JP2005325048A - Compound containing metal complex and fluorene compound containing metal complex and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound containing a metal complex and a fluorene compound containing metal complex and to provide a method for producing the same. <P>SOLUTION: The fluorene compound containing metal complex is represented by general formula (1). In the formula X<SP>1</SP>and X<SP>2</SP>are each independently the same or different functional group with halogenous character, R<SP>1</SP>s and R<SP>2</SP>s are each independently the same or different univalent organic group. R<SP>3</SP>and R<SP>4</SP>are each the same or different single bond or divalent organic group. At least one of R<SP>5</SP>and R<SP>6</SP>represents a region of the metal complex and the other represents the region for a univalent organic group or the metal complex and each may be the same or different. n1 is an integer of 0-3, n2 is an integer of 0-3. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a metal complex-containing compound, a metal complex-containing fluorene compound, and a method for producing the same.

  An organic electroluminescence element (hereinafter also referred to as “organic EL element”) can be driven by a DC voltage, is a self-luminous element, has a wide viewing angle, high visibility, and a response speed. Since it has excellent characteristics such as high speed, it is expected as a next-generation display element, and its research is being actively conducted.

The functional organic material constituting the light emitting layer in such an organic EL element is required to have a high light emission luminance. Recently, in order to realize high emission luminance, attempts have been made to use energy of triplet state molecules as an excited state for light emission of the organic EL element. Specifically, according to the organic EL element having such a configuration, it is possible to obtain an external quantum efficiency of 8% exceeding 5%, which was conventionally considered as a limit value of the external quantum efficiency of the organic EL element. Has been reported (for example, see Non-Patent Document 1).
However, since the functional organic material constituting the organic EL element has a low molecular weight, there is a problem that physical durability and thermal durability are small.

“Applied Physics Letters”, 1999, vol. 75, p. 4

The present invention has been made based on the above circumstances, and has been completed as a result of repeated research on monomers for obtaining a functional organic material having excellent luminescent properties and durability. It is an object of the present invention to provide a novel metal complex-containing compound and a metal complex-containing fluorene compound.
Another object of the present invention is to provide a method for producing the novel metal complex-containing fluorene compound as described above.

The metal complex-containing compound of the present invention is characterized in that a metal complex-containing group having a phenylpyridine structure is bonded to an aromatic compound having two halogen functional groups.
In addition, the metal complex-containing fluorene compound of the present invention is characterized by having a structure represented by the following general formula (1).

In the general formula (1), X ¹ and X ² each independently represent a halogenated functional group, and may be the same or different from each other. R ¹ and R ² each independently represent a monovalent organic group, and may be the same or different from each other. R ³ and R ⁴ represent a single bond or a divalent organic group, and may be the same or different from each other. At least one of R ⁵ and R ⁶ represents a metal complex moiety represented by the following general formula (2) or general formula (3), and the other is a monovalent organic group, or the following general formula (2) or general formula The metal complex part shown by (3) is shown, and may be the same or different from each other. n1 is an integer of 0 to 3, and n2 is an integer of 0 to 3.

In the general formula (2), R ⁷ and R ⁸ each independently represent a fluorine atom, an alkyl group or an aryl group, which may be unsubstituted or may form a ring structure, The same or different ones may be used. M represents a divalent to tetravalent metal atom, and L represents an organic ligand. m1 is an integer of 0 to 4, m2 is an integer of 0 to 3, and w is an integer of 1 to 3.

In the general formula (3), R ⁷ and R ⁸ each independently represent a fluorine atom, an alkyl group or an aryl group, which may be unsubstituted or may form a ring structure, The same or different ones may be used. M represents a divalent to tetravalent metal atom, and L represents an organic ligand. m3 is an integer of 0 to 3, m4 is an integer of 0 to 4, and w is an integer of 1 to 3.

The method for producing a metal complex-containing fluorene compound of the present invention is a method for producing the above metal complex-containing fluorene compound,
A phenylpyridine compound represented by the following general formula (4) and a diphenyl compound represented by the following general formula (5) are reacted to obtain an intermediate reaction product (1),
The intermediate reaction product (1) is reacted with a metal complex compound represented by the following general formula (6).

In the general formula (4), X ³ represents a halogen atom. R ⁷ and R ⁸ each independently represent a fluorine atom, an alkyl group or an aryl group, which may be unsubstituted or may form a ring structure and are the same as each other May be different. m1 is an integer of 0 to 4, and m2 is an integer of 0 to 3.

In the general formula (5), X ¹ and X ² each independently represent a halogenated functional group, and may be the same or different from each other. R ¹ and R ² each independently represent a monovalent organic group, and may be the same or different from each other. R ^LV represents a monovalent organic group. n1 is an integer of 0 to 3, and n2 is an integer of 0 to 3.

In the general formula (6), R ¹¹ represents a bidentate chelate ligand having two coordination atoms, M represents a divalent to tetravalent metal atom, and L represents an organic ligand. . w is an integer of 1-3.

The method for producing a metal complex-containing fluorene compound of the present invention is a method for producing the above metal complex-containing fluorene compound,
A phenylpyridine derivative represented by the following general formula (7) and a fluorene derivative represented by the following general formula (8) are reacted to obtain an intermediate reaction product (2-1).
This intermediate reaction product (2-1) is reacted with halogen to obtain an intermediate reaction product (2-2).
The intermediate reaction product (2-2) is reacted with the metal complex compound represented by the general formula (6).

In the general formula (7), R ⁷ and R ⁸ each independently represent a fluorine atom, an alkyl group or an aryl group, which may or may not be substituted, and may form a ring structure, The same or different ones may be used. X ⁴ represents a reactive halogen functional group or a reactive boron derivative functional group. m1 is an integer of 0 to 4, and m2 is an integer of 0 to 3.

In the general formula (8), X ⁵ represents a reactive halogen functional group or a reactive boron derivative functional group, and is different from X ⁴ in the general formula (7). R ¹ and R ² each independently represent a monovalent organic group, and may be the same or different from each other. R ¹² and R ¹³ each independently represent a monovalent organic group, and may be the same or different from each other. n1 is an integer of 0 to 3, n2 is an integer of 0 to 3, q1 is an integer of 0 to 4, and q2 is an integer of 0 to 4.

The method for producing a metal complex-containing fluorene compound of the present invention is a method for producing the above metal complex-containing fluorene compound,
The phenylpyridine compound represented by the general formula (4) and the fluorenone compound represented by the following general formula (9) are reacted to obtain an intermediate reaction product (3-1).
This intermediate reaction product (3-1) is reacted with benzene having 1 to 5 substituents composed of a monovalent organic group to obtain an intermediate reaction product (3-2).
The intermediate reaction product (3-2) is reacted with the metal complex compound represented by the general formula (6).

In the general formula (9), X ¹ and X ² each independently represent a halogenated functional group, and may be the same or different from each other. R ¹ and R ² each independently represent a monovalent organic group, and may be the same or different from each other. n1 is an integer of 0 to 3, and n2 is an integer of 0 to 3.

The method for producing a metal complex-containing fluorene compound of the present invention is a method for producing the above metal complex-containing fluorene compound,
A phenol pyridine compound represented by the following general formula (10) is reacted with a dihalide of an organic group having halogen atoms at both ends of the main chain to obtain an intermediate reaction product (4-1).
This intermediate reaction product (4-1) is reacted with a fluorene compound represented by the following general formula (11) to obtain an intermediate reaction product (4-2).
The intermediate reaction product (4-2) is reacted with the metal complex compound represented by the general formula (6).

In the general formula (10), in the formula, R ⁷ and R ⁸ each independently represent a fluorine atom, an alkyl group or an aryl group, which may or may not be substituted, and form a ring structure. They may be the same or different from each other. m1 is an integer of 0 to 4, and m2 is an integer of 0 to 3.

In the general formula (11), X ¹ and X ² each independently represent a halogenated functional group, and may be the same or different from each other. R ¹ and R ² each independently represent a monovalent organic group, and may be the same or different from each other. n1 is an integer of 0 to 3, and n2 is an integer of 0 to 3.

The method for producing a metal complex-containing fluorene compound of the present invention is a method for producing the above metal complex-containing fluorene compound,
The intermediate reaction product (5-1) is obtained by reacting the hydroxypyridine derivative represented by the following general formula (12) with a dihalide of an organic group having halogen atoms at both ends of the main chain, and this intermediate reaction The product (5-1) is reacted with a benzene derivative represented by the following general formula (13) to obtain an intermediate reaction product (5-2).
This intermediate reaction product (5-2) is reacted with the fluorene compound represented by the general formula (11) to obtain an intermediate reaction product (5-3).
The intermediate reaction product (5-3) is reacted with the metal complex compound represented by the general formula (6).

In the general formula (12), R ⁷ represents a fluorine atom, an alkyl group or an aryl group, may or may not be substituted, and may form a ring structure. X ⁶ represents a reactive halogen functional group or a reactive boron derivative functional group. m3 is an integer of 0-3.

In the general formula (13), R ⁸ represents a fluorine atom, an alkyl group or an aryl group, may be unsubstituted or may form a ring structure. X ⁷ represents a reactive halogen functional group or a reactive boron derivative functional group, and is different from X ⁶ in the general formula (12). m4 is an integer of 0-4.

  According to the present invention, a metal complex-containing compound in which a metal complex-containing group having a phenylpyridine structure is bonded to an aromatic compound having two halogenated functional groups, and two halogenated functional groups and a metal complex site. There is provided a novel metal complex-containing fluorene compound having a skeleton structure derived from fluorene having benzene. The novel metal complex-containing compound of the present invention, and the metal complex-containing fluorene compound, for example, form a light-emitting layer of an organic electroluminescence device, and synthesize a polymer as a functional organic material excellent in light emission characteristics and durability. There is a possibility that it can be suitably used as a monomer used in the above.

  According to the method for producing a metal complex-containing fluorene compound of the present invention, a novel metal complex-containing fluorene compound can be obtained.

Hereinafter, the best mode for carrying out the present invention will be described in detail.
<Metal complex-containing fluorene compound>
The metal complex-containing fluorene compound of the present invention is a compound having a structure represented by the general formula (1).

In the above general formula (1), X ¹ and X ² are each independently a halogenated functional group, which may be the same or different, but may be the same. preferable. Specific examples of the halogenated functional group include a group derived from —Cl group, —Br group, —I group, triflate (CF ₃ SO ₃ ⁻ ), a group derived from tosylate, or a group derived from mesylate. Among these, -Br group or -I group can be particularly preferably mentioned.
Here, in the said General formula (1), it is preferable that X < ¹ > and X < ² > are couple | bonded with the carbon atom of position number 2 and 7, respectively.

R ¹ and R ² each independently represent a monovalent organic group, and may be the same or different from each other, but are preferably the same. Examples of the monovalent organic group related to R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a phenyl group.

  n1 and n2 each independently represent an integer of 0 to 3, and it is particularly preferred that both n1 and n2 are 0. When n1 or n2 is 0, it means that there is no substituent and a hydrogen atom is bonded.

R ³ and R ^{4 each} represent a single bond or a divalent organic group, and may be the same or different from each other, but are preferably the same. Specific examples of the divalent organic group include a divalent group formed by losing one hydrogen atom from an alkoxyl group having 1 to 8 carbon atoms, an alkylene group having 1 to 8 carbon atoms, and the like. 1 to 3 ring divalent aromatic groups (for example, a phenylene group, a naphthylene group, an anthrylene group, or a xylylene group) with or without a substituent. In the above, R ³ and R ⁴ are preferably a single bond, a divalent group formed by losing one hydrogen atom from a specific alkoxyl group having 1 to 8 carbon atoms, or a phenylene group.

At least one of R ⁵ and R ⁶ represents a metal complex moiety represented by the general formula (2) or the general formula (3), and the other is a monovalent organic group, the general formula (2) or the general formula The metal complex part shown by (3) is shown, and may be the same or different from each other.

In the general formula (2) and the general formula (3), R ⁷ and R ⁸ are each independently a fluorine atom, an alkyl group, or an aryl group (in the case of forming a ring structure, a group derived therefrom). R ⁷ and R ⁸ may be substituted or unsubstituted or may form a ring structure and may be the same or different from each other. It is preferable that they do not form a ring structure and are identical to each other.
Here, R ⁷ and R ⁸ may each be bonded to a plurality of carbon atoms forming a benzene ring or a pyridine ring to form a polycyclic structure.

Specific examples of the alkyl group according to R ⁷ and R ⁸ include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-butyl group, an isobutyl group, a hexyl group, and an octyl group.
Specific examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, and a naphthyl group.

m1 represents an integer of 0 to 4, m2 represents an integer of 0 to 3, m3 represents an integer of 0 to 3, m4 represents an integer of 0 to 4, and in particular, m1, m2, m3 and All of m4 are preferably 0.
Here, when any one of m1, m2, m3 and m4 is 0, it means that there is no substituent and a hydrogen atom is bonded.

In the said General formula (2) and General formula (3), M is a metal atom whose valence is 2-4. Examples of the metal atom include an iridium atom, a platinum atom, a palladium atom, a rubidium atom, an osmium atom, and a rhenium atom. Among these, an iridium atom is preferable.
L is an organic ligand. This organic ligand is formed by an organic compound having a coordination property with respect to the metal atom which is M. The number w of the organic ligand is an integer of 1 to 3, and is selected in consideration of the valence of the metal atom used and the stable coordination number of the neutral complex with the metal atom.

Here, as an organic ligand, what can form an ortho metalated complex is mentioned, For example, a nitrogen-containing heterocyclic derivative is used. Specifically, pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, pyridazine derivatives, quinoline derivatives, phenanthroline derivatives, pyrrole derivatives, imidazole derivatives, pyrazole derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, thiadiazole derivatives, benzimidazole derivatives, Examples include benzoxazole derivatives and benzthiazole derivatives.
Here, the “orthometalated complex” refers to, for example, Yamamoto Akio, “Organic Metal Chemistry: Fundamentals and Applications”, pages 150 and 232, Hankabosha (published in 1982), H. Yersin, “Photochemistry and “Photophysics of Coordination Compounds”, pages 71 to 77, pages 135 to 146, Springer-Verlag (published in 1987), and the like.

  Moreover, as an organic ligand, what is formed with the organic compound used as monodentate organic ligands, such as a halogen, a carbonyl group, and a cyano group, acetylacetone, hexafluoroacetylacetone, 5, 5-dimethyl-2, 4-hexadione Β-diketones such as, diamines such as ethylenediamine and dipyridyl, and those formed by organic compounds which become multidentate organic ligands such as 9-hydroxyquinoline, picolinic acid and salicylic acid. The organic compounds that form these organic ligands can be used singly or in combination of two or more.

  In the above, as a preferable specific example of the metal complex containing fluorene compound of this invention, the metal complex containing fluorene compound which has a structure shown by following Structural formula (1)-Structural formula (5) can be mentioned.

Here, in the metal complex-containing fluorene compound represented by the structural formula (3), R ³ and R ⁴ are single bonds, R ⁵ is a metal complex moiety represented by the general formula (2), and R ⁶ Is a methylphenyl group.

A method for producing the metal complex-containing fluorene compound as described above will be described below.
<First manufacturing method>
The manufacturing method of the 1st metal complex containing fluorene compound can obtain the metal complex containing fluorene compound which has a structure shown, for example by the said Structural formula (1).

  That is, in the first production method, the metal complex-containing fluorene compound of the present invention includes a phenylpyridine compound represented by the above general formula (4) (hereinafter also simply referred to as “specific phenylpyridine compound”) and the above general formula. An intermediate reaction product (1) is obtained by reacting with a diphenyl compound represented by the formula (5) (hereinafter also simply referred to as “specific diphenyl compound”) (hereinafter, this reaction step is referred to as “reaction step (1)”. -1) "), and then the intermediate reaction product (1) is reacted with the metal complex compound represented by the general formula (6) (hereinafter also simply referred to as" specific metal complex compound "). (Hereinafter, this reaction step is also referred to as “reaction step (1-2)”).

[Reaction step (1-1)]
In the general formula (4) showing the specific phenylpyridine compound used in the reaction step (1-1), X ³ is a halogen atom such as a bromine atom or an iodine atom, and preferably includes a bromine atom. it can.

Specific examples of such a specific phenylpyridine compounds, for example the general formula (4), m1 and m2 are 0 together, X ³ can be cited particularly preferably those which are bromine atoms.

Moreover, in General formula (5) which shows the specific diphenyl compound used for reaction process (1-1), ^RLV is a leaving group which consists of monovalent organic groups, Preferably a methyl group is mentioned. it can.

As a specific example of such a specific diphenyl compound, for example, in the general formula (5), X ¹ and X ² are bonded to carbon atoms at position number 2 and position number 7 in the formed fluorene skeleton, respectively. Particularly preferred are those in which n1 and n2 are both 0 and ^RLV is a methyl group.

The above reaction process (1-1) consists of two process steps, a pre-reaction process and a post-reaction process.
Specifically, the pre-reaction treatment is performed by treating a specific phenylpyridine compound in the presence of a lithiation reagent, so that a bromine atom as X ³ is substituted with a lithium atom and a specific diphenyl compound. The reaction is performed.

  Specific examples of the lithiation reagent used in the pre-reaction treatment include n-butyllithium, s-butyllithium, and t-butyllithium, and n-butyllithium is particularly preferably used.

  In the pre-reaction treatment, a polar solvent is used, and usually tetrahydrofuran is preferably used.

  The post-reaction treatment is performed under acidic conditions. For example, a combination of sulfuric acid and acetic acid is preferably used.

[Reaction step (1-2)]
In the general formula showing a specific metal complex compound used in the reaction step (1-2) (6), R 11 , together with two coordinating atoms, bound to the metal as a central metal by the coordination atoms And bidentate specific reactive chelating ligands. Specifically, as the specific reactive chelate ligand, an acetylacetonato ligand, a phenylpyridine ligand having a reactive substituent, and the like are preferably used.

Specific examples of the specific metal complex compound having the specific reactive chelate ligand as described above include, for example, in the general formula (6), R ¹¹ is an acetylacetonato ligand, and M is an iridium atom. And L is a divalent pyridine derivative formed by losing a hydrogen atom from phenylpyridine.

  In the reaction step (1-2), an appropriate solvent is used. Specific examples of such a solvent include glycerin, methoxyethanol, ethoxyethanol and the like, and these solvents can be used alone or in combination of two or more. In these, it is preferable to use glycerol.

As various reaction conditions in the reaction step (1-2), for example, the reaction temperature is 150 to 300 ° C, preferably 200 to 250 ° C.
The reaction time is 10 to 50 hours, preferably 15 to 30 hours.

<Second production method>
The manufacturing method of the 2nd metal complex containing fluorene compound can obtain the metal complex containing fluorene compound which has a structure shown, for example by the said Structural formula (2).

  That is, in the second production method, the metal complex-containing fluorene compound of the present invention includes a phenylpyridine derivative represented by the above general formula (7) (hereinafter also simply referred to as “specific phenylpyridine derivative”) and the above general formula. An intermediate reaction product (2-1) is obtained by reacting with a fluorene derivative represented by the formula (8) (hereinafter also simply referred to as “specific fluorene derivative”) (hereinafter, this reaction step is referred to as “reaction step”). Next, the intermediate reaction product (2-1) and halogen are reacted to obtain an intermediate reaction product (2-2) (hereinafter, this reaction step is referred to as “reaction”). In addition, the intermediate reaction product (2-2) is reacted with a specific metal complex compound (hereinafter, this reaction step is referred to as “reaction step (2-3)”. "). It is also possible to.

[Reaction step (2-1)]
In the general formula (7) indicating the specific phenylpyridine derivative used in the reaction step (2-1), X ⁴ represents a reactive halogen functional group or a boron derivative functional group, and the above general formula (8) Is different from X ⁵ in FIG.

Specific examples of the halogenated functional group include a group derived from —Cl group, —Br group, —I group, triflate (CF ₃ SO ₃ ⁻ ), a group derived from tosylate, or a group derived from mesylate. Among these, -Br group or -I group can be particularly preferably mentioned.

Examples of the boron derivative functional group include a boronic acid group, a boronic ester group, and a borane group represented by the formula -B (OH ₂ ).
The boronic acid ester group is preferably a group represented by the formula -B (OR ²⁰ ) (OR ²¹ ) or a group represented by the formula -B (OR ²² O).
As the borane group, a group represented by the formula -BR ²³ R ²⁴ is preferable.

Here, R ^{20 according} to the boronic acid ester group is an alkyl group having 1 to 6 carbon atoms, and may or may not be substituted.
R ²¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may or may not be substituted.
R ²² is a divalent hydrocarbon group in which (OR ²² O) in the formula is a 5-membered or 6-membered ester ring, specifically, an alkylene group having 2 or 3 carbon atoms An orthophenylene group or a metaphenylene group is preferable. These alkylene groups and phenylene groups may or may not be substituted.

  Preferred examples of the boronic acid ester group having such a structure include alcohols having 1 to 6 carbon atoms, ethanediol such as pinacol, ortho aromatic diols such as propanediol or 1,2-dihydroxybenzene, and the like. Included are groups derived from products from esterification with boronic acids.

R ²³ and R ²⁴ related to the borane group are each independently an alkyl group having 1 to 6 carbon atoms, which may or may not be substituted.

Specific examples of such specific phenylpyridine derivatives, for example, in the above general formula (7), m1 and m2 are both 0, it may be mentioned particularly preferably those X ⁴ is a bromine atom.

In general formula showing a specific fluorene derivative used for the reaction step (2-1) in (8), X ⁵ is a reactive halogen functional group, or indicates a boron derivative functional group, the general formula ( It is different from X ⁴ in 7).
Specific examples of the halogen functional group include the same as those mentioned as X ⁴ above, and in particular, a —Br group or an —I group can be preferably mentioned.
Moreover, as a boron derivative functional group, the same thing as what was mentioned as said X < ⁴ > can be mentioned, Especially the group represented by Formula-B (OR < ²² > O) can be mentioned preferably.

R ¹² and R ¹³ each independently represent a monovalent organic group, and may be the same or different from each other, but are preferably the same. Examples of the monovalent organic group according to R ¹² and R ¹³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a phenyl group.

  q1 and q2 each independently represent an integer of 0 to 4, and it is particularly preferred that both q1 and q2 are 0. When either q1 or q2 is 0, it means that there is no substituent and a hydrogen atom is bonded.

As a specific example of such a specific fluorene derivative, for example, in the general formula (8), X ⁵ is an alkylene group in which R ²² is represented by the formula —C (CH ₃ ) ₂ C (CH ₃ ) ₂ —. Particularly preferred is a group represented by the formula -B (OR ²² O), wherein all of n1, n2, q1 and q2 are 0.

  The above reaction step (2-1) utilizes the method disclosed in Organometallics 3, 1261 (1984) (hereinafter also referred to as “Suzuki method”). In the reaction solvent, the coupling reaction is performed in the presence of a base compound and a palladium catalyst.

  As the reaction solvent, water, an inert organic solvent, or a mixture of water and an inert organic solvent can be used, and among these, a mixture of water and an inert organic solvent is preferably used.

Examples of the inert organic solvent include ethers such as dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diisopropyl ether and tert-butyl methyl ether, hydrocarbons such as hexane, heptane, cyclohexane, toluene and xylene, methanol, ethanol, Alcohols such as 1-propanol, 2-propanol, 1-butyl alcohol, tert-butyl alcohol and ethylene glycol, ketones such as ethyl methyl ketone and isobutyl methyl ketone, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone And mixtures thereof. These inert organic solvents can be used alone or in combination of two or more.
Among these, it is preferable to use dimethoxyethane, tetrahydrofuran, cyclohexane, toluene, xylene, ethanol, 1-propanol, 2-propanol, 1-butyl alcohol, tert-butyl alcohol, and mixtures thereof.

  Preferable specific examples of the reaction solvent include a mixture of water and toluene, a mixture of water, toluene and tetrahydrofuran, and a mixture of water, toluene and ethanol.

Examples of the base compound include alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate, alkali metal acetate, alkaline earth metal acetate, alkali metal hydrogen carbonate, alkaline earth metal Hydrogen carbonate, alkali metal alkoxide, alkaline earth metal alkoxide, primary amine, secondary amine, tertiary amine, and the like can be used.
Among these, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, and alkali metal hydrogen carbonates are preferably used.

  The amount of the base compound used is preferably 150 to 400 mol%, particularly preferably 180 to 250 mol%, based on the total number of moles of the boron derivative functional group related to the specific phenylpyridine derivative or specific fluorene derivative subjected to the reaction. is there.

As the palladium catalyst, a palladium (0) complex or a palladium (II) salt can be used, but a palladium (0) complex is preferably used.
Among these, it is preferable to use tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ).

  The usage-amount of a palladium catalyst is 0.05-3 mol% normally with respect to the total number of moles of the monomer with which reaction is used, Preferably it is 0.1-1.5 mol%.

As various reaction conditions in the reaction step (2-1), for example, the reaction temperature is 30 to 200 ° C., preferably 60 to 120 ° C.
The reaction time is 5 to 150 hours, preferably 10 to 100 hours.

[Reaction step (2-2)]
Examples of the halogen used in the reaction step (2-2) include bromine and iodine, with bromine being particularly preferable.

  In the reaction step (2-2), a halogen-based solvent is used, and preferably chloroform is used.

  Moreover, it is preferable to perform a reaction process (2-2) in presence of an oxidizing agent. As the oxidizing agent, iron chloride is preferably used.

As various reaction conditions in reaction process (2-2), reaction temperature shall be 30-150 degreeC, for example, Preferably it is 50-100 degreeC.
The reaction time is 5 to 30 hours, preferably 10 to 20 hours.

[Reaction step (2-3)]
The reaction step (2-3) can be performed in the same manner as the reaction step (1-2).

<Third production method>
The manufacturing method of the 3rd metal complex containing fluorene compound can obtain the metal complex containing fluorene compound which has a structure shown, for example by the said Structural formula (3).

  That is, in the third production method, the metal complex-containing fluorene compound of the present invention is also referred to as a specific phenylpyridine compound and a fluorenone compound represented by the general formula (9) (hereinafter simply referred to as “specific fluorenone compound”). ) To obtain an intermediate reaction product (3-1) (hereinafter, this reaction step is also referred to as “reaction step (3-1)”), and then the intermediate reaction product (3-1). And benzene having 1 to 5 substituents composed of a monovalent organic group to obtain an intermediate reaction product (3-2) (hereinafter, this reaction step is referred to as “reaction step (3-2)”). Furthermore, by reacting the intermediate reaction product (3-2) with a specific metal complex compound (hereinafter, this reaction step is also referred to as “reaction step (3-3)”). It can also be manufactured.

[Reaction step (3-1)]
Examples of specific phenylpyridine compound used in the reaction step (3-1), for example, the general formula (4), a 0 m1 and m2 are both particularly preferably ones X ³ is bromine atom Can be mentioned.

Moreover, as a specific example of the specific fluorenone compound used in the reaction step (3-1), for example, in the general formula (9), X ¹ and X ² are respectively position number 2 and position number 7 in the fluorene skeleton. Particularly preferred are those having a bromine atom bonded to the carbon atom of n1 and n1 and n2 being both 0.

  The reaction step (3-1) can be performed in the same manner as the pre-reaction treatment in the reaction step (1-1) except that a specific fluorenone compound is used instead of the specific diphenyl compound.

[Reaction step (3-2)]
In the benzene having 1 to 5 substituents composed of a monovalent organic group used in the reaction step (3-2), specific examples of the monovalent organic group that is a substituent include, for example, a methyl group and an ethyl group. , A propyl group, an isopropyl group, a phenyl group, and the like, and particularly preferably toluene.

  The reaction step (3-2) is performed under acidic conditions, and for example, sulfuric acid is preferably used.

[Reaction step (3-3)]
The reaction step (3-3) can be carried out in the same manner as the reaction step (1-2).

<Fourth manufacturing method>
The manufacturing method of the 4th metal complex containing fluorene compound can obtain the metal complex containing fluorene compound which has a structure shown, for example by the said Structural formula (4).

  That is, in the fourth production method, the metal complex-containing fluorene compound of the present invention is a phenol pyridine compound represented by the above general formula (10) (hereinafter also simply referred to as “specific phenol pyridine compound”) and its main component. An intermediate reaction product (4-1) is obtained by reacting with a dihalide of an organic group having a halogen atom at both ends of the chain (hereinafter also simply referred to as “specific dihalide”) (hereinafter referred to as this reaction). The step is also referred to as “reaction step (4-1)”), then the intermediate reaction product (4-1), and the fluorene compound represented by the general formula (11) (hereinafter simply referred to as “specific fluorene compound”). To obtain an intermediate reaction product (4-2) (hereinafter, this reaction step is also referred to as “reaction step (4-2)”), and further, an intermediate reaction product (4- 2) , Reacting the specific metal complex compound (hereinafter, also referred to the reaction step "reaction step (4-3).") By can also be prepared.

[Reaction step (4-1)]
As a specific phenol pyridine compound used in the reaction step (4-1), for example, in the general formula (10), those in which m1 and m2 are both 0 are particularly preferable.

The specific dihalide used in the reaction step (4-1) is composed of a divalent organic group and two halogen atoms. Examples of the divalent organic group include those having 1 to 8 carbon atoms. Examples thereof include an alkylene group and a 1 to 3 ring divalent aromatic group (for example, a phenylene group, a naphthylene group, an anthrylene group, or a xylylene group) having or not having a substituent, and preferably has 1 carbon atom. Is an alkylene group of ˜8.
As such a specific dihalide, for example, dibromobutane can be particularly preferably mentioned.

  In the reaction step (4-1), an appropriate solvent is used. Specific examples of such a solvent include dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetamide and the like. These solvents can be used alone or in combination of two or more, and among them, dimethyl sulfoxide is preferably used.

In addition, the reaction step (4-1) is preferably performed in the presence of a base compound. Specific examples thereof include, for example, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal acetates, alkaline earth metal acetates, alkali metal hydrogen carbonates, alkaline earth metal hydroxides. Gen carbonate, alkali metal alkoxide, alkaline earth metal alkoxide, primary amine, secondary amine, tertiary amine, and the like can be used.
In the above, potassium carbonate can be preferably used.
Such a basic compound is used in the range of, for example, 1 to 10 mol, preferably 3 to 7 mol.

  The reaction step (4-1) is preferably performed in the presence of a catalytic amount of potassium iodide in order to increase the activity of the reaction.

As various reaction conditions in reaction process (4-1), reaction temperature shall be 20-100 degreeC, for example, Preferably it is 30-60 degreeC.
The reaction time is 5 to 30 hours, preferably 10 to 20 hours.

[Reaction step (4-2)]
As a specific fluorene compound used in the reaction step (4-2), for example, in the above general formula (11), X ¹ and X ² are bonded to carbon atoms at position number 2 and position number 7 in the fluorene skeleton, respectively. Particularly preferred are those in which n1 and n2 are both 0.

  Here, the reaction step (4-2) can be performed in the same manner as the reaction step (4-1).

[Reaction step (4-3)]
The reaction step (4-3) can be carried out in the same manner as in the reaction step (1-2).

<Fifth manufacturing method>
The manufacturing method of the 5th metal complex containing fluorene compound can obtain the metal complex containing fluorene compound which has a structure shown by the said Structural formula (5), for example.

  That is, in the fifth production method, the metal complex-containing fluorene compound of the present invention includes a hydroxypyridine derivative represented by the general formula (12) (hereinafter also simply referred to as “specific hydroxypyridine derivative”) and a specific compound. An intermediate reaction product (5-1) is obtained by reacting with a dihalide (hereinafter, this reaction step is also referred to as “reaction step (5-1)”), and then the intermediate reaction product (5-1). ) And a benzene derivative represented by the general formula (13) (hereinafter also simply referred to as “specific benzene derivative”) to obtain an intermediate reaction product (5-2) (hereinafter referred to as this reaction step). Is also referred to as “reaction step (5-2)”), and further, the intermediate reaction product (5-2) is reacted with a specific fluorene compound to obtain an intermediate reaction product (5-3) (hereinafter referred to as “reaction step (5-2)”). , This reaction process Reaction step (5-3) ”), and further reacting the intermediate reaction product (5-3) with a specific metal complex compound (hereinafter, this reaction step is referred to as“ reaction step (5-4) ”. ) ").) Can also be produced.

[Reaction step (5-1)]
In the general formula (12) indicating the specific hydroxypyridine derivative used in the reaction step (5-1), X ⁶ represents a reactive halogenated functional group or a boron derivative functional group, and the above general formula (13) Is different from X ⁷ in FIG.

Specific examples of the halogenated functional group may include the same as those mentioned as X ⁴ in the specific phenylpyridine derivative used in the above reaction step (2-1), and in particular, —Br group or —I Preference is given to groups.
As the boron derivative functional group include the same as those exemplified as X ⁴ in particular phenyl pyridine derivative used in the reaction step (2-1), in particular, the formula -B (OH ₂₎ The boronic acid group represented by these can be mentioned preferably.

Such specific hydroxypyridine derivatives, for example, the general formula (12), the m3 is 0, X ⁶ can be cited particularly preferably those which are bromine atoms.

  As the specific dihalide used in the reaction step (5-1), for example, dibromobutane can be particularly preferably mentioned.

  The above reaction process (5-1) can be performed similarly to the said reaction process (4-1).

[Reaction step (5-2)]
In the general formula (13) indicating the specific benzene derivative used in the reaction step (5-2), X ⁷ represents a reactive halogenated functional group or a boron derivative functional group, and the above general formula (12) And X ⁶ in the above.

Specific examples of the halogen functional group include the same as those mentioned as X ⁶ above, and in particular, a —Br group or an —I group can be preferably exemplified.
As the boron derivative functional groups, said X those same can be exemplified as mentioned as ^6, in particular, can be preferably exemplified a group represented by the formula -B (OH _2).

As a specific example of such a specific benzene derivative, for example, in the general formula (13), X ⁷ is a boronic acid group represented by the formula -B (OH ₂ ), and m4 is 0. Particularly preferred examples are listed.

  The above reaction step (5-2) utilizes the Suzuki method and can be performed in the same manner as the reaction step (2-1).

[Reaction step (5-3)]
As a specific fluorene compound used in the reaction step (5-3), for example, in the above general formula (11), X ¹ and X ² are bonded to carbon atoms at position number 2 and position number 7 in the fluorene skeleton, respectively. Particularly preferred are those in which n1 and n2 are both 0.

  In the reaction step (5-3), an appropriate solvent is used. Specific examples of such a solvent include dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetamide and the like. These solvents can be used alone or in combination of two or more, and among them, dimethyl sulfoxide is preferably used.

  The reaction step (5-3) is preferably performed in the presence of an appropriate catalyst, and for example, triethylbenzylammonium chloride is preferably used.

  The reaction step (5-3) is preferably carried out in an alkaline solution. For example, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, or an aqueous solution of barium hydroxide is preferably used. An aqueous solution of is preferably used.

As various reaction conditions in reaction process (5-3), reaction temperature shall be 20-100 degreeC, for example, Preferably it is 30-60 degreeC.
The reaction time is 5 to 70 hours, preferably 10 to 50 hours.

[Reaction step (5-4)]
The reaction step (5-4) can be carried out in the same manner as in the reaction step (1-2).

  As mentioned above, although the manufacturing method of the metal complex containing fluorene compound was demonstrated, the metal complex containing fluorene compound which concerns on this invention is not limited to what was manufactured by said manufacturing method, It manufactures by another manufacturing method It may be what was done.

  According to the present invention, a novel metal complex-containing fluorene compound having a fluorene skeleton structure having two halogen functional groups and a specific metal complex site, and a method for producing the same are provided. Such a metal complex-containing fluorene compound is suitably used as a monomer used for the synthesis of a polymer as a functional organic material having excellent light-emitting properties and durability, for example, used for forming an organic EL device. Could be possible.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

(Synthesis of phenylpyridine compounds)
A system in which 24.5 g (155 mmol) of 2-bromopyridine was dissolved in 400 ml of dehydrated diethyl ether was cooled to −78 ° C. using an acetone-dry ice bath, and then n-butyllithium (1.6 M hexane solution) was added to the system. 97 ml was added dropwise and then stirred for 30 minutes. Subsequently, after 32.2 g (310 mmol) of trimethoxyborane was dropped, the system was removed from the acetone-dry ice bath and allowed to rise to room temperature, and then stirred for 24 hours. The obtained reaction solution was washed with water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure to obtain Intermediate (1).

The total amount (155 mmol) of intermediate (1) obtained above, 146.3 g (620 mmol) of dibromobenzene and 5 g (4.3 mmol) of tetrakis (triphenylphosphine palladium) were added to 600 ml of toluene and 2N aqueous Na ₂ CO ₃ solution. The system added to 300 ml of the mixed solvent was heated to 90 ° C. and stirred for 30 hours. Then, after confirming the consumption of the raw material, 1N hydrochloric acid was added dropwise to complete the reaction. Thereafter, the system was extracted with toluene, the obtained toluene solution was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure.

  The resulting crude product was purified by column chromatography to obtain 25 g (107 mmol) of bromophenylpyridine.

<Reaction step (1-1)>
(Pre-reaction treatment)
A system in which 20 g (85.4 mmol) of bromophenylpyridine obtained was dissolved in 150 ml of tetrahydrofuran was cooled to −78 ° C. using an acetone-dry ice bath, and then n-butyllithium (1.6 M hexane solution) was added to the system. 53.3 ml was added dropwise and then stirred for 60 minutes. Subsequently, a solution prepared by dissolving 15.5 g (42 mmol) of 4,4′-dibromobiphenyl carboxylexoxide methyl ester (JACS, 1956, 78, 3196) in 40 ml of tetrahydrofuran was dropped, and then the system was added to an acetone-dry ice bath. And then allowed to warm to room temperature and then stirred for 24 hours. The obtained reaction solution was washed with water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure.

(Post-reaction treatment)
The obtained product was mixed with 200 ml of acetic acid to which 4 ml of sulfuric acid was added, and heated to reflux until a white precipitate was formed.
The obtained precipitate was filtered through a filter and purified by column chromatography to obtain 20 g of an intermediate reaction product (1).

<Reaction step (1-2)>
A system in which 2.0 g (3 mmol) of the intermediate reaction product (1) and 3.7 g (6.2 mmol) of bis (2-phenylpyridine) iridium acetylacetonate were dissolved in 50 ml of glycerol was heated to 200 ° C. and stirred for 3 hours. did. Thereafter, chloroform was added to the system cooled to room temperature, and the resulting chloroform solution was washed with saturated brine. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure.
The obtained crude product was purified by column chromatography to obtain 2.5 g of the final reaction product (1).

  As a result of analyzing the obtained final reaction product (1) by time-of-flight mass spectrometry, the final reaction product (1) was a metal complex-containing fluorene compound represented by the structural formula (1).

  The reaction step (1-1) and reaction (1-2) according to Example 1 described above relate to the following reaction formula (1).

(Synthesis of fluorene derivatives)
A system in which 24.1 g (94.3 mmol) of 1,4-dibromobenzene was dissolved in 150 ml of tetrahydrofuran was cooled to −78 ° C. using an acetone-dry ice bath, and then t-butyllithium (1.5 M hexane was added to the system. Solution) 126 ml was added dropwise and then stirred for 1 hour. Subsequently, a solution in which 10 g (48 mmol) of methyl 2-phenylbenzoate was dissolved in 50 ml of tetrahydrofuran was dropped, and then the system was removed from the acetone-dry ice bath to room temperature, and then stirred for 12 hours. The obtained reaction solution was washed with saturated brine, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. A system in which the obtained product was added to 100 g of polyphosphoric acid was heated to 80 ° C., and heating was continued until a white precipitate was formed. Thereafter, ether was added to the system for extraction treatment, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained crude product was purified by column chromatography to obtain 20 g of a fluorene derivative precursor.

  A system in which 9.5 g (20 mmol) of a fluorene derivative precursor was dissolved in 200 ml of tetrahydrofuran (THF) was cooled to −78 ° C. using an acetone-dry ice bath, and then n-butyllithium (1.6 M hexane solution) 26. 2 ml was added dropwise and then stirred for 2 hours. Next, after 11.2 g (60 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise, the system was removed from the acetone-dry ice bath to room temperature. And then stirred for 24 hours. The obtained reaction solution was washed with water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The obtained solid product was purified by recrystallization from methanol to obtain 8.5 g of a fluorene derivative.

<Reaction step (2-1)>
2.8 g (5 mmol) of the fluorene derivative, 2.6 g (11 mmol) of bromophenylpyridine obtained in Example 1 and 0.2 g (0.15 mmol) of tetrakis (triphenylphosphine) palladium (0) were dissolved in toluene. A system added to a mixed solvent of 15 ml and 7.5 ml of a 2N Na ₂ CO ₃ aqueous solution was heated to 90 ° C. and stirred for 24 hours. After confirming that the raw material was consumed in the reaction, 1N hydrochloric acid was added dropwise to complete the reaction. The obtained reaction solution was extracted with toluene, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure.
The obtained crude product was purified by column chromatography to obtain 2.0 g of an intermediate reaction product (2-1).

<Reaction step (2-2)>
In a system in which 2.0 g (3.3 mmol) of the intermediate reaction product (2-1) and 0.05 g (0.3 mmol) of iron (III) chloride were dissolved in 5 ml of chloroform, 0.4 ml (7.2 mmol) of bromine Was added dropwise at room temperature. Thereafter, the system was stirred for 8 hours, and then an aqueous sodium thiosulfate solution was added dropwise. The obtained reaction solution was washed with water three times, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure.
The obtained crude product was purified by column chromatography to obtain 2.2 g of an intermediate reaction product (2-2).

<Reaction step (2-3)>
Except for using a system in which 2.0 g (2.6 mmol) of the intermediate reaction product (2-2) and 3.4 g (5.6 mmol) of bis (2-phenylpyridine) iridium acetylacetonate were dissolved in 50 ml of glycerol. The reaction process was performed in the same manner as in the reaction step (1-2) of Example 1, and the obtained crude product was purified to obtain 1.5 g of the final reaction product (2).

  As a result of analyzing the obtained final reaction product (2) by time-of-flight mass spectrometry, the final reaction product (2) was a metal complex-containing fluorene compound represented by the structural formula (2).

  The above reaction process (2-1) to reaction process (2-3) according to Example 2 relate to the following reaction formula (2).

<Reaction step (3-1)>
A system in which 2.3 g (10 mmol) of bromophenylpyridine obtained in Example 1 was dissolved in 20 ml of tetrahydrofuran was cooled to −78 ° C. using an acetone-dry ice bath, and then n-butyllithium (1. 6.8 ml of 6M hexane solution) was added dropwise and then stirred for 60 minutes. Subsequently, a solution of 3.4 g (10 mmol) of 2,7-dibromofluorenone dissolved in 5 ml of tetrahydrofuran was dropped, and then the system was removed from the acetone-dry ice bath to room temperature, and then stirred for 24 hours. . Chloroform was added to the obtained reaction solution, the obtained chloroform solution was washed with water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure.
The obtained crude product was purified by column chromatography to obtain 3.6 g of an intermediate reaction product (3-1).

<Reaction step (3-2)>
2 ml of sulfuric acid was added to a system in which 3.5 g (7.1 mmol) of the intermediate reaction product (3-1) was dissolved in 50 ml of toluene, and the mixture was heated to reflux until a white precipitate was formed.
The obtained precipitate was filtered through a filter and purified by column chromatography using chloroform as a developing solvent to obtain 2.9 g of an intermediate reaction product (3-2).

<Reaction step (3-3)>
Except for using a system in which 3.0 g (6.3 mmol) of the intermediate reaction product (3-2) and 3.9 g (6.5 mmol) of bis (2-phenylpyridine) iridium acetylacetonate were dissolved in 65 ml of glycerol. The reaction process was performed in the same manner as in the reaction step (1-2) of Example 1, and the obtained crude product was purified to obtain 2.7 g of the final reaction product (3).

  As a result of analyzing the obtained final reaction product (3) by time-of-flight mass spectrometry, the final reaction product (3) was a metal complex-containing fluorene compound represented by the structural formula (3).

  The reaction step (3-1) to the reaction step (3-3) according to Example 3 relate to the following reaction formula (3).

(Synthesis of phenol pyridine compounds)
A system in which 10 g (38.9 mmol) of bromotetrahydropyranyloxybenzene was dissolved in 80 ml of tetrahydrofuran was cooled to −78 ° C. using an acetone-dry ice bath, and then n-butyllithium (1.6 M hexane solution) was added to the system. 26 ml was added dropwise and then stirred for 2 hours. Then, 5 ml (44.6 mmol) of trimethoxyborane was added dropwise, and then the system was removed from the acetone-dry ice bath to room temperature, and then stirred for 8 hours. The obtained reaction solution was washed with water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure to obtain 6.9 g of intermediate (4-1).

Intermediate (4-1) 6.9 g (28 mmol), 2-bromopyridine (3.9 ml, 40 mmol), tetrakis (triphenylphosphine) palladium (0) 2.3 g (2.16 mmol), toluene A system dissolved in a mixed solvent of 160 ml and 80 ml of 2N Na ₂ CO ₃ aqueous solution was heated to 110 ° C. and stirred for 30 hours. Thereafter, the system was extracted with toluene, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure.
The obtained crude product was purified by column chromatography to obtain 5.1 g of intermediate (4-2).

  1 ml of concentrated hydrochloric acid was added to a system in which 5.1 g of intermediate (4-2) was dissolved in 50 ml of 75% aqueous ethanol, and the system was heated to reflux for 6 hours. Subsequently, ethanol was distilled off under reduced pressure, and ether and an aqueous potassium hydroxide solution were added to the remaining solution for extraction treatment, and the organic layer was removed. Thereafter, the pH of the obtained aqueous layer is acidified by adding hydrochloric acid, and further, ether is added for extraction treatment, the organic layer is removed, and the pH of the obtained aqueous layer is adjusted with an aqueous sodium carbonate solution. The mixture was neutralized by addition, and further extracted with chloroform. The obtained organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure to obtain 3.2 g of phenolpyridine.

<Reaction step (4-1)>
In a system in which 3.0 g (17.5 mmol) of phenolpyridine, 0.01 g of potassium iodide, and 6.9 g (50 mmol) of potassium carbonate were dissolved in 50 ml of dimethyl sulfoxide, 19.3 g of dibromobutane was added to 30 ml of dimethyl sulfoxide. The dissolved solution was added dropwise and the system was heated to 50 ° C. and stirred for 12 hours. Thereafter, 5 ml of water was dropped into the obtained reaction solution to terminate the reaction, the reaction solution was extracted with chloroform, the resulting chloroform solution was washed with water three times, and the organic layer was dried over anhydrous magnesium sulfate. Further, the solvent was distilled under reduced pressure to obtain 3.7 g of an intermediate reaction product (4-1).

<Reaction step (4-2)>
A system in which 3.1 g (10 mmol) of the intermediate reaction product (4-1), 1.5 g (4.5 mmol) of 2,7-dibromofluorene and 10 g (72 mmol) of potassium carbonate were dissolved in 50 ml of dimethyl sulfoxide. The mixture was heated to 80 ° C. and stirred for 12 hours. The resulting reaction solution was cooled to room temperature and extracted by adding chloroform and water. Furthermore, it wash | cleaned in order of water and a saturated salt solution, the organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure.
The obtained crude product was purified by column chromatography to obtain 4.3 g of an intermediate reaction product (4-2).

<Reaction step (4-3)>
Except that 1.0 g (1.3 mmol) of the intermediate reaction product (4-2) and 1.5 g (2.6 mmol) of bis (2-phenylpyridine) iridium acetylacetonate were dissolved in 5 ml of glycerol were used. The reaction process was performed in the same manner as in the reaction step (1-2) of Example 1, and the resulting crude product was purified to obtain 2.7 g of the final reaction product (4).

  As a result of analyzing the obtained final reaction product (4) by time-of-flight mass spectrometry, the final reaction product (4) was a metal complex-containing fluorene compound represented by the structural formula (4).

  The above reaction process (4-1) to reaction process (4-3) according to Example 4 relate to the following reaction formula (4).

<Reaction step (5-1)>
To a system in which 17.4 g (100 mmol) of 2-bromo-3-hydroxypyridine, 0.82 g (5 mmol) of potassium iodide and 41.4 g (300 mmol) of potassium carbonate were dissolved in 200 ml of dimethyl sulfoxide, 54 ml of dibromobutane was added. A solution of (448 mmol) dissolved in 100 ml of dimethyl sulfoxide was added dropwise and stirred at 50 ° C. for 24 hours. After confirming the consumption of the raw materials, the reaction solution was extracted by adding chloroform and water. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure.
The obtained crude product was purified by column chromatography to obtain 26.0 g of an intermediate reaction product (5-1).

<Reaction step (5-2)>
Intermediate reaction product (5-1) 26 g (84 mmol), phenylboronic acid 15.2 g (126 mmol), tetrakis (triphenylphosphine) palladium (0) 2.9 g (2.51 mmol), toluene 100 ml and A system dissolved in a mixed solvent of 50 ml of 2N Na ₂ CO ₃ was heated to 110 ° C. and stirred for 48 hours. The resulting reaction solution was cooled to room temperature and extracted by adding toluene and water. The obtained organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure.
The obtained crude product was purified by column chromatography using chloroform as a developing solvent to obtain 4.1 g of an intermediate reaction product (5-2).

<Reaction step (5-3)>
To a system in which 3.2 g (10 mmol) of 2,7-dibromofluorene and 4.5 g (20 mmol) of triethylbenzylammonium chloride were dissolved in 20 ml of dimethyl sulfoxide, a 10% aqueous solution of 50% sodium hydroxide was added dropwise. A solution of 4.1 g (13 mmol) of the product (5-2) in 20 ml of dimethyl sulfoxide was added dropwise and stirred at 50 ° C. for 24 hours. The resulting reaction solution was cooled to room temperature and extracted by adding chloroform and water. Next, the organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure.
The obtained crude product was purified by column chromatography to obtain 6.7 g of an intermediate reaction product (5-3).

<Reaction step (5-4)>
Example 1 except that 7.0 g (9 mmol) of the intermediate reaction product (5-3) and 12.0 g (20 mmol) of bis (2-phenylpyridine) iridium acetylacetonate were dissolved in 150 ml of glycerol. The reaction treatment was performed in the same manner as in the reaction step (1-2), and the resulting crude product was purified to obtain 4.0 g of the final reaction product (5).

  As a result of analyzing the obtained final reaction product (5) by time-of-flight mass spectrometry, the final reaction product (5) was a metal complex-containing fluorene compound represented by the structural formula (5).

  The above reaction step (5-1) to reaction step (5-4) according to Example 5 relate to the following reaction formula (5).

Claims (7)

  A metal complex-containing compound, wherein a metal complex-containing group having a phenylpyridine structure is bonded to an aromatic compound having two halogenated functional groups. The metal complex containing fluorene compound characterized by having the structure represented by following General formula (1).

[In formula, X < ¹ > and X < ² > show a halogeno functional group each independently, and may mutually be same or different. R ¹ and R ² each independently represent a monovalent organic group, and may be the same or different from each other. R ³ and R ⁴ represent a single bond or a divalent organic group, and may be the same or different from each other. At least one of R ⁵ and R ⁶ represents a metal complex moiety represented by the following general formula (2) or general formula (3), and the other is a monovalent organic group, or the following general formula (2) or general formula The metal complex part shown by (3) is shown, and may be the same or different from each other. n1 is an integer of 0 to 3, and n2 is an integer of 0 to 3. ]

[Wherein, R ⁷ and R ⁸ each independently represent a fluorine atom, an alkyl group or an aryl group, which may or may not be substituted, may form a ring structure, and are the same as each other; It may be different or different. M represents a divalent to tetravalent metal atom, and L represents an organic ligand. m1 is an integer of 0 to 4, m2 is an integer of 0 to 3, and w is an integer of 1 to 3. ]

[Wherein, R ⁷ and R ⁸ each independently represent a fluorine atom, an alkyl group or an aryl group, which may or may not be substituted, may form a ring structure, and are the same as each other; It may be different or different. M represents a divalent to tetravalent metal atom, and L represents an organic ligand. m3 is an integer of 0 to 3, m4 is an integer of 0 to 4, and w is an integer of 1 to 3. ] A method for producing the metal complex-containing fluorene compound according to claim 2,
A phenylpyridine compound represented by the following general formula (4) and a diphenyl compound represented by the following general formula (5) are reacted to obtain an intermediate reaction product,
A method for producing a metal complex-containing fluorene compound, comprising reacting the intermediate reaction product with a metal complex compound represented by the following general formula (6).

[Wherein X ³ represents a halogen atom. R ⁷ and R ⁸ each independently represent a fluorine atom, an alkyl group or an aryl group, which may be unsubstituted or may form a ring structure and are the same as each other May be different. m1 is an integer of 0 to 4, and m2 is an integer of 0 to 3. ]

[In formula, X < ¹ > and X < ² > show a halogeno functional group each independently, and may mutually be same or different. R ¹ and R ² each independently represent a monovalent organic group, and may be the same or different from each other. R ^LV represents a monovalent organic group. n1 is an integer of 0 to 3, and n2 is an integer of 0 to 3. ]

[Wherein R ¹¹ represents a bidentate chelate ligand having two coordination atoms, M represents a divalent to tetravalent metal atom, and L represents an organic ligand. w is an integer of 1-3. ] A method for producing the metal complex-containing fluorene compound according to claim 2,
A phenylpyridine derivative represented by the following general formula (7) and a fluorene derivative represented by the following general formula (8) are reacted to obtain an intermediate reaction product (1).
This intermediate reaction product (1) is reacted with halogen to obtain an intermediate reaction product (2).
A process for producing a metal complex-containing fluorene compound, comprising reacting the intermediate reaction product (2) with a metal complex compound represented by the following general formula (6).

Wherein, R ⁷ and R ⁸ are each independently a fluorine atom, an alkyl group or an aryl group, which may or may not be substitution, may form a ring structure, identical to each other It may be different or different. X ⁴ represents a reactive halogen functional group or a reactive boron derivative functional group. m1 is an integer of 0 to 4, and m2 is an integer of 0 to 3. ]

[Wherein, X ⁵ represents a reactive halogen functional group or a reactive boron derivative functional group, and is different from X ⁴ in the general formula (7). R ¹ and R ² each independently represent a monovalent organic group, and may be the same or different from each other. R ¹² and R ¹³ each independently represent a monovalent organic group, and may be the same or different from each other. n1 is an integer of 0 to 3, n2 is an integer of 0 to 3, q1 is an integer of 0 to 4, and q2 is an integer of 0 to 4. ]

[Wherein R ¹¹ represents a bidentate chelate ligand having two coordination atoms, M represents a divalent to tetravalent metal atom, and L represents an organic ligand. w is an integer of 1-3. ] A method for producing the metal complex-containing fluorene compound according to claim 2,
A phenylpyridine compound represented by the following general formula (4) and a fluorenone compound represented by the following general formula (9) are reacted to obtain an intermediate reaction product (1).
This intermediate reaction product (1) is reacted with benzene having 1 to 5 substituents composed of a monovalent organic group to obtain an intermediate reaction product (2).
A process for producing a metal complex-containing fluorene compound, comprising reacting the intermediate reaction product (2) with a metal complex compound represented by the following general formula (6).

[Wherein X ³ represents a halogen atom. R ⁷ and R ⁸ each independently represent a fluorine atom, an alkyl group or an aryl group, which may be unsubstituted or may form a ring structure and are the same as each other May be different. m1 is an integer of 0 to 4, and m2 is an integer of 0 to 3. ]

[In formula, X < ¹ > and X < ² > show a halogeno functional group each independently, and may mutually be same or different. R ¹ and R ² each independently represent a monovalent organic group, and may be the same or different from each other. n1 is an integer of 0 to 3, and n2 is an integer of 0 to 3. ]

[Wherein R ¹¹ represents a bidentate chelate ligand having two coordination atoms, M represents a divalent to tetravalent metal atom, and L represents an organic ligand. w is an integer of 1-3. ] A method for producing the metal complex-containing fluorene compound according to claim 2,
A phenol pyridine compound represented by the following general formula (10) is reacted with a dihalide of an organic group having a halogen atom at both ends of the main chain to obtain an intermediate reaction product (1).
This intermediate reaction product (1) is reacted with a fluorene compound represented by the following general formula (11) to obtain an intermediate reaction product (2).
A process for producing a metal complex-containing fluorene compound, comprising reacting the intermediate reaction product (2) with a metal complex compound represented by the following general formula (6).

[Wherein, R ⁷ and R ⁸ each independently represent a fluorine atom, an alkyl group or an aryl group, which may or may not be substituted, may form a ring structure, and are the same as each other; It may be different or different. m1 is an integer of 0 to 4, and m2 is an integer of 0 to 3. ]

[In formula, X < ¹ > and X < ² > show a halogeno functional group each independently, and may mutually be same or different. R ¹ and R ² each independently represent a monovalent organic group, and may be the same or different from each other. n1 is an integer of 0 to 3, and n2 is an integer of 0 to 3. ]

[Wherein R ¹¹ represents a bidentate chelate ligand having two coordination atoms, M represents a divalent to tetravalent metal atom, and L represents an organic ligand. w is an integer of 1-3. ] A method for producing the metal complex-containing fluorene compound according to claim 2,
By reacting a hydroxypyridine derivative represented by the following general formula (12) with a dihalide of an organic group having a halogen atom at both ends of the main chain, an intermediate reaction product (1) is obtained.
This intermediate reaction product (1) is reacted with a benzene derivative represented by the following general formula (13) to obtain an intermediate reaction product (2).
This intermediate reaction product (2) is reacted with a fluorene compound represented by the following general formula (11) to obtain an intermediate reaction product (3).
The manufacturing method of the metal complex containing fluorene compound characterized by making this intermediate reaction product (3) react with the metal complex compound shown by following General formula (6).

[Wherein, R ⁷ represents a fluorine atom, an alkyl group or an aryl group, may or may not be substituted, and may form a ring structure. X ⁶ represents a reactive halogen functional group or a reactive boron derivative functional group. m3 is an integer of 0-3. ]

[Wherein R ⁸ represents a fluorine atom, an alkyl group or an aryl group, may or may not be substituted, and may form a ring. X ⁷ represents a reactive halogen functional group or a reactive boron derivative functional group, and is different from X ⁶ in the general formula (12). m4 is an integer of 0-4. ]

[In formula, X < ¹ > and X < ² > show a halogeno functional group each independently, and may mutually be same or different. R ¹ and R ² each independently represent a monovalent organic group, and may be the same or different from each other. n1 is an integer of 0 to 3, and n2 is an integer of 0 to 3. ]

[Wherein R ¹¹ represents a bidentate chelate ligand having two coordination atoms, M represents a divalent to tetravalent metal atom, and L represents an organic ligand. w is an integer of 1-3. ]