JP2002105055A - Method for manufacturing indium complex or its tautomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an indium complex compound useful as a material for a light emission element, especially various kinds of ortho-matalated complex of indium (III) which are particularly useful, easily in high yield. SOLUTION: A method for manufacturing an ortho-metalated complex of indium (III) using an indium complex having a specific structure or its tautomer as a raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an iridium complex compound useful as a material for a light-emitting element capable of emitting light by converting electric energy into light.

[0002]

2. Description of the Related Art At present, research and development on various display elements are active. Among them, an organic electroluminescence (EL) element has been attracting attention as a promising display element because it can emit light with high luminance at a low voltage. ing. Orthometallated iridium complexes (Ir (pp
y) ₃ : tris-ortho-metallatedC
omeplex of Iridium (III) wit
h 2-Phenylpyridene) has been reported as a green light-emitting device using light emission (Applie).
d Physics Letters 75, 4 (19
99). ).

[0003] Such orthometalated iridium (II
I) Iridium (II
I) Method using acetylacetonate as a raw material (Inor
Ganic Chemistry, 30, 1685 (1
991)), a method using iridium (III) chloride as a raw material (Journal of the American C
chemical Society, 107, 1431
(1985)), etc., all of which have low yields, and all three iridium ligands could be synthesized only in the same manner.

A method using a compound represented by the following general formula (IV) as a raw material has also been reported (Inorganic).
Chemistry, 33, 545 (1994)),
In this method, two different ligands can be introduced into iridium, but in addition to low yield, operability is poor due to the use of a hygroscopic raw material such as silver trifluoromethanesulfonate. All of the synthesis methods have been desired to be improved in that the reaction time is long.

[0005]

An object of the present invention is to provide various orthometallated iridium (II) compounds which are particularly promising among iridium complex compounds useful as materials for light emitting devices.
I) An object of the present invention is to provide a production method capable of easily obtaining a complex at a high yield.

[0006]

According to the present invention, a method for producing an iridium complex having the following constitution and a method for producing a raw material thereof are provided, and the above object of the present invention is achieved. 1. A method for producing an iridium complex represented by the following general formula (I) or a tautomer thereof, comprising using a compound represented by the general formula (II) or a tautomer thereof as a raw material. General formula (I)

[0007]

Embedded image

In the general formula (I), Z ¹¹ , Z ¹² , Z ²¹ and Z ²² each independently represent a group of nonmetallic atoms necessary for forming a 5- or 6-membered ring. The formed ring may have a substituent, and may further form a condensed ring with another ring. L ¹ and L ² each independently represent a single bond or a divalent group. Y ¹ and Y ² each independently represent a nitrogen atom or a carbon atom. When Y ¹ is a nitrogen atom, Q ¹
Represents that the carbon atom and Y ¹ are bonded by a single bond. When Y ¹ is a carbon atom, Q ¹ represents that the carbon atom and Y ¹ are bonded by a double bond. When Y ² is a nitrogen atom, Q ² represents that a carbon atom and Y ² are bonded by a single bond. When Y ² is a carbon atom, Q ² represents that the carbon atom and Y ² are bonded by a double bond. General formula (II)

[0009]

Embedded image

In the general formula (II), Z ¹¹ , Z ¹² , L ¹ , Y ¹ and Q ¹ have the same meaning as in the general formula (I). R ¹ and R ³ each independently represent an aliphatic group, an aromatic group or a heterocyclic group. R ² represents a hydrogen atom or a substituent. However, R ¹ and R ² and R ² and R ³ may be bonded to each other to form a ring. 2. The method according to the above item 1, wherein the compound represented by the general formula (II) or a tautomer thereof is reacted with the compound represented by the general formula (III) or a tautomer thereof. . General formula (III)

[0011]

Embedded image

In the general formula (III), Z ²¹ , Z ²² , Y ² , Q ²
And L ² have the same meaning as in the case of formula (I). 3. A compound represented by the following general formula (IV) or a tautomer thereof is produced from a hexahalide iridium (III) salt or a hexahalide iridium (IV) salt as a raw material, and the compound represented by the produced general formula (IV) A method for producing a compound represented by the general formula (II) or a tautomer thereof, wherein the compound represented by the formula or a tautomer thereof is used as a raw material. General formula (IV)

[0013]

Embedded image

In the general formula (IV), X represents a halogen atom, and Z ¹¹ , Z ¹² , Y ¹ , Q ¹ and L ¹ have the same meanings as in the case of the general formula (I).

[0015]

Embodiments of the present invention will be described below in detail. In the present specification, the aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group and a substituted aralkyl group. The alkyl group may have a branch or may form a ring.
The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 18 carbon atoms. The alkyl part of the substituted alkyl group is the same as the above-mentioned alkyl group.
The alkenyl group may have a branch and may form a ring. The alkenyl group has 2 to 20 carbon atoms.
Is preferable, and it is more preferable that it is 2-18. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. The alkynyl group may have a branch or may form a ring. The alkynyl group preferably has 2 to 20 carbon atoms,
More preferably, it is 18. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. The alkyl moiety of the aralkyl group and the substituted aralkyl group is
The same as the above alkyl group. The aryl part of the aralkyl group and the substituted aralkyl group is the same as the following aryl group. Examples of the substituent of the alkyl portion of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group and the substituted aralkyl group include a halogen atom, cyano, nitro, a heterocyclic group,
-OR ¹¹¹ , -SR ¹¹² , -CO ₂ R ¹¹³ , -NR
¹¹⁴ R ¹¹⁵ , -CONR ¹¹⁶ R ¹¹⁷ , -SO ₂ R ¹¹⁸ and-
SO ₂ NR ¹¹⁹ R ¹²⁰ is included. R ¹¹¹ , R ¹¹² , R ¹¹³ ,
R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ and R
¹²⁰ are each independently a hydrogen atom, an aliphatic group or an aromatic group. Examples of the substituent of the aryl portion of the substituted aralkyl group are the same as the following examples of the substituent of the substituted aryl group.

In the present specification, an aromatic group means an aryl group and a substituted aryl group. These aromatic groups may be condensed with an aliphatic ring, another aromatic ring or a heterocyclic ring. The number of carbon atoms in the aromatic group is preferably from 6 to 40, more preferably from 6 to 30, and even more preferably from 6 to 20. Among them, the aryl group is preferably phenyl or naphthyl, and phenyl is particularly preferable.

The aryl moiety of the substituted aryl group is
It is the same as the reel base. Examples of substituents of substituted aryl groups
Is a halogen atom, cyano, nitro, aliphatic group, heterocycle
Group, -OR¹²¹, -SR¹²², -CO_TwoR^{one two Three}, -NR¹²⁴
R¹²⁵, -CONR ¹²⁶R¹²⁷, -SO_TwoR¹²⁸And -S
O_TwoNR¹²⁹R¹³⁰Is included. R¹²¹, R¹²², R^{one two Three}, R
¹²⁴, R¹²⁵, R¹²⁶, R¹²⁷, R¹²⁸, R¹²⁹And R¹³⁰
Is independently a hydrogen atom, an aliphatic group or an aromatic
Group.

In the present specification, the heterocyclic group has 5 members or
It preferably contains a 6-membered saturated or unsaturated heterocycle.
An aliphatic ring, an aromatic ring, or another heterocyclic ring is fused to a heterocyclic ring.
May be. Examples of heteroatoms in the heterocycle include B, N,
O, S, Se and Te are included. As a heteroatom
Is preferably N, O and S. Heterocycles have free carbon atoms.
(A heterocyclic group is attached to a carbon atom)
And bond). Preferred Heterocyclic Char
The number of elementary atoms is 1 to 40, more preferably 1 to 30
And more preferably 1 to 20. Examples of saturated heterocycles
Has a pyrrolidine ring, a morpholine ring, 2-bora-1,3
-Including a dioxolane ring and a 1,3-thiazolidine ring
It is. Examples of unsaturated heterocycles include imidazole ring, thiazo
Ring, benzothiazole ring, benzoxazole ring,
Benzotriazole ring, benzoselenazole ring, pyridi
Ring, pyrimidine ring and quinoline ring. Complex
The ring group may have a substituent. Examples of substituents include
Logen atom, cyano, nitro, aliphatic group, aromatic group, compound
Ring group, -OR¹³¹, -SR¹³², -CO_TwoR¹³³, -NR
¹³⁴R¹³⁵, -CONR¹³⁶R¹³⁷, -SO_TwoR¹³⁸And-
SO_TwoNR ¹³⁹R¹⁴⁰Is included. R¹³¹, R¹³², R¹³³,
R¹³⁴, R¹³⁵, R¹³⁶, R¹³⁷, R^{1 38}, R¹³⁹And R
¹⁴⁰Are each independently a hydrogen atom, an aliphatic group or an aromatic
Group.

The compounds represented by formulas (I) to (IV) will be described. In the general formula (I), Z ¹¹ ,
Z ¹² , Z ²¹ and Z ²² represent a group of non-metallic atoms necessary for forming a 5- or 6-membered ring. For example, in the case of Z ¹¹ , it represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring together with Y ¹ , Q ¹ and a carbon atom. The five-membered ring or the six-membered ring may have a substituent, and may form a condensed ring with another ring. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, cyano, nitro, —OR ¹¹ , —SR ¹² , and —CO ₂ R
^{13, -OCOR 14, -NR 15 R} 16, -CONR 17 R 18,
_{^{-SO 2 R 19, -SO 2 NR}} 20 R 21, -NR 22 CONR 23
_{^{R 24, -NR 25 CO 2 R}} 26, -COR 27, -NR 28 CO
R ²⁹ or —NR ³⁰ SO ₂ R ³¹ is mentioned. Where R
^{11, R 12, R 13,} R 14, R 15, R 16, R 17, R 18,
R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R
²⁷ , R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ each independently represent
It is a hydrogen atom, an aliphatic group or an aromatic group.

Among them, preferred substituents are a halogen atom, an aliphatic group, an aromatic group, -OR ¹¹ , -SR ¹² , -NR
¹⁵ R ¹⁶ , -SO ₂ R ¹⁹ , -NR ²² CONR ²³ R ²⁴ , -N
R ²⁵ CO ₂ R ²⁶ , —NR ²⁸ COR ²⁹ and —NR ³⁰ SO ₂
R ³¹ ; more preferably, a halogen atom, an aliphatic group, an aromatic group, -OR ¹¹ , -SR ¹² , -NR ¹⁵ R ¹⁶ and -SO ₂ R ¹⁹ ; further more preferably, a halogen atom, an alkyl group A substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group, a phenoxy group, a substituted phenoxy group, a dialkylamino group, and a substituted dialkylamino group; 10 alkyl groups, substituted alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, substituted aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms and carbon atoms 1 to 1
It is a substituted alkoxy group having 0, and most preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms and a substituted alkyl group having 1 to 4 carbon atoms.

The 5- or 6-membered ring formed by Z ¹¹ and Z ²¹ is preferably an aromatic ring or a heteroaromatic ring, for example, a furan ring, a thiophene ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrrole ring. , A pyrazole ring,
Examples include 1,2,3-triazole ring, 1,2,4-triazole ring, selenazole ring, oxadiazole ring, thiadiazole ring, benzene ring, pyridine ring, pyrimidine ring, pyrazine ring and pyridazine ring. Of these, a thiophene ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrrole ring, a pyrazole ring, a benzene ring and a pyridine ring are preferred, a thiazole ring, a pyrrole ring, a benzene ring and a pyridine ring are more preferred, and a benzene ring is most preferred. The 5- or 6-membered ring formed by Z ¹² and Z ²² is preferably a heteroaromatic ring, for example, an imidazole ring, a thiazole ring, an oxazole ring, a pyrrole ring, a pyrazole ring, a 1,2,3-triazole ring,
There are 1,2,4-triazole ring, selenazole ring, oxadiazole ring, thiadiazole ring, pyridine ring, pyrimidine ring, pyrazine ring and pyridazine ring. Of these, an imidazole ring, a thiazole ring, an oxazole ring, a pyrrole ring, a pyrazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, a pyridine ring and a pyrimidine ring are preferable, and an imidazole ring, a thiazole ring, A pyrrole ring, a pyrazole ring, a pyridine ring and a pyrimidine ring are more preferred, and a pyrazole ring and a pyridine ring are more preferred.

L¹And L^TwoRepresents a single bond or a divalent group
You. As the divalent group, for example, -C (R⁴¹) (R⁴²)
-, -N (R⁴³)-, -O-, -P (R⁴⁴)-And-
S-. Where R⁴¹And R⁴²Respectively
Independently represents a hydrogen atom or a substituent;
For example, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group,
Cyano, nitro, -OR⁵¹, -SR⁵², -CO_TwoR⁵³,
-OCOR⁵⁴, -NR⁵⁵R⁵⁶, -CONR⁵⁷R⁵⁸, -S
O_TwoR⁵⁹, -SO_TwoNR⁶⁰R⁶¹, -NR⁶²CONR
⁶³R⁶⁴, -NR⁶⁵CO_TwoR⁶⁶, -COR⁶⁷, -NR⁶⁸C
OR⁶⁹Or -NR⁷⁰SO_TwoR⁷¹Is mentioned. here
And R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷,
R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R
⁶⁶, R⁶⁷, R⁶⁸, R⁶⁹, R⁷⁰And R⁷¹Is German
Specifically, it is a hydrogen atom, an aliphatic group or an aromatic group. R⁴³
Represents an aliphatic group, an aromatic group or a heterocyclic group;
⁴⁴Is an aliphatic group, an aromatic group, a heterocyclic group or -OR⁷²The table
Then R⁷²Represents a hydrogen atom, an aliphatic group or an aromatic group.
You.

Each of L ¹ and L ² is preferably a single bond or —C (R ⁴¹ ) (R ⁴² ) —, more preferably a single bond or —C (R ⁴¹ ) (R ⁴² ) — ⁴¹ and R
⁴² is a hydrogen atom, an aliphatic group or an aromatic group,
Particularly preferably, it is a single bond or —C (R ⁴¹ ) (R ⁴² ) —, wherein R ⁴¹ and R ⁴² are each a hydrogen atom or a group having 1 to 4 carbon atoms.
This is the case of the aliphatic group of

Y ¹ and Y ² each independently represent a nitrogen atom or a carbon atom. When Y ¹ is a nitrogen atom, Q ¹ is
Represents a single bond between a carbon atom and Y ¹ . When Y ¹ is a carbon atom, Q ¹ represents a double bond between the carbon atom and Y ¹ . When Y ² is a nitrogen atom, Q ² represents a single bond between a carbon atom and Y ² . When Y ² is a carbon atom, Q ² is a carbon atom and Y ²
Represents a double bond between

In the general formula (II), Z ¹¹ , Z ¹² , L ¹ ,
Y ¹ and Q ¹ have the same meanings as in formula (I);
¹ and R ³ represent an aliphatic group, an aromatic group or a heterocyclic group, preferably an aliphatic group having 1 to 10 carbon atoms,
Represents an aromatic group of 12 or a heterocyclic group having 1 to 5 carbon atoms,
More preferably, it represents an aliphatic group having 1 to 4 carbon atoms or an aromatic group having 6 to 8 carbon atoms.

R^TwoRepresents a hydrogen atom or a substituent;
Examples of substituents include Z¹¹, Z¹², Z^{twenty one}And Z^{twenty two}Substituent
Is the same as that shown as an example. Preferred R^TwoIs
Hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocycle
Group, cyano or nitro, more preferably hydrogen
, An aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms
Group, a heterocyclic group having 1 to 5 carbon atoms or cyano
You. The most preferred R ^TwoIs a hydrogen atom.

Z in the general formula (III)^{twenty one}, Z^{twenty two}, L^Two,
Y^TwoAnd Q^TwoIs the same as in the case of the general formula (I)
And Z in the general formula (IV)¹¹, Z¹², L¹, Y¹You
And Q ¹Is the same as in the case of the general formula (I).

X in the general formula (IV) represents a halogen atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

Specific examples of the compounds represented by formulas (I), (II), (III) and (IV) are shown below.
The present invention is not limited to them. In the following specific examples, for example, (I-1) is a specific example of the general formula (I), and (VI-1) is a specific example of the general formula (VI).

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

Next, the manufacturing method will be described in detail.
The method for producing the compound of the general formula (I) of the present invention is represented by the following <Scheme 1>. <Scheme 1>

[0041]

Embedded image

In formulas (I), (II) and (III), Z ¹¹ , Z ¹² , Z ²¹ , Z ²² , L ¹ , L ² , R ¹ , R
² and R ³ are groups as defined above.

The conversion of the compounds of the general formulas (II) and (III) into the compounds of the general formula (I) can be carried out according to the general formula (II)
Compound of the general formula (III)
0 equivalents, preferably 0.8 to 3.0 equivalents, more preferably 0.9 to 1.2 equivalents, without water or as a solvent, water or an amide solvent (N, N-dimethylformamide,
N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, etc.), sulfone solvents (such as sulfolane), sulfoxide solvents (such as dimethyl sulfoxide), ureide solvents (such as teramethylurea), ether solvents (such as dioxane, Alcohol solvents (glycerol, ethylene glycol, 2-methoxyethanol,
2- (2-hydroxyethoxy) ethanol, 2- [2
-(2-hydroxyethoxy) ethoxy] ethanol, etc.), hydrocarbon solvents (n-dodecane, toluene, xylene) or halogen solvents (methylene chloride, chloroform, chlorobenzene, 1,2-dichloroethane, etc.)
Singly or in combination of two or more. Of these, preferably no solvent or a solvent, water, an ether solvent, an alcohol solvent, a hydrocarbon solvent or a halogen solvent is used alone or in combination of two or more,
More preferably glycerol without solvent or as a solvent,
This is the case where ethylene glycol or 2-methoxyethanol is used alone or in combination with water.

The reaction temperature is 25 to 300 ° C., preferably 6
The temperature is 0 to 250C, more preferably 100 to 200C. The reaction time is 5 minutes to 72 hours, preferably 10 minutes to 6 hours.
Time, more preferably 30 minutes to 3 hours. It is also preferable to carry out the reaction under a nitrogen atmosphere or an argon atmosphere.

It is also preferable to use microwave irradiation as an alternative to heating. In this case, the reaction time is preferably 15 seconds to 1 hour, more preferably 1 minute to 30 minutes, and still more preferably 3 minutes to 15 minutes.

The products obtained by these reactions are:
After treatment according to the usual post-treatment of the synthesis reaction, the product can be purified or provided without purification. As a method of the post-treatment, for example, extraction, cooling, crystallization by adding water or an organic solvent, and an operation of distilling off the solvent from the reaction mixture can be performed alone or in combination.
As a purification method, recrystallization, distillation, sublimation, column chromatography or the like can be performed alone or in combination.

The compound represented by the general formula (II) can be synthesized based on the following <Scheme 2>. <Scheme 2>

[0048]

Embedded image

Compounds 1 and 2 in the above scheme, Z ¹¹ , Z ¹² , L ¹ , X,
R ¹ , R ² and R ³ are groups as defined above. Also M
Represents a monovalent cation, and X represents a halogen atom. Compound 1 may be a commercially available product or may be used in Journal.
of Organic Chemistry, 49,
5237 (1984).

The conversion of the M ₃ IrX ₆ or M ₂ IrX ₆ to compounds of general formula (IV) M ₃ IrX ₆ or M ₂ Ir
Compound 1 0.8 to 20 equivalents relative to X _6, preferably 1.0 to 10 equivalents, and more preferably using 1.0 to 3.0 equivalents, using the solvents mentioned solvent-free or <Scheme 1> Can be done. Preferably, water or an ether-based solvent or an alcohol-based solvent is used alone or in combination of two or more as a solvent. More preferably, glycerol, ethylene glycol or 2-methoxyethanol is used alone or as a solvent without water or as a solvent. This is the case when used in combination with.

The reaction temperature is usually 25 to 300 ° C., preferably 80 to 250 ° C., more preferably 100 to 200 ° C.
It is. The reaction time is generally 5 minutes to 72 hours, preferably 10 minutes to 6 hours, more preferably 30 minutes to 3 hours. It is also preferable to carry out the reaction under a nitrogen atmosphere or an argon atmosphere.

It is also preferable to use microwave irradiation as an alternative to heating. In this case, the reaction time is preferably 15 seconds to 2 hours, more preferably 1 minute to 30 minutes, even more preferably 3 minutes to 15 minutes.

The products obtained by these reactions are <
It can be provided after-treatment, purification or without purification by the method described in Scheme 1>.

The conversion of the compound of the general formula (IV) into the compound of the general formula (II) is carried out by using 2.0 to 20 equivalents, preferably 2. 0
The reaction is performed using no solvent or the solvent described in <Scheme 1> using 10 to 10 equivalents, more preferably 2.0 to 3.0 equivalents. Preferably, no solvent or a solvent using water, an ether-based solvent, an alcohol-based solvent, a halogen-based solvent, or a hydrocarbon-based solvent alone or in combination of two or more, more preferably a system using dichloroethane, chloroform, or methylene chloride. It is.

It is preferable to use a base in this reaction. As the base, organic (triethylamine, diazabicycloundecene, etc.), inorganic (sodium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc.), or alcoholate (sodium methoxide, sodium-t-butoxide, Potassium-t-
Butoxide) are preferred, and triethylamine, diazabicycloundecene, sodium methoxide, and potassium-t-butoxide are more preferred. The reaction is usually carried out using 2.0 to 20 equivalents, preferably 2.0 to 10 equivalents, more preferably 2.0 to 3.0 equivalents, of the compound of the formula (IV). The most preferred amount of the base is when 1.0 equivalent is used based on Compound 2.

The reaction temperature is usually 0 to 150 ° C., preferably 10 to 100 ° C., more preferably 25 to 100 ° C. The reaction time is generally 5 minutes to 12 hours, preferably 10 minutes to 6 hours, more preferably 30 minutes to 3 hours. It is also preferable to carry out the reaction under a nitrogen atmosphere or an argon atmosphere.

The products obtained by these reactions are <
According to the method described in Scheme 1>, the compound can be provided after treatment, purification, or without purification.

[0058]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not construed as being limited to Examples.

Example 1 (Example compound (I-1: Inorganic Chem)
issue, 30, 1685 (1991) and Jou.
rnal of the American Chem
Ial Society, vol. 107, 1431
(Synthesis of compound described in (1985))) Synthesis of Exemplified Compound (II-1) 5.22 g of K ₃ IrCl ₆ , 15.5 g of 2-phenylpyridine and 50 ml of glycerol were put into a _three- necked flask, and argon was added. The mixture was stirred for 2 hours while heating the internal temperature at 180 ° C. in an atmosphere. Thereafter, the mixture was cooled until the internal temperature reached 40 ° C., 150 ml of methanol was added, and the mixture was stirred.
After stirring for 1 hour as it was, suction filtration was performed to obtain the desired intermediate (IV-1) as crystals. The crystals obtained earlier, 10.0 g of acetylacetone, chloroform 5 were placed in a three-necked flask.
Then, while stirring at room temperature, 20.1 ml of a 28% methanol solution of sodium methylate was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours, and then 40 ml of saturated saline and 400 ml of water were added.
Extracted. The obtained chloroform layer was washed with saturated saline 30m.
After washing 4 times with a mixed solution of l and 300 ml of water, the solution was dried over anhydrous sodium sulfate and concentrated by a rotary evaporator. The residue thus obtained was purified by silica gel column chromatography to purify the target compound (II-
4.44 g of 1) was obtained (yield 74%). Synthesis of Exemplified Compound (I-1) 6.00 g of Exemplified Compound (II-1) in a three-necked flask,
15.5 g 2-phenylpyridine and 6 glycerol
0 ml was added, and the mixture was stirred for 2 hours while heating the internal temperature to 170 ° C. under an argon atmosphere. Thereafter, the mixture was cooled to an internal temperature of 40 ° C., 150 ml of methanol was added, the mixture was stirred for 1 hour, and the precipitated crystals were filtered by suction. The obtained crystals were purified by silica gel column chromatography to obtain 6.09 g of the desired Exemplified Compound (I-1) (93% yield).

Example 2 (Synthesis of Exemplified Compound (I-2)) Synthesis of Exemplified Compound (II-10) In a three-necked flask, 4.83 g of K ₂ IrCl ₆ , 16.9 g of 2-benzylpyridine, 50 ml of glycerol was added, and the mixture was stirred for 1 hour while heating the internal temperature to 200 ° C. under an argon atmosphere. Thereafter, the mixture was cooled until the internal temperature reached 40 ° C., and 150 ml of methanol was added. After stirring for 1 hour as it is, the crystals obtained by suction filtration were purified by silica gel column chromatography, and the target intermediate (IV
-9) was obtained as crystals. 10. The crystals obtained above, 560 ml of chloroform, and acetylacetone in a three-necked flask.
Then, 20.1 ml of a 28% methanol solution of sodium methylate was added to 20 g of the solution while stirring at room temperature.
Dropped over minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours, and then extracted by adding 40 ml of saturated saline and 400 ml of water. The obtained chloroform layer was washed with saturated saline (300 ml).
After washing four times with a mixed solution of water and 30 ml of water, the solution was dried over anhydrous sodium sulfate and concentrated by a rotary evaporator. The residue thus obtained was purified by silica gel column chromatography to give the desired Exemplified Compound (II-10)
Was obtained (yield 69%). Synthesis of Exemplified Compound (I-2) 6.28 Exemplified Compound (II-10) was placed in a three-necked flask.
g, 15.5 g of 2-phenylpyridine and 63 ml of glycerol, and the internal temperature was 170 ° C. under an argon atmosphere.
And stirred for 15 minutes. After this, the internal temperature becomes 40
After cooling to ℃, chloroform 500 ml, saturated saline 40 ml and water 400 ml were added for extraction. The obtained chloroform layer was washed with 40 ml of saturated saline and 400 m of water.
The mixture was washed four times with 1 liter of the mixture and dried over anhydrous sodium sulfate. This was concentrated by a rotary evaporator, and the obtained residue was purified by silica gel column chromatography to obtain 5.60 g of the desired exemplary compound (I-2) (yield: 82%).

Example 3 (Synthesis of Exemplified Compound (I-3)) Synthesis of Exemplified Compound (II-11) In a three-necked flask, 5.22 g of K ₃ IrCl ₆ , 14.4 g of 1-phenylpyrazole, 25 ml of 2-methoxyethanol and 25 ml of water are added, and 3
The mixture was stirred under reflux with heating for hours. Thereafter, the mixture was cooled until the internal temperature reached 40 ° C., 150 ml of methanol was added, and the mixture was stirred. After stirring for 1 hour as it was, suction filtration was performed to obtain the desired intermediate (IV-5) as crystals. The crystals obtained earlier, 10.0 g of acetylacetone, chloroform 5 were placed in a three-necked flask.
Then, while stirring at room temperature, 20.1 ml of a 28% methanol solution of sodium methylate was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours, and then 40 ml of saturated saline and 400 ml of water were added.
Extracted. The obtained chloroform layer was washed with saturated saline 30m.
After washing 4 times with a mixed solution of l and 300 ml of water, the solution was dried over anhydrous sodium sulfate and concentrated by a rotary evaporator. The residue thus obtained was purified by silica gel column chromatography to purify the target compound (II-1).
4.68 g of 1) was obtained (81% yield). -Synthesis | combination of illustration compound (I-3) 5.78 of illustration compound (II-11) in a three-necked flask.
g, 2- (4-fluorophenyl) pyridine in 17.3
g and glycerol (70 ml), and the mixture was stirred for 15 minutes while heating the internal temperature to 200 ° C. in an argon atmosphere. Thereafter, the internal temperature is cooled to 40 ° C., and methanol 150
Then, the mixture was stirred for 1 hour, and the precipitated crystals were filtered by suction. The obtained crystals were purified by silica gel column chromatography to obtain the desired exemplary compound (I-3).
5.79 g was obtained (89% yield).

Example 4 (Synthesis of Exemplified Compound (I-8)) In a three-necked flask, 6.28 g of Exemplified Compound (II-10), 14.4 g of 1-phenylpyrazole and 60 ml of glycerol were put, and an argon atmosphere was added. The mixture was stirred for 15 minutes while heating the internal temperature to 170 ° C under the following conditions. Thereafter, the mixture is cooled until the internal temperature reaches 40 ° C., and chloroform 500 ml, saturated saline 40 ml, water 400
ml was added for extraction. The obtained chloroform layer was washed four times with a mixed solution of 40 ml of saturated saline and 400 ml of water, and dried over anhydrous sodium sulfate. This was concentrated by a rotary evaporator, and the obtained residue was purified by silica gel column chromatography to obtain 5.17 g of the desired Exemplified Compound (I-8) (77% yield).

Example 5 (Synthesis of Exemplified Compound (I-20)) In a three-necked flask, 6.00 g of Exemplified Compound (II-1), 14.4 g of 1-phenylpyrazole and 60 ml of glycerol were put, and an argon atmosphere was added. The mixture was stirred for 3 hours while heating the internal temperature to 180 ° C under the following conditions. Thereafter, the mixture was cooled to an internal temperature of 40 ° C., 150 ml of methanol was added, the mixture was stirred for 1 hour, and the precipitated crystals were filtered by suction. The obtained crystals were purified by silica gel column chromatography to obtain 5.42 g of the desired exemplified compound (I-20) (yield 84%).

[0064]

According to the production method of the present invention, various orthometallated iridium (III) complexes, which are particularly promising among iridium complex compounds useful as a material for a light emitting device, can be easily obtained in high yield.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 231/12 C07D 231/12 Z 241/12 241/12 249/04 501 249/04 501 277/66 277 / 66 401/04 401/04 405/04 405/04 409/04 409/04 417/04 417/04 C07F 15/00 C07F 15/00 EF term (reference) 4C034 CE03 4C055 AA01 BA02 BA08 BA13 BA16 BA47 BB04 CA01 DA01 DA27 DB02 FA01 GA02 4C063 AA01 BB01 CC62 CC76 CC92 DD12 DD25 EE10 4H050 AB92 WB11 WB14 WB21

Claims (3)

[Claims] 1. Production of an iridium complex represented by the following general formula (I) or a tautomer thereof, wherein the compound represented by the general formula (II) or a tautomer thereof is used as a raw material. Method. General formula (I) In the general formula (I), Z ¹¹ , Z ¹² , Z ²¹ and Z ²² each independently represent a group of non-metallic atoms necessary to form a 5- or 6-membered ring. The formed ring may have a substituent, and may further form a condensed ring with another ring. L
¹ and L ² each independently represent a single bond or a divalent group. Y ¹ and Y ² each independently represent a nitrogen atom or a carbon atom. When Y ¹ is a nitrogen atom, Q ¹ represents a single bond between a carbon atom and Y ¹ . When Y ¹ is a carbon atom, Q ¹
Represents a double bond between a carbon atom and Y ¹ . When Y ² is a nitrogen atom, Q ² represents a single bond between a carbon atom and Y ² . Y
^{When 2} is a carbon atom, Q ² represents a double bond between the carbon atom and Y ² . General formula (II) In the general formula (II), Z ¹¹ , Z ¹² , L ¹ , Y ¹ and Q ¹ are
It has the same meaning as in the case of the general formula (I). R ¹ and R ³ each independently represent an aliphatic group, an aromatic group or a heterocyclic group.
R ² represents a hydrogen atom or a substituent. Where R ¹ and R ²
And R ² and R ³ may combine with each other to form a ring. 2. The compound represented by the general formula (II) or a tautomer thereof is reacted with the compound represented by the general formula (III) or a tautomer thereof. 2. The production method according to 1. General formula (III) In the general formula (III), Z ²¹ , Z ²² , Y ² , Q ² and L ² are
It has the same meaning as in the case of the general formula (I). 3. A compound represented by the following general formula (IV) or a tautomer thereof produced by using a iridium (III) hexahalide salt or an iridium (IV) hexahalide salt as a raw material, A method for producing a compound represented by the general formula (II) or a tautomer thereof, wherein the compound represented by the formula (IV) or a tautomer thereof is used as a raw material. General formula (IV) In the general formula (IV), X represents a halogen atom, Z ¹¹ ,
Z ¹² , Y ¹ , Q ¹ and L ¹ have the same meanings as in the case of the general formula (I).