JP2021113186A - Method for producing iridium binuclear complex - Google Patents

Abstract

To provide a method for producing an iridium binuclear complex in which a reaction time is significantly shortened.SOLUTION: The method for producing an iridium binuclear complex represented by formula (1) comprises reacting iridium chloride with a compound represented by formula (2) without adding water in an alkoxyalcohol. [In the formula (1) and formula (2), R1-R8 are each independently H, a halogen atom, an alkyl group or the like; and two adjacent groups out of R3-R8 may be bonded to each other to form a ring together with carbon atoms to which they are respectively bonded, provided that at least one of R1 and R2 is a halogen atom, an alkyl group or the like.]SELECTED DRAWING: None

Description

The present invention relates to a method for producing an iridium binuclear complex suitable as a light emitting material used for a light emitting layer of an organic electroluminescence device.

An iridium complex having high emission quantum efficiency is required as a light emitting material used for a light emitting layer of an organic electroluminescence device. The iridium complex is known to be derived from the iridium dikaryon complex, and the iridium dikaryon complex is synthesized by, for example, the production methods described in Patent Documents 1 to 4.

In Patent Documents 1 and 2, iridium chloride and a compound serving as a ligand are reacted in the presence of water and an organic solvent, but since the internal temperature of the reaction vessel does not exceed 100 ° C. because it contains water, the reaction is carried out. The time is long.

In Patent Document 3, for the purpose of improving the reaction temperature, the reaction is carried out under the condition that the internal temperature of the reaction vessel after distillation is 100 ° C. or higher by undergoing a distillation step in addition to the conditions of Patent Documents 1 and 2. The reduction in reaction time is inadequate.

In Patent Document 4, iridium chloride and the ligand compound (A) are reacted at an internal temperature of 100 ° C. or higher without adding water at the stage of mixing the raw materials, but the reaction time is shortened. Insufficient.

Japanese Unexamined Patent Publication No. 2008-179617 Special Table 2005-521210 Japanese Unexamined Patent Publication No. 2015-189678 Japanese Unexamined Patent Publication No. 2006-213686

An object of the present invention is to provide a more efficient method for producing an iridium dikaryon complex. Specifically, it is an object of the present invention to provide a method for producing an iridium dikaryon complex in which the reaction time is significantly shortened.

As a result of studies for solving the above-mentioned problems, the present invention includes a compound represented by the formula (2) having a predetermined structure (a compound serving as a ligand) in an alkoxyalcohol without adding water. It has been found that the reaction time of the reaction for producing an iridium binuclear complex can be significantly shortened by reacting with iridium chloride. Based on such findings, further studies have led to the completion of the present invention.

The present invention provides the following [1] to [10].
[1] A method for producing an iridium binuclear complex represented by the formula (1), in which iridium chloride is reacted with a compound represented by the formula (2) in an alkoxy alcohol without adding water. A manufacturing method characterized by allowing.

[In equations (1) and (2),
R ^{1 to} R ⁸ are independently hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl. Group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent It represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron, and these groups may have a substituent. Two adjacent groups of R ^{3 to} R ⁸ may be bonded to each other to form a ring together with a carbon atom to which each is bonded, and the ring may have a substituent.

However, ^{at least one of R 1} and R ² is a halogen atom, an alkyl group, or the formula (3):

It is a group represented by.

A represents = CH- or = N-, and if A is = CH-, it may have a substituent, and if A is = N-, two or more A's are = N-. Is. A plurality of A's may be the same or different.

［式（１）及び式（２）中、
Ｒ^１〜Ｒ^８は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールアルキニル基、置換カルボキシル基、シアノ基、又はデンドロンを表し、これらの基は置換基を有していてもよい。Ｒ^３〜Ｒ^８のうち隣り合う２つの基が互いに結合してそれぞれが結合する炭素原子とともに環を形成してもよく、当該環は置換基を有していてもよい。
但し、Ｒ^１及びＲ^２の少なくとも一方は、ハロゲン原子、アルキル基、又は、式（３）：

で表される基である。
Ａは、＝ＣＨ−又は＝Ｎ−を表し、Ａが＝ＣＨ−である場合は置換基を有していてもよく、Ａが＝Ｎ−である場合は２つ以上のＡが＝Ｎ−である。複数存在するＡは、同一でも異なっていてもよい。
Ｒ^９及びＲ^１０は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールアルキニル基、置換カルボキシル基、シアノ基、又はデンドロンを表し、これらの基は置換基を有していてもよい。］

［式（４）中、
Ｒ^１１〜Ｒ^１８は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールアルキニル基、置換カルボキシル基、シアノ基、又はデンドロンを表し、これらの基は置換基を有していてもよい。Ｒ^１１〜Ｒ^１８のうち隣り合う２つの基が互いに結合してそれぞれが結合する炭素原子とともに環を形成してもよい。］

［式（５）中、Ｒ^１〜Ｒ^８及びＲ^１１〜Ｒ^１８は前記に同じ。］ R ⁹ and R ¹⁰ are independently hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl. Group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent It represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron, and these groups may have a substituent. ]
[2] At ^{least one of R 5 to} R ⁸ is a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, or an arylalkyl group. , Arylalkoxy groups, arylalkylthio groups, acyl groups, acyloxy groups, amide groups, acidimide groups, imine residues, substituted amino groups, substituted silyl groups, substituted silyloxy groups, substituted silylthio groups, substituted silylamino groups, monovalent complex The production method according to [1], wherein the ring group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron.
[3] ^{Two adjacent groups of R 5 to} R ⁸ are bonded to each other to form a ring together with a carbon atom to which each is bonded, and the ring may have a substituent, [1] or. The manufacturing method according to [2].
[4] ^{The production method according to any one of [1] to [3], wherein one of R 1} and R ² is a halogen atom, an alkyl group, or a group represented by the formula (3).
[5] ^{The production method according to any one of [1] to [4], wherein R 2} is a halogen atom, an alkyl group, or a group represented by the formula (3).
[6] The production method according to any one of [1] to [5], wherein ^{R 2 is a group represented by the formula (3).}
[7] The production according to any one of [1] to [6], wherein A is all = N-, or all = CH-, and the = CH- may have a substituent. Method.
[8] The production method according to any one of [1] to [7], wherein the alkoxy alcohol is an alkoxy alcohol having 3 to 12 carbon atoms.
[9] The production method according to any one of [1] to [8], wherein the internal temperature of the reaction vessel (temperature of the reaction solution) at the time of the reaction is 115 ° C. or higher.
[10] A method for producing a compound (iridium complex) represented by the formula (5), wherein iridium chloride and the compound represented by the formula (2) are mixed in an alkoxyalcohol without adding water. A production method, which comprises reacting and reacting the obtained compound represented by the formula (1) with the formula (4).

[In equations (1) and (2),
R ^{1 to} R ⁸ are independently hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl. Group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent It represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron, and these groups may have a substituent. Two adjacent groups of R ^{3 to} R ⁸ may be bonded to each other to form a ring together with a carbon atom to which each is bonded, and the ring may have a substituent.
However, ^{at least one of R 1} and R ² is a halogen atom, an alkyl group, or the formula (3):

It is a group represented by.
A represents = CH- or = N-, and if A is = CH-, it may have a substituent, and if A is = N-, two or more A's are = N-. Is. A plurality of A's may be the same or different.
R ⁹ and R ¹⁰ are independently hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl. Group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent It represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron, and these groups may have a substituent. ]

[In equation (4),
R ^{11 to} R ¹⁸ are independently hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group and arylalkyl. Group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent complex It represents a ring group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron, and these groups may have a substituent. Two adjacent groups of R ^{11 to} R ¹⁸ may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

[In formula (5), R ^{1 to} R ⁸ and R ^{11 to} R ¹⁸ are the same as described above. ]

According to the production method of the present invention, the reaction time when synthesizing an iridium dikaryon complex can be significantly shortened.

Hereinafter, embodiments of the present invention will be described.
1. 1. Explanation of Common Terms Unless otherwise specified, the terms commonly used in the present specification have the following meanings.

Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

The "alkyl group" may be either linear or branched. The number of carbon atoms of this alkyl group is usually 1 to 12 (hereinafter, it may be referred to as "C1 to C12 alkyl"). The alkyl group may have a substituent, and specific examples of the alkyl group which may have the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tert. -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluoro Examples thereof include a butyl group, a perfluorohexyl group and a perfluorooctyl group. Of these, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group and a 3,7-dimethyloctyl group are preferable.

The number of carbon atoms of the "cycloalkyl group" is usually 3 to 12 (hereinafter, it may be referred to as "C3 to C12 cycloalkyl"). The cycloalkyl group may have a substituent, and specific examples of the cycloalkyl group which may have the substituent include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, and the like. Cyclohexylethyl group and the like can be mentioned.

The "alkoxy group" may be either linear or branched. The number of carbon atoms of this alkoxy group is usually 1 to 12 (hereinafter, it may be referred to as "C1 to C12 alkoxy"). The alkoxy group may have a substituent, and specific examples of the alkoxy group which may have the substituent include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and an isobutoxy group. , Tert-Butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy Examples thereof include a group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyl group, a perfluorooctyl group, a methoxymethyloxy group, a 2-methoxyethyloxy group and the like. Of these, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group are preferable.

The number of carbon atoms of the "cycloalkoxy group" is usually 3 to 12 (hereinafter, it may be referred to as "C3 to C12 cycloalkoxy"). The cycloalkoxy group may have a substituent, and specific examples of the cycloalkoxy group which may have the substituent include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group. And so on.

The "alkylthio group" may be either linear or branched. The number of carbon atoms of this alkylthio group is usually 1 to 12. The alkylthio group may have a substituent, and specific examples of the alkylthio group which may have the substituent include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group and an isobutylthio group. , Tart-butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group and the like. .. Of these, a pentylthio group, a hexylthio group, an octylthio group, a 2-ethylhexylthio group, a decylthio group and a 3,7-dimethyloctylthio group are preferable.

The number of carbon atoms of the "cycloalkylthio group" is usually 3 to 12. The cycloalkylthio group may have a substituent, and specific examples of the cycloalkylthio group which may have the substituent include a cyclopropylthio group, a cyclobutylthio group, a cyclopentylthio group, and a cyclohexylthio group. And so on.

"Aryl group" means the remaining atomic group excluding one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The aromatic hydrocarbon includes a hydrocarbon having a fused ring, an independent benzene ring, and two or more selected from the fused rings bonded directly or via a group such as vinylene. The number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 48, and more preferably 6 to 20. For example, a phenyl group, a naphthyl group, an anthrasenyl group, a phenanthrenyl group, a pyrenyl group and the like can be mentioned.

The aryl group may have a substituent. Examples of the substituent include an alkoxy group (particularly C1 to C12 alkoxy group, etc.), a cycloalkoxy group (particularly C3 to C12 cycloalkoxy group, etc.), an alkyl group (particularly C1 to C12 alkyl group, etc.), and a cycloalkyl group (particularly C3 to C3 to). C12 cycloalkyl group, etc.), chlorine atom, bromine atom, alkoxyphenyl group (particularly C1 to C12 alkoxyphenyl group), alkylphenyl group (particularly C1 to C12 alkylphenyl group), monovalent heterocyclic group and the like. The aryl group may have 1 to 5 groups (particularly 1 to 3) selected from the group consisting of these substituents.

Examples of the aryl group that may have the substituent include a phenyl group, a C1 to C12 alkoxyphenyl group, a C1 to C12 alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthrasenyl group, and a 2-anthrasenyl group. Examples thereof include a group, a 9-anthrasenyl group, a pentafluorophenyl group, a mono or di (C1 to C12 alkoxyphenyl) phenyl group, and a mono or di (C1 to C12 alkylphenyl) phenyl group. Of these, C1-C12 alkoxyphenyl groups, C1-C12 alkylphenyl groups, di (C1-C12 alkoxyphenyl) phenyl groups, di (C1-C12 alkylphenyl) phenyl groups and the like are preferable.

The C1 to C12 alkoxyphenyl groups include methoxyphenyl group, ethoxyphenyl group, dimethoxyphenyl group, propyloxyphenyl group, 1,3,5-trimethoxyphenyl group, methoxyethoxyphenyl group, isopropyloxyphenyl group and butoxyphenyl group. , Isobutoxyphenyl group, tert-butoxyphenyl group, pentyloxyphenyl group, isoamyloxyphenyl group, hexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, dodecyloxyphenyl The group and the like are exemplified.

Examples of C1 to C12 alkylphenyl groups include methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group and tert-butylphenyl group. , Pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

The "arylene group" means the remaining atomic group excluding the two hydrogen atoms directly bonded to the carbon atoms constituting the ring from the aromatic hydrocarbon. The number of carbon atoms of the arylene group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18.

The arylene group may have a substituent (for example, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a bromine atom, etc.) and has the substituent. Examples of the arylene group which may be used include a phenylene group, a naphthalenediyl group, an anthracendiyl group, a phenanthrendiyl group, a dihydrophenantrenidyl group, a naphthacendyl group, a fluorinatedyl group, a pyrenedyl group, a perylenediyl group, a chrysendiyl group and a dibenzo. Examples thereof include a cycloheptandiyl group and a group in which these groups have a substituent, and the groups represented by the formulas (A-1) to (A-23) are preferable. The arylene group includes a group in which a plurality of these groups are bonded.

[Wherein, R and R ^a each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, cycloalkoxy group, an aryl group or a monovalent heterocyclic group. R and R ^a there are a plurality, each may be the same or different, bonded R ^a each other to each other, they may form a ring together with the atoms bonded thereto. ]

The "trivalent aromatic hydrocarbon group" means the remaining atomic group excluding the three hydrogen atoms directly bonded to the carbon atoms constituting the ring from the aromatic hydrocarbon. The number of carbon atoms of the trivalent aromatic hydrocarbon group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18.

The trivalent aromatic hydrocarbon group may have a substituent (for example, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a bromine atom, etc.). Examples of the trivalent aromatic hydrocarbon group which may have the substituent include a benzenetriyl group, a naphthalentryyl group, an anthracentriyl group, a phenanthrentriyl group and a dihydrophenanthrentriyl group. Examples thereof include a naphthalcentriyl group, a fluorentriyl group, a pyrentryyl group, a perylenetriyl group, a crescentlyyl group, a dibenzocycloheptantriyl group, and a group in which these groups have a substituent, preferably of the formula (A). -1) Among the divalent groups represented by the formulas (A-23), a trivalent group in which one R is a binder can be mentioned. The trivalent aromatic hydrocarbon group includes a group in which a plurality of these groups are bonded.

The number of carbon atoms of the "aryloxy" group is usually 6 to 60, preferably 7 to 48. The aryloxy group may have a substituent (alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, bromine atom, etc.), and may have the substituent as an aryloxy group. Examples thereof include a phenoxy group, a C1-C12 alkoxyphenoxy group, a C1-C12 alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a pentafluorophenyloxy group and the like. Of these, C1-C12 alkoxyphenoxy groups and C1-C12 alkylphenoxy groups are preferable.

Examples of the C1 to C12 alkoxyphenoxy groups include a methoxyphenoxy group, an ethoxyphenoxy group, a dimethoxyphenoxy group, a propyloxyphenoxy group, a 1,3,5-trimethoxyphenoxy group, a methoxyethoxyphenoxy group, an isopropyloxyphenoxy group and a butoxyphenoxy group. , Isobutoxyphenoxy group, tert-butoxyphenoxy group, pentyloxyphenoxy group, isoamyloxyphenoxy group, hexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group, dodecyloxyphenoxy Groups and the like are exemplified.

Examples of the C1 to C12 alkylphenoxy groups include methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-trimethylphenoxy group, methylethylphenoxy group, isopropylphenoxy group, butylphenoxy group and isobutylphenoxy. Examples thereof include a group, a tert-butylphenoxy group, a pentylphenoxy group, an isoamylphenoxy group, a hexylphenoxy group, a heptylphenoxy group, an octylphenoxy group, a nonylphenoxy group, a decylphenoxy group, a dodecylphenoxy group and the like.

The number of carbon atoms of the "arylthio group" is usually 6 to 60, preferably 7 to 48. The arylthio group may have a substituent (for example, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a bromine atom, etc.) and has the substituent. Examples of the arylthio group which may be used include a phenylthio group, a C1-C12 alkoxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a pentafluorophenylthio group and the like. Of these, C1-C12 alkoxyphenylthio groups and C1-C12 alkylphenylthio groups are preferable.

The "arylalkyl group" usually has 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. The arylalkyl group may have a substituent (for example, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a bromine atom, etc.) and has the substituent. Examples of the arylalkyl group which may be used include a phenyl-C1 to C12 alkyl group, a C1 to C12 alkoxyphenyl-C1 to C12 alkyl group, a C1 to C12 alkylphenyl-C1 to C12 alkyl group, and a 1-naphthyl-C1 to C12. Alkyl groups, 2-naphthyl-C1-C12 alkyl groups and the like are exemplified. Of these, C1 to C12 alkoxyphenyl-C1 to C12 alkyl groups and C1 to C12 alkylphenyl-C1 to C12 alkyl groups are preferable.

The "arylalkoxy group" usually has 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. The arylalkoxy group may have a substituent (for example, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a bromine atom, etc.) and has the substituent. Examples of the arylalkoxy groups that may be used include phenyl-C1 to C12 such as phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyroxy group, phenylhexyloxy group, phenylheptyroxy group, and phenyloctyroxy group. Alkoxy groups; C1-C12 alkoxyphenyl-C1-C12 alkoxy groups, C1-C12 alkylphenyl-C1-C12 alkoxy groups, 1-naphthyl-C1-C12 alkoxy groups, 2-naphthyl-C1-C12 alkoxy groups and the like are exemplified. NS. Of these, C1 to C12 alkoxyphenyl-C1 to C12 alkoxy groups and C1 to C12 alkylphenyl-C1 to C12 alkoxy groups are preferable.

The number of carbon atoms of the "arylalkylthio group" is usually 7 to 60, preferably 7 to 48. The arylalkylthio group may have a substituent (for example, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a bromine atom, etc.) and has the substituent. Examples of the arylalkylthio group which may be used include a phenyl-C1 to C12 alkylthio group, a C1 to C12 alkoxyphenyl-C1 to C12 alkylthio group, a C1 to C12 alkylphenyl-C1 to C12 alkylthio group, and a 1-naphthyl-C1 to C12 group. Alkoxythio groups, 2-naphthyl-C1-C12 alkylthio groups and the like are exemplified. Of these, C1 to C12 alkoxyphenyl-C1 to C12 alkylthio groups and C1 to C12 alkylphenyl-C1 to C12 alkylthio groups are preferable.

The "acyl group" usually has 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. The acyl group may have a substituent (for example, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a bromine atom, a fluorine atom, etc.) or may have the substituent. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, a pentafluorobenzoyl group and the like.

The number of carbon atoms of the "acyloxy group" is usually 2 to 20, preferably 2 to 18. The acyloxy group may have a substituent (for example, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a bromine atom, etc.), or as an acyloxy group which may have the substituent. Examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

The "amide group" usually has 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. The amide group also includes those having a substituent (for example, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a bromine atom, a fluorine atom, etc.) on the amide nitrogen atom. .. Examples of the amide group include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group and ditri. Examples thereof include a fluoroacetamide group and a dipentafluorobenzamide group.

The "acidimide group" means a monovalent residue obtained by removing one hydrogen atom bonded to the nitrogen atom from the acidimide. The number of carbon atoms of this acidimide group is usually 2 to 60, preferably 2 to 48. Examples of the acidimide group include groups represented by the following structural formulas.

（式中、窒素原子から延びた線は結合手を表し、Ｍｅはメチル基、Ｅｔはエチル基、ｎ−Ｐｒはｎ−プロピル基を表す。以下、同じである。）

(In the formula, the line extending from the nitrogen atom represents a bond, Me represents a methyl group, Et represents an ethyl group, and n-Pr represents an n-propyl group. The same applies hereinafter.)

An "imine residue" is an imine compound (ie, an organic compound having -N = C- in the molecule. Examples thereof are aldimine, ketimine, and a hydrogen atom bonded to a nitrogen atom in these molecules. However, it means a monovalent residue obtained by removing one hydrogen atom from a compound or the like substituted with an alkyl group or the like. This imine residue usually has 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specifically, the groups represented by the following structural formulas are exemplified.

（式中、ｉ−Ｐｒはイソプロピル基、ｎ−Ｂｕはｎ−ブチル基、ｔ−Ｂｕはｔｅｒｔ−ブチル基を表す。波線で示した結合は、「楔形で表される結合」及び／又は「破線で表される結合」であることを意味する。ここで、「楔形で表される結合」とは、紙面からこちら側に向かって出ている結合を意味し、「破線で表される結合」とは、紙面の向こう側に出ている結合を意味する。）

(In the formula, i-Pr represents an isopropyl group, n-Bu represents an n-butyl group, and t-Bu represents a tert-butyl group. Bonds shown by wavy lines are "bonds represented by wedges" and / or "bonds represented by wedges" and / or " It means that it is a "bond represented by a broken line". Here, "a bond represented by a wedge shape" means a bond protruding from the paper surface toward this side, and "a bond represented by a broken line". "" Means the bond that appears on the other side of the paper.)

"Substituted amino group" means an amino group substituted with one or two groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group is a substituent (for example, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, monovalent heterocyclic group, bromine atom. Etc.). The number of carbon atoms of the substituted amino group is usually 1 to 60, preferably 2 to 48, not including the number of carbon atoms of the substituent.

Substituted amino groups include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group and tert-butylamino. Group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group , Dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C1-C12 alkoxyphenylamino group, di (C1-C12 alkoxyphenyl) Amino group, di (C1-C12 alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridadinylamino group, pyrimidylamino group, pyrazilamino group, triazil Amino groups phenyl-C1 to C12 alkylamino groups, C1 to C12 alkoxyphenyl-C1 to C12 alkylamino groups, C1 to C12 alkylphenyl-C1 to C12 alkylamino groups, di (C1 to C12 alkoxyphenyl-C1 to C12 alkyl) Examples thereof include amino groups, di (C1-C12 alkylphenyl-C1-C12 alkyl) amino groups, 1-naphthyl-C1-C12 alkylamino groups, 2-naphthyl-C1-C12 alkylamino groups and the like.

"Substituted silyl group" means a silyl group substituted with 1, 2 or 3 groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The substituted silyl group usually has 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.

Substituted silyl groups include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, tert-butylsilyldimethylsilyl group, pentyldimethylsilyl group and hexyl. Dimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, phenyl- C1 to C12 alkylsilyl groups, C1 to C12 alkoxyphenyl-C1 to C12 alkylsilyl groups, C1 to C12 alkylphenyl-C1 to C12 alkylsilyl groups, 1-naphthyl-C1 to C12 alkylsilyl groups, 2-naphthyl-C1 to C12 alkylsilyl group, phenyl-C1-C12 alkyldimethylsilyl group, triphenylsilyl group, tri-p-xysilylsilyl group, tribenzylsilyl group, diphenylmethylsilyl group, tert-butyldiphenylsilyl group, dimethylphenylsilyl group, etc. Illustrated.

The "substituted silyloxy group" means a silyloxy group substituted with 1, 2 or 3 groups selected from the group consisting of an alkoxy group, an aryloxy group, an arylalkoxy group and a monovalent heterocyclic oxy group. The substituted silyloxy group usually has 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms. The alkoxy group, aryloxy group, arylalkoxy group or monovalent heterocyclic oxy group may have a substituent.

As the substituted silyloxy group, trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, tri-isopropylsilyloxy group, dimethyl-isopropylsilyloxy group, diethyl-isopropylsilyloxy group, tert-butylsilyldimethylsilyl group, Pentyldimethylsilyloxy group, hexyldimethylsilyloxy group, heptyldimethylsilyloxy group, octyldimethylsilyloxy group, 2-ethylhexyl-dimethylsilyloxy group, nonyldimethylsilyloxy group, decyldimethylsilyloxy group, 3,7-dimethyl Octyl-dimethylsilyloxy group, lauryldimethylsilyloxy group, phenyl-C1-C12 alkylsilyloxy group, C1-C12 alkoxyphenyl-C1-C12 alkylsilyloxy group, C1-C12 alkylphenyl-C1-C12 alkylsilyloxy group , 1-naphthyl-C1-C12 alkylsilyloxy groups, 2-naphthyl-C1-C12 alkylsilyloxy groups, phenyl-C1-C12 alkyldimethylsilyloxy groups, triphenylsilyloxy groups, tri-p-xylsilyloxyoxy Examples thereof include a group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a tert-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.

"Substituted silylthio group" means a silylthio group substituted with 1, 2 or 3 groups selected from the group consisting of an alkylthio group, an arylthio group, an arylalkylthio group and a monovalent heterocyclic thio group. The substituted silylthio group usually has 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms. The alkoxy group, arylthio group, arylalkylthio group or monovalent heterocyclic thiogroup may have a substituent.

Substituted silylthio groups include trimethylsilylthio group, triethylsilylthio group, tripropylsilylthio group, tri-isopropylsilylthio group, dimethyl-isopropyrylsilylthio group, diethyl-isopropylsilylthio group, tert-butylsilyldimethylsilylthio group. , Pentyl dimethyl silylthio group, hexyl dimethyl silyl thio group, heptyl dimethyl silyl thio group, octyl dimethyl silyl thio group, 2-ethylhexyl-dimethyl silyl thio group, nonyl dimethyl silyl thio group, decyl dimethyl silyl thio group, 3,7- Dimethyloctyl-dimethylsilylthio group, lauryldimethylsilylthio group, phenyl-C1-C12 alkylsilylthio group, C1-C12 alkoxyphenyl-C1-C12 alkylsilylthio group, C1-C12 alkylphenyl-C1-C12 alkylsilylthio group Group, 1-naphthyl-C1-C12 alkylsilylthio group, 2-naphthyl-C1-C12 alkylsilylthio group, phenyl-C1-C12 alkyldimethylsilylthio group, triphenylsilylthio group, tri-p-xysilylsiri Examples thereof include a ruthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a tert-butyldiphenylsilylthio group, a dimethylphenylsilylthio group and the like.

"Substituted silylamino group" means a silylamino group substituted with 1, 2 or 3 groups selected from the group consisting of an alkylamino group, an arylamino group, an arylalkylamino group and a monovalent heterocyclic amino group. .. The substituted silylamino group usually has 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms. The alkoxy group, arylamino group, arylalkylamino group or monovalent heterocyclic amino group may have a substituent.

Substituted silylamino groups include trimethylsilylamino group, triethylsilylamino group, tripropylsilylamino group, tri-isopropylsilylamino group, dimethyl-isopropyrylsilylamino group, diethyl-isopropylsilylamino group, tert-butylsilyldimethylsilylamino. Group, pentyldimethylsilylamino group, hexyldimethylsilylamino group, heptyldimethylsilylamino group, octyldimethylsilylamino group, 2-ethylhexyl-dimethylsilylamino group, nonyldimethylsilyloamino group, decyldimethylsilylamino group, 3, 7-Dimethyloctyl-dimethylsilylamino group, lauryldimethylsilylamino group, phenyl-C1-C12 alkylsilyloxy group, C1-C12 alkoxyphenyl-C1-C12alkylsilylamino group, C1-C12alkylphenyl-C1-C12alkyl Cyrilamino group, 1-naphthyl-C1-C12 alkylsilylamino group, 2-naphthyl-C1-C12 alkylsilylamino group, phenyl-C1-C12 alkyldimethylsilylamino group, triphenylsilylamino group, tri-p-key Examples thereof include a silylsilylamino group, a tribenzylsilylamino group, a diphenylmethylsilylamino group, a tert-butyldiphenylsilyloamino group, and a dimethylphenylsilylamino group.

A "p-valent heterocyclic group" (p represents an integer of 1 or more) is p of hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound. It means the remaining atomic group excluding the hydrogen atom of. The p-valent heterocyclic group may have a substituent. Here, the heterocyclic compound is an organic compound having a cyclic structure in which the element constituting the ring contains not only a carbon atom but also a heteroatom such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. Say something. Examples of the heterocyclic compound include aromatic heterocyclic compounds and aliphatic heterocyclic compounds. Among the p-valent heterocyclic groups, it is the remaining atomic group obtained by removing p hydrogen atoms from the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring from the aromatic heterocyclic compound. A "p-valent aromatic heterocyclic group" is preferable, and a "p-valent nitrogen-containing aromatic heterocyclic group" is more preferable.

The "aromatic heterocyclic compound" is a heterocyclic compound such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphor, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphol. Even if the compound whose ring itself exhibits aromaticity and the heterocycle itself such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, and benzopyran do not exhibit aromaticity, the aromatic ring is fused to the heterocycle. Means a compound.

Examples of the "aliphatic heterocyclic compound" include hydrofuran, pyran, hydropyran, dioxane, pyrrolidine, imidazolidine, pyrazolidine, piperidine, piperazine, morpholine, quinuclidine, hydrothiophene, thian and the like.

The number of carbon atoms of the "monovalent heterocyclic group" (p = 1) is usually 2 to 60, preferably 3 to 20. The number of carbon atoms of the monovalent heterocyclic group does not include the number of carbon atoms of the substituent.

The monovalent heterocyclic group may have a substituent, and examples of the monovalent heterocyclic group which may have the substituent include a thienyl group, a pyrrolyl group, a furyl group and a pyridyl group. , Pyrazineyl group, pyrimidinyl group, pyridadinyl group, piperidinyl group, quinolinyl group, isoquinolinyl group, pyrimidinyl group, triazinyl group, and the hydrogen atom in these groups is an alkyl group (C1 to C12 alkyl, etc.), an alkoxy group (C1 to C1 to Examples thereof include a C12 alkoxy group, etc.), an aryl group, a group substituted with a bromine atom, and the like.

The number of carbon atoms of the "divalent heterocyclic group" (p = 2) is usually 2 to 60, preferably 3 to 20. The number of carbon atoms of the divalent heterocyclic group does not include the number of carbon atoms of the substituent.

The divalent heterocyclic group may have a substituent, and examples of the divalent heterocyclic group which may have the substituent include pyridine, diazabenzene, triazine, azanaphthalene and diaza. A hydrogen atom directly bonded to a carbon atom or a hetero atom constituting a ring from naphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilol, phenoxazine, phenothiazine, aclysine, dihydroaclysine, furan, thiophene, azole, diazole and triazole. Of these, a divalent group excluding two hydrogen atoms (these groups may have substituents such as an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and a bromine atom. ), Which is preferably a group represented by the formulas (AA-1) to (AA-34). The divalent heterocyclic group includes a group in which a plurality of these groups are bonded.

［式中、Ｒ及びＲ^ａは、前記と同じ意味を表す。］

[In the formula, R and ^Ra have the same meanings as described above. ]

The number of carbon atoms of the "trivalent heterocyclic group" (p = 3) is usually 2 to 60, preferably 3 to 20. The number of carbon atoms of the trivalent heterocyclic group does not include the number of carbon atoms of the substituent.

The trivalent heterocyclic group may have a substituent, and examples of the trivalent heterocyclic group which may have the substituent include pyridine, diazabenzene, triazine, azanaphthalene and diaza. A hydrogen atom directly bonded to a carbon atom or a hetero atom constituting a ring from naphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilol, phenoxazine, phenothiazine, aclysine, dihydroaclysine, furan, thiophene, azole, diazole and triazole. Of these, a trivalent group excluding three hydrogen atoms (these groups may have substituents such as an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group and a bromine atom). ), And preferably, among the divalent groups represented by the above formulas (AA-1) to (AA-34), a trivalent group in which one R is a binding agent can be mentioned. The trivalent heterocyclic group includes a group in which a plurality of these groups are bonded.

The number of carbon atoms of the "heteroaryloxy group" is usually 3 to 60, preferably 3 to 48. The heteroaryloxy group may have a substituent, and the heteroaryloxy group which may have the substituent includes a thienyloxy group, a C1 to C12 alkoxythienyloxy group, and a C1 to C12 alkylthienyloxy group. Examples thereof include a group, a pyridyloxy group, a C1-C12 alkoxypyridyloxy group, a C1-C12 alkylpyridyloxy group, and an isoquinolyloxy group. Of these, C1-C12 alkoxypyridyloxy groups and C1-C12 alkylpyridyloxy groups are preferable.

Examples of the C1 to C12 alkoxypyridyloxy groups include methoxypyridyloxy group, ethoxypyridyloxy group, propyloxypyridyloxy group, isopropyloxypyridyloxy group, butoxypyridyloxy group, isobutoxypyridyloxy group, and tert-butoxypyridyloxy group. , Pentyloxypyridyloxy group, hexyloxypyridyloxy group, cyclohexyloxypyridyloxy group, heptyloxypyridyloxy group, octyloxypyridyloxy group, 2-ethylhexyloxypyridyloxy group, nonyloxypyridyloxy group, decyloxypyridyloxy group , 3,7-Dimethyloctyloxypyridyloxy group, lauryloxypyridyloxy group and the like are exemplified.

Examples of the C1 to C12 alkylpyridyloxy groups include methylpyridoxy group, ethylpyridyloxy group, dimethylpyridyloxy group, propylpyridyloxy group, 1,3,5-trimethylpyridyloxy group, methylethylpyridyloxy group and isopropylpyridyl. Oxy group, butylpyridyloxy group, isobutylpyridyloxy group, tert-butylpyridyloxy group, pentylpyridyloxy group, isoamylpyridyloxy group, hexylpyridyloxy group, heptylpyridyloxy group, octylpyridyloxy group, nonylpyridyloxy group, Examples thereof include decylpyridyloxy group and dodecylpyridyloxy group.

The number of carbon atoms of the "heteroarylthio group" is usually 6 to 60, preferably 7 to 48. The heteroarylthio group may have a substituent, and the heteroarylthio group which may have the substituent includes a pyridylthio group, a C1-C12 alkoxypyridylthio group, and a C1-C12 alkylpyridylthio group. , Isoquinolylthio group and the like are exemplified. Of these, C1-C12 alkoxypyridylthio groups and C1-C12 alkylpyridylthio groups are preferable.

The "arylalkenyl group" usually has 8 to 60 carbon atoms, preferably 8 to 48 carbon atoms. The arylalkenyl group may have a substituent, and the arylalkenyl group which may have the substituent includes a phenyl-C2-C12 alkenyl group (“C2-C12 alkenyl” is the carbon of the alkenyl moiety. It means that the number of atoms is 2 to 12. The same applies hereinafter.), C1 to C12 alkoxyphenyl-C2 to C12 alkenyl group, C1 to C12 alkylphenyl-C2 to C12 alkenyl group, 1-naphthyl-C2. ~ C12 alkenyl group, 2-naphthyl-C2-C12 alkenyl group and the like are exemplified. Of these, C1-C12 alkoxyphenyl-C2-C12 alkenyl groups and C1-C12 alkylphenyl-C2-C12 alkenyl groups are preferable.

The number of carbon atoms of the "arylalkynyl group" is usually 8 to 60, preferably 8 to 48. The arylalkynyl group may have a substituent, and the arylalkynyl group which may have the substituent includes a phenyl-C2-C12 alkynyl group (“C2-C12 alkynyl” is the carbon of the alkynyl moiety. It means that the number of atoms is 2 to 12. The same applies hereinafter.), C1 to C12 alkoxyphenyl-C2 to C12 alkynyl group, C1 to C12 alkylphenyl-C2 to C12 alkynyl group, 1-naphthyl-C2. ~ C12 alkynyl group, 2-naphthyl-C2-C12 alkynyl group and the like are exemplified. Of these, C1-C12 alkoxyphenyl-C2-C12 alkynyl groups and C1-C12 alkylphenyl-C2-C12 alkynyl groups are preferable.

The "substituted carboxyl group" usually has 2 to 60 carbon atoms, preferably 2 to 48, and contains a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. means. Substituted carboxyl groups include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxy. Carbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl Examples thereof include a group, a pentafluoroethoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, a perfluorooctyloxycarbonyl group, a pyridyloxycarbonyl group, a naphthoxycarbonyl group, a pyridyloxycarbonyl group and the like. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The number of carbon atoms of the substituted carboxyl group does not include the number of carbon atoms of the substituent.

In the case of " ^{two adjacent groups of R 3} to R ⁸ are bonded to each other to form a ring together with a carbon atom to which each is bonded", for example, the following groups are examples of the groups in which two adjacent groups are bonded to each other. Illustrated. The group includes an alkyl group, an aryl group, an alkylaryl group, a cycloalkyl group, a halogen atom, a 1,3,5-triazine-2-yl group having an aryl group as a substituent at the 4- and 6-positions, a 4-position and the like. It may have a substituent selected from 1,3-pyrimidin-2-yl group, dendron and the like having an aryl group as a substituent at the 6-position.

[In the formula, * indicates a carbon atom to which two adjacent groups of ^{R 3} to R ^{8 are bonded to each other.} ]

A "dendron" is a group having a regular dendritic bifurcated structure with an atom or ring as a bifurcation point. Examples of the metal complex having dendron as a partial structure (hereinafter, also referred to as “metal complex having dendron”) include International Publication No. 02/067343, JP-A-2003-231692, and International Publication No. 2003 /. Examples thereof include the structures described in 079736, International Publication No. 2006/09717, and the like.

The dendron is preferably a group represented by the formula (D-A) or the formula (D-B).

[During the ceremony,
m ^DA1 , m ^DA2, and m ^DA3 independently represent integers of 0 or more and 10 or less.

G ^DA represents a nitrogen atom, a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and these groups may have a substituent.

Ar ^DA1 , Ar ^DA2 and Ar ^DA3 independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. When ^{there are a plurality of Ar DA1} , Ar ^DA2, and Ar ^DA3 , they may be the same or different from each other.

T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of T ^DAs may be the same or different. ]

[During the ceremony,
m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 each independently represent an integer of 0 or more and 10 or less.

G ^DA represents a nitrogen atom, a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and these groups may have a substituent. The plurality of G ^DAs may be the same or different.

Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 each independently represent an arylene group or a divalent heterocyclic group, even if these groups have substituents. good. If there are multiple Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 , they may be the same or different.

T ^DA represents an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. A plurality of T ^DAs may be the same or different. ]

m ^DA1 , m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 are preferably an integer of 5 or less, more preferably an integer of 2 or less, and further preferably 0 or 1. It is preferable that m ^DA2 , m ^DA3 , m ^DA4 , m ^DA5 , m ^DA6 and m ^DA7 are the same integer. m ^DA1 may be an integer of 1 or more and 10 or less.

The G ^DA is preferably a group consisting of a benzene ring, a pyridine ring, a pyrimidine ring, a triazine ring or a carbazole ring except for three hydrogen atoms directly bonded to a carbon atom or a nitrogen atom constituting the ring. The group of may have a substituent.

The ^{substituent that G DA} may have is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and more preferably an alkyl group. It is a cycloalkyl group, an alkoxy group or a cycloalkoxy group, more preferably an alkyl group or a cycloalkyl group, and these groups may have a substituent.

G ^DA is preferably a group represented by the formulas (GDA-11) to (GDA-15), and more preferably a group represented by the formulas (GDA-11) to (GDA-14). , More preferably a group represented by the formula (GDA-11) or the formula (GDA-14).

[During the ceremony,
* Is, Ar ^DA1 in the formula (DA), Ar ^DA1 in the formula (DB), Ar in formula (DB) ^DA2, or represents a bond between Ar ^DA3 in the formula (DB).

** is, Ar ^DA2 in the formula (DA), Ar ^DA2 in the formula (DB), Ar in formula (DB) ^DA4, or represents a bond between Ar ^DA6 in the formula (DB).

*** The, Ar ^DA3 in the formula (DA), Ar ^DA3 in the formula (DB), Ar in formula (DB) ^DA5, or represents a bond between Ar ^DA7 in formula (DB).

R ^DA represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups may further have a substituent. If there are multiple R ^DAs , they may be the same or different. ]
The R ^DA is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, more preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and these groups have a substituent. You may.

Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 are preferably a phenylene group, a fluorinatedyl group or a carbazolediyl group, and more preferably a formula (ArDA-1) to a formula (ArDA-1) to a formula. It is a group represented by (ArDA-5), more preferably a group represented by the formulas (ArDA-1) to (ArDA-3), and particularly preferably a group represented by the formula (ArDA-1) or the formula (ArDA). It is a group represented by -2), particularly preferably a group represented by the formula (ArDA-2), and these groups may have a substituent.

[During the ceremony,
R ^DA has the same meaning as described above.

R ^DB represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. If there are multiple R ^DBs , they may be the same or different. ]

The R ^DB is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group or a monovalent heterocyclic group, still more preferably an aryl group, and these. The group may have a substituent.

Examples and preferred ranges of substituents that Ar ^DA1 , Ar ^DA2 , Ar ^DA3 , Ar ^DA4 , Ar ^DA5 , Ar ^DA6 and Ar ^DA7 may have are examples of substituents that G ^DA may have and Same as the preferred range.

The T ^DA is preferably a group represented by the formulas (TDA-1) to (TDA-3), and more preferably a group represented by the formula (TDA-1).

［式中、Ｒ^DA及びＲ^DBは、前記と同じ意味を表す。］

[In the formula, R ^DA and R ^DB have the same meanings as described above. ]

The group represented by the formula (DA) is preferably a group represented by the formulas (D-A1) to (D-A5), and more preferably the formula (D-A1) or the formula (D-A3). ~ A group represented by the formula (D-A5), more preferably a group represented by the formula (D-A1), the formula (D-A3) or the formula (D-A5).

The groups represented by the formula (DB) are preferably the groups represented by the formulas (D-B1) to (D-B6), and more preferably the groups represented by the formulas (D-B1) to (D-B3). , A group represented by the formula (D-B5) or the formula (D-B6), more preferably a group represented by the formula (D-B1), the formula (D-B3) or the formula (D-B5). It is particularly preferable that it is a group represented by the formula (D-B1).

Examples of the group represented by the formula (DA) include groups represented by the formulas (DA-1) to (DA-12).

［式中、Ｒ^Dは、水素原子、メチル基、エチル基、イソプロピル基、ｔｅｒｔ−ブチル基、ヘキシル基、２−エチルヘキシル基、ｔｅｒｔ−オクチル基、シクロヘキシル基、メトキシ基、２−エチルヘキシルオキシ基又はシクロへキシルオキシ基を表す。Ｒ^Dが複数存在する場合、それらは同一でも異なっていてもよい。］

[In the formula, ^RD is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a tert-octyl group, a cyclohexyl group, a methoxy group, a 2-ethylhexyloxy group or Represents a cyclohexyloxy group. If R ^D is plurally present, they may be the same or different. ]

Examples of the group represented by the formula (D-B) include groups represented by the formulas (DB-1) to (DB-7).

［式中、Ｒ^Dは、水素原子、メチル基、エチル基、イソプロピル基、ｔｅｒｔ−ブチル基、ヘキシル基、２−エチルヘキシル基、ｔｅｒｔ−オクチル基、シクロヘキシル基、メトキシ基、２−エチルヘキシルオキシ基又はシクロへキシルオキシ基を表す。Ｒ^Dが複数存在する場合、それらは同一でも異なっていてもよい。］

[In the formula, ^RD is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a tert-octyl group, a cyclohexyl group, a methoxy group, a 2-ethylhexyloxy group or Represents a cyclohexyloxy group. If R ^D is plurally present, they may be the same or different. ]

The ^RD is preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group or a tert-octyl group.

In the present specification, unless otherwise specified, the "substituted group" includes, for example, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, and the like. Aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio Examples thereof include a group, a substituted silylamino group, a monovalent heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group and a dendron. The substituent may be a cross-linking group.

2. Method for Producing Iridium Dinuclear Complex The method for producing the iridium dinuclear complex represented by the formula (1) of the present embodiment is represented by the formula (2) with iridium chloride in an alkoxyalcohol without adding water. It is characterized by reacting with a compound. That is, it is characterized in that iridium chloride is reacted with the compound represented by the formula (2) in an alkoxyalcohol under a condition substantially free of water.

Any of the compounds represented by the formula (2) can be produced according to or according to a known method. For example, it can be synthesized by Suzuki coupling, Grignard coupling, Stille coupling or the like of a 2-phenylpyridine derivative and a ring aromatic compound or a heterocyclic aromatic compound. More specifically, these compounds can be synthesized by dissolving them in an organic solvent, if necessary, and reacting them at a temperature equal to or higher than the melting point of the organic solvent and lower than the boiling point using, for example, an alkali or an appropriate catalyst. This synthesis includes, for example, "Organic Syntheses", Collective Volume VI, pp. 407-411, John Wiley & Sons, Inc., 1988; Chemical Review ( Chem. Rev.), Vol. 106, p. 2651 (2006); Chemical Review (Chem. Rev.), Vol. 102, p. 1359 (2002); Chemical Review (Chem. Rev.), Vol. 95, 2457 (1995); Journal of Organomet.Chem., Vol. 576, 147 (1999), etc. can be used.

The heterocyclic aromatic compound is "HOUBEN-WEYL METHODS OF ORGANIC CHEMISTRY 4T H EDITION", Volume E9b, page 1, GEORG THIEME VERLAG STUTTGART; HOUBEN-WEYL METHODS OF ORGANIC CHEMISTRY 4T H EDITION, Volume E9c, page 667. , GEORG THIEME VERLAG STUTTGART, etc. can be synthesized by the method described.

The reaction temperature of the present embodiment is such that the outside temperature of the reaction vessel is usually 110 ° C. or higher, preferably 115 ° C. or higher, more preferably 115-250 ° C., still more preferably 115-200 ° C. Alternatively, it is preferably 120 ° C. or higher, more preferably 120 to 200 ° C., and even more preferably 130 to 160 ° C. The internal temperature of the reaction vessel is usually 110 ° C. or higher, preferably 115 ° C. or higher, more preferably 115-250 ° C., still more preferably 115-200 ° C. Alternatively, it is preferably 120 ° C. or higher, more preferably 120 to 200 ° C., and even more preferably 130 to 160 ° C. Here, the internal temperature refers to the temperature of the solution or suspension in the reaction vessel, and the external temperature means the temperature of a heat medium such as an oil bath that heats the reaction vessel from the outside.

The reaction time is usually 1 minute to 3 hours, preferably 5 minutes to 2 hours. The reaction time means the time from the start of the reaction to the end (stop) of the reaction. When the reaction is completed (stopped), the reaction solution is sampled multiple times at regular time intervals (for example, 1 minute to 3 hour intervals) and analyzed by liquid chromatography (LC), and LC of the iridium binuclear complex is analyzed. This is the time when there is no change in the area percentage value. Specifically, the method described in the examples can be adopted. After completion of the reaction, an iridium dikaryon complex represented by the formula (1) can be obtained by using a known method.

In this reaction, an alkoxyalcohol is used as a solvent and reaction conditions that do not substantially contain water are adopted, so that the reaction temperature can be raised above the boiling point of water, but since water is not contained, the solubility of iridium chloride in the solvent Was expected to be low and the reaction to be slow. However, under the above reaction conditions, a compound represented by the formula (2) having a specific structure together with iridium chloride (in the formula, ^{at least one of R 1} and R ² has a halogen atom, an alkyl group, or the formula (3)). By reacting the compound having a group represented by (1), contrary to the above expectation, the reaction is dramatically promoted, and it is clear that the iridium dinuclear complex represented by the formula (1) can be produced in a short time. became. Moreover, since the reaction time is shortened, the amount of by-products is reduced, and the yield of the iridium dikaryon complex represented by the formula (1) is also improved.

The solvent used in this reaction is an alkoxy alcohol. The alkoxy alcohol means an alcohol having an alkoxy group, and examples thereof include alcohols having a boiling point of 120 ° C. or higher, preferably 120 ° C. to 350 ° C., and more preferably 120 to 210 ° C. at normal pressure. An alkoxy alcohol having 3 or more carbon atoms is preferable, an alkoxy alcohol having 3 to 12 carbon atoms is more preferable, and an alkoxy alcohol having 3 to 6 carbon atoms is more preferable. Specifically, for example, 2-methoxyethanol, 2-ethoxyethanol, 2-n-propoxyethanol, 2-isopropoxyethanol, 2-n-butoxyethanol, 2-isobutoxyethanol, 2-sec-butoxyethanol, C2-C3 alkylene glycol mono C1-4 alkyl ethers such as 2-tert-butoxyethanol, 1,3-propanediol monomethyl ether, 1,3-propanediol monoethyl ether, propylene glycol 1-monomethyl ether; diethylene glycol monomethyl ether, Di (C2-C3 alkylene glycol) mono-C1-4 alkyl ethers such as diethylene glycol monoethyl ether (carbitol) and dipropylene glycol monomethyl ether, poly (particularly tri or) such as triethylene glycol monomethyl ether and tetraethylene glycol monomethyl ether. Tetra) (C2-C3 alkylene glycol) mono-C1-4 alkyl ethers can be mentioned. Of these, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, carbitol, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether and the like are preferable.

The amount of the alkoxy alcohol used (volume v: ml) is, for example, 10 times (v / w) or more with respect to the pure content (mass w: g) of iridium chloride from the viewpoint of the fluidity of the reaction solution. It is preferably 30 times (v / w) or more, and more preferably 30 to 85 times (v / w). Here, the pure content of iridium chloride means iridium chloride or a salt thereof excluding water of the hydrate when iridium chloride is a hydrate. Alternatively, the amount of the alkoxyalcohol used is such that the molar concentration of the pure content of iridium chloride is, for example, 0.30 mol / l or less, preferably 0.02 to 0.20 mol / l, and more preferably 0.03 to 0. It can be set to .15 mol / l.

In addition to the alkoxy alcohol, the solvent used in this reaction may contain other organic solvents as long as the effects of the present invention are not adversely affected. Examples of the other organic solvent include those having a boiling point of 120 ° C. or higher at normal pressure (for example, 1 atm). For example, n-octane, n-nonane, n-decane, xylene, monochlorobenzene, o-dichlorobenzene, dimethylformamide, dimethyl sulfoxide, 1-pentanol, 1-octanol, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol. , Triethylene glycol and the like. The solvent preferably contains an alkoxy alcohol as a main component, and the content of the alkoxy alcohol in the total solvent is usually 80% by volume or more, preferably 90% by volume or more, and more preferably 95% by volume or more. It is particularly preferably 98% by volume or more.

This reaction is carried out by mixing the above-mentioned alkoxy alcohol, iridium chloride, and the compound represented by the formula (2), but the order of addition to the reaction system is not particularly limited and may be any order.

In the present invention, the reaction is carried out without adding water to the reaction system containing the above solvent, iridium chloride and the compound represented by the formula (2). In other words, the reaction is carried out in a reaction system containing the above solvent, iridium chloride and the compound represented by the formula (2) under conditions substantially free of water. As a result, the reaction proceeds rapidly, and the reaction time for forming the iridium dikaryon complex represented by the formula (1) is significantly shortened. Here, when water is not substantially contained, the content of water should be reduced as much as possible so that the internal temperature of the reaction vessel does not easily rise above the boiling point of water and the reaction is not delayed. It does not just mean that it does not contain water at all. The content of water that can be contained in the reaction system is usually 5% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably less than 1% by mass in the total solvent. When iridium chloride hydrate is used in the production method of the present invention, the effect of the present invention is usually not adversely affected because the amount of water generated from the hydrate is very small. Therefore, the water derived from the hydrate of iridium chloride is not included in the water added to the reaction system in this reaction.

Iridium chloride used in this reaction includes anhydrous iridium chloride, salts thereof, or hydrates thereof. The iridium contained in iridium chloride is preferably trivalent. Specifically, iridium (III) chloride, iridium (III) chloride monohydrate, iridium (III) chloride dihydrate, iridium (III) chloride trihydrate, iridium (III) chloride n-hydrate. , Anhydrous or n-hydrate of sodium iridium (III) chloride (Na ₃ [IrCl ₆ ]), anhydrous or n-hydrate of potassium iridium (III) chloride (K ₃ [IrCl ₆ ]), chloride Examples thereof include anhydrides or n-hydrates of ammonium iridium (III) acid ((NH ₄ ) ₃ [IrCl ₆ ]) (n is a number exceeding 0).

Preferred embodiments of the iridium dikaryon complex represented by the formula (1) and the compound represented by the formula (2) include the following.

R ^{3 to} R ⁸ are hydrogen atom, halogen atom, alkyl group, cycloalkyl group, aryl group, arylalkyl group, substituted amino group, monovalent heterocyclic group, dendron (these groups have substituents). It may be). Further, R ^{5 to} R ⁸ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, a monovalent heterocyclic group, and a dendron (these groups may have a substituent). Is preferable.

Further, ^{two adjacent groups of R 3 to} R ⁸ are bonded to each other to form a ring together with a carbon atom to which each is bonded (the formed ring may further have a substituent). ) Is preferable. Further, ^{two adjacent groups of R 5 to} R ⁸ are bonded to each other to form a ring together with a carbon atom to which each is bonded (this formed ring may further have a substituent). ) Is preferable.

One of R ¹ and R ² is preferably a halogen atom, an alkyl group, or a group represented by the formula (3), and more preferably a halogen atom or a group represented by the formula (3). It is more preferable that the group is represented by the formula (3). The other of R ¹ and R ² is preferably a hydrogen atom.

It is preferable ^{that R 2} is a halogen atom, an alkyl group, or a group represented by the formula (3), and R ¹ is a hydrogen atom. It is more preferable that R ² is a halogen atom or a group represented by the formula (3) and R ^{1 is a hydrogen atom.} It is particularly preferable that R ² is a group represented by the formula (3) and R ^{1 is a hydrogen atom.}

The halogen atom is preferably a chlorine atom or a bromine atom, and more preferably a bromine atom.

The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. The alkyl group may be either linear or branched.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 5 to 10 carbon atoms.

In the group represented by the formula (3), two or more A's may be = N-, or all A's may be = CH- and the = CH- may have a substituent. preferable. Further, it is particularly preferable that all A's are = N− or all A's are = CH− and the = CH− may have a substituent.

In this reaction, the amount of the compound represented by the formula (2) to be used is usually 2 mol or more, preferably 2.1 mol or more, and more preferably 2.2 mol with respect to 1 mol of iridium chloride. That is all.

More preferred embodiments of the iridium dinuclear complex represented by the formula (1) and the compound represented by the formula (2) are the iridium dinuclear complex represented by the formula (1A) and the iridium binuclear complex represented by the formula (2A). Examples include compounds.

（式中、Ｒ^１、Ｒ^２、Ｒ^６及びＲ^７は、前記に同じ。）

(In the formula, R ¹ , R ² , R ⁶ and R ⁷ are the same as described above.)

Examples of the metal complex represented by the above formula (1A) include the metal complexes shown below.

The iridium binuclear complex obtained by the production method of the present embodiment is used as a synthetic intermediate of a light emitting material (iridium complex) used for the light emitting layer of the organic electroluminescence element. The iridium dikaryon complex can be converted into a light emitting material (iridium complex) by a known method (for example, Patent Document 1 or the like).

3. 3. Method for Producing Iridium Complex The iridium complex represented by the formula (5) of the present embodiment includes the iridium dikaryon complex represented by the formula (1) obtained above and the compound represented by the formula (4). Is obtained by reacting.

As for the reaction temperature of the present embodiment, the outside temperature of the reaction vessel is usually 80 ° C. or higher, preferably 80 to 200 ° C., more preferably 90 to 180 ° C., and further preferably 100 to 160 ° C. The internal temperature of the reaction vessel is usually 80 ° C. or higher, preferably 80 ° C. or higher, more preferably 90 to 180 ° C., still more preferably 100 to 160 ° C. Here, the internal temperature refers to the temperature of the solution or suspension in the reaction vessel, and the external temperature means the temperature of a heat medium such as an oil bath that heats the reaction vessel from the outside.

The reaction time is usually 1 hour or more, preferably 1 to 100 hours, more preferably 1 to 50 hours, still more preferably 1 to 10 hours.

This reaction is usually carried out in a solvent. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, 2-methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol; diethyl ether, tetrahydrofuran, dioxane, cyclopentylmethyl ether and 1,2-dimethoxy. Ether solvents such as ethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, 1,4-dioxane, 4-methyltetrahydropyran; methylene chloride, chloroform, mono Halogenized hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene; nitrile solvents such as acetonitrile and benzonitrile; hydrocarbon solvents such as n-hexane, n-heptane, n-octane, decalin, toluene, xylene and mesitylen; N, An amide solvent such as N-dimethylformamide, N, N-dimethylacetamide; acetone, dimethylsulfoxide, water and the like can be mentioned, preferably an ether solvent and an alcohol solvent, and more preferably an ether solvent.

The ether solvent is preferably dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and more preferably diethylene glycol dimethyl ether.

The amount of the solvent used (volume v: ml) is, for example, 3 times (v / v /) the pure content (mass w: g) of the compound represented by the formula (1) from the viewpoint of the fluidity of the reaction solution. w) or more, preferably 5 times (v / w) or more, and more preferably 10 to 25 times (v / w) or more.

The solvent used in this reaction preferably contains an ether solvent and / or an alcohol solvent as a main component, and the content of the solvent and / or alcohol solvent in the total solvent is usually 80% by volume or more, preferably 80% by volume or more. Is 90% by volume or more, more preferably 95% by volume or more, and particularly preferably 98% by volume or more.

This reaction can be carried out by mixing the solvent described above, the compound represented by the formula (1), the compound represented by the formula (4), the silver compound, and if necessary, a base. The order in which the components are added to the reaction system is not particularly limited, and may be any order.

The silver compound used in this reaction is, for example, preferably silver trifluoromethanesulfonate, silver trifluoroacetate, or the like, and more preferably silver trifluoromethanesulfonate.

This reaction may or may not use a base, but a base is preferably used. The base used may be either an organic base or an inorganic base, but is preferably an organic base. Examples of the organic base include ammonia, triethylamine, 2,6-lutidine and the like, and 2,6-lutidine is preferable.

Preferred embodiments of the iridium complex represented by the formula (5) include the following.
R ^{3 to} R ⁸ are hydrogen atom, halogen atom, alkyl group, cycloalkyl group, aryl group, arylalkyl group, substituted amino group, monovalent heterocyclic group, dendron (these groups have substituents). It may be). Further, R ^{5 to} R ⁸ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, a monovalent heterocyclic group, and a dendron (these groups may have a substituent). Is preferable.

Further, ^{two adjacent groups of R 3} to R ⁸ may be bonded to each other to form a ring together with a carbon atom to which each is bonded (the formed ring may further have a substituent). good. Further, ^{two adjacent groups of R 5 to} R ⁸ may be bonded to each other to form a ring together with the carbon atom to which each is bonded (the formed ring may further have a substituent). good.

One of R ¹ and R ² is preferably a halogen atom, an alkyl group, or a group represented by the formula (3), and more preferably a halogen atom or a group represented by the formula (3). It is more preferable that the group is represented by the formula (3). The other of R ¹ and R ² is preferably a hydrogen atom.

It is preferable ^{that R 2} is a halogen atom, an alkyl group, or a group represented by the formula (3), and R ¹ is a hydrogen atom. It is more preferable that R ² is a halogen atom or a group represented by the formula (3) and R ^{1 is a hydrogen atom.} It is particularly preferable that R ² is a group represented by the formula (3) and R ^{1 is a hydrogen atom.}

The halogen atom is preferably a chlorine atom or a bromine atom, and more preferably a bromine atom.

The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. The alkyl group may be either linear or branched.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 5 to 10 carbon atoms.

In the group represented by the formula (3), two or more A's may be = N-, or all A's may be = CH- and the = CH- may have a substituent. preferable. Further, it is particularly preferable that all A's are = N− or all A's are = CH− and the = CH− may have a substituent.

R ^{13 to} R ¹⁸ are hydrogen atom, halogen atom, alkyl group, cycloalkyl group, aryl group, arylalkyl group, substituted amino group, monovalent heterocyclic group and dendron (these groups have substituents). It may be). Further, R ^{15 to} R ¹⁸ are hydrogen atom, halogen atom, alkyl group, aryl group, arylalkyl group, monovalent heterocyclic group and dendron (these groups may have a substituent). Is preferable.

Further, ^{two adjacent groups of R 13 to} R ¹⁸ may be bonded to each other to form a ring together with a carbon atom to which each is bonded (the formed ring may further have a substituent). good. Further, ^{two adjacent groups of R 15 to} R ¹⁸ may be bonded to each other to form a ring together with the carbon atom to which each is bonded (the formed ring may further have a substituent). good.

［式中、
Ａ^１は、＝ＣＨ−又は＝Ｎ−を表し、Ａ^１が＝ＣＨ−である場合は置換基を有していてもよく、Ａ^１が＝Ｎ−である場合は２つ以上のＡ^１が＝Ｎ−である。複数存在するＡ^１は、同一でも異なっていてもよい。
Ｒ^１９及びＲ^２０は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールアルキニル基、置換カルボキシル基、シアノ基、又はデンドロンを表し、これらの基は置換基を有していてもよい。］ One of R ¹¹ and R ¹² is preferably a halogen atom, an alkyl group, or a group represented by the formula (6), and more preferably a halogen atom or a group represented by the formula (6). It is more preferable that the group is represented by the formula (6). The other of R ¹¹ and R ¹² is preferably a hydrogen atom.

[During the ceremony,
A ¹ is, = CH- or = N- and represents, when ^{A 1} is = a CH- may have a substituent, and when ^{A 1} is = N- two or more of ^{A 1} Is = N-. A plurality of A ^1s may be the same or different.
R ¹⁹ and R ²⁰ are independently hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl. Group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent It represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron, and these groups may have a substituent. ]

It is preferable ^{that R 12} is a halogen atom, an alkyl group, or a group represented by the formula (6), and R ¹¹ is a hydrogen atom. It is more preferable that R ¹² is a halogen atom or a group represented by the formula (6), and R ^{11 is a hydrogen atom.} It is particularly preferable that R ¹² is a group represented by the formula (6) and R ^{11 is a hydrogen atom.}

The halogen atom is preferably a chlorine atom or a bromine atom, and more preferably a bromine atom.

The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. The alkyl group may be either linear or branched.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 5 to 10 carbon atoms.

In the group represented by the formula (6), two or more of ^{A 1} is = N- at either, or all of ^{A 1} is = CH- and is the = CH- may be substituted Is preferable. Furthermore, either all of ^{A 1} is = a N-, or all of ^{A 1} is = CH- the = CH- may be may have a substituent group particularly preferred.

In this reaction, the amount of the compound represented by the formula (4) to be used is usually 2 to 20 mol, preferably 2 to 10 mol, based on 1 mol of the compound represented by the formula (1). More preferably, it is 2 to 3 mol.
In this reaction, the amount of the silver compound used is usually 2 to 20 mol, preferably 2 to 10 mol, more preferably 2 to 3 mol, based on 1 mol of the compound represented by the formula (1). Is.
When a base is used in this reaction, the amount of the base used is usually 2 to 20 mol, preferably 2 to 10 mol, more preferably 2 to 10 mol, based on 1 mol of the compound represented by the formula (1). 2-3 mol.

（式中、Ｒ^１、Ｒ^２、Ｒ^６、Ｒ^７、Ｒ^１１、Ｒ^１２、Ｒ^１６、及びＲ^１７は、前記に同じ。） A preferred embodiment of the iridium complex represented by the formula (5), include an iridium complex represented by the formula (1C), as the more preferred embodiment, the iridium complex represented by the formula (1C) is R ¹ This is the case of = R ¹¹ , R ² = R ¹² , R ⁶ = R ¹⁶ , and R ⁷ = R ¹⁷ .

(In the formula, R ¹ , R ² , R ⁶ , R ⁷ , R ¹¹ , R ¹² , R ¹⁶ and R ¹⁷ are the same as described above.)

Specific examples of the metal complex represented by the above formula (1C) include the following metal complexes.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples, and the value of high performance liquid chromatography (HPLC) area percentage is used as an index of the purity of the compound. .. Unless otherwise specified, this value is a value at UV = 254 nm by HPLC (manufactured by Shimadzu Corporation, trade name: LC-20A). At this time, the compound to be measured was dissolved in toluene or chloroform so as to have a concentration of 0.01 to 0.2% by mass, and 1 to 10 μL was injected into HPLC depending on the concentration. For the mobile phase of HPLC, the ratio of acetonitrile / tetrahydrofuran was changed from 100/0 to 0/100 (volume ratio), and the flow rate was 1.0 mL / min. As the column, SUMIPAX ODS Z-CLUE (manufactured by Sumika Chemical Analysis Service) or an ODS column having equivalent performance was used. A photodiode array detector (manufactured by Shimadzu Corporation, trade name: SPD-M20A) was used as the detector.

<Synthesis Example 1> (Compound L-1)
Compound L-1, which will be described later, was synthesized according to the method described in JP-A-2016-64998.

<Synthesis Example 2> (Compound L-2)
Compound L-2a (5-bromo-2- (4-tert-butylphenyl) pyridine) was synthesized according to the method described in Japanese Patent No. 5128728. Compound L-2b (4,5,5-tetramethyl-2- (2'-methyl-4,4''-bis (2,4,5-trimethylpentan-2-yl)-[1,1 ': 3', 1''-terphenyl] -5-yl) -1,3,2-dioxaborolane) was synthesized according to the method described in JP-A-2014-224101.

Compound L-2a (14.8 g, 51.2 mmol), compound L-2b (31.3 g, 52.7 mmol), tetrakistriphenylphosphine palladium (0.230 g, 1.02 mmol), 40% by mass in a reaction vessel. An aqueous solution of tetrabutylammonium hydroxide (132 g, 205 mmol) and toluene (148 mL) were weighed and stirred at 85 ° C. for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the liquid was separated and the organic layer was recovered. Ion-exchanged water was added to the organic layer, washing with water was repeated until the pH reached 8, dried over anhydrous magnesium sulfate, activated carbon (2.97 g) was added, and the mixture was stirred for 30 minutes. The obtained mixed solution was filtered through silica gel Celite, washed with toluene, and then concentrated to dryness. Toluene (59.4 ml) was added to the concentrated residue, and the mixture was dissolved by heating at 75 ° C. After adjusting the temperature to 55 ° C., acetonitrile (178 ml) was added dropwise, and the mixture was stirred for 1 hour and then cooled to 0 ° C. The precipitated white solid was collected by filtration, washed with a mixed solvent of toluene: acetonitrile (1: 3), and dried to obtain crude crystals. Toluene (125 ml) was added to the obtained crude crystals, and the mixture was heated and dissolved at 75 ° C. After adjusting the temperature to 55 ° C., acetonitrile (376 ml) was added dropwise, and the mixture was kept warm at 55 ° C. for 1 hour and then cooled to 0 ° C. The precipitated white solid was collected by filtration, washed with a mixed solvent of toluene: acetonitrile (1: 3), and dried to give compound L-2 (30.4 g, 44.8 mmol) in a yield of 88%.
_{^{1 H-NMR (CDCl 3,}} 300MHz): δ (ppm) = 0.75 (s, 18H), 1.37 (s, 9H), 1.44 (s, 12H), 1.77 (s, 4H ), 2.14 (s, 3H), 7.31-7.51 (m, 12H), 7.76 (d, 1H), 7.95-8.00 (m, 3H), 8.96 ( d, 1H)))

<Synthesis Example 3> (Compound L-3)
As the compound L-3a (5-bromo-2-phenylpyridine), a commercially available reagent (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. Compound L-3b was synthesized according to the method described in JP-A-2011-195829.

In a reaction vessel, compound L-3a (12.8 g, 54.6 mmol), compound L-3b (30.7 g, 65.5 mmol), potassium phosphate (20.9 g, 98.3 mmol), bis (triphenylphosphine). ) Palladium dichloride (38.3 mg, 0.0546 mmol), ion-exchanged water (19.2 ml), n-butanol (94.6 ml), and toluene (29.4 mL) were weighed and weighed in a nitrogen atmosphere for 3 hours. The mixture was stirred at 80 ° C. After cooling to room temperature, toluene (76.7 ml) was added to the reaction solution, and the mixture was stirred and separated to recover the organic layer. Ion-exchanged water (25.6 ml) was added to the organic layer, and after stirring and liquid separation, the organic layer was concentrated. Toluene (162.6 ml) was added to the concentrated residue and dissolved by heating. N-Heptane (65.0 ml) was added dropwise to this solution, and the mixture was cooled to room temperature. The precipitated white solid was collected by filtration, washed with n-heptane, and dried to give compound L-3 (11.72 g, 24.8 mmol).
^{1 1} H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 1.39 (s, 18H), 7.44-7.55 (m, 7H), 7.63-7.67 (m, 4H) , 7.79 (d, 2H), 7.83-7.86 (m, 2H), 8.03-8.10 (m, 3H), 9.03 (dd, 1H)

<Synthesis Example 4> (Compound L-4)
Compound L-4 was synthesized according to the method described in JP2012-36388A.

<Synthesis Example 5> (Compound CL-1)
Compound CL-1 was synthesized according to the method described in Japanese Patent Application Laid-Open No. 2012-131995.

(Compound L-6)
As the compound L-6 (2,6-diphenylpyridine), a commercially available reagent (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

(Compound L-7)
As the compound L-7 (2-methyl-6-phenylpyridine), a commercially available reagent (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

(Compound L-8)
As the compound L-8 (5-methyl-2-phenylpyridine), a commercially available reagent (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

(Compound L-9)
As the compound L-9 (2-bromo-6-phenylpyridine), a commercially available reagent (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

(Compound L-11)
As the compound L-11 (4-bromo-2-phenylpyridine), a commercially available reagent (manufactured by AstaTech) was used.

<Example 1> (Synthesis of compound M-1 without addition of water)
Compound L-1 (3.14 g, 3.73 mmol), iridium chloride n hydrate (0.619 g, 1.67 mmol), and 2-ethoxyethanol (41.7 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 150 ° C. (inside temperature of 132 ° C.). The water content at the start of the reaction was 0.3% by mass. The reaction stopped 40 minutes after the reaction started. The LC analysis value of compound M-1 at 40 minutes was 60% (area percentage value).

The reaction solution was sampled twice or more at 10-minute intervals and analyzed by liquid chromatography (LC), and the time when the change in the LC area percentage value of the iridium binuclear complex disappeared was determined to be the time when the reaction was completed (stopped). did.

<Example 2> (Synthesis of compound M-1 without addition of water)
Compound L-1 (0.940 g, 1.12 mmol), iridium chloride n hydrate (0.180 g, 0.500 mmol), and 2-butoxyethanol (12.5 mL) were weighed into a reaction vessel, and a nitrogen stream was added. Below, it was heated at an outside temperature of 150 ° C. The water content at the start of the reaction was 0.3% by mass. The reaction stopped 50 minutes after the reaction started. The LC analysis value of compound M-1 at 50 minutes was 71% (area percentage value).

The reaction solution is sampled twice or more at intervals of 10 to 40 minutes and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium dikaryon complex disappears. I decided.

<Comparative Example 1> (Synthesis of compound M-1 by water addition)
In a reaction vessel, compound L-1 (6.25 g, 7.44 mmol), iridium chloride n hydrate (1.24 g, 3.35 mmol), 2-ethoxyethanol (83.3 mL), and water (13.3 mL). ) Was weighed and heated at an outside temperature of 150 ° C. (inside temperature of 109 ° C.) under a nitrogen stream. The water content at the start of the reaction was 13.8% by mass. The reaction was not completed 48 hours after the start of the reaction. The LC analysis value of compound M-1 at 48 hours was 29% (area percentage value).

Sampling was performed at intervals of 3.5 to 15 hours.

<Example 3> (Synthesis of compound M-2 without addition of water)
Compound L-2 (2.00 g, 2.95 mmol), iridium chloride n hydrate (0.495 g, 1.34 mmol), and 2-ethoxyethanol (12.0 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 152 ° C. (inside temperature of 130 ° C.). The water content at the start of the reaction was 0.6% by mass. The reaction was stopped 1.5 hours after the start of the reaction. The LC analysis value of compound M-2 at 1.5 hours was 82% (area percentage value).
The reaction solution is sampled twice or more at intervals of 15 to 30 minutes and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium dikaryon complex disappears. I decided.

<Example 4> (Synthesis of compound M-3 without addition of water)
Compound L-3 (0.943 g, 1.86 mmol), iridium chloride n hydrate (0.31 g, 0.837 mmol), and 2-ethoxyethanol (17.5 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 150 ° C. (inside temperature of 135 ° C.). The water content at the start of the reaction was 0.3% by mass. The reaction was stopped 1 hour after the start of the reaction. The LC analysis value of compound M-3 at 1 hour was 68% (area percentage value).

The reaction solution is sampled twice or more at intervals of 15 to 30 minutes and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium dikaryon complex disappears. I decided.

<Example 5> (Synthesis of compound M-4 without addition of water)
Compound L-4 (2.13 g, 4.27 mmol), iridium chloride n hydrate (0.686 g, 1.92 mmol), and 2-ethoxyethanol (17.2 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 150 ° C. The water content at the start of the reaction was 0.6% by mass. The reaction stopped 35 minutes after the reaction started. The LC analysis value of compound M-4 at 35 minutes was 78% (area percentage value).

The reaction solution is sampled twice or more at intervals of 25 to 30 minutes and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium dikaryon complex disappears. I decided.

<Example 6> (Synthesis of compound M-4 without addition of water)
In a reaction vessel, weigh compound L-4 (2.13 g, 4.27 mmol), iridium chloride n hydrate (0.686 g, 1.92 mmol), and 2-butoxyethanol (17.2 mL), and add a nitrogen stream. Below, it was heated at an outside temperature of 150 ° C. The water content at the start of the reaction was 0.6% by mass. The reaction stopped 35 minutes after the reaction started. The LC analysis value of compound M-4 at 35 minutes was 74% (area percentage value).

The reaction solution is sampled twice or more at intervals of 25 to 30 minutes and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium dikaryon complex disappears. I decided.

<Example 7> (Synthesis of compound M-4 without addition of water)
Compound L-4 (1.85 g, 3.72 mmol), iridium chloride n hydrate (0.619 g, 1.67 mmol), and carbitol (15.0 mL) were weighed in a reaction vessel and placed under a nitrogen stream. It was heated at an outside temperature of 150 ° C. (inside temperature of 132 ° C.). The water content at the start of the reaction was 0.7% by mass. The reaction stopped 10 minutes after the reaction started. The LC analysis value of compound M-4 at 10 minutes was 76% (area percentage value).

The reaction solution was sampled twice or more at 10-minute intervals and analyzed by liquid chromatography (LC), and the time when the change in the LC area percentage value of the iridium binuclear complex disappeared was determined to be the time when the reaction was completed (stopped). did.

<Example 8> (Synthesis of compound M-6 without addition of water)
Compound L-6 (1.00 g, 4.33 mmol), iridium chloride n hydrate (0.720 g, 1.95 mmol), and 2-ethoxyethanol (40.7 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 156 ° C. (inside temperature of 133 ° C.). The water content at the start of the reaction was 0.4% by mass. The reaction was stopped 1 hour after the start of the reaction. The LC analysis value of compound M-6 at 1 hour was 24% (area percentage value).
The reaction solution is sampled twice or more at intervals of 15 to 30 minutes and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium dikaryon complex disappears. I decided.

<Example 9> (Synthesis of compound M-7 without addition of water)
Compound L-7 (0.98 g, 5.79 mmol), iridium chloride n hydrate (0.779 g, 2.61 mmol), and 2-ethoxyethanol (54.5 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 150 ° C. (inside temperature of 118 ° C.). The water content at the start of the reaction was 0.4% by mass. The reaction stopped 45 minutes after the reaction started. The LC analysis value of compound M-7 at 45 minutes was 22% (area percentage value).
The reaction solution is sampled twice or more at intervals of 15 to 30 minutes and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium dikaryon complex disappears. I decided.

<Example 10> (Synthesis of compound M-8 without addition of water)
Compound L-8 (0.98 g, 5.79 mmol), iridium chloride n hydrate (0.779 g, 2.61 mmol), and 2-ethoxyethanol (54.5 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 152 ° C. (inside temperature of 132 ° C.). The water content at the start of the reaction was 0.4% by mass. The reaction was stopped 1 hour after the start of the reaction. The LC analysis value of Compound M-8 at 1 hour was 39% (area percentage value).
The reaction solution is sampled twice or more at intervals of 15 to 30 minutes and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium dikaryon complex disappears. I decided.

<Example 11> (Synthesis of compound M-9 without addition of water)
Compound L-9 (1.00 g, 4.28 mmol), iridium chloride n hydrate (0.713 g, 1.93 mmol), and 2-ethoxyethanol (40.3 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 157 ° C. (inside temperature of 130 ° C.). The water content at the start of the reaction was 0.3% by mass. The reaction was stopped 1 hour after the start of the reaction. The LC analysis value of Compound M-9 at 1 hour was 48% (area percentage value).
The reaction solution is sampled twice or more at intervals of 15 to 30 minutes and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium dikaryon complex disappears. I decided.

<Example 12> (Synthesis of compound M-10 without addition of water)
Compound L-3a (1.00 g, 4.28 mmol), iridium chloride n hydrate (0.713 g, 1.93 mmol), and 2-ethoxyethanol (40.3 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 154 ° C. (inside temperature of 133 ° C.). The water content at the start of the reaction was 0.3% by mass. The reaction was stopped 3 hours after the start of the reaction. The LC analysis value of compound M-10 at 2 hours was 82% (area percentage value).
The reaction solution is sampled twice or more at intervals of 1 to 2 and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium binuclear complex disappears. I decided.

<Example 13> (Synthesis of compound M-11 without addition of water)
Compound L-11 (0.93 g, 3.96 mmol), iridium chloride n hydrate (0.659 g, 1.78 mmol), and 2-ethoxyethanol (37.2 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 151 ° C. (inside temperature of 137 ° C.). The water content at the start of the reaction was 0.3% by mass. The reaction was stopped 1.5 hours after the start of the reaction. The LC analysis value of compound M-11 at 1.5 hours was 54% (area percentage value).
The reaction solution is sampled twice or more at intervals of 1 to 2 and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium binuclear complex disappears. I decided.

<Example 14> (Synthesis of compound M-1 without addition of water)
Compound L-1 (3.14 g, 3.73 mmol), iridium chloride n hydrate (0.619 g, 1.67 mmol), and carbitol (41.7 mL) were weighed in a reaction vessel and placed under a nitrogen stream. It was heated at an outside temperature of 203 ° C. (inside temperature of 191 ° C.). The water content at the start of the reaction was 0.3% by mass. The reaction stopped within 1 minute after the reaction started. The LC analysis value of compound M-1 immediately after the start of the reaction was 66% (area percentage value).
The reaction solution was sampled twice or more at 15-minute intervals and analyzed by liquid chromatography (LC), and the time when the change in the LC area percentage value of the iridium binuclear complex disappeared was determined to be the time when the reaction was completed (stopped). did.

<Example 15> (Synthesis of compound M-1 without addition of water)
Compound L-1 (3.14 g, 3.73 mmol), iridium chloride n hydrate (0.619 g, 1.67 mmol), and 2-methoxyethanol (41.7 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 154 ° C. (inside temperature of 125 ° C.). The water content at the start of the reaction was 0.3% by mass. The reaction was stopped 1 hour after the start of the reaction. The LC analysis value of compound M-1 at 1 hour was 60% (area percentage value).
The reaction solution was sampled twice or more at intervals of 15 to 30 minutes and analyzed by liquid chromatography (LC), and the reaction was terminated (stopped) when the change in the LC area percentage value of the iridium dikaryon complex disappeared. I decided it was time.

<Comparative Example 2> (Synthesis of compound CM-1 without addition of water)
Compound CL-1 (1.85 g, 0.37 mmol), iridium chloride n hydrate (0.618 g, 1.67 mmol), and 2-ethoxyethanol (35.0 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 150 ° C. (inside temperature of 135 ° C.). The water content at the start of the reaction was 0.3% by mass. The reaction was stopped 4 hours after the start of the reaction. The LC analysis value (UV = 264 nm) of the compound CM-1 at 4 hours was 54% (area percentage value).

The reaction solution is sampled twice or more at intervals of 25 to 60 minutes and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium dikaryon complex disappears. I decided.

<Comparative Example 3> (Synthesis of compound CM-1 by water addition)
Iridium chloride n hydrate (1.00 g, 2.71 mmol) and water (9.00 mL) were weighed in a reaction vessel and heated to 60 ° C. under a nitrogen stream. After confirming the dissolution of iridium chloride, an aqueous solution of iridium chloride was prepared by cooling to room temperature. In another reaction vessel, weigh compound CL-1 (2.99 g, 6.04 mmol), 2-ethoxyethanol (70.0 mL), and ion-exchanged water (5.00 mL), and under a nitrogen stream, the above-mentioned chloride. The iridium aqueous solution was added dropwise over 1 hour under the condition of an internal temperature of 100 ° C. The water content at the end of the dropping was 17.1% by mass. After completion of the dropping, heating was continued at an outside temperature of 115 ° C. (inside temperature of 105 ° C.), and the reaction was stopped in 14 hours. The LC analysis value (UV = 264 nm) of the compound CM-1 at 14 hours was 82% (area percentage value).

The reaction solution is sampled twice or more at intervals of 2 to 3 hours and analyzed by liquid chromatography (LC). When the reaction ends (stops) when the change in the LC area percentage value of the iridium binuclear complex disappears. I decided.

<Example 16> (Synthesis of compound T-1)
Compound L-1 (6.28 g, 7.47 mmol), iridium chloride n hydrate (1.24 g, 3.35 mmol), and 2-ethoxyethanol (83.3 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 154 ° C. (inside temperature of 134 ° C.). The water content at the start of the reaction was 0.3% by mass. The reaction stopped 45 minutes after the reaction started. The LC analysis value of compound M-1 at 45 minutes was 58% (area percentage value).
After completion of the reaction, the reaction mixture was cooled to room temperature and methanol (23 ml) was added dropwise. The precipitated crystals were filtered, washed with methanol (16 ml), and dried under reduced pressure to obtain crude crystals (6.15 g). The obtained crude crystals were purified by silica gel chromatography (toluene: normal heptane = 1: 1) to obtain compound M-1 (3.90 g) in a yield of 61%.
^{1 1} H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 1.35 (s, 72H), 2.15 (s, 12H), 6.02 (d, 4H), 6.66 (d, 4H) ), 6.86 (dd, 4H), 7.03 (d, 4H), 7.11-7.57 (m, 80H), 8.44-8.48 (m, 12H), 9.26- 9.28 (m, 8H), 11.1 (d, 4H)

In a reaction vessel, compound M-1 (0.601 g, 1.58 mmol), compound L-1 (0.278 g, 3.31 mmol), AgOTf (0.109 g, 4.25 mmol), 2,6-lutidine (0). .0456 g (4.25 mmol) and jiglime (12.0 mL) were weighed and heated at an outside temperature of 158 ° C. (inside temperature: 151 ° C.) for 8 hours under a nitrogen stream. The reaction mixture was cooled to room temperature, methanol (27 ml) was added dropwise, and the mixture was stirred for 1 hour. The precipitated crystals were filtered, washed with methanol (4 ml), the obtained crude crystals were dissolved in toluene (14 ml), and silica gel Celite filtration was performed. The solid obtained after concentration to dryness was purified by silica gel chromatography (toluene: normal heptane = 7: 3) to obtain compound T-1 (0.42 g) in a yield of 76%.
^{1 1} H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 1.36 (s, 54H), 2.16 (s, 9H), 7.11-7.44 (m, 48H), 7.55 (S, 6H), 7.73 (m, 12H), 7.99-8.09 (m, 12H), 8.57 (dd, 3H), 8.79 (d, 6H), 9.93 ( dd, 3H)

<Example 17> (Synthesis of compound T-2)
Compound L-2 (2.66 g, 3.92 mmol), iridium chloride n hydrate (0.656 g, 1.85 mmol), and 2-ethoxyethanol (16.0 mL) were weighed into a reaction vessel, and a nitrogen stream was used. Below, it was heated at an outside temperature of 150 ° C. (inside temperature of 130 ° C.). The water content at the start of the reaction was 0.7% by mass. The reaction was stopped 1 hour after the start of the reaction. The LC analysis value of compound M-2 at 1 hour was 84% (area percentage value).
After completion of the reaction, the reaction mixture was cooled to room temperature and ion-exchanged water (5.33 ml) was added dropwise. The precipitated crystals were filtered, washed with methanol (8.00 ml), and dried under reduced pressure to obtain crude crystals. The obtained crude crystals were dissolved in toluene (13.3 ml) and washed with water repeatedly until the pH reached 7. The organic layer was dehydrated with magnesium sulfate (1.60 g), filtered through silica gel Celite, washed with toluene, and the organic solvent was distilled off under reduced pressure. Dichloromethane (11.2 ml) was added to the obtained concentrated residue, dissolved by heating at 50 ° C., and then methanol (13.8 ml) was added dropwise at 40 ° C. After keeping warm at 40 ° C. for 1 hour, the mixture was cooled to 25 ° C., and the precipitated crystals were collected by filtration and washed with a mixed solvent of dichloromethane and methanol (2: 1). The obtained crystals were dried under reduced pressure to obtain Compound M-2 (2.57 g) in a yield of 91%.
_{^{1 H-NMR (CDCl 3,}} 300MHz): δ (ppm) = 0.77 (s, 72H), 0.88 (s, 36H) 1.47 (s, 24H), 1.50 (s, 24H) 1.77 (d, 8H), 1.84 (s, 8H), 2.13 (s, 12H), 5.99 (d, 4H), 6.73 (dd, 4H), 6.93 ( d, 4H), 6.96 (s, 8H), 7.06 (d, 4H), 7.23 (d, 16H), 7.32 (dd, 4H), 7.43 (d, 16H), 9.80 (d, 4H)

In a reaction vessel, compound M-2 (2.00 g, 0.632 mmol), compound L-2 (1.07 g, 1.58 mmol), AgOTf (0.357 g, 1.39 mmol), 2,6-lutidine (0). .169 g, 1.58 mmol) and jiglime (30.0 mL) were weighed and heated at an outside temperature of 107 ° C. (inside temperature of 102 ° C.) for 6 hours under a nitrogen stream. The reaction mixture was cooled to room temperature, acetonitrile (18.0 ml) was added dropwise, and the precipitated crystals were filtered and washed with acetonitrile (12.0 ml). The obtained crude crystals were dissolved in toluene (40 ml), filtered through silica gel Celite, washed with toluene (16.0 ml), and concentrated to dryness. Toluene (4.20 ml) was added to the concentrated residue, and the mixture was dissolved by heating at 40 ° C., and then acetonitrile (2.00 ml) was added dropwise at 35 ° C. After keeping warm at 35 ° C. for 1 hour, acetonitrile (4.60 ml) was further added dropwise, and the mixture was stirred for 30 minutes. After cooling to 0 ° C., the precipitated crystals are filtered, washed with a mixed solvent of toluene and acetonitrile (1: 1.6), and dried under reduced pressure to obtain compound T-2 (2.26 g) in a yield of 81%. Obtained.
^{1 1} H-NMR (CDCl ₃ , 300 MHz): δ (ppm) = 0.75 (s, 54H), 1.13 (s, 27H), 1.38 (s, 18H), 1.39 (s, 18H) ), 1.76 (s, 12H), 1.94 (s, 9H), 6.91-6.95 (m, 9H), 7.09-7.11 (m, 15H), 7.33 ( d, 12H), 7.43 (dd, 3H), 7.51 (d, 3H), 7.58 (d, 3H), 7.74 (d, 3H)

The following points were clarified from Examples 1 to 17 and Comparative Examples 1 to 3.

^{When a compound having a substituent at the position of R 2 in} the formula (2) (Compound L-1) was used as the ligand, the reaction completion time was as short as less than 1 hour when the alkoxy alcohol was used as the solvent. On the other hand, when alkoxy alcohol and water were used as the solvents, the internal temperature did not rise, so the reaction was not completed even after 48 hours (Comparative Example 1).

^{When a compound having no substituent at the position of R 2 in} the formula (2) (Compound CL-1) is used as the ligand, the internal temperature rises to 135 ° C. when alkoxyalcohol is used as the solvent. The reaction completion time was 4 hours (Comparative Example 2). On the other hand, when alkoxyalcohol and water were used as the solvent, the reaction completion time was 14 hours because the internal temperature did not rise (Comparative Example 3).

^{When compounds having a substituent at the position of R 2 in} the formula (2) (Compound L-3 and Compound L-4) were used as the ligand, and when alkoxy alcohol was used as the solvent, the reaction completion time was achieved. Was as short as 2 hours or less.

These results, iridium chloride with a compound having a substituent at the position of R ² of formula (2) as a ligand, alkoxyalkyl alcohol, by reaction without addition of water, in the formula (1) It was found that the reaction completion time in the production of the represented iridium binuclear complex can be significantly shortened.

According to the production method of the present invention, the reaction time for synthesizing an iridium binuclear complex, which is a synthetic intermediate of a light emitting material (iridium complex) used for a light emitting layer of an organic electroluminescence element, can be significantly shortened.

Claims (10)

A method for producing an iridium binuclear complex represented by the formula (1), wherein iridium chloride is reacted with a compound represented by the formula (2) in an alkoxy alcohol without adding water. A characteristic manufacturing method.

[In equations (1) and (2),
R ^{1 to} R ⁸ are independently hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl. Group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent It represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron, and these groups may have a substituent. Two adjacent groups of R ^{3 to} R ⁸ may be bonded to each other to form a ring together with a carbon atom to which each is bonded, and the ring may have a substituent.
However, ^{at least one of R 1} and R ² is a halogen atom, an alkyl group, or the formula (3):

It is a group represented by.
A represents = CH- or = N-, and if A is = CH-, it may have a substituent, and if A is = N-, two or more A's are = N-. Is. A plurality of A's may be the same or different.
R ⁹ and R ¹⁰ are independently hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl. Group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent It represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron, and these groups may have a substituent. ] At ^{least one of R 5 to} R ⁸ is a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy. Group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, The production method according to claim 1, which is a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron. The ^{first or second claim, wherein two adjacent groups of R 5 to} R ⁸ are bonded to each other to form a ring together with a carbon atom to which each is bonded, and the ring may have a substituent. Manufacturing method. The production method according to any one of claims 1 to 3, wherein one of R ¹ and R ² is a halogen atom, an alkyl group, or a group represented by the formula (3). The production method according to any one of claims 1 to 4, wherein R ² is a halogen atom, an alkyl group, or a group represented by the formula (3). The production method according to any one of claims 1 to 5, wherein R ^{2 is a group represented by the formula (3).} The production method according to any one of claims 1 to 6, wherein A is all = N-, or all = CH-, and the = CH- may have a substituent. The production method according to any one of claims 1 to 7, wherein the alkoxy alcohol is an alkoxy alcohol having 3 to 12 carbon atoms. The production method according to any one of claims 1 to 8, wherein the internal temperature of the reaction vessel at the time of the reaction is 115 ° C. or higher. A method for producing a compound represented by the formula (5), which is obtained by reacting iridium chloride with a compound represented by the formula (2) in an alkoxyalcohol without adding water. A production method, which comprises reacting the compound represented by (1) with the formula (4).

[In equations (1) and (2),
R ^{1 to} R ⁸ are independently hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl. Group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent It represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron, and these groups may have a substituent. Two adjacent groups of R ^{3 to} R ⁸ may be bonded to each other to form a ring together with a carbon atom to which each is bonded, and the ring may have a substituent.
However, ^{at least one of R 1} and R ² is a halogen atom, an alkyl group, or the formula (3):

It is a group represented by.
A represents = CH- or = N-, and if A is = CH-, it may have a substituent, and if A is = N-, two or more A's are = N-. Is. A plurality of A's may be the same or different.
R ⁹ and R ¹⁰ are independently hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl. Group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent It represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron, and these groups may have a substituent. ]

[In equation (4),
R ^{11 to} R ¹⁸ are independently hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group and arylalkyl. Group, arylalkoxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent complex It represents a ring group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a substituted carboxyl group, a cyano group, or a dendron, and these groups may have a substituent. Two adjacent groups of R ^{11 to} R ¹⁸ may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]

[In formula (5), R ^{1 to} R ⁸ and R ^{11 to} R ¹⁸ are the same as described above. ]