JP7083995B2 - Phenyltriazole metal complex and light emitting device - Google Patents

Description

The present invention relates to phenyltriazole compounds, phenyltriazole metal complexes and light emitting devices.

As a light emitting material used for the light emitting layer of an organic electroluminescence device (hereinafter, may be referred to as "light emitting element"), a metal complex exhibiting light emission from a triplet excited state (hereinafter, may be referred to as "phosphorescent light emission"). Is known to provide higher emission efficiency as compared to fluorescent materials that emit light from a single-term excited state. Examples of the blue light emitting metal complex exhibiting phosphorescent light emission include a metal complex 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. -A metal complex having a triazole derivative as a ligand (Patent Documents 3 and 4) and the like are known.

International Publication No. 2002/015645 International Publication No. 2007/097153 International Publication No. 2013/151989 Japanese Unexamined Patent Publication No. 2013-147450

However, the conventional light emitting device using a blue light emitting metal complex exhibiting phosphorescent light emission has a problem that the device life is short.

The problem to be solved by the present invention is a novel phenyltriazole compound, a phenyltriazole metal complex having the phenyltriazole compound as a ligand, and a long-life blue phosphorescent light emission using the phenyltriazole metal complex. It is an object of the present invention to provide a light emitting element capable of capable.

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。

( ^RA , ^RB , ^RC , ^RD and ^RE are each independently a hydrogen atom, an alkyl group or a heterocycle represented by the following formula (2), and are ^RA , ^RB , ^RC . , R ^D and ^RE at least one is a heterocycle 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。）

(YA, ^YB , ^YC , ^YD and ^YE are independently ^CR or ^N , and at least one of YA, ^YB , ^YC , ^YD and ^YE 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 bond site.)

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

[2] The phenyltriazole compound according to the above [1], wherein ^RA and ^RE are alkyl groups.
[3] The phenyltriazole compound according to the above [1] or [2], wherein ^RB , ^RC or ^RD is a heterocycle represented by the above 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。

( ^RA , ^RB , ^RC , ^RD and ^RE are each independently a hydrogen atom, an alkyl group or a heterocycle represented by the following formula (2), and are ^RA , ^RB , ^RC . , R ^D and ^RE at least one is a heterocycle 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。）

(YA, ^YB , ^YC , ^YD and ^YE are independently ^CR or ^N , and at least one of YA, ^YB , ^YC , ^YD and ^YE 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 bond site.)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independent alkyl groups substituted with hydrogen atoms, halogen atoms, alkyl groups, and halogen atoms, respectively. , Alkyloxy group or aryl group. X ¹ , X ² and X ³ are independently CR, N or NR ¹⁰ , X ⁴ is C or N, and R and R ¹⁰ are independent hydrogen and halogen atoms, respectively. It is 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 the above [4], wherein ^RA and ^RE are alkyl groups.
[6] The phenyltriazole metal complex according to the above [4] or [5], wherein ^RB , ^RC or ^RD is a heterocycle represented by the above formula (2).

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

Since the phenyltriazole compound of the present invention has an electron-withdrawing heterocycle in addition to the ring coordinated to the metal, it can enhance electron injectability and electron resistance and maintain blue light emission. Thereby, the phenyltriazole metal complex using this phenyltriazole compound as a ligand is useful for producing a light emitting element capable of promoting the recombination of electrons and holes and emitting blue phosphorescence with a long life.

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 the formula (1), ^RA , ^RB , ^RC , ^RD and ^RE are each independently a hydrogen atom, an alkyl group or a heterocycle represented by the following formula (2), and ^RA , At least one of ^RB , ^RC , ^RD and R ^E is a heterocycle represented by the following formula (2). R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen atom, halogen atom, alkyl group, alkyl group substituted with halogen atom, alkyloxy group or aryl group, respectively.

Y ^A , Y ^B , Y ^C , Y ^D and Y ^E are independently CR or N, and at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N. Yes, 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 the binding site.

The alkyl groups represented by ^RA , RB, ^RC , R ^D , ^RE , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^are linear, branched or cyclic. Either may be used. The linear and branched alkyl groups preferably have 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 4 carbon atoms. The number of carbon atoms in the cyclic alkyl group is preferably 3 to 30, more preferably 3 to 12, and particularly preferably 3 to 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 and octyl group. Examples thereof 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, tert-butyl group are preferable. R ¹ is preferably an alkyl group.

Replaced 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, an iodine atom and the like, 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 linear and branched alkyloxy groups preferably have 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 4 carbon atoms. The number of carbon atoms of the cyclic alkyloxy group is preferably 3 to 30, more preferably 3 to 12, and particularly preferably 3 to 10. The alkyloxy group may have a substituent, but the carbon number of the substituent is not included in the above carbon number.

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 Examples include a group, a perfluorohexyloxy group, a perfluorooctyloxy group, a methyloxymethyloxy group, a 2-methyloxyethyloxy group, and the like, a methyloxy group, an ethyloxy group, a propyloxy group, an iso-propyloxy group, and a butyloxy group. Groups, iso-butyloxy groups and tert-butyloxy groups are preferred.

The aryl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R usually has 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. 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 to C12 alkyloxyphenyl group (“C1 to C12 alkyloxy” means that the alkyloxy moiety has 1 to 12 carbon atoms, and the same applies hereinafter. ), C1 to C12 alkylphenyl group (“C1 to C12 alkyl” means that the alkyl moiety has 1 to 12 carbon atoms; the same applies hereinafter), 1-naphthyl group, 2-naphthyl. Examples thereof include a group, a 1-anthrasenyl group, a 2-anthrasenyl group, a 9-anthrasenyl group, a pentafluorophenyl group and the like, and a C1-C12 alkyloxyphenyl group and a C1-C12 alkylphenyl group are preferable. Here, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. The aromatic hydrocarbons include those having a fused ring and those in which two or more selected from an independent benzene ring and / or a fused ring are directly bonded or via a group such as vinylene.

The above-mentioned C1 to C12 alkyl are alkyls having 1 to 12 carbon atoms, and are the same as those described and exemplified by the above alkyl groups. Therefore, for example, as the C1 to C12 alkyloxy in the group, methyloxy, ethyloxy, propyloxy, iso-propyloxy, butyloxy, iso-butyloxy, tert-butyloxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, and the like. Examples thereof include octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy and lauryloxy. The C1 to C12 alkylphenyls in the group include methylphenyl, ethylphenyl, dimethylphenyl, propylphenyl, mesityl, methylethylphenyl, iso-propylphenyl, butylphenyl, iso-butylphenyl, tert-butylphenyl and 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. Further, among 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). Since at least one of the ortho positions of N among Y ^A , Y ^B , Y ^C , Y ^D , and Y ^E is CR ¹¹ , it is possible to suppress an undesired coordination to the transition metal during complex synthesis. 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 heterocycle represented by the above formula (2) include, but are not limited to, the heterocycles represented by the following formulas (2-1) to (2-6).

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

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

In formula (1), ^RA and ^RE are preferably alkyl groups. Since ^RA and ^RE are alkyl groups, the planarity between the benzene ring having these alkyl groups and the triazole ring can be reduced to break the conjugate relationship and maintain blue light emission. As the alkyl group of ^RA and ^RE , a linear or branched alkyl group having 1 to 4 carbon atoms is more preferable.

In the formula (1), it is preferable that ^RB , ^RC or ^RD is a heterocycle represented by the above formula (2). Examples of the heterocycle represented by the formula (2) as ^RB , ^RC or ^RD include the heterocycle represented by the formulas (2-1) to (2-6) and the formula (2-1). -1) -The heterocycle represented by the equation (2-6-2) can be mentioned.

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).

<Manufacturing method of phenyltriazole compound>
The phenyltriazole compound represented by the formula (1) can be synthesized, for example, by the reaction formulas of the formulas (3-1) to (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 independent hydrogen atoms or alkyl groups, respectively, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independent hydrogen atoms, respectively. , Halogen atom, alkyl group, alkyl group substituted with halogen atom, alkyloxy group or aryl group. Y ^A , Y ^B , Y ^C , Y ^D and Y ^E are independently CR or N, respectively. Yes, 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 applies to the formulas (3-2) and (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 independent hydrogen atoms or alkyl groups, respectively, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independent, respectively. , Hydrogen atom, halogen atom, alkyl group, alkyl group substituted with halogen atom, alkyloxy group or aryl group. Y ^A , Y ^B , Y ^C , Y ^D and Y ^E are independently CR. Or N, at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N, where 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. Hereinafter, the same applies to the 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 independent hydrogen atoms or alkyl groups, respectively, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independent, respectively. , Hydrogen atom, halogen atom, alkyl group, alkyl group substituted with halogen atom, alkyloxy group or aryl group. Y ^A , Y ^B , Y ^C , Y ^D and Y ^E are independently CR. Or N, at least one of Y ^A , Y ^B , Y ^C , Y ^D and Y ^E is N, where 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. Hereinafter, the same applies to the formulas (3-8) and (3-9).

The raw material compounds used in the reactions of the formulas (3-1) to (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 independent hydrogen atoms, alkyl groups or halogen atoms, respectively, and R ^a ', R ^b ', R ^c ', respectively. At least one of R ^d' and R ^e'is a halogen atom. R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen atoms, halogen atoms, alkyl groups and halogen atoms, respectively. It is 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。

( ^RA , ^RB , ^RC , ^RD and ^RE are each independently a hydrogen atom, an alkyl group or a heterocycle represented by the following formula (2), and are ^RA , ^RB , ^RC . , R ^D and ^RE at least one is a heterocycle 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。）

(YA, ^YB , ^YC , ^YD and ^YE are independently ^CR or ^N , and at least one of YA, ^YB , ^YC , ^YD and ^YE 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 bond site.)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independent alkyl groups substituted with hydrogen atom, halogen atom, alkyl group and halogen atom, respectively. , Alkyloxy group or aryl group. X ¹ , X ² and X ³ are independently CR, N or NR ¹⁰ , X ⁴ is C or N, and R and R ¹⁰ are independent hydrogen and halogen atoms, respectively. It is 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, the three ligands in the formula (A) are preferably 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, it is preferable that the two ligands in the formula (A) are the same ligand (that is, one kind of ligand).

Of the phenyltriazole metal complex represented by the formula (A), n ligands are the phenyltriazole compound. 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 independently hydrogen atom, halogen atom, alkyl group, alkyl group substituted with halogen atom, alkyloxy group or aryl group, respectively. X ¹ , X. ² and X ³ are independently CR, N or NR ¹⁰ , X ⁴ is C or N, and R and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups and halogens, respectively. It is an atomically substituted alkyl group, an alkyloxy group or an aryl group.)

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 independent hydrogen atoms, halogen atoms, alkyl groups, alkyl groups substituted with halogen atoms, alkyloxy groups or aryl groups, respectively. R is hydrogen. It is 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 Rs may be the same or different.)

As the ligands represented by the formulas (4-1) to (4-4), the ligands represented by the following formulas (4-1-0) to (4-4-0) are 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 independent hydrogen atoms, halogen atoms, alkyl groups, alkyl groups substituted with halogen atoms, alkyloxy groups or aryl groups, respectively. R is hydrogen. Atom, halogen atom, alkyl group, alkyl group substituted with halogen atom, alkyloxy group or aryl group.)

Examples of the ligand represented by the following formulas (4-1-0) to (4-4-0) are represented by the following formulas (4-1-1) to (4-4-1). Included are ligands that are used.

Among the phenyltriazole metal complexes represented by the formula (A), the complex in which the transition metal M is Ir is a homoreptic complex (m = 0, n = 3) represented by the following formula (5-1). , The heteroreptic complex (m = 1, n = 2) represented by the following formula (5-2) and the heteroreptic complex (m = 2, n = 1) represented by the following formula (5-3). Can be 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。）

( ^RA , ^RB , ^RC , ^RD and ^RE are each independently a hydrogen atom, an alkyl group or a heterocycle represented by the formula (2), and are ^RA , ^RB , ^RC , respectively. At least one of R ^D and ^RE is a heterocycle represented by the formula (2). R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen atoms and halogen atoms, respectively. , 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。）

( ^RA , ^RB , ^RC , ^RD and ^RE are each independently a hydrogen atom, an alkyl group or a heterocycle represented by the formula (2), and are ^RA , ^RB , ^RC , respectively. At least one of R ^D and ^RE is a heterocycle 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. X ¹ , X ² and X ³ are independently CR. , N or NR ¹⁰ , X ⁴ is C or N, and R and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups, alkyl groups substituted with halogen atoms, alkyloxy groups or It is an aryl group. The same shall apply hereinafter.)

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

Examples of the heteroreptic complex represented by the formula (5-2) include heteroreptic complexes represented by the following formulas (5-2-1) to (5-2-10). Not limited to these.

Examples of the heteroreptic complex represented by the formula (5-3) include heteroreptic complexes represented by the following formulas (5-3-1) to (5-3-10). 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 homoreptic complex (m = 0, n = 2) represented by the following formula (5-4). And the heteroreptic complex (m = 1, n = 1) represented by the following formula (5-5) can be mentioned.

Examples of the homoreptic complex represented by the formula (5-4) include homoreptic complexes represented by the following formulas (5-4-1) to (5-4-10). Not limited to these.

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

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

Examples of the phenyltriazole metal complex represented by the formula (A) in which the transition metal M is Rh include a homoreptic complex (m = 0, n = 3) represented by the following formula (5-7) and the following formula. Examples thereof include a heteroreptic complex (m = 1, n = 2) represented by (5-8) and a heteroreptic complex (m = 2, n = 1) represented by the following formula (5-9). ..

Examples of the homoreptic complex represented by the formula (5-7) include homoreptic complexes represented by the following formulas (5-7-1) to (5-7-10). Not limited to these.

Examples of the heteroreptic complex represented by the formula (5-8) include heteroreptic complexes represented by the following formulas (5-8-1) to (5-8-10). Not limited to these.

Examples of the heteroreptic complex represented by the formula (5-9) include heteroreptic complexes represented by the following formulas (5-9-1) to (5-9-10). 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. 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。

( ^RA , ^RB , ^RC , ^RD and ^RE are each independently a hydrogen atom, an alkyl group or a heterocycle represented by the following formula (2), and are ^RA , ^RB , ^RC . , R ^D and ^RE at least one is a heterocycle 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。）

(YA, ^YB , ^YC , ^YD and ^YE are independently ^CR or ^N , and at least one of YA, ^YB , ^YC , ^YD and ^YE 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 bond site.)

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen atoms, halogen atoms, alkyl groups, alkyl groups substituted with halogen atoms, alkyloxy groups or aryl groups, respectively. 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. )

The inorganic metal raw material may be a hydrate of MCl _n · nH ₂ O, an anhydrate of MCl _n , or an anhydrate of K ₂ MCl _{n + 2} . However, M is Ir, Pt, Au or Rh, n = 3 when M is Ir or Rh, n = 2 when M is Pt, and n = 1 when M is Au. be.

When M is Ir or Rh and m = 2 and n = 1, the phenyltriazole metal complex (heteroreptic 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 independently hydrogen atom, halogen atom, alkyl group, alkyl group substituted with halogen atom, alkyloxy group or aryl group, respectively. X ¹ , X. ² and X ³ are independently CR, N or NR ¹⁰ , X ⁴ is C or N, and R and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups and halogens, respectively. It is an atomically substituted alkyl group, alkyloxy group or aryl group. 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 anhydrate of MCl ₃ . , K2 _{MCl 5 anhydrous} . However, M is Ir or Rh.

When M is Ir or Rh and m = 1 and n = 2, the phenyltriazole metal complex (heteroreptic 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 anhydrate of MCl ₃ . , K2 _{MCl 5 anhydrous} .

When M is Pt and m = 1 and n = 1, the phenyltriazole metal complex (heteroreptic complex) represented by the formula (A) can be synthesized, for example, according to the following reaction formula. 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 anhydrate of PtCl ₂ , or an anhydride of K ₂ PtCl ₄ .

<< Light emitting element >>
The light emitting device 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 an embodiment of a light emitting device of the present invention. In the light emitting element 1 of FIG. 1, the anode 20, the hole injection layer 30, the hole transport layer 40, the light emitting layer 50, the electron transport layer 60, the electron injection layer 70, and the cathode 80 are laminated in this order on the base material 10. The light emitting layer 50 contains the phenyltriazole metal complex.

In the light emitting element of the present invention, the light emitting layer can inject holes from the anode, the hole injection layer or the hole transport layer when an electric field is applied, and injects electrons from the cathode, the electron injection layer or the electron transport layer. It has the function of being able to perform, the function of moving the injected electric charge (electrons and holes) by the force of an electric field, and the function of providing a field of recombination of electrons and holes and connecting this to light emission. Since the phenyltriazole has an electron-withdrawing complex ring in addition to the ring coordinated to the metal, electron injectability and electron resistance can be enhanced, whereby the phenyltriazole compound is used as a ligand. The layer containing the phenyltriazole metal complex promotes the recombination of electrons and holes, and can provide a light emitting device having high light emission efficiency and a long device life. The light emitting layer may contain a host material having the phenyltriazole metal complex as a guest material. As the host material, a known material can be appropriately selected and used. Further, by mixing and applying the host material and a light emitting material such as a metal complex, or by co-depositing the host material, a light emitting layer in which the light emitting material is doped with the host material can be formed.

In the light emitting device of the present invention, the anode supplies holes to the hole injection layer, the hole transport layer, the light emitting layer, and the like. As the material of 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 an electron injection layer, an electron transport layer, a light emitting layer, and the like. As the material of 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 the material of these layers, a known material can be appropriately selected and used.

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

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
Further, "%" in the compositions of the following Examples and Comparative Examples means "% by 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 according to the following scheme.

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

The mass spectrometry result of compound (A-1) and the measurement result of ¹ H-NMR are shown below.
[M]: 162
^{1 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).

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) under a nitrogen atmosphere. 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 maintained 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. .. Then, 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. THF (250 mL) was added to the obtained solid, the mixture was ice-cooled, and a 50% NaOH aqueous solution (125 g) was added dropwise at an internal temperature of 5 to 8 ° C. over 40 minutes. The aqueous layer was extracted 4 times with THF (50 mL), 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 a 4M HCl dioxane solution (34 mL, 138 mmol) was added. The precipitated solid was collected by filtration and washed 3 times with THF (100 mL). By drying this, compound (A-2) (23.15 g, yield 86%) was obtained.

Acetic acid (42.4 mL, 740 mmol) was added to a mixture of compound (A-1) (12.00 g, 74 mmol), compound (A-2) (22.28 g, 104 mmol) and DMF (170 mL) at room temperature, and 3 at 90 ° C. The mixture was heated and stirred 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 subsequently recrystallized from hexane to obtain compound (A-3) (20.35 g, yield 80%). ) Was obtained.

The mass spectrometry result of compound (A-3) and the measurement result of ¹ H-NMR are shown below.
[M]: 341
^{1 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).

Under nitrogen atmosphere, 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 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, the aqueous layer was separated, extracted twice with ethyl acetate, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and then purified by silica gel column chromatography (silica gel 120 g, mobile phase: hexane / ethyl acetate = 2/1 → 1/1 → 1/2) to obtain a phenyltriazole compound (A-4) ( 6.67 g, yield 57%) was obtained.

The mass spectrometry result of the phenyltriazole compound (A-4) and the measurement result of ¹ H-NMR are shown below.
[M]: 354
^{1 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) under an argon atmosphere. The mixture was heated under reflux for 24 hours. After allowing to cool, water was added, 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 cerite, the solvent was distilled off under reduced pressure, and then recrystallized from a mixed dichloromethane / hexane solvent to obtain a yellow solid (1.15 g).

To this mixture of yellow solid (1.10 g), silver trifluoromethanesulfonate (0.36 g, 1.4 mmol) and 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 this mixture, the black solid was removed by filtration, and the mixture was washed with ethanol and dichloromethane. The solvent was distilled off under reduced pressure and then purified by silica gel column chromatography (silica gel 150 g, mobile phase: ethyl acetate → dichloromethane / methanol = 10/1). Example 1 was purified again by silica gel column chromatography (silica, 150 g, mobile phase: ethyl acetate → dichloromethane / methanol = 10/1), then recrystallized from a mixed solvent of dichloromethane / hexane, and suspended and washed with ethanol. The phenyltriazole metal complex (A-1-1) (0.12 g, yield 2%) was obtained as a yellow solid.

The measurement result of ^{1 1} H-NMR of the phenyltriazole metal complex (A-1-1) of Example 1 is shown below.
^{1 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) , 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 recovering and concentrating the organic layer was separated and purified by silica gel column chromatography (eluent: a mixed solvent of ethyl acetate and hexane). The yield of compound (C-1) was 95%.

The measurement results of ¹ H-NMR of compound (C-1) are shown below.
^{1 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), 60 ml of toluene and 5 ml of water were reacted at 116 ° C. for 16 hours under an argon atmosphere. After cooling the reaction solution to room temperature, ethyl acetate and water were added for extraction. The product obtained by recovering and concentrating the organic layer was separated and purified by silica gel column chromatography (eluent: a mixed solvent of ethyl acetate and hexane). The resulting product was recrystallized from ethyl acetate and hexanes. The yield of the phenyltriazole compound (C-2) was 70%.

The measurement results of ¹ H-NMR of the phenyltriazole compound (C-2) are shown below.
^{1 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).

3 Iridium chloride trihydrate 0.403 g (1.14 mmol), compound (C-2) 1.0 g (2.52 mmol), 2-ethoxyethanol 45 ml, water 15 ml are reacted at 120 ° C. for 20 hours under an argon atmosphere. I let you. The solid cooled to room temperature and precipitated was recovered 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 compound (B-1), 0.856 g (2.15 mmol) of 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 passed through a cerite layer and filtered, 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 from dichloromethane and hexane. The yield of the phenyltriazole metal complex (A-1-2) of Example 2 was 39%.

The ¹ H-NMR data of the phenyltriazole metal complex (A-1-2) of Example 2 is shown below.
^{1 1} H-NMR (400MHz / 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. The mixture was cooled to −15 ° C., 15.0 g of the compound represented by the formula (C-3) was added dropwise, and the mixture was stirred for 20 minutes. An aqueous solution prepared by dissolving 9.4 g of sodium nitrite in 20 mL of water was added dropwise, and the mixture was 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 the mixture was stirred for 2 hours. The temperature was raised to room temperature, and the mixture was stirred for 3 hours. The reaction solution was ice-cooled, and a 10 M aqueous sodium hydroxide solution was added dropwise to adjust the pH of the reaction solution to 10. The mixture was extracted 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. After filtering the precipitate, purification was carried out by recrystallization (ethanol) to obtain 17.9 g of the compound represented by the formula (C-4).

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 to the reaction vessel. 20 mL of acetic acid was added, and the mixture was heated and stirred at 90 ° C. for 5 hours. After cooling to room temperature, the reaction solution was poured into a 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 the compound represented by the formula (C-5).

The measurement results of ¹ H-NMR of the compound represented by the formula (C-5) are shown below.
^{1 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, 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 were added to the reaction vessel at 120 ° C. The mixture was heated and stirred for 22 hours. It was cooled to room temperature and the reaction solution was poured into water. The precipitate was filtered and then washed with water. It was 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 under an argon atmosphere. The reaction solution was passed through a cerite layer and filtered, and the obtained filtrate was concentrated under reduced pressure to obtain the product (C-7).

Subsequently, the whole 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 under an argon atmosphere. rice field. The solid that had been cooled to room temperature and precipitated was recovered by filtration, and separated and purified using silica gel chromatography (eluent: dichloromethane). The obtained solid was recrystallized from dichloromethane and hexane. The yield of the phenyltriazole metal complex (A-1-3) was 45%.

The measurement result of ^{1 1} H-NMR of the phenyltriazole metal complex (A-1-3) of Example 3 is shown below.
^{1 1} H-NMR (400MHz / 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), K3 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. , 116 ° C. for 16 hours. After cooling the reaction solution to room temperature, ethyl acetate and water were added for extraction. The product obtained by recovering and concentrating the organic layer was separated and purified by silica gel column chromatography (eluent: a mixed solvent of ethyl acetate and hexane). The yield of compound (D-1) was 91%.

The ¹ H-NMR data of compound (D-1) is shown below.
^{1 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 compound (C-7) synthesized by the method of Example 3, 2.08 g (5.64 mmol) of compound (D-1), and 49 ml of ethanol were added to 280 at 90 ° C. under an argon atmosphere. Reacted for time. The solid that had been cooled to room temperature and precipitated was recovered by filtration, and separated and purified using silica gel chromatography (eluent: dichloromethane). The obtained solid was recrystallized from dichloromethane and hexane. The yield of the phenyltriazole metal complex (A-1-4) of Example 4 was 32%.

The ¹ H-NMR data of the phenyltriazole metal complex (A-1-4) of Example 4 is shown below.
^{1 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.

0.278 g (0.185 mmol) of the compound (E-1) synthesized by the method described in paragraphs [0204] to [0205] of International Publication No. 2007/097153 (Patent Document 2), silver trifluoromethanesulfonate 0 .105 g (0.409 mmol), 13 ml of dichloromethane and 0.2 ml of methanol were reacted at room temperature for 17 hours under an argon atmosphere. The reaction solution was passed through a cerite layer and filtered, and the obtained filtrate was concentrated under reduced pressure to obtain compound (E-2).

The total 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 under an argon atmosphere. The solid that had been cooled to room temperature and precipitated was recovered by filtration, and separated and purified using silica gel chromatography (eluent: a mixed solvent of dichloromethane and ethyl acetate). The yield of the phenyltriazole metal complex (A-1-5) of Example 5 was 13%.

The ¹ H-NMR data of the phenyltriazole metal complex (A-1-5) of Example 5 is shown below.
^{1 1} H-NMR (400 MHz / Deuterated-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.

1.26 g (1.23 mmol) of the compound (F-1) 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 passed through a cerite layer and filtered, and the obtained filtrate was concentrated under reduced pressure to obtain compound (F-2).

The total 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 under an argon atmosphere. The solid that had been cooled to room temperature and precipitated was recovered by filtration, and separated and purified using silica gel chromatography (eluent: a 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 1} H-NMR data of compound (F-3) is shown below.
^{1 1} H-NMR (400MHz / 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 1} H-NMR data of compound (F-4) is shown below.
^{1 1} H-NMR (400MHz / 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) pyrimidin 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 (dibenzilidenacetone) ) Dipalladium (0) 0.0241 g (0.0263 mmol), 3.5 ml of toluene and 0.3 ml of water were reacted at 110 ° C. for 24 hours under an argon atmosphere. After cooling the reaction solution to room temperature, ethyl acetate and water were added for extraction. The product obtained by recovering and concentrating the organic layer was separated and purified by silica gel column chromatography (eluent: a mixed solvent of dichloromethane and ethyl acetate). The resulting product was recrystallized from ethyl acetate and hexanes. The yield of the phenyltriazole metal complex (A-1-6) of Example 6 was 76%.

The ¹ H-NMR data of the phenyltriazole metal complex (A-1-6) of Example 6 is shown below.
^{1 1} H-NMR (400MHz / 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))
A phenyltriazole metal complex (A-1-7) was synthesized according to the scheme shown in Example 6.

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 (dibenzilidenacetone) 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. After cooling the reaction solution to room temperature, ethyl acetate and water were added for extraction. The product obtained by recovering and concentrating the organic layer was separated and purified by silica gel column chromatography (eluent: a mixed solvent of dichloromethane and ethyl acetate). The resulting product was recrystallized from ethyl acetate and hexanes. 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 1} H-NMR (400MHz / 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.

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) under a nitrogen atmosphere. The temperature in the reaction system was kept below -1 ° C., 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 minutes, the internal temperature was kept at -2 ° C, and a solution of SnCl ₂ · H ₂ O (108.7 g, 482 mmol) in concentrated hydrochloric acid (55 mL) and water (55 mL) was added dropwise over 2.5 hours, and then for 2 hours. Stirred. The precipitated solid was collected by filtration and washed with saturated brine. THF (250 mL) was added to the obtained solid, ice-cooled, and a 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 4 times with THF (50 mL), 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 a 4M HCl dioxane solution (53 mL, 211 mmol) was added. The precipitated solid was collected by filtration and washed 3 times with THF (100 mL). By drying this, compound (H-1) (26.47 g, yield 66%) was obtained.

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

The mass spectrometry result of compound (H-2) and the measurement result of ¹ H-NMR are shown below.
[M]: 297
^{1 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, n-butyllithium (1.6 M hexane solution, 37.5 mL, 60 mmol) was added to -78 in a diisopropyl ether (240 mL) solution of 3-bromo-2,6-dimethylpyridine (7.5 g, 40 mmol). The mixture was added dropwise at ° 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. Diisopropyl ether was added dropwise, and saturated brine was added at room temperature. The aqueous layer was extracted 6 times with dichloromethane, 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) was removed. %) Was obtained.

The mass spectrometry result of compound (H-3) and the measurement result of ¹ H-NMR are shown below.
[M]: 233
^{1 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 / Aqueous solution of tripotassium L phosphate (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 the mixture was stirred at 100 ° C. for 3 hours. Water was added to the reaction solution returned to room temperature, the aqueous layer was separated, extracted three times with ethyl acetate, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, 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) again gives a phenyltriazole compound (H-4) (3.27 g, yield 88%). rice field.

The mass spectrometry result of the phenyltriazole compound (H-4) and the measurement result of ¹ H-NMR are shown below.
[M]: 368
^{1 1} H-NMR (400MHz / 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 under an argon atmosphere. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel column chromatography (eluent: ethyl acetate). The obtained solid was dissolved in dichloromethane, this solution was added dropwise to hexane to reprecipitate, and the solution was filtered to obtain a yellow solid. The solvent of the filtrate was distilled off under reduced pressure, and reprecipitation was repeated. The combined solids are reprecipitated (dichloromethane / hexane), purified using alumina column chromatography (eluent: dichloromethane), and reprecipitated (dichloromethane / hexane) to form a phenyltriazole metal complex (A-1-8). ) (0.21 g, yield 6%) was obtained as a yellow solid.

The measurement results of ¹ H-NMR of the phenyltriazole metal complex (A-1-8) are shown below.
^{1 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.

The 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 at room temperature for 17 hours under an argon atmosphere. The reaction solution was passed through a cerite layer and filtered, 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 the compound (A-3) and 49 ml of ethanol were reacted at 90 ° C. for 236 hours under an argon atmosphere. The solid that had been cooled to room temperature and precipitated was recovered by filtration, and separated and purified using silica gel chromatography (eluent: a mixed solvent of dichloromethane and ethyl acetate). The obtained solid was recrystallized from dichloromethane and hexane. The yield of compound (I-1) was 89%.

The ¹ H-NMR data of compound (I-1) is shown below.
^{1 1} H-NMR (400MHz / 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 (dibenzilidenacetone) 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 under an argon atmosphere. After cooling the reaction solution to room temperature, ethyl acetate and water were added for extraction. The product obtained by recovering and concentrating the organic layer was separated and purified by silica gel column chromatography (eluent: a mixed solvent of dichloromethane and ethyl acetate). The resulting product was recrystallized from ethyl acetate and hexanes. The yield of the phenyltriazole metal complex (A-1-9) of Example 9 was 78%.

The ¹ H-NMR data of the phenyltriazole metal complex (A-1-9) of Example 9 is shown below.
^{1 1} H-NMR (400MHz / 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 passed through a cerite layer and filtered, and the obtained filtrate was concentrated under reduced pressure to obtain compound (F-2).

The total 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 under an argon atmosphere. The solid that had been cooled to room temperature and precipitated was recovered by filtration, and separated and purified using silica gel chromatography (eluent: a mixed solvent of dichloromethane and ethyl acetate). The resulting product was recrystallized from dichloromethane and hexanes. 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 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))
The phenyltriazole metal complex (B-1-1) was synthesized according to the following scheme with reference to the description of Synthesis Example 4 of International Publication No. 2013/151989 (Patent Document 3: Japanese Patent Application Laid-Open No. 2015-511306).

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 maintained 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. .. Then, the mixture was stirred at room temperature for 3 hours. The precipitated solid was collected by filtration and washed with saturated brine. THF (300 mL) was added to the obtained solid, the mixture was ice-cooled, and a 10 M 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 hour. The precipitated solid was collected by filtration and dried to give compound (X-2) (4.3 g, yield 21%).

Add acetic acid (7.4 mL, 130 mmol) to a mixture of compound (A-1) (2.09 g, 13 mmol), compound (X-2) (3.34 g, 18 mmol) and DMF (30 mL) at room temperature and add 3 at 90 ° C. The mixture was heated and stirred 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 subsequently recrystallized from hexane to obtain compound (X-3) (3.70 g, yield 80%). ..

The mass spectrometric results of compound (X-3) are shown below.
[M]: 277

Argon 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) Under the atmosphere, it was heated and refluxed for 15 hours. After allowing to cool, water was added and the mixture was 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 this mixture of solid (0.84 g), silver trifluoromethanesulfonate (0.56 g, 2.2 mmol) and 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 heated and stirred at ° C for 13 hours. Methanol was added to this mixture and filtration was performed to obtain a black solid. This was purified by silica gel column chromatography (silica gel 3 g, mobile phase: dichloromethane → dichloromethane / methanol = 100/1). The phenyltriazole metal complex (B-1-1) of Comparative Example 1 (0.68 g, yield 61%) was purified again by silica gel column chromatography (silica gel 4 g, mobile phase: dichloromethane / ethyl acetate = 25/1). ) Was obtained as a yellow solid.

The ¹ H-NMR data of the phenyltriazole metal complex (B-1-1) of Comparative Example 1 is shown below.
^{1 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 a light emitting material. After dissolving the luminescent material in THF (manufactured by Kanto Chemical Co., Ltd .: grade for spectroscopic analysis) to a concentration of 1 × 10 ^-6 mol / L and aerating argon gas, the absolute PL quantum yield manufactured by Hamamatsu Photonics Co., Ltd. The emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using a measuring device (C9920).

PL measurement was performed using the phenyltriazole metal complex synthesized in Example 6 as a light emitting material. After dissolving the luminescent material in toluene (manufactured by Tokyo Kasei Kogyo Co., Ltd .: grade for absorption analysis) to a concentration of 1 × 10 ^-6 mol / L and aerating argon gas, the absolute PL quantum yield manufactured 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 a light emitting material. After dissolving the luminescent material in THF (manufactured by Kanto Chemical Co., Ltd .: grade for spectroscopic analysis) to a concentration of 1 × 10 ^-6 mol / L and aerating argon gas, the absolute PL quantum yield manufactured by Hamamatsu Photonics Co., Ltd. The emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using a measuring device (C9920).

PL measurement was performed using the phenyltriazole metal complex synthesized in Example 8 as a light emitting material. After dissolving the luminescent material in THF (manufactured by Kanto Chemical Co., Ltd .: grade for spectroscopic analysis) to a concentration of 1 × 10 ^-6 mol / L and aerating argon gas, the absolute PL quantum yield manufactured by Hamamatsu Photonics Co., Ltd. The emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using a measuring device (C9920).

PL measurement was performed using the phenyltriazole metal complex synthesized in Example 9 as a light emitting material. After dissolving the luminescent material in THF (manufactured by Kanto Chemical Co., Ltd .: grade for spectroscopic analysis) to a concentration of 1 × 10 ^-6 mol / L and aerating argon gas, the absolute PL quantum yield manufactured by Hamamatsu Photonics Co., Ltd. The emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using a measuring device (C9920).

PL measurement was performed using the phenyltriazole metal complex synthesized in Example 10 as a light emitting material. After dissolving the luminescent material in THF (manufactured by Kanto Chemical Co., Ltd .: grade for spectroscopic analysis) to a concentration of 1 × 10 ^-6 mol / L and aerating argon gas, the absolute PL quantum yield manufactured by Hamamatsu Photonics Co., Ltd. The emission spectrum (excitation wavelength: 350 nm) at room temperature was measured using a measuring device (C9920).
The results of CIE (x, y), maximum emission wavelength (λmax), and 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 emits blue light in THF or toluene.

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

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

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 the light emitting layer (EML).

A thin film (thickness: 35 nm) was formed using 50% ETL-A (ETL material manufactured by Chemipro Kasei Co., Ltd.) and 50% Liq as the electron transport layer (ETL).

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 it had a thickness of 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 manufacture an organic electroluminescence device having the following structure.

(Light emitting device produced 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 produced 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 produced 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 produced 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 produced 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 device manufactured by using the 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 (International Commission on Illumination, 1931) of the manufactured light emitting element, the maximum value of the light emitting wavelength (λmax), and the time until the initial light emitting brightness at 500 cd / m ² is halved (LT50) are as follows. It is described in Table 2 of.

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

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 (4)

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

( ^RA , ^RB , ^RC , ^RD and ^RE are each independently a hydrogen atom, an alkyl group or a heterocycle represented by the following formula (2), and are ^RA , ^RB , ^RC . , R ^D and ^RE at least one is a heterocycle represented by the following formula (2).

(YA, ^YB , ^YC , ^YD and ^YE are independently ^CR or ^N , and at least one of YA, ^YB , ^YC , ^YD and ^YE 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 bond site.)
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independent alkyl groups substituted with hydrogen atoms, halogen atoms, alkyl groups, and halogen atoms, respectively. , Alkyloxy group or aryl group. X ¹ is CR, X ² is NR ¹⁰ , X ³ is NR ¹⁰ , X ⁴ is C, and R and R ¹⁰ are independently substituted with hydrogen atom, halogen atom, alkyl group, and halogen atom, respectively. It is an alkyl group, an alkyloxy group or an aryl group. M is Ir, Pt or Rh, m is 1 or 2, and n is 1 or 2 . However, when M is Ir or Rh, m + n = 3, and when M is Pt, m + n = 2 . ) The phenyltriazole metal complex according to claim 1 , wherein ^RA and ^RE are alkyl groups. The phenyltriazole metal complex according to claim 1 or 2 , wherein ^RB , ^RC or ^RD is a heterocycle represented by the above formula (2). A light emitting device comprising an anode, a cathode, and a layer provided between the anode and the cathode and containing the phenyltriazole metal complex according to any one of claims 1 to 3 .

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