WO2014044110A1

WO2014044110A1 - Synthetic method of iridium compound

Info

Publication number: WO2014044110A1
Application number: PCT/CN2013/082066
Authority: WO
Inventors: 赵洪玉
Original assignee: Zhao Hongyu
Priority date: 2012-09-21
Filing date: 2013-08-22
Publication date: 2014-03-27
Also published as: CN102887922A; CN102887922B

Abstract

Provided is a synthetic method of an organic metal iridium compound. The synthetic method comprises: (1) carrying out reaction between tri-halogenated iridium hydrate A and neutral ligand B to obtain an iridium compound with a halogenated bridge shown as L₂Ir(μ-X)₂IrL₂, wherein L represents dual-ligand annular metal ligand formed by the neutral ligand, and (μ-X) represents bridge shaped halogen; and (2) implementing reaction between the iridium compound with the halogenated bridge and slightly excessive ligand C to obtain formula (I), wherein LX represents another ligand formed by the ligand C. According to the synthetic method, the reaction time is shortened, the yield is improved, a product can be obtained directly after filtering at the end of the reaction, and red lights with high purity of more than 99% can be obtained by the product without purification, so that the cost is saved, and it is beneficial to promote a red light emitting material.

Description

Method for synthesizing terpenoids

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the synthesis of anthraquinone materials in organic light-emitting materials, in particular to the synthesis of anthraquinone red light materials, mainly to the improvement of conventional methods, the improved method improves the yield, shortens the reaction time, and is beneficial to the crucible. Promotion of class materials. Background technique

In recent years, organic electroluminescent devices have been extensively researched and developed. In the basic structure of such a light-emitting element, a layer containing a light-emitting substance is interposed between a pair of electrodes, and by applying a voltage to the element, light emission from the light-emitting substance can be obtained.

Since such light-emitting elements are self-luminous elements, they have advantages in terms of high pixel visibility and elimination of backlighting requirements with respect to liquid crystal displays, and thus are considered to be suitable for flat panel display elements, for example. Light-emitting elements are also highly advantageous because they are thin and lightweight. A very high speed response is one of the features of this component.

Further, since such a light-emitting element can be formed in the form of a film, planar light emission can be provided. Therefore, an element having a large area can be easily formed. This is a feature that is difficult to obtain with a point light source typified by an incandescent lamp and an LED or a linear light source typified by a fluorescent lamp. Therefore, the light-emitting element also has a large potential as a planar light source or the like which can be applied to illumination.

The excited state formed by the organic compound may be singlet or triplet. The emission from the singlet excited state (s*) is fluorescence, and the emission from the triplet excited state CT) is called phosphorescence. Further, it is considered that the statistical generation ratio in the light-emitting element is S* : T* = 1 : 3. In the compound which converted the energy of the singlet excited state into light emission, no emission from the triplet excited state was observed at room temperature, and only emission from the singlet excited state was observed. Therefore, it is considered that the internal word efficiency of a light-emitting element using a fluorescent compound has a theoretical limit of 25%, based on a ratio of S* to T* of 1:3. Therefore, organic electrophosphorescent materials are recently attracting a class of materials, organic electroluminescent materials having high luminous efficiency and luminescent brightness, which utilize the method of introducing heavy metal atoms to utilize the originally forbidden triplet transition at room temperature. Thus, the internal quantum efficiency theory can reach 100%, which is 4 times that of a single fluorescent material (1, Cao Y., Parker ID, Heeger J. , Nature, 1999, 397 : 414-417. 2 , Wohlgenann M., et al. Nature, 2001, 409 : 494-497. ) ₀ The heavy metal atoms commonly used in organic electrophosphorescent materials are mostly transition metals, of which铱 is the most widely used and most studied, because metal ruthenium complexes have high efficiency, strong phosphorescence at room temperature, and the wavelength of the luminescence can be adjusted by the adjustment of the ligand structure to make the color of the electroluminescent device cover the entire Visible light area. Therefore, designing and synthesizing new and highly efficient metal ruthenium complexes is of great significance for the development of phosphorescent materials.

As the 0LED three-color display, red light materials are the most widely used, mainly quinoline, isoquinoline and pyrazine, among which acetylacetone and its derivatives account for a large proportion, and three identical ligands are synthesized. It is also converted from an acetylacetone intermediate. At present, the synthetic methods reported in the literature mainly react with ethylene glycol monoethyl ether or methyl ether and potassium carbonate for 24-48 hours. This method has problems such as long reaction time, low yield, and many side reactions. Summary of the invention

In view of the problem of red light in the synthesis of acetylacetone red light, the inventors of the present invention carefully analyzed different types of red light materials, analyzed the reaction mechanism of red light materials, and proposed an improved scheme. The reaction is carried out by alkali, acetylacetone loses protons, converts to enol form, and then reacts with chlorine bridge to obtain red light material; wherein acetylacetone reacts with carbonate to react heterogeneously, which determines the speed of the whole reaction. The chlorine bridge will be coordinated to the solvent molecule in a solvent such as acetone, ethanol or methanol to form a solution, and the enol form of acetylacetone will rapidly react with it to obtain a red light material. The traditional method is synthesized under heterogeneous and high temperature conditions (above 130 degrees). The reaction between acetylacetone and carbonate is relatively slow, the chlorine bridge is relatively stable, and the reaction rate is also determined, and the yield is relatively low. For example, pyrazines reported by Nippon Semiconductor Co., Ltd. (CN101270133, CN102190653, because the ligand reaction is weak, the conventional method cannot obtain a high yield product (10-20%), and it needs to be under the action of ultrasonic waves, so it is not suitable for industrial applications. To solve the problems of low yield and long reaction time, it needs to be solved by two methods: chlorine bridge and acetylacetone. The chlorine bridge can dissociate, form a coordination molecule with the solvent molecule, and select a solvent to form a coordination molecule with the chlorine bridge; The selected base energy is homogeneous with the solvent, does not cause side reactions, promotes the formation of the enol form (11), and increases the reaction rate. The inventors of the present invention have improved the conventional synthesis method on the basis of a large number of experiments.

A method for synthesizing an organometallic ruthenium compound, comprising two separate reactions: (1) ruthenium trihalide hydrate A reacts with neutral ligand B to form a ruthenium compound with a halogen bridge: L2Ir (-X) 2IrL2, L : Represents a bi-coordinating cyclic metal ligand formed by a neutral ligand, (μ _Χ): represents a bridged halogen, (2) a hydrazine compound with a halogenated bridge reacts with a slight excess of ligand C to obtain [CN ] ₂ (LX). LX represents another ligand formed by ligand C; characterized in that: the first step reaction comprises the steps of: adding a ruthenium trihalide hydrate, a neutral ligand to a water-soluble organic solvent, water, and refluxing the number of reactions After hours, cold, pour into water, add certain inorganic salts to the water, and filter the product to obtain a hydrazine compound with a halogen bridge: L2Ir (-X) 2IrL2.

1. The water-soluble organic solvent M is a water-soluble alcohol such as 2-ethoxyethanol, 2-methoxyethanol, 1, 3-propanediol, 1, 2-propanediol, ethylene glycol or glycerin; The volume ratio of the water-soluble organic solvent to water is any ratio. At the end of the reaction, a certain inorganic salt is added to the water. The inorganic salt type is not particularly limited as long as it is a water-soluble inorganic salt; the addition of the inorganic salt is advantageous for purification and post-treatment of the product, especially for a product having a large solubility. Good choice.

2. The ruthenium trihalide hydrate is ruthenium trichloride hydrate or ruthenium tribromide hydrate.

3. The second step reaction comprises the steps of: adding ligand C, L2Ir(-X) 2IrL2 to solvent N, adding an appropriate amount of catalyst X, and stirring at a certain temperature for several hours to separate the product.

The two-step reaction ligand C can be the following structural formula:

Al~6: H, methyl, ethyl, propyl, isopropyl, F, CF _3, phenyl; Al~6 may be the same or different. 4. Catalyst X is one of organic bases. A suitable organic base is miscible with solvent N, causing ligand C to react rapidly with L2Ir(-X)2IrL2. The addition reaction temperature of the catalyst X may be from -78 ° C to 110 ° C, preferably in the range of from -50 ° C to 110 ° C, and more preferably in the range of from -50 ° C to 100 ° C. The reaction time can be from 30 minutes to 10 hours, and the better time can be from 30 minutes to 6 hours. The reaction is directly filtered, and the obtained product has a purity of 99%, which can meet the requirements of industrial applications.

5. The amount of catalyst X added is 1% to 10 times that of L2Ir( -X)2IrL2, and the preferred range is 5% to 10 times, and more preferably 5% to 8 times. The addition amount of ligand C is L2Ir(-X)2IrL2 from 2 to 20 times, and the optimization range is from 2 to 15 times, and the optimum range is from 2 to 10 times.

6. According to claim 5, the catalyst X can be:

(1) An alcohol sodium salt or a potassium salt such as sodium t-butoxide, sodium t-butoxide, lithium t-butoxide, sodium methoxide, sodium ethoxide or sodium isopropoxide.

(2) Organic amines such as methylamine, dimethylamine, ethylamine, diethylamine, triethylamine and tributylamine.

(3) Organic lithium such as methyl lithium, n-butyl lithium, isobutyl lithium or t-butyl lithium.

7. The second solvent N: may be methanol, ethanol, isopropanol, isobutanol, tert-butanol, acetone, butanone, THF, diethyl ether, propyl ether, etc., which are useful for chlorine bridge dissociation of alcohols or ethers. A mixture of one or more of the solvents, the temperature is controlled at -78 to 110 °. .

Through extensive experiments by the inventors of the present invention, it has been found that the improved method is suitable for the synthesis of red light, which greatly shortens the reaction time and improves the yield; more importantly, the reaction can be directly filtered to obtain the desired product without purification. More than 99% of high-purity red light is obtained, which saves cost and is beneficial to the promotion of red light materials. DRAWINGS

Figure 1 is a ruthenium, bis[5-fluoro-2-(1-isoquinoline)-4-methylphenyl (2, 4-pentanedione)-nuclear magnetic spectrum, except for the product peak, the reaction solvent and A trace of the ligand peak.

Figure 2 is bis(2-phenylquinoline) (acetylacetone) ruthenium (III) (Ir(2-phq) 2 (acac)) ₀ Figure 3 is bis(2-phenylquinoline) (2, 2, 6, 6-tetramethylheptane-3, 5-one) ruthenium (III)

(Ir(dpm)PQ2).

Figure 4 is a bismuth, bis(5-bis[f,h]pyrazine-)(acetylacetonate)-, except for the product peak, a solvent and a trace of the ligand peak.

Figure 5 is hydrazine, bis[2-(3,5-diphenyl-2-pyrazine-N1)phenyl-] (2, 2, 6, 6-tetramethyl 1_3, 5-heptanedione) - In addition to the product peaks are reaction solvents and traces of ligand peaks. BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides an improved method for preparing red light. In order to make the objects, technical solutions and effects of the present invention clearer and more complete, the following is a further detailed description of the present invention. It is to be understood that the examples herein are merely illustrative of the invention and are not intended to limit the scope of the invention.

Example 1. Synthesis of ruthenium, bis[5-fluoro-2-(1-isoquinoline)-4-methylphenyl (2,4-pentanedione)-

500ML four-necked bottles were sequentially added 1. 5G hydrated antimony trichloride A, 4G ligand B1 (Reference Dalton Trans., 2005, 1583-1590), 200ML ethylene glycol ether, 50ML water. Nitrogen was added for 30 minutes and heated to reflux overnight. 2 L of water and 200 g of lithium chloride were stirred and dissolved, and the reaction solution was poured into water to precipitate a large amount of red solid, which was filtered and dried to obtain a red solid powder of 2. 6 g in a yield of 90%.

The 3L four-necked bottle was sequentially added with Wl 25G, acetylacetone (CI) 8G, sodium methoxide 20G, 2L methanol, stirred under nitrogen for 30 minutes, and heated to reflux (64 degrees) for 2 hours to obtain a large number of bright red solids, filtered, and washed with methanol 200ML. Drying gave 27G red solid with a yield of 95%. HNMR sees the drawing.

Example 2 Synthesis of bis(2-phenylquinoline)(acetylacetonate) ruthenium (Ι Π) ( Ir (2-phq) 2 (acac )

The 3L four-necked bottle was sequentially added with 25G hydrated antimony trichloride A, 37G ligand B2 (Reference Dalton Trans., 2005, 1583-1590), 1500ML ethylene glycol, 500ML water. Nitrogen was added for 30 minutes and heated to reflux overnight to give a red solid. 5 L of water and 1 KG of potassium chloride were stirred and dissolved, and the reaction solution was poured into water to precipitate a large amount of solid, which was filtered and dried to obtain a 45 G red solid powder, and the yield was 92%.

The 3L four-necked bottle was sequentially added with W2 25G, acetylacetone (C1) 8G, dimethylamine 20G, 2L methanol, stirred under nitrogen for 30 minutes, and heated to reflux (64 degrees) for 2 hours to obtain a large number of bright red solids, filtered, methanol 200ML Washing and drying gave a 27G red solid with a yield of 94%. HNMR sees the drawing.

Example 3, Di(2-phenylquinoline)(2,2,6,6-tetramethylheptane-3,5-one)indole (I I I) ( Ir (dpm) PQ2 )

The 500 ML four-necked flask was sequentially added with 1.5 g of ruthenium trichloride A, 4G ligand B3 (Reference Dalton Trans., 2005, 1583-1590), 200 ML glycerol, 100 ML water. Nitrogen filling for 30 minutes, heating and refluxing Overnight. 2, The red solid powder was obtained in a yield of 90%. The solution was poured into water, and the reaction solution was poured into water, and a large amount of solid was precipitated.

3L four-necked flask was sequentially added with W3 25G, 2,2,6,6-tetramethylheptane-3,5-keto(2) 156, diethylamine 20G, 2L methanol, ethanol (1:1), nitrogen-filled After stirring for 30 minutes, the mixture was heated to reflux for 1 hour to obtain a large amount of bright red solid, which was filtered, washed with methanol, and then dried to give 28 g of red solid, yield 95%. HNMR See the attached drawing.

Example 4, hydrazine, bis(5-di[f,h]pyrazine-) (acetylacetone) -

500ML four-necked bottles were sequentially added with 1. 5G hydrated antimony trichloride A, 4G ligand B4 (Reference Dalton Trans., 2005, 1583-1590, US7696348), 200ML ethylene glycol methyl ether, 50ML water. Nitrogen was added for 30 minutes and heated to reflux overnight to give a red solid. 2 L of water and 200 g of lithium chloride were stirred and dissolved, and the reaction solution was poured into water to precipitate a large amount of solid, which was filtered and dried to obtain a red solid powder of 2. 5 g in a yield of 90%.

3L four-necked bottle was sequentially added with W4 25G, acetylacetone (C1) 15G, tributylamine 20G, 2L methanol, ethanol (1:1), stirred under nitrogen for 30 minutes, and heated to reflux for 2 hours to obtain a large number of bright red solids. Washing and drying with methanol 200ML gave 26G red solid with a yield of 90%. (Document Adv. Mater. 2003, 15, 224 - 228 reported 70%, reaction time 12 hours.)

Example 5, hydrazine, bis[2-(3,5-diphenyl-2-pyrazine-N1)phenyl-] (2,2,6,6-tetramethyl 1-3, 5-heptane Dione) -

500ML four-necked bottles were sequentially added with 1.5G hydrated antimony trichloride A, 4G ligand B5 (Ref. US7696348), 200ML1, 2-propanediol, 50ML water. Nitrogen was added for 30 minutes and heated to reflux overnight to give a red solid. 2 L of water and 200 g of sodium chloride were stirred and dissolved, and the reaction solution was poured into water to precipitate a large amount of solid, which was filtered and dried to obtain a red solid powder of 2.6 g in a yield of 90%.

The 3L four-necked bottle was sequentially added with W525G, 2, 2, 6, 6-tetramethylheptane-3, 5-ketone (C2) 15G, 2LTHF, stirred under nitrogen for 30 minutes, and added with methyl methoxide 30ML at -20 degrees ( 2.5 mol / l, diethyl ether solution), the reaction was carried out for 2 hours to obtain a large amount of bright red solid, which was filtered, washed with methanol 200 ml, and dried to give a red solid of 28 g, yield 95%. HNMR sees the drawing.

Claims

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1. A method for synthesizing organometallic ruthenium compounds, including two independent reactions: (1) ruthenium trihalide hydrate A reacts with neutral ligand B to form a ruthenium compound with a halogen bridge: L2Ir (μ-X) 2IrL2 , L: represents a bi-coordinated cyclic metal ligand formed by a neutral ligand, (μ -Χ): represents a bridged halogen, (2) an anthracene compound with a halogenated bridge and a slight excess of ligand C The reaction gives [CN] ₂ (LX) _; LX represents another ligand formed by ligand C; characterized in that the first step reaction comprises the following steps: ruthenium trihalide hydrate, neutral ligand B added The water-soluble organic solvent and water are refluxed for several hours, cooled, poured into water, and the product is filtered to obtain a hydrazine compound having a halogen bridge: L2Ir (-X) 2IrL2.

The synthesis method according to claim 1, wherein the water-soluble organic solvent M is 2-ethoxyethanol, 2-methoxyethanol, 1, 3-propanediol, 1, 2-propanediol, and ethylene A water-soluble alcohol such as an alcohol or glycerin; and a volume ratio of the water-soluble organic solvent to water is an arbitrary ratio.

The synthesis method according to claim 1, wherein the reaction is completed, and a certain inorganic salt is added to the water. The inorganic salt species is not particularly limited as long as it is a water-soluble inorganic salt; the addition of the inorganic salt is advantageous for the purification of the product. And post processing.

The synthesis method according to claim 1, wherein the ruthenium trihalide hydrate is ruthenium trichloride hydrate or ruthenium tribromide hydrate.

The synthesis method according to claim 1, wherein the second step reaction comprises the steps of: adding a ligand C, L2Ir ( -X) 2IrL2 to the solvent N, adding an appropriate amount of the catalyst X, and stirring the number at a certain temperature. In hours, separate the product.

6. The synthesis method according to claim 1, wherein the second step reaction ligand C may be the following structural formula:

I

Al~6: H, methyl, ethyl, propyl, isopropyl, F, CF _3, phenyl; Al~6 may be the same or different.

The synthesis method according to claim 5, wherein the catalyst X is one of an organic base, and a suitable organic base is miscible with the solvent N, causing the ligand C to react rapidly with L2Ir(-X)2IrL2 without causing Other side reactions; the reaction temperature of the catalyst X may be from -78 ° C to 110 ° C, preferably in the range of -50 ° C to 110 ° C, more preferably in the range of -50 ° C to 100 ° C _; It can be 30 minutes to 10 hours, and the better time can be 30 minutes to 6 hours; the reaction is directly filtered, and the obtained product has a purity of 99%, which can meet the requirements of industrial applications.

The synthesis method according to claim 5, wherein the catalyst X is added in an amount of 1% to 10 times L2Ir (μ - X) 2IrL2, preferably in a range of 5% to 10 times, and more preferably in a range of 5 %~8 times; the addition amount of ligand C is L2Ir(-X)2IrL2 from 2 to 20 times, the optimization range is from 2 to 15 times, and the optimization range is from 2 to 10 times.

9. According to claim 5, wherein the catalyst X can be:

(1) an alcohol such as sodium t-butoxide, sodium t-butoxide, lithium t-butoxide, sodium methoxide, sodium ethoxide or sodium isopropoxide; sodium salt; potassium salt;

(2) organic amines such as methylamine, dimethylamine, ethylamine, diethylamine, triethylamine and tributylamine;

10. The method according to claim 5, wherein the second solvent N is methanol, ethanol, isopropanol, isobutanol, tert-butanol, acetone, butanone, THF, diethyl ether, propyl ether, etc. A mixture of one or more of the alcohol or ether solvents dissociated from the bridge, and the temperature is controlled at -78 ° C to 110 ° C.