropriately selected and used. In addition, a light-emitting layer in which the host material is doped with the host material can be formed by mixing the host material and a light-emitting material such as the metal complex, or by performing co-evaporation.

  In the light emitting device of the present invention, the anode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like. As the material for the anode, known materials such as metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof can be appropriately selected and used.

  In the light emitting device of the present invention, the cathode supplies electrons to the electron injection layer, the electron transport layer, the light emitting layer, and the like. As a material for the cathode, a known material such as a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, or a mixture thereof can be appropriately selected and used.

  The hole injection layer and the hole transport layer may have any of a function of injecting holes from the anode, a function of transporting holes, and a function of blocking electrons injected from the cathode. . As materials for these layers, known materials can be appropriately selected and used.

  The electron injection layer and the electron transport layer may have any one of the function of injecting electrons from the cathode, the function of transporting electrons, and the function of blocking holes injected from the anode. Known materials can be appropriately selected and used.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples at all.
Further, “%” in the compositions of the following Examples and Comparative Examples means “mass%”.

The following abbreviations are used in the description of the examples.
DMF: N, N-dimethylformamide THF: tetrahydrofuran Ac: acetyl group Tf: trifluoromethylsulfonyl group amphos: di-t-butyl (p-dimethylaminophenyl) phosphine dppf: 1,1′-bis (diphenylphosphino) Ferrocene dba: dibenzylideneacetone SPhos: 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl Bu: butyl Pr: propyl

[Example 1]
(Synthesis of Complex (A-1-1))
A phenyltriazole compound (A-4) and a phenyltriazole metal complex (A-1-1) were synthesized along the following scheme.

  A mixture of acetamidine hydrochloride (20 g, 213 mmol), sodium hydroxide (33% aqueous solution, 425 mmol), and acetone (200 mL) was added with a solution of benzoyl chloride (28 g, 200 mmol) in acetone (150 mL) for 10 minutes under ice cooling. And dripped. After stirring for 15 minutes under ice cooling, saturated brine was added, and the solvent of the obtained organic layer was evaporated under reduced pressure. Water was added thereto, and the mixture was extracted 3 times with dichloromethane, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and then recrystallized from a dichloromethane / hexane mixed solvent to obtain compound (A-1) (27.09 g, yield 84%).

The mass analysis result and ¹ H-NMR measurement result of the compound (A-1) are shown below.
[M]: 162
¹ H-NMR (400 MHz / CDCl ₃ , TMS): δ (ppm) = 10.36 (brs, 1H), 8.22 (d, 2H), 7.47 (m, 3H), 6.15 (brs) , 1H), 2.22 (s, 3H).

Under a nitrogen atmosphere, 4-bromo-2,6-dimethylaniline (25 g, 125 mmol) was added to a mixture of concentrated hydrochloric acid (32 mL, 375 mmol) and H ₂ O (6.4 mL). The temperature in the reaction system was kept at −2 to −3 ° C., and a solution of NaNO ₂ (9.1 g, 131 mmol) in H ₂ O (22.6 mL) was added over 2 hours. After stirring at −4 ° C. for 30 minutes, the internal temperature was kept at −3 ° C., and a solution of SnCl ₂ .H ₂ O (70.5 g, 313 mmol) in concentrated hydrochloric acid (35 mL) and water (35 mL) was added dropwise over 2.5 hours. . Thereafter, the mixture was stirred at -3 ° C for 1 hour and at room temperature for 3 hours. The precipitated solid was collected by filtration and washed with saturated brine. To the obtained solid, THF (250 mL) was added and ice-cooled, and 50% aqueous NaOH solution (125 g) was added dropwise at an internal temperature of 5 to 8 ° C. over 40 minutes. The aqueous layer was extracted four times with THF (50 mL), and the combined organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was concentrated in half. This was ice-cooled and 4M HCl in dioxane (34 mL, 138 mmol) was added. The precipitated solid was collected by filtration and washed three times with THF (100 mL). This was dried to obtain compound (A-2) (23.15 g, yield 86%).

  To a mixture of compound (A-1) (12.00 g, 74 mmol), compound (A-2) (22.28 g, 104 mmol) and DMF (170 mL), acetic acid (42.4 mL, 740 mmol) was added at room temperature, Stir for hours. The reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution (1 L), and the precipitated solid was collected by filtration. This was purified by silica gel column chromatography (silica gel 75 g, mobile phase: hexane / ethyl acetate = 7/3), and then recrystallized from hexane to give compound (A-3) (20.35 g, yield 80% )

The mass spectrometry result and ¹ H-NMR measurement result of the compound (A-3) are shown below.
[M]: 341
¹ H-NMR (400 MHz / CDCl ₃ , TMS): δ (ppm) = 7.45 (m, 2H), 7.32 (m, 5H), 2.52 (s, 3H), 1.95 (s , 6H).

Compound (A-3) (11.3 g, 33 mmol), dichlorobis [di-t-butyl (p-dimethylaminophenyl) phosphino] palladium (II) (1.7 g, 1.0 mmol), 2 mol / L potassium carbonate under nitrogen atmosphere Aqueous solution (36 mL, 72 mmol) and THF (150 mL) were mixed and heated to 60 ° C. Under heating, a solution of 6-methylpyridine-3-boronic acid (5.0 g, 36 mmol) in THF (50 mL) / H ₂ O (50 mL) was added dropwise, and the mixture was stirred at 60 ° C. for 9 hours. Water was added to the reaction solution returned to room temperature, and the aqueous layer was separated and extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (silica gel 120 g, mobile phase: hexane / ethyl acetate = 2/1 → 1/1 → 1/2) to obtain the phenyltriazole compound (A-4) ( 6.67 g, 57% yield) was obtained.

The results of mass spectrometry analysis and ¹ H-NMR measurement of the phenyltriazole compound (A-4) are shown below.
[M]: 354
¹ H-NMR (400 MHz / CDCl ₃ , TMS): δ (ppm) = 8.75 (s, 1H), 7.80 (dd, 1H), 7.45 (m, 8H), 2.62 (s) , 3H), 2.54 (s, 3H), 2.05 (s, 6H).

A mixture of iridium (III) chloride n hydrate (1.4 g, 4 mmol), compound (A-4) (3.5 g, 10 mmol), 2-ethoxyethanol (220 mL), H ₂ O (73 mL) was added under an argon atmosphere. Heated to reflux for 24 hours. After standing to cool, water was added and the mixture was filtered, and the filtrate was distilled off under reduced pressure. The aqueous layer was extracted with dichloromethane, washed with saturated brine, and dried over anhydrous sodium sulfate. This was filtered through Celite, the solvent was distilled off under reduced pressure, and then recrystallized from a dichloromethane / hexane mixed solvent to obtain a yellow solid (1.15 g).

  To a mixture of this yellow solid (1.10 g), silver trifluoromethanesulfonate (0.36 g, 1.4 mmol), compound (A-4) (2.1 g, 5.9 mmol), diethylene glycol dimethyl ether (20 mL) was added under an argon atmosphere, The mixture was heated and stirred at 170 ° C. for 48 hours. Ethanol was added to the mixture and the black solid was removed by filtration and washed with ethanol and dichloromethane. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (silica gel 150 g, mobile phase: ethyl acetate → dichloromethane / methanol = 10/1). The product was purified again by silica gel column chromatography (silica gel 150 g, mobile phase: ethyl acetate → dichloromethane / methanol = 10/1), followed by recrystallization from a dichloromethane / hexane mixed solvent and suspension washing with ethanol. The phenyltriazole metal complex (A-1-1) (0.12 g, 2% yield) was obtained as a yellow solid.

The measurement result of ¹ H-NMR of the phenyltriazole metal complex (A-1-1) of Example 1 is shown below.
¹ H-NMR (400 MHz / CDCl ₃ , TMS): δ (ppm) = 8.80 (s, 3H), 7.85 (dd, 3H), 7.45 (d, 6H), 7.27 (d 3H), 6.61 (m, 12H), 2.63 (s, 9H), 2.28 (s, 9H), 2.15 (s, 9H), 1.91 (s, 9H).

[Example 2]
(Synthesis of Complex (A-1-2))
A phenyltriazole compound (C-2) and a phenyltriazole metal complex (A-1-2) were synthesized according to the following scheme.

Compound (A-3) 3.00 g (8.77 mmol), bis (pinacolato) diboron 4.90 g (19.3 mmol), potassium acetate 2.59 g (26.38 mmol), PdCl ₂ (dppf) · CH ₂ Cl ₂ 0.215 g (0.264 mmol) Then, 50 ml of dehydrated 1,4-dioxane was reacted at 90 ° C. for 16 hours under an argon atmosphere. The reaction solution was cooled to room temperature, the reaction solvent was distilled off under reduced pressure, and dichloromethane and water were added for extraction. The product obtained by collecting and concentrating the organic layer was separated and purified using silica gel column chromatography (eluent: mixed solvent of ethyl acetate and hexane). The yield of compound (C-1) was 95%.

The measurement result of ¹ H-NMR of compound (C-1) is shown below.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.58 (s, 2H), 7.44 (d, 2H), 7.33 (t, 1H), 7.25 (t, 2H) ), 2.52 (s, 3H), 1.97 (s, 6H), 1.38 (t, 12H).

Compound (C-1) 3.00 g (7.71 mmol), 5-bromo-2-tert-butylpyrimidine 1.82 g (8.48 mmol), K ₃ PO ₄ 5.40 g (25.4 mmol), SPhos 0.139 g (0.339 mmol), Pd ₂ (dba) ₃ 0.0776 g (0.0847 mmol), toluene 60 ml, and water 5 ml were reacted at 116 ° C. for 16 hours in an argon atmosphere. The reaction solution was cooled to room temperature, and extracted with ethyl acetate and water. The product obtained by collecting and concentrating the organic layer was separated and purified using silica gel column chromatography (eluent: mixed solvent of ethyl acetate and hexane). The obtained product was recrystallized using ethyl acetate and hexane. The yield of the phenyltriazole compound (C-2) was 70%.

The measurement result of ¹ H-NMR of the phenyltriazole compound (C-2) is shown below.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 8.90 (s, 2H), 7.51 (d, 2H), 7.28-7.39 (m, 5H), 2.54 (S, 3H), 2.06 (s, 6H), 1.46 (s, 9H).

  Reaction of 0.403 g (1.14 mmol) of iridium trichloride trihydrate, 1.0 g (2.52 mmol) of compound (C-2), 45 ml of 2-ethoxyethanol, and 15 ml of water at 120 ° C. for 20 hours under an argon atmosphere I let you. The solid precipitated after cooling to room temperature was collected by filtration and recrystallized using dichloromethane and methanol. The yield of compound (B-1) was 93%. Compound (B-1) was used in the next step without further purification.

  1.10 g (0.539 mmol) of the compound (B-1), 0.856 g (2.15 mmol) of the compound (C-2), 0.305 g (1.19 mmol) of silver trifluoromethanesulfonate, and 3 ml of diglyme under an argon atmosphere The reaction was carried out at 166 ° C. for 19 hours. After cooling to room temperature, the reaction solution was filtered through a celite layer, and the obtained filtrate was concentrated under reduced pressure. This was separated and purified using silica gel chromatography (eluent: dichloromethane and ethyl acetate). The obtained solid was recrystallized using dichloromethane and hexane. The yield of the phenyltriazole metal complex (A-1-2) of Example 2 was 39%.

¹ H-NMR data of the phenyltriazole metal complex (A-1-2) of Example 2 are shown below.
¹ H-NMR (400 MHz / acetone-d6): δ (ppm) = 9.13 (s, 6H), 7.85 (s, 3H), 7.77 (s, 3H), 6.55-6. 69 (m, 12H), 2.33 (s, 9H), 2.19 (s, 9H), 1.92 (s, 9H), 1.45 (s, 27H).

[Example 3]
(Synthesis of Complex (A-1-3))
A phenyltriazole metal complex (A-1-3) was synthesized according to the following scheme.

  20 mL of water and 34.2 g of concentrated hydrochloric acid were added to the reaction vessel. It cooled to -15 degreeC, the compound represented by Formula (C-3) 15.0g was dripped, and it stirred for 20 minutes. An aqueous solution in which 9.4 g of sodium nitrite was dissolved in 20 mL of water was added dropwise and stirred for 1 hour. An aqueous solution prepared by dissolving 69.8 g of tin (II) chloride dihydrate in 35 mL of water and 35 mL of concentrated hydrochloric acid was added dropwise and stirred for 2 hours. The mixture was warmed to room temperature and stirred for 3 hours. The reaction solution was ice-cooled, and 10M aqueous sodium hydroxide solution was added dropwise to adjust the pH of the reaction solution to 10. Extraction was performed with diisopropyl ether, and the organic layer was washed with brine. After purification by column chromatography (alumina, diisopropyl ether), 1M hydrogen chloride / diethyl ether was added. The precipitate was filtered and then purified by recrystallization (ethanol) to obtain 17.9 g of a compound represented by the formula (C-4).

  To the reaction vessel, 6.2 g of the compound represented by the formula (A-1), 50 mL of N, N-dimethylformamide, and 6.3 g of the compound represented by the formula (C-4) were added. Acetic acid (20 mL) was added, and the mixture was heated with stirring at 90 ° C for 5 hours. After cooling to room temperature, the reaction solution was poured into an aqueous sodium bicarbonate solution. The precipitate was filtered and washed with water. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate (5: 1)) and recrystallization (hexane) to obtain 7.9 g of a compound represented by the formula (C-5).

The measurement result of ¹ H-NMR of the compound represented by the formula (C-5) is shown below.
¹ H-NMR (CDCl ₃ ) δ 1.98 (s, 6H), 2.53 (s, 3H), 7.15 (d, 2H), 7.25-7.36 (m, 4H), 7 .47 (m, 2H) ppm.

    Under an argon atmosphere, add 560.1 mg of the compound represented by the formula (C-5), 300.0 mg of iridium (III) chloride hydrate, 12 mL of 2-ethoxyethanol, and 4 mL of ion-exchanged water to a reaction vessel at 120 ° C. The mixture was heated and stirred for 22 hours. After cooling to room temperature, the reaction solution was poured into water. The precipitate was filtered and washed with water. Dissolved in dichloromethane and dried over sodium sulfate. By reprecipitation with hexane, 580.0 mg of the compound represented by the formula (C-6) was obtained.

  Compound (C-6) 0.850 g (0.565 mmol), AgOTf 0.319 g (1.24 mmol), dichloromethane 40 mL and methanol 0.8 mL were reacted at room temperature for 17 hours in an argon atmosphere. The reaction solution was filtered through a celite layer, and the obtained filtrate was concentrated under reduced pressure to obtain a product (C-7).

  Subsequently, the total amount of the product (C-7) obtained above, 1.12 g (2.82 mmol) of the compound (C-2) synthesized in Example 2, and 25 mL of ethanol were reacted at 90 ° C. for 105 hours in an argon atmosphere. It was. After cooling to room temperature, the precipitated solid was recovered by filtration, and separated and purified using silica gel chromatography (eluent: dichloromethane). The obtained solid was recrystallized using dichloromethane and hexane. The yield of the phenyltriazole metal complex (A-1-3) was 45%.

The measurement result of ¹ H-NMR of the phenyltriazole metal complex (A-1-3) of Example 3 is shown below.
¹ H-NMR (400 MHz / acetone-d6): δ (ppm) = 9.12 (s, 2H), 7.83 (s, 1H), 7.75 (s, 1H), 7.48 (t, 2H), 7.41 (d, 2H), 7.33 (d, 2H), 6.53-6.67 (m, 10H), 6.41 (d, 2H), 2.32 (s, 3H) ), 2.22 (s, 6H), 2.15 (s, 6H), 2.14 (s, 3H), 1.90 (s, 3H), 1.81 (s, 6H), 1.44 (S, 9H).

[Example 4]
(Synthesis of complex (A-1-4))
A phenyltriazole compound (D-1) and a phenyltriazole metal complex (A-1-4) were synthesized according to the following scheme.

Compound (C-1) 3.50 g (8.99 mmol), 3-bromo-2,6-dimethylpyridine 1.84 g (9.89 mmol), K ₃ PO ₄ 6.30 g (29.7 mmol), 2-dicyclohexyl Phosphino-2 ′, 6′-dimethoxybiphenyl 0.161 g (0.392 mmol), tris (dibenzylideneacetone) dipalladium (0) 0.0898 g (0.0980 mmol), toluene 58 ml, water 6 ml under an argon atmosphere , Reacted at 116 ° C. for 16 hours. The reaction solution was cooled to room temperature, and extracted with ethyl acetate and water. The product obtained by collecting and concentrating the organic layer was separated and purified using silica gel column chromatography (eluent: mixed solvent of ethyl acetate and hexane). The yield of compound (D-1) was 91%.

¹ H-NMR data of the compound (D-1) are shown below.
¹ H-NMR (400 MHz / CDCl ₃ ): δ (ppm) = 7.52 (d, 2H), 7.42 (d, 1H), 7.37 (dd, 1H), 7.30 (dd, 2H) ), 7.08 (s, 2H), 7.05 (d, 1H), 2.58 (s, 3H), 2.55 (s, 3H), 2.48 (s, 3H), 2.02 (S, 6H).

  2.04 g (2.26 mmol) of the compound (C-7) synthesized by the method of Example 3, 2.08 g (5.64 mmol) of the compound (D-1), and 49 ml of ethanol were 280 at 90 ° C. under an argon atmosphere. Reacted for hours. After cooling to room temperature, the precipitated solid was recovered by filtration, and separated and purified using silica gel chromatography (eluent: dichloromethane). The obtained solid was recrystallized using dichloromethane and hexane. The yield of the phenyltriazole metal complex (A-1-4) of Example 4 was 32%.

¹ H-NMR data of the phenyltriazole metal complex (A-1-4) of Example 4 are shown below.
¹ H-NMR (400 MHz / acetone-d6): δ (ppm) = 7.58 (s, 1H), 7.47 (t, 2H), 7.32-7.41 (m, 6H), 7. 17 (d, 1H), 6.51-6.67 (m, 10H), 6.41 (d, 2H), 2.51 (s, 3H), 2.50 (s, 3H), 2.28 (S, 3H), 2.22 (s, 6H), 2.16 (s, 3H), 2.15 (s, 3H), 2.14 (s, 3H), 1.87 (s, 3H) , 1.81 (s, 6H).

[Example 5]
(Synthesis of Complex (A-1-5))
A phenyltriazole metal complex (A-1-5) was synthesized according to the following scheme.

  Compound (E-1) 0.278 g (0.185 mmol) synthesized by the method described in paragraphs [0204] to [0205] of WO 2007/097153 (Patent Document 2), silver trifluoromethanesulfonate 0 105 g (0.409 mmol), dichloromethane (13 ml) and methanol (0.2 ml) were reacted at room temperature for 17 hours under an argon atmosphere. The reaction solution was filtered through a celite layer, and the obtained filtrate was concentrated under reduced pressure to obtain compound (E-2).

  The whole amount of the compound (E-2) obtained above, 0.344 g (0.865 mmol) of the compound (C-2), and 8 ml of ethanol were reacted at 90 ° C. for 156 hours in an argon atmosphere. After cooling to room temperature, the precipitated solid was recovered by filtration, and separated and purified using silica gel chromatography (eluent: mixed solvent of dichloromethane and ethyl acetate). The yield of the phenyltriazole metal complex (A-1-5) of Example 5 was 13%.

¹ H-NMR data of the phenyltriazole metal complex (A-1-5) of Example 5 are shown below.
¹ H-NMR (400 MHz / acetone-d6): δ (ppm) = 9.13 (s, 2H), 9.12 (s, 2H), 7.82 (s, 1H), 7.79 (s, 1H), 7.77 (s, 1H), 7.76 (s, 1H), 7.19 (s, 1H), 7.10 (s, 1H), 7.06 (s, 1H), 6. 96 (s, 1H), 6.75 (d, 1H), 6.47-6.67 (m, 10H), 6.28 (d, 1H), 2.40 (s, 3H), 2.30 (S, 3H), 2.27 (s, 3H), 2.18 (s, 3H), 2.16 (s, 3H), 2.09 (s, 3H), 2.02 (s, 3H) , 1.93 (s, 3H), 1.68 (s, 3H), 1.44 (s, 18H).

[Example 6]
(Synthesis of Complex (A-1-6))
A phenyltriazole metal complex (A-1-6) was synthesized according to the following scheme.

  Compound (F-1) 1.26 g (1.23 mmol) synthesized by the method described in J. Am. Chem. Soc., 2003, 125, 7377-7387, 0.694 g (2.70 mmol) of silver trifluoromethanesulfonate ), 83 ml of dichloromethane and 1.5 ml of methanol were reacted at room temperature for 17 hours under an argon atmosphere. The reaction solution was filtered through a celite layer, and the obtained filtrate was concentrated under reduced pressure to obtain compound (F-2).

  The whole amount of the compound (F-2) obtained above, 2.10 g (6.137 mmol) of the compound (A-3), and 9 ml of ethanol were reacted at 90 ° C. for 155 hours in an argon atmosphere. After cooling to room temperature, the precipitated solid was recovered by filtration, and separated and purified using silica gel chromatography (eluent: mixed solvent of dichloromethane and ethyl acetate). The yield of compound (F-3) was 21%, and the yield of compound (F-4) was 36%.

¹ H-NMR data of the compound (F-3) are shown below.
¹ H-NMR (400 MHz / acetone-d6): δ (ppm) = 8.49 (d, 1H), 8.48 (d, 1H), 7.56 (d, 2H), 7.44 (t, 2H), 7.42 (d, 1H), 7.02 (d, 1H), 6.82-6.89 (m, 3H), 6.75 (d, 1H), 6.62-6.67. (M, 4H), 6.54-6.59 (m, 2H), 6.49 (t, 1H), 6.40 (d, 1H), 2.08 (s, 3H), 1.85 ( s, 3H), 1.72 (s, 3H).

¹ H-NMR data of the compound (F-4) are shown below.
¹ H-NMR (400 MHz / acetone-d6): δ (ppm) = 8.53 (d, 1H), 7.59 (d, 2H), 7.57 (s, 1H), 7.54 (s, 1H), 7.47 (d, 1H), 7.42 (d, 1H), 6.87 (dd, 1H), 6.76 (d, 1H), 6.55-6.67 (m, 8H) ), 6.45 (d, 1H), 6.43 (d, 1H), 2.16 (s, 3H), 2.14 (s, 3H), 2.07 (s, 3H), 1.90. (S, 3H), 1.77 (s, 3H), 1.72 (s, 3H).

Compound (F-3) 0.432 g (0.527 mmol), 2- (tert-butyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyrimidine 0.152 g (0.580 mmol), K ₃ PO ₄ 0.336 g (1.58 mmol), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl 0.0433 g (0.105 mmol), tris (dibenzylideneacetone) ) Dipalladium (0) 0.0241 g (0.0263 mmol), toluene 3.5 ml, and water 0.3 ml were reacted at 110 ° C. for 24 hours under an argon atmosphere. The reaction solution was cooled to room temperature, and extracted with ethyl acetate and water. The product obtained by collecting and concentrating the organic layer was separated and purified using silica gel column chromatography (eluent: mixed solvent of dichloromethane and ethyl acetate). The obtained product was recrystallized using ethyl acetate and hexane. The yield of the phenyltriazole metal complex (A-1-6) of Example 6 was 76%.

¹ H-NMR data of the phenyltriazole metal complex (A-1-6) of Example 6 are shown below.
¹ H-NMR (400 MHz / acetone-d6): δ (ppm) = 9.10 (s, 2H), 8.50 (d, 1H), 8.49 (d, 1H), 7.75 (d, 2H), 7.43-7.48 (m, 3H), 7.03 (d, 1H), 6.83-6.90 (m, 3H), 6.76 (d, 1H), 6.60. -6.68 (m, 5H), 6.50-6.55 (m, 2H), 6.46 (d, 1H), 2.18 (s, 3H), 1.94 (s, 3H), 1.75 (s, 3H), 1.43 (s, 9H).

[Example 7]
(Synthesis of Complex (A-1-7))
According to the scheme shown in Example 6, a phenyltriazole metal complex (A-1-7) was synthesized.

Compound (F-4) 0.450 g (0.442 mmol), 2- (tert-butyl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) 0 .255 g (0.974 mmol), K ₃ PO ₄ 0.564 g (2.66 mmol), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl 0.0727 g (0.177 mmol), tris (dibenzylideneacetone) 0.0405 g (0.0442 mmol) of dipalladium (0), 3 ml of toluene, and 0.3 ml of water were reacted at 110 ° C. for 24 hours under an argon atmosphere. The reaction solution was cooled to room temperature, and extracted with ethyl acetate and water. The product obtained by collecting and concentrating the organic layer was separated and purified using silica gel column chromatography (eluent: mixed solvent of dichloromethane and ethyl acetate). The obtained product was recrystallized using ethyl acetate and hexane. The yield of the phenyltriazole metal complex (A-1-7) of Example 7 was 89%.

The ¹ H-NMR data of the phenyltriazole metal complex (A-1-7) of Example 7 is shown below.
¹ H-NMR (400 MHz / acetone-d6): δ (ppm) = 9.11 (s, 4H), 8.55 (d, 1H), 7.80 (d, 2H), 7.77 (s, 1H), 7.74 (s, 1H), 7.49 (d, 1H), 7.46 (d, 1H), 6.89 (t, 1H), 6.79 (d, 1H), 6. 49-6.71 (m, 10H), 2.27 (s, 3H), 2.24 (s, 3H), 2.13 (s, 3H), 2.01 (s, 3H), 1.87 (S, 3H), 1.76 (s, 3H), 1.43 (s, 18H).

[Example 8]
(Synthesis of Complex (A-1-8))
A phenyltriazole metal complex (A-1-8) was synthesized according to the following scheme.

Under a nitrogen atmosphere, 3-chloro-2,6-dimethylaniline (30 g, 193 mmol) was added to a mixture of concentrated hydrochloric acid (49 mL, 375 mmol) and H ₂ O (98 mL). The temperature in the reaction system was kept at -1 ° C or lower, and a solution of NaNO ₂ (14.0 g, 203 mmol) in H ₂ O (35 mL) was added over 2 hours. After stirring for 50 min, maintaining the internal temperature at _{-2 ℃, SnCl 2 · H 2} O (108.7 g, 482mmol) in concentrated hydrochloric acid (55 mL), added dropwise over water (55 mL) solution for 2.5 hours, then 2 hours Stir. The precipitated solid was collected by filtration and washed with saturated brine. To the obtained solid, THF (250 mL) was added and ice-cooled, and 50% NaOH aqueous solution (150 mL) was added dropwise at an internal temperature of 8 to 12 ° C. over 40 minutes. The aqueous layer was extracted four times with THF (50 mL), and the combined organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was concentrated in half. This was ice-cooled and 4M HCl dioxane solution (53 mL, 211 mmol) was added. The precipitated solid was collected by filtration and washed three times with THF (100 mL). This was dried to obtain compound (H-1) (26.47 g, yield 66%).

  To a mixture of compound (A-1) (15.0 g, 93 mmol), compound (H-1) (26.0 g, 126 mmol) and DMF (400 mL), acetic acid (55 mL, 960 mmol) was added at room temperature, and the mixture was stirred at 90 ° C. for 5 hours. Stir with heating. Water (1 L) was added to the reaction solution, extracted three times with ethyl acetate, and the combined organic layer was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (silica gel 100 g, mobile phase: hexane / ethyl acetate = 1/1), then suspended and washed with hexane, and impurities were precipitated with a hexane / ethyl acetate mixed solvent. Compound (H-2) (21.84 g, yield 81%).

The mass spectrometry result of compound (H-2) and the measurement result of ¹ H-NMR are shown below.
[M]: 297
¹ H-NMR (400 MHz / CDCl ₃ , TMS): δ (ppm) = 7.35 (m, 6H), 7.10 (d, 1H), 2.53 (s, 3H), 2.01 (s , 3H), 1.93 (s, 3H).

  Under a nitrogen atmosphere, 3-bromo-2,6-dimethylpyridine (7.5 g, 40 mmol) in diisopropyl ether (240 mL) was charged with n-butyllithium (1.6 M hexane solution, 37.5 mL, 60 mmol) at −78. The solution was added dropwise at 0 ° C. and stirred for 45 minutes. A solution of pinacol isopropoxyboronate (15.3 g, 80 mmol) in diisopropyl ether (80 mL) was added dropwise at −78 ° C., and the mixture was stirred for 4 hours. Isopropyl ether was added dropwise, and saturated brine was added at room temperature. The aqueous layer was extracted 6 times with dichloromethane, and the combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, the solvent was distilled off, and the compound (H-3) (9.02 g, gas chromatography purity 70 %).

The results of mass spectrometry analysis and ¹ H-NMR measurement of the compound (H-3) are shown below.
[M]: 233
¹ H-NMR (400 MHz / CDCl ₃ , TMS): δ (ppm) = 7.90 (d, 1H), 6.95 (d, 1H), 2.71 (s, 3H), 2.52 (s , 3H), 1.34 (s, 12H).

  Under nitrogen atmosphere, compound (H-2) (3.0 g, 10 mmol), dichlorobis [di-t-butyl (p-dimethylaminophenyl) phosphino] palladium (II) (0.2 g, 0.3 mmol), 2 mol / L tripotassium phosphate aqueous solution (15 mL, 30 mmol) and 1,4-dioxane (100 mL) were mixed and heated to 100 ° C. Under heating, a solution of compound (H-3) (6.8 g, purity 70%, 20 mmol) in 1,4-dioxane (50 mL) was added dropwise and stirred at 100 ° C. for 3 hours. Water was added to the reaction solution returned to room temperature, and the aqueous layer was separated and extracted three times with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (silica gel 20 g, mobile phase: hexane / ethyl acetate = 1/1) and dried.

  Purification by silica gel column chromatography (silica gel 25 g, mobile phase: hexane / ethyl acetate = 2/1 → 1/1) gave a phenyltriazole compound (H-4) (3.27 g, yield 88%). It was.

The results of mass spectrometry analysis and ¹ H-NMR measurement of the phenyltriazole compound (H-4) are shown below.
[M]: 368
¹ H-NMR (400 MHz / CDCl ₃ , TMS): δ (ppm) = 7.49 (m, 2H), 7.37 (m, 1H), 7.29 (m, 3H), 7.24 (m , 1H), 7.17 (m, 1H), 7.03 (m, 1H), 2.57-1.95 (m, 15H).

  Compound (C-7) (3.5 mmol), compound (H-4) (3.27 g, 8.8 mmol), and 90 ml of ethanol were reacted at 90 ° C. for 170 hours in an argon atmosphere. After cooling to room temperature, the solvent was distilled off under reduced pressure, and separation and purification were performed using silica gel column chromatography (eluent: ethyl acetate). The obtained solid was dissolved in dichloromethane, and this solution was added dropwise to hexane to reprecipitate, followed by filtration to obtain a yellow solid. The solvent of the filtrate was distilled off under reduced pressure, and reprecipitation was repeated. The combined solid was reprecipitated (dichloromethane / hexane), purified using alumina column chromatography (eluent: dichloromethane), and reprecipitated (dichloromethane / hexane), whereby the phenyltriazole metal complex (A-1-8) was obtained. ) (0.21 g, 6% yield) was obtained as a yellow solid.

The measurement result of ¹ H-NMR of the phenyltriazole metal complex (A-1-8) is shown below.
¹ H-NMR (400 MHz / CDCl ₃ , TMS): δ (ppm) = 7.40-7.21 (m, 9H), 7.06 (m, 1H), 6.69-6.48 (m, 10H), 6.41 (m, 2H), 2.58 (d, 3H), 2.37-2.06 (m, 21H), 1.91-1.81 (m, 9H).

[Example 9]
(Synthesis of Complex (A-1-9))
A phenyltriazole metal complex (A-1-9) was synthesized according to the following scheme.

  Compound (C-6) (1.0 g, 0.666 mmol), silver trifluoromethanesulfonate (0.375 g, 1.47 mmol), dichloromethane (47 ml), and methanol (1 ml) were reacted in an argon atmosphere at room temperature for 17 hours. The reaction solution was filtered through a celite layer, and the obtained filtrate was concentrated under reduced pressure to obtain compound (C-7).

  The total amount of the compound (C-7) obtained above, 1.14 g (3.33 mmol) of compound (A-3), and 49 ml of ethanol were reacted at 90 ° C. for 236 hours in an argon atmosphere. After cooling to room temperature, the precipitated solid was recovered by filtration, and separated and purified using silica gel chromatography (eluent: mixed solvent of dichloromethane and ethyl acetate). The obtained solid was recrystallized using dichloromethane and hexane. The yield of compound (I-1) was 89%.

The ¹ H-NMR data of compound (I-1) is shown below.
¹ H-NMR (400 MHz / acetone-d6): δ (ppm) = 7.62 (s, 1H), 7.55 (s, 1H), 7.46 (t, 2H), 7.39 (d, 2H), 7.32 (d, 2H), 6.53-6.66 (m, 9H), 6.46 (d, 1H), 6.39 (d, 2H), 2.22 (s, 3H) ), 2.20 (s, 6H), 2.10-2.12 (m, 9H), 1.80 (s, 9H).

Compound (I-1) 0.40 g (0.378 mmol), 2-methyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine 0.0912 g ( 0.416 mmol), K ₃ PO ₄ 0.241 g (1.13 mmol), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl 0.0311 g (0.0757 mmol), tris (dibenzylideneacetone) dipalladium ( 0) 0.0173 g (0.0189 mmol), 2.4 ml of toluene, and 0.2 ml of water were reacted at 110 ° C. for 24 hours in an argon atmosphere. The reaction solution was cooled to room temperature, and extracted with ethyl acetate and water. The product obtained by collecting and concentrating the organic layer was separated and purified using silica gel column chromatography (eluent: mixed solvent of dichloromethane and ethyl acetate). The obtained product was recrystallized using ethyl acetate and hexane. The yield of the phenyltriazole metal complex (A-1-9) of Example 9 was 78%.

¹ H-NMR data of the phenyltriazole metal complex (A-1-9) of Example 9 are shown below.
¹ H-NMR (400 MHz / acetone-d6): δ (ppm) = 8.43 (d, 1H), 7.70 (s, 1H), 7.62 (s, 1H), 7.54 (s, 1H), 7.45 (d, 1H), 7.35 (t, 2H), 7.28 (d, 2H), 7.20 (d, 2H), 6.38-6.54 (m, 10H) ), 6.28 (d, 2H), 2.46 (s, 3H), 2.18 (s, 3H), 2.09 (s, 6H), 2.02 (s, 6H), 2.01 (S, 3H), 1.77 (s, 3H), 1.68 (s, 6H).

[Example 10]
(Synthesis of Complex (A-1-10))
A phenyltriazole metal complex (A-1-10) was synthesized according to the following scheme.

  0.364 g (0.354 mmol) of the compound (F-1) synthesized by the method described in J. Am. Chem. Soc., 2003, 125, 7377-7387, 0.20 g (0.779 mmol) of silver trifluoromethanesulfonate ), 24 ml of dichloromethane and 0.5 ml of methanol were reacted at room temperature for 17 hours under an argon atmosphere. The reaction solution was filtered through a celite layer, and the obtained filtrate was concentrated under reduced pressure to obtain compound (F-2).

  The whole amount of the compound (F-2) obtained above, 0.650 g (1.770 mmol) of the compound (D-1), and 9 ml of ethanol were reacted at 75 ° C. for 94 hours in an argon atmosphere. After cooling to room temperature, the precipitated solid was recovered by filtration, and separated and purified using silica gel chromatography (eluent: mixed solvent of dichloromethane and ethyl acetate). The resulting product was recrystallized using dichloromethane and hexane. The yield of the phenyltriazole metal complex (A-1-10) was 0.2%.

The ¹ H-NMR data of the phenyltriazole metal complex (A-1-10) is shown below.
¹ H-NMR (400 MHz / acetone-d6): δ (ppm) = 8.50 (dd, 1H), 7.55 (d, 2H), 7.43-7.48 (m, 3H), 7. 33 (d, 2H), 7.15 (d, 1H), 7.03 (d, 1H), 6.83-6.90 (m, 3H), 6.76 (d, 1H), 6.63 -6.69 (m, 4H), 6.60 (t, 1H), 6.55 (dd, 1H), 6.51 (t, 1H), 6.46 (d, 1H), 2.50 ( s, 3H), 2.48 (s, 3H), 2.14 (s, 3H), 1.91 (s, 3H), 1.75 (s, 3H).

[Comparative Example 1]
(Synthesis of Complex (B-1-1))
A phenyltriazole metal complex (B-1-1) was synthesized according to the following scheme with reference to the description in Synthesis Example 4 of International Publication No. 2013/151989 (Patent Document 3: Special Tables 2015-519306).

Under a nitrogen atmosphere, 2,4,6-trimethylaniline (15.0 g, 111 mmol) was added to a mixture of concentrated hydrochloric acid (34 g, 333 mmol) and H ₂ O (56 mL). The temperature in the reaction system was kept at −8 to −10 ° C., and a solution of NaNO ₂ (8.1 g, 117 mmol) in H ₂ O (20 mL) was added over 25 minutes. After stirring at −10 ° C. for 30 minutes, the internal temperature was kept at −6 ° C. to −12 ° C., and a solution of SnCl ₂ (52.6 g, 277 mmol) in concentrated hydrochloric acid (31 mL) and water (31 mL) was added dropwise over 4 hours. . Thereafter, the mixture was stirred at room temperature for 3 hours. The precipitated solid was collected by filtration and washed with saturated brine. To the obtained solid, THF (300 mL) was added and ice-cooled, and 10M NaOH aqueous solution (200 mL) was added dropwise at an internal temperature of 5 to 8 ° C. over 15 minutes. Water (100 mL) was added, the aqueous layer was extracted twice with THF (50 mL), and the combined organic layer was dried over anhydrous sodium sulfate. This was ice-cooled, 4M HCl dioxane solution (27 mL, 108 mmol) was added, and the mixture was stirred for 1 hr. The precipitated solid was collected by filtration and dried to obtain compound (X-2) (4.3 g, yield 21%).

  To a mixture of compound (A-1) (2.09 g, 13 mmol), compound (X-2) (3.34 g, 18 mmol) and DMF (30 mL), acetic acid (7.4 mL, 130 mmol) was added at room temperature, Stir for hours. The reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution (230 mL), and the precipitated solid was collected by filtration. This was purified by silica gel column chromatography (silica gel 18 g, mobile phase: hexane / ethyl acetate), and then recrystallized from hexane to obtain compound (X-3) (3.70 g, yield 80%). .

The mass analysis result of the compound (X-3) is shown below.
[M]: 277

A mixture of iridium (III) chloride n hydrate (0.8 g, 2.1 mmol), compound (X-3) (1.3 g, 4.7 mmol), 2-ethoxyethanol (22 mL), H ₂ O (7.5 mL) was added to argon. The mixture was heated to reflux for 15 hours under an atmosphere. After standing to cool, water was added and filtered. The obtained solid was dissolved in dichloromethane and dried over anhydrous sodium sulfate. This was filtered and the solvent was distilled off under reduced pressure to obtain a solid (1.71 g).

  To a mixture of this solid (0.84 g), silver trifluoromethanesulfonate (0.56 g, 2.2 mmol), compound (X-3) (1.2 g, 4.3 mmol), diethylene glycol dimethyl ether (10 mL) was added under an argon atmosphere, and 155 The mixture was stirred at 13 ° C. for 13 hours. Methanol was added to the mixture, and a black solid was obtained by filtration. This was purified by silica gel column chromatography (silica gel 3 g, mobile phase: dichloromethane → dichloromethane / methanol = 100/1). It was purified again by silica gel column chromatography (silica gel 4 g, mobile phase: dichloromethane / ethyl acetate = 25/1) to give phenyltriazole metal complex (B-1-1) of Comparative Example 1 (0.68 g, 61% yield). ) Was obtained as a yellow solid.

¹ H-NMR data of the phenyltriazole metal complex (B-1-1) of Comparative Example 1 are shown below.
¹ H-NMR (400 MHz / CDCl ₃ , TMS): δ (ppm) = 7.03 (d, 6H), 6.65 (t, 3H), 6.56 (t, 6H), 6.44 (d , 3H), 2.39 (s, 9H), 2.14 (s, 9H), 2.09 (s, 9H), 1.78 (s, 9H).

<PL (photoluminescence) measurement>

PL measurement was performed using the phenyltriazole metal complex synthesized in Examples 2 to 5 as the light emitting material. After dissolving a luminescent material in THF (Kanto Chemical Co., Ltd .: grade for spectroscopic analysis) so that it may become 1 * 10 < ^-6 > mol / L and ventilating argon gas, absolute PL quantum yield made by Hamamatsu Photonics Co., Ltd. The emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using a measuring apparatus (C9920).

PL measurement was performed using the phenyltriazole metal complex synthesized in Example 6 as a light-emitting material. A luminescent material is dissolved in toluene (Tokyo Kasei Kogyo Co., Ltd .: grade for absorption analysis) so as to be 1 × 10 ⁻⁶ mol / L, and after argon gas is passed through, absolute PL quantum yield produced by Hamamatsu Photonics Co., Ltd. The emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using a rate measuring device (C9920).

PL measurement was performed using the phenyltriazole metal complex synthesized in Example 7 as the light-emitting material. After dissolving a luminescent material in THF (Kanto Chemical Co., Ltd .: grade for spectroscopic analysis) so that it may become 1 * 10 < ^-6 > mol / L and ventilating argon gas, absolute PL quantum yield made by Hamamatsu Photonics Co., Ltd. The emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using a measuring apparatus (C9920).

PL measurement was performed using the phenyltriazole metal complex synthesized in Example 8 as the light emitting material. After dissolving a luminescent material in THF (Kanto Chemical Co., Ltd .: grade for spectroscopic analysis) so that it may become 1 * 10 < ^-6 > mol / L and ventilating argon gas, absolute PL quantum yield made by Hamamatsu Photonics Co., Ltd. The emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using a measuring apparatus (C9920).

PL measurement was performed using the phenyltriazole metal complex synthesized in Example 9 as the light emitting material. After dissolving a luminescent material in THF (Kanto Chemical Co., Ltd .: grade for spectroscopic analysis) so that it may become 1 * 10 < ^-6 > mol / L and ventilating argon gas, absolute PL quantum yield made by Hamamatsu Photonics Co., Ltd. The emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using a measuring apparatus (C9920).

PL measurement was performed using the phenyltriazole metal complex synthesized in Example 10 as a light-emitting material. After dissolving a luminescent material in THF (Kanto Chemical Co., Ltd .: grade for spectroscopic analysis) so that it may become 1 * 10 < ^-6 > mol / L and ventilating argon gas, absolute PL quantum yield made by Hamamatsu Photonics Co., Ltd. The emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using a measuring apparatus (C9920).
The results of CIE (x, y), the maximum emission wavelength (λmax), and the quantum yield are shown in Table 1 below. From the evaluation results in Table 1, it was found that the compound of the present invention efficiently emitted blue light in THF or toluene.

<Production of light-emitting element>
Using the phenyltriazole metal complex synthesized in Examples 1 to 4 and 9 and Comparative Example 1 as the light emitting material, a light emitting element (that is, an organic electroluminescence element) was produced. The structure of the material used is shown below.

First, on a glass substrate on which an ITO film having a thickness of 150 nm is formed as an anode, in a vacuum (pressure: 1 × 10 ⁻⁴ Pa) as a hole injection layer (HIL) using a normal vacuum deposition method. A HAT-CN film having a thickness of 30 nm was formed.

  A thin film (thickness: 30 nm) was formed using NPB as the hole transport layer (HTL).

  A thin film (thickness: 30 nm) was formed using a light emitting material (15% of the phenyltriazole metal complex) and a host material (85% of 26DCzPPy) as a light emitting layer (EML).

  As an electron transport layer (ETL), a thin film (thickness: 35 nm) was formed using 50% ETL-A (chemipro Kasei ETL material) and 50% Liq.

  A thin film (thickness: 0.5 nm) was formed using Liq as the electron injection layer (EIL).

  Finally, Al was deposited as a cathode until the thickness reached 80 nm.

  The inside of the vacuum chamber was returned to atmospheric pressure, and the obtained laminate was taken out from the vapor deposition apparatus to produce an organic electroluminescence device having the following structure.

(Light-emitting device manufactured using the phenyltriazole metal complex (A-1-1) of Example 1)
Glass substrate / ITO (150 nm) / HAT-CN (30 nm) / NPB (30 nm) / 85% 26DCzPPy: 15% phenyltriazole metal complex (A-1-1) (30 nm) / ETL-A (50%), Liq (50%) (35 nm) / Liq (0.5 nm) / Al (80 nm).

(Light-emitting device manufactured using the phenyltriazole metal complex (A-1-2) of Example 2)
Glass substrate / ITO (150 nm) / HAT-CN (30 nm) / NPB (30 nm) / 85% 26DCzPPy: 15% phenyltriazole metal complex (A-1-2) (30 nm) / ETL-A (50%), Liq (50%) (35 nm) / Liq (0.5 nm) / Al (80 nm).

(Light-emitting device manufactured using the phenyltriazole metal complex (A-1-3) of Example 3)
Glass substrate / ITO (150 nm) / HAT-CN (30 nm) / NPB (30 nm) / 85% 26DCzPPy: 15% phenyltriazole metal complex (A-1-3) (30 nm) / ETL-A (50%), Liq (50%) (35 nm) / Liq (0.5 nm) / Al (80 nm).

(Light-emitting device manufactured using the phenyltriazole metal complex (A-1-4) of Example 4)
Glass substrate / ITO (150 nm) / HAT-CN (30 nm) / NPB (30 nm) / 85% 26DCzPPy: 15% phenyltriazole metal complex (A-1-4) (30 nm) / ETL-A (50%), Liq (50%) (35 nm) / Liq (0.5 nm) / Al (80 nm).

(Light-emitting device manufactured using the phenyltriazole metal complex (A-1-9) of Example 9)
Glass substrate / ITO (150 nm) / HAT-CN (30 nm) / NPB (30 nm) / 85% 26DCzPPy: 15% phenyltriazole metal complex (A-1-9) (30 nm) / ETL-A (50%), Liq (50%) (35 nm) / Liq (0.5 nm) / Al (80 nm).

(Light-Emitting Element Fabricated Using Phenyltriazole Metal Complex (B-1-1) of Comparative Example 1)
Glass substrate / ITO (150 nm) / HAT-CN (30 nm) / NPB (30 nm) / 85% 26DCzPPy: 15% phenyltriazole metal complex (B-1-1) (30 nm) / ETL-A (50%), Liq (50%) (35 nm) / Liq (0.5 nm) / Al (80 nm).

The CIE (x, y) value of the manufactured light-emitting element (International Lighting Commission, 1931), the maximum value of the emission wavelength (λmax), and the time until the initial emission luminance at 500 cd / m ² is halved (LT50) are as follows: Table 2 below.

  As shown in the results of Table 2, the light-emitting element produced using the phenyltriazole metal complex of the present invention was able to emit blue phosphorescence with a longer lifetime than the conventional light-emitting element.

  DESCRIPTION OF SYMBOLS 1 ... Light emitting element, 10 ... Base material, 20 ... Anode, 30 ... Hole injection layer, 40 ... Hole transport layer, 50 ... Light emitting layer, 60 ... Electron Transport layer, 70 ... electron injection layer, 80 ... cathode

Claims (7)

The phenyl triazole compound represented by following formula (1).

(R ^A , R ^B , R ^C , R ^D and R ^E are each independently a hydrogen atom, an alkyl group or a heterocyclic ring represented by the following formula (2), and R ^A , R ^B , R ^C , R ^D and R ^E are each a heterocyclic ring represented by the following formula (2).

(Y ^A , Y ^B , Y ^C , Y ^D and Y ^E are each independently CR or N, and at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N R is a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group, and * represents a bonding site.
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group. ) The phenyltriazole compound according to claim 1, wherein R ^A and R ^E are alkyl groups. The phenyl triazole compound according to claim 1 or 2, wherein R ^B , R ^C or R ^D is a heterocyclic ring represented by the formula (2). A phenyltriazole metal complex represented by the following formula (A).

(R ^A , R ^B , R ^C , R ^D and R ^E are each independently a hydrogen atom, an alkyl group or a heterocyclic ring represented by the following formula (2), and R ^A , R ^B , R ^C , R ^D and R ^E are each a heterocyclic ring represented by the following formula (2).

(Y ^A , Y ^B , Y ^C , Y ^D and Y ^E are each independently CR or N, and at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N R is a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group or an aryl group, and * represents a bonding site.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group, or an alkyl group substituted with a halogen atom. , An alkyloxy group or an aryl group. X ¹ , X ² and X ³ are each independently CR, N or NR ¹⁰ , X ⁴ is C or N, and R and R ¹⁰ are each independently a hydrogen atom, a halogen atom, An alkyl group, an alkyl group substituted with a halogen atom, an alkyloxy group, or an aryl group. M is Ir, Pt, Au or Rh, m is 0, 1 or 2, and n is 1, 2 or 3. However, when M is Ir or Rh, m + n = 3, when M is Pt, m + n = 2, and when M is Au, m + n = 1. ) The phenyltriazole metal complex according to claim 4, wherein R ^A and R ^E are alkyl groups. The phenyltriazole metal complex according to claim 4 or 5, wherein R ^B , R ^C or R ^D is a heterocyclic ring represented by the formula (2).   A light emitting element provided with an anode, a cathode, and the layer containing the phenyl triazole metal complex as described in any one of Claims 4-6 provided between this anode and this cathode.

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