WO2017035973A1 - Novel aromatic amine compound and preparation and application thereof - Google Patents

Abstract

Disclosed in the present application is a novel aromatic amine compound, having the following general formula: R1, R2, and R3 all being one of an alkyl group having 1-30 hydrogen atoms or carbon atoms, an aryl group having 6-50 carbon atoms, a heterocyclyl group having 5-50 carbon atoms, or an aromatic amine group having 6-30 carbon atoms; and Ar₁ and Ar₂ are both one of an alkylaryl group having 7-50 hydrogen atoms or carbon atoms, an alkaryloxy group having 7-50 carbon atoms, an alkarylmercapto group having 7-50 carbon atoms, an aryl group having 6-50 carbon atoms, a heterocyclyl group having 5-50 carbon atoms, an aromatic amine group having 6-30 carbon atoms, an aryloxy group having 6-50 carbon atoms, or an aryloxyarylmercapto group having 6-50 carbon atoms. The present aromatic heterocyclic compound is used for manufacturing organic electroluminescent devices, and devices manufactured using the novel heterocyclic diffractive matter have the characteristics of high brightness, good heat resistance, long service life, and high efficiency.

Description

A new aromatic amine compound and preparation and application thereof

This application claims priority to Chinese Patent Application No. 201510546562.0, entitled "A New Aromatic Amine Compound and Its Preparation and Application", filed on August 31, 2015, the entire contents of which is hereby incorporated by reference. This is incorporated herein by reference.

Technical field

The invention relates to the field of electroluminescent materials, in particular to a novel aromatic amine compound and its preparation and application.

Background technique

The host material in the electroluminescent device mainly has two types of small molecule host materials and polymer host materials. Many high-efficiency electroluminescent devices have been prepared by doping a phosphorescent complex with a small molecule host material as a light-emitting layer. In recent years, the preparation of electroluminescent devices by doping various phosphorescent complex guest bodies with a polymer host material as a light-emitting layer has received much attention. Due to the rapid development of optoelectronic communication and multimedia in recent years, organic optoelectronic materials have become the core of the modern social information and electronics industry.

Organic electroluminescent device (OLED) is a new type of flat display device. Compared with small molecule electroluminescent devices, it has energy saving, fast response, stable color, strong environmental adaptability, no radiation, long life and light weight. Thin thickness and other characteristics. An organic electroluminescent device generally consists of two opposing electrodes and at least one layer of an organic luminescent compound interposed between the two electrodes. Charge is injected into the organic layer formed between the anode and the cathode to form electron and hole pairs, causing light emission of an organic compound having fluorescent or phosphorescent properties. A voltage is applied between the anode and the cathode, and holes are injected from the anode through the hole transport layer into the light-emitting layer, while electrons are injected from the cathode through the electron transport layer into the light-emitting layer. In the region of the light-emitting layer, carriers are rearranged to form excitons. The excited exciton transitions to the ground state, causing the luminescent layer molecules to emit light, and the image is thus formed.

Representative materials of hole transport materials in organic electroluminescent devices are as follows:

The properties of the currently required materials are that the materials have thermal stability and rapid electron mobility and high efficiency and long life of the illuminants, but the existing materials have general properties.

Summary of the invention

The object of the present invention is to provide a novel aromatic amine compound and its preparation and application, which is a hole transporting material with good luminous efficiency, which will be raised by a pyrido[3,2-g]quinoline compound. Electron mobility, and the preparation of this new heterocyclic compound diffractive material into a device, has good luminous efficiency.

The invention adopts the following technical solutions:

The present invention provides a novel aromatic amine compound whose molecular formula is:

Wherein R1, R2 and R3 are each a hydrogen atom or an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 50 carbon atoms or a heterocyclic group having 5 to 50 carbon atoms or an aromatic group having 6 to 30 carbon atoms; One of the amine groups;

Ar ₁ and Ar ₂ are each a hydrogen atom or an alkylaryl group having 7 to 50 carbon atoms, an alkaryloxy group having 7 to 50 carbon atoms or an alkylarylcarbonyl group having 7 to 50 carbon atoms or a carbon number of 6 to 50. An aryl group or a heterocyclic group having 5 to 50 carbon atoms or an aromatic amine group having 6 to 30 carbon atoms or an aryloxy group having 6 to 50 carbon atoms or an aryloxyarylfluorenyl group having 6 to 50 carbon atoms. One of them.

Preferably, in the formula, R1, R2, and R3 are independently selected from any one of the following chemical formulas, wherein the above definition is satisfied:

Wherein X and Y are independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkaryloxy group having 7 to 30 carbon atoms a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms And one of a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms.

Further, the aromatic amine compound molecule may be selected from any one of the following:

The invention also provides a preparation method of an aromatic amine compound, comprising the following steps:

Step 1, according to the following reaction formula, the coupling reaction and methoxy detachment are carried out to obtain a 3-PQDO compound.

Step 2, the following formula includes a chlorination displacement reaction of a ketone group and a coupling reaction to synthesize a compound

The method specifically includes the following steps:

Step 11, preparing intermediate 1

0.2 mol-0.3 mol of the reactant 2 was dissolved in 300 mL of anhydrous diethyl ether, a dry ice bath at -77 ° C - 79 ° C, under the condition of isolating oxygen, 44 mL of 2.5 M butyl lithium was added, and the reaction was stirred for 1 hour. 0.1 mol-0.2 mol of the reactant 1 is added, and the reaction is carried out for 2 hours, and then gradually raised to 15 to 25 ° C. The reaction is terminated by adding water, and then the reaction product is separated, the aqueous layer is separated, and the aqueous layer is extracted with ethyl acetate. Drying the organic solvent, separating with a volume ratio of 9:1 dichloromethane and polyethylene = 9:1 to obtain intermediate 1;

Step 12, preparing intermediate 2

41 mmol-42 mmol of Intermediate 1 was dissolved in 250 mL-300 mL of tetrahydrofuran, and the temperature was lowered to 0 ° C. After the mixture was added to LTMP, the reaction was stirred at 0 ° C for 2 hours;

Synthesis of LTMP: 500 mL of tetrahydrofuran dissolves 0.13 mol of butyllithium and 0.14 mol of 2,2,6,6-tetramethylpiperidine at 0 ° C;

Then, 200 mL of water was added to terminate the reaction, the aqueous layer was separated, the organic layer was spun dry, and separated by a 10:1 volume ratio of dichloromethane and petroleum ether to obtain Intermediate 2;

Step 21, intermediate 3 is obtained by displacement of a ketone group

Accurately weigh 10g-15g of intermediate 2 into the reaction flask, add 200mL-300mL acetonitrile, and then weigh 30g-50g of phosphorus oxychloride slowly into the reaction bottle, slowly increase the temperature to 60 °C-70 after the addition is completed. °C, the reaction time is 4-6 hours, after the reaction is completed, add water carefully to remove, add a larger amount of sodium carbonate saturated solution to adjust the pH value of 7-8, then add dichloromethane, extract three times, spin dry to obtain intermediate 3;

Step 22, preparing an aromatic amine compound by a coupling reaction

14g-16g of intermediate 3, 17g-19g of reactant 3, tetrakistriphenylphosphine palladium 3g-5g were added to the reaction flask, and then a mixture of toluene, ethanol and water in a volume ratio of 2:1:1 was added. 500mL-600mL, nitrogen protection, stirring and heating to 110 ° C reaction 22-24 hours, after which the system is cooled, liquid separation, spinning toluene, adding dichloromethane to dissolve solids, passing the column, with a volume ratio of 2:1 petroleum ether Rinse with ethyl acetate to prepare an aromatic amine compound;

Wherein reactant 1 is

Reactant 2 is

Reactant 3 is

Intermediate 1 is

Intermediate 2 is

Intermediate 3 is

The present invention also provides the use of a novel aromatic amine compound for use in the fabrication of organic electroluminescent devices.

The device includes a first electrode, a second electrode, and one or more organic compound layers disposed between the two electrodes, the at least one organic compound layer comprising at least one of the aromatic amine-based compounds.

The organic layer includes a hole injection layer, a hole transport layer, and a hole transporting skill layer, a hole transporting skill layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron injecting layer, and an electron transporting skill. It also has an electron injection skill layer.

The organic electro-optic device further includes an organic light-emitting device, an organic solar cell, an electronic paper, an organic photoreceptor, or an organic thin film transistor.

The beneficial effects of the invention:

The novel heterocyclic diffractive material of the present invention is an introduction of Ar ₁ , Ar ₂ and R ₁ -R3 in pyrido[2,3-g]quinoline to increase electron density and upward skill, in addition to pyrido[3,2-g]quinoline The side chains R ₁ and R ₂ have the advantages of improved performance and improved skill.

The device manufactured by using the novel heterocyclic diffractive material of the present invention has characteristics of high brightness, excellent heat resistance, long life, and high efficiency.

detailed description

The technical solutions in the embodiments of the present invention are clearly and completely described in the following with reference to the accompanying drawings in the embodiments of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.

The invention provides a novel aromatic amine compound having the molecular formula:

Wherein R ₁ , R ₂ and R ₃ are each a hydrogen atom or an alkyl group having 1 to 30 carbon atoms or an alkyl group having 6 to 50 carbon atoms or a heterocyclic group having 5 to 50 carbon atoms or a carbon number of 6 to 50; One of 30 aromatic amine groups;

Ar ₁ and Ar ₂ are each a hydrogen atom or an alkylaryl group having 7 to 50 carbon atoms, an alkaryloxy group having 7 to 50 carbon atoms or an alkylarylcarbonyl group having 7 to 50 carbon atoms or a carbon number of 6 to 50. An aryl group or a heterocyclic group having 5 to 50 carbon atoms or an aromatic amine group having 6 to 30 carbon atoms or an aryloxy group having 6 to 50 carbon atoms or an aryloxyarylfluorenyl group having 6 to 50 carbon atoms. One of them.

The new aromatic amine compound molecule can be selected from any of the following:

The method for preparing an aromatic amine compound of the present invention comprises the following steps:

Step 1, the coupling reaction and the methoxy detachment are carried out according to the following reaction formula to obtain a 3-PQDO compound.

Step 2, the following formula includes a chlorination displacement reaction of a ketone group and a coupling reaction to synthesize a compound

The method specifically includes the following steps:

Step 11, preparing intermediate 1

0.2 mol to 0.3 mol of the reactant 2 was dissolved in 300 mL of anhydrous diethyl ether, a dry ice bath at -77 ° C to 79 ° C, and under the condition of isolating oxygen, 44 mL of 2.5 M butyl lithium was added, and the reaction was stirred for 1 hour. Adding 0.1 mol to 0.2 mol of the reactant 1 and reacting for 2 hours, then gradually increasing to 15 to 25 ° C, adding water to terminate the reaction, and then separating the reaction product, separating the aqueous layer, and the aqueous layer is ethyl acetate. After extraction, the organic solvent was spin-dried, separated by a 9:1 volume ratio of dichloromethane and polyethylene = 9:1 to obtain intermediate 1;

Step 12, preparing intermediate 2

41 mmol to 42 mmol of the intermediate 1 was dissolved in 250 mL to 300 mL of tetrahydrofuran, and the temperature was lowered to 0 ° C. After the mixture was added with LTMP, the reaction was stirred at 0 ° C for 2 hours;

Synthesis of LTMP: 500 mL of tetrahydrofuran dissolves 0.13 mol of butyllithium and 0.14 mol of 2,2,6,6-tetramethylpiperidine at 0 ° C;

Then, 200 mL of water was added to terminate the reaction, the aqueous layer was separated, the organic layer was spun dry, and separated by a 10:1 volume ratio of dichloromethane and petroleum ether to obtain Intermediate 2;

Step 21, intermediate 3 is obtained by displacement of a ketone group

Accurately weigh 10g-15g of intermediate 2 into the reaction flask, add 200mL-300mL acetonitrile, and then weigh 30g-50g of phosphorus oxychloride slowly into the reaction bottle, slowly increase the temperature to 60 °C-70 after the addition is completed. °C, the reaction time is 4-6 hours, after the reaction is completed, add water carefully to remove, add a larger amount of sodium carbonate saturated solution to adjust the pH value of 7-8, then add dichloromethane, extract three times, spin dry to obtain intermediate 3;

Step 22, preparing an aromatic amine compound by a coupling reaction

14g-16g of intermediate 3, 17g-19g of reactant 3, tetrakistriphenylphosphine palladium 3g-5g were added to the reaction flask, and then a mixture of toluene, ethanol and water in a volume ratio of 2:1:1 was added. 500mL-600mL, nitrogen protection, stirring and heating to 110 ° C reaction 22-24 hours, after which the system is cooled, liquid separation, spinning toluene, adding dichloromethane to dissolve solids, passing the column, with a volume ratio of 2:1 petroleum ether Rinse with ethyl acetate to prepare an aromatic amine compound;

Wherein reactant 1 is

Reactant 2 is

Reactant 3 is

Intermediate 1 is

Intermediate 2 is

Intermediate 3 is

The aromatic heterocyclic compound of the present invention is used for the production of an organic electroluminescent device.

The present invention provides the use of the aromatic amine compound of the above technical solution or the aromatic amine compound obtained by the preparation method of the above technical solution in an organic electroluminescent device, wherein the aromatic amine compound is used as a hole transport Material or hole blocking material.

The present invention has no special requirements on the structure of the organic electroluminescent device, and a conventional organic electroluminescent device can be used. In the present invention, the organic electroluminescent device can be specifically an organic solar cell, an OLED for illumination, Flexible OLED, organic photoreceptor, organic transistor. In the present invention, the organic electroluminescent device preferably includes a first electrode, a second electrode, and one or more organic layer disposed between the two electrodes; more preferably at least one organic layer in the organic layer An aromatic amine compound obtained by the above-described method of the aromatic amine compound or the above-described technical solution, and at least one organic layer in the organic layer contains the aromatic amine compound as described in the above technical solution or The aromatic amine compound and other substances obtained by the preparation method described in the above technical scheme.

The invention has no special requirements on the organic layer of the organic electroluminescent device, according to the conventional The organic layer of the organic electroluminescent device can be set. In the present invention, the organic layer preferably includes at least a hole injection layer, a hole transport layer, a charge transport layer having both hole injection and hole transporting skills, an electron blocking layer, a light emitting layer, and a hole blocking layer. And an electron transport layer, an electron injection layer, and one of a transfer layer having both electron transport and electron injection skills; more preferably, the hole injection layer and the hole transport layer have both hole injection and At least one of the three layers of the hole transporting technique is a substance containing a conventional hole injecting substance, a hole transporting substance, a substance having both hole injection and hole transporting ability, or an electron transporting substance.

Further preferably, the light-emitting layer is a red, yellow or cyan light-emitting layer. When the above-mentioned light-emitting layer is cyan, the above novel heterocyclic derivative is used in a cyan main body or a cyan doping application, and provides an organic light-emitting device having high efficiency, high brightness, high resolution, and long life.

Example: Synthesis of intermediates

Synthesis of Intermediate 2-Chloro-6-Phenylpyridine (1-1)

Synthetic method: 2-bromo-6-chloropyridine (21.2 g, 0.11 mol), phenylboronic acid (12.2 g, 0.10 mol), tetrakistriphenylphosphine palladium 0.5 g, added to a 1000 ML reaction flask, added toluene 400 ML, carbonic acid The sodium aqueous solution (2N, 150 mL) was protected with nitrogen and the oil was reacted at 80 ° C for 24 hours.

Post-treatment process: cool down, stand still for 30 minutes, retain the organic layer, spin dry toluene, dissolve the solid with methylene chloride, separate the column, PE: DCM = 1:1, get 1-1 (9.6 g, y=51%).

Synthesis of intermediates 1-2 and 1-3

The above synthesis method of the intermediate 1-1 gives the following compounds:

Synthesis of the intermediate 6-chloro-N,N-diphenylpyridin-2-amine (1-4):

Synthetic method: Diphenylamine (16.9 g, 0.10 mol) and sodium t-butoxide (28 g, 0.30 mol), 400 mL of toluene were added to the reaction flask, stirred for 30 minutes, protected with nitrogen, and then 6-bromo-2-chloropyridine was added. (23.09 g, 0.12 mol), 1.5 g of tris(diisopropylideneacetone)dipalladium, and finally 4 g of tri-tert-butylphosphine, and the mixture was heated to 100 ° C for 24 hours. Post-treatment process: the system is cooled, the reaction is stopped by adding water, filtered, the filtrate is separated, the toluene is spun dry, a small amount of dichloromethane is added to dissolve the solid, and petroleum ether: dichloromethane = 3:1 (volume ratio) is separated by column to obtain a solid. (1-4) (14.03g, y=50%).

Synthesis of Intermediates 1-5 and 1-6

The above intermediate 1-4 synthesis method gave the following compounds:

Synthesis of Intermediate 6-Phenyl-2-pyridineboronic Acid (2-1)

2-Chloro-6-phenylpyridine (8.04 g, 42.4 mmol) was added to a three-necked flask, 100 mL of THF was added, and the mixture was stirred under nitrogen for 30 minutes at -78 ° C, then 21 mL of n-butyllithium (2.5 M) was added. In an hour, 14 g of triisopropyl borate was further added, and the reaction was carried out at a low temperature for 1 hour, and gradually returned to room temperature. After the work-up process, 2M hydrochloric acid was added to the system to make the pH of the solution 4-5, and the solution was separated and the aqueous layer was extracted with ethyl acetate. The organic layer was combined and dried to give white solid (2-1) (6.8 g) , y=80%).

Synthesis of intermediates 2-2 to -6

The above synthesis method of the intermediate 2-1 gave the following compounds:

Synthesis of intermediate 3-(pyridine-2-carbonyl)pyridinecarboxylic acid methyl ester (3-1)

Synthetic method: 3-pyridine boronic acid (0.1 mol) was dissolved in 300 mL of anhydrous diethyl ether, and dried in an ice bath at -78 ° C. Under the condition of isolating oxygen, 44 mL of butyl lithium (2.5 M) was added, and the reaction was stirred for 1 hour. Methyl 2-bromo-picolinate (0.1 mol) was added, and the reaction was carried out for 2 hours, and then gradually increased to 15 to 25 ° C, and the reaction was terminated by adding water.

Post-treatment process: the reaction product was separated, the aqueous layer was separated, the aqueous layer was extracted with ethyl acetate, and the organic solvent was spun and separated by dichloromethane: polyethylene = 9:1 (volume ratio). White solid 3-1 (yield 51%).

Synthesis of Intermediates 3-2 to 3-7

The above synthesis of the intermediate 3-1 gave the following compounds:

Synthesis of intermediate pyridine [2,3-g]quinoline-5,10-dione (4-1)

Synthetic method: 3-1 (41.5 mmol) was dissolved in 300 mL of tetrahydrofuran, and the temperature was lowered to 0 ° C. After the mixture was added with LTMP, the reaction was stirred at 0 ° C for 2 hours.

Synthesis of LTMP: 500 mL of tetrahydrofuran dissolved 0.13 mol of butyllithium and 0.14 mol of 2,2,6,6-tetramethylpiperidine at 0 °C.

After the treatment: the reaction was terminated by adding 200 mL of water, the aqueous layer was separated, the organic layer was dried, and then separated with dichloromethane: petroleum ether = 10:1 to give a solid (4-1) (3.8 g, yield 4%).

Synthesis of Intermediates 4-2 to 4-7

The above intermediate 4-1 synthesis method gave the following compounds:

Synthesis of Intermediate 5,10-Dichloropyrido[2,3-g]quinoline (5-1)

Accurately weigh 4-1 (10g, 47.8mmol) into the reaction flask, add 200mL acetonitrile, and then weigh 30g of phosphorus oxychloride slowly into the reaction bottle, slowly increase the temperature to 60 ° C after the addition, the reaction time It is 5 hours. After the reaction is completed, the mixture is carefully extracted by adding water, and then the saturated sodium carbonate saturated solution is added to adjust the pH value of 7-8, and then dichloromethane is added, extracted three times, and dried to obtain a solid (5-1) (7.5 g, y = 63%).

Synthesis of Intermediates 5-2 to 5-7

The above intermediate 5-1 synthesis method gave the following compounds:

Example: Synthesis of Aromatic Amine Compounds

Example

Synthesis of 5,10-diphenylpyrido[2,3-g]quinoline (6-1)

The prepared 5,10-dichloro-pyrido[g]quinoline 5-1 (14.8 g, 0.6 mmol), 4-boric acid pyridine (18 g, 0.146 mmol), tetrakistriphenylphosphine palladium 4 g was added to the reaction flask. In addition, a total of 600 mL of a 2:1:1 (volume ratio) mixture of toluene, ethanol and water was added, and the mixture was purged with nitrogen, and the mixture was heated to 110 ° C for 24 hours. Post-treatment process: system cooling, liquid separation, spinning dry toluene. Dichloromethane was added to dissolve the solid, and the mixture was washed with petroleum ether: ethyl acetate = 2:1 (volume ratio) to give solid (6-1) (13 g, y = 65%).

Synthesis of Examples 6-2 to 6-17

The above synthesis method of Example 6-1 gave the following compounds:

Example

Synthesis of N5,N5,N10,N10-Tetraphenylpyrido[2,3-g]quinoline-5,10-diamine (6-23)

According to the synthesis method of the intermediate 1-4, 5,10-dichloropyrido[3,2-g]quinoline (6.0 g, 24 mmol), diphenylamine (4.4, 24 mmol) was used as a raw material to obtain N5. N5, N10, N10-tetraphenylpyrido[3,2-g]quinoline-5,10-diamine (6.17 g, y=50%).

Example

Synthesis of 5,10-bis(1-naphthyloxy)pyrido[2,3-g]quinoline (6-24)

1-hydroxynaphthalene (14g, 0.1mol) was dissolved in 100mL of anhydrous tetrahydrofuran, stirred, accurately weighed NaH (0.96g, 0.4mol) was added to the reaction bottle in batches, not too fast, to prevent too much bubble generation After the addition, the solution appeared yellow, and then 5,10-dichloropyrido[3,2-g]quinoline (27.50 g, 0.11 mol) was added, which was also added in portions and allowed to react at room temperature overnight. Post-treatment: filtration, removal of solid matter, the filtrate was spun dry, dissolved in dichloromethane, and the column was washed with petroleum ether: ethyl acetate = 1:5 (volume ratio) to obtain a solid (23.20 g, y = 50%). ).

Example

Synthesis of 5,10-bis(1-naphthylthio)pyrido[2,3-g]quinoline (6-25)

1-Naphthylthiol (1.6 g, 10 mmol), 5,10-dichloropyrido[3,2-g]quinoline (2.48 g, 10 mmol), potassium hydroxide (840 mg, 15 mmol), mPANI/pFe3O4 ( 2.5 g, 5 mol%) H2O (30 mL) was mixed and heated for 8 hours. The organic phase was extracted with EtOAc (EtOAc):EtOAc (EtOAc)

Example

Synthesis of 5-(1-naphthyl)-10-(2-naphthyl)pyrido[2,3-g]quinoline (6-26)

Synthetic method: Referring to the synthesis of E-1, 5,10-dichloropyrido[3,2-g]quinoline (4.41 g, 17.8 mmol) and 2-naphthaleneboronic acid (3.4 g, 19.6 mmol) were added to obtain a solid. 5-bromo-10-(2-naphthyl)pyrido[3,2-g]quinoline (2.91 g, yield 48%).

Example

Synthesis method: With reference to the synthesis of E-1, 5-bromo-10-(2-naphthyl)pyrido[3,2-g]quinoline (2.91 g, 8.5 mmol) and 1-naphthaleneboronic acid (1.65 g, 9.6 mmol) gave solid E-23 (1.76 g, yield 48%).

Experimental example:

Preparation of organic light-emitting device

Will Fisher's coating thickness is

The ITO glass substrate was washed twice in distilled water, ultrasonically washed for 30 minutes, washed sequentially with isopropanol, acetone, and methanol for 30 minutes, repeatedly washed twice with distilled water, ultrasonically washed for 10 minutes, dried, and transferred to a plasma cleaning. In the machine, the substrate was washed for 5 minutes and sent to a vapor deposition machine. Evaporation of the hole injection layer 2-TNATA on the prepared ITO transparent electrode

Hole transport layer a-NPD evaporation

Cyan body AND/doped 5% TPPDA evaporation

Substance blocking layer and hole transport layer TPBi or material evaporation of Example E

cathode

The above process organic evaporation rate is maintained

LiF is

Al is

The electroluminescence characteristics of the organic light-emitting device manufactured by the above method are shown in the following table.

From the results of the above table, it can be seen that the luminous efficiency and life characteristics of the novel organic amine derivative of the present invention are remarkably improved.

The present invention is an organic light-emitting device using a novel aromatic amine derivative, and as a result of obtaining good luminous efficiency and longevity, the present invention is useful in the highly practical OLED industry. The organic light-emitting device of the present invention is suitable for use in a flat panel display, a planar light-emitting body, a surface-emitting OLED light-emitting body for illumination, a flexible light-emitting body, a copying machine, a printer, an LCD backlight, or a light source, a display panel, a logo, and the like.

The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., which are included in the spirit and scope of the present invention, should be included in the present invention. Within the scope of protection.

Claims (9)

1. A novel aromatic amine compound characterized in that the molecular formula of the compound is:

   

   Wherein R1, R2 and R3 are each a hydrogen atom or an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 50 carbon atoms or a heterocyclic group having 5 to 50 carbon atoms or an aromatic group having 6 to 30 carbon atoms; One of the amine groups;

   Ar ₁ and Ar ₂ are each a hydrogen atom or an alkylaryl group having 7 to 50 carbon atoms, an alkaryloxy group having 7 to 50 carbon atoms or an alkylarylcarbonyl group having 7 to 50 carbon atoms or a carbon number of 6 to 50. An aryl group or a heterocyclic group having 5 to 50 carbon atoms or an aromatic amine group having 6 to 30 carbon atoms or an aryloxy group having 6 to 50 carbon atoms or an aryloxyarylfluorenyl group having 6 to 50 carbon atoms. One of them.
2. The aromatic amine compound according to claim 1, wherein R1, R2 and R3 in the molecular formula of the compound are independently selected from any one of the following chemical formulas:

   

   

   Wherein X and Y are independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkaryloxy group having 7 to 30 carbon atoms a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms And one of a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms.
3. A novel aromatic amine compound according to claim 1 or claim 2, wherein the compound molecule is selected from any one of the following:

   
4. A method for producing an aromatic amine compound according to any one of claims 1 to 3, which comprises the steps of:

   Step 1, according to the following reaction formula, the coupling reaction and methoxy detachment are carried out to obtain a 3-PQDO compound.

   

   Step 2, the following formula includes a chlorination displacement reaction of a ketone group and a coupling reaction to synthesize a compound

   
5. The method according to claim 4, characterized in that it comprises the following steps:

   Step 11, preparing intermediate 1

   0.2 mol-0.3 mol of the reactant 2 was dissolved in 300 mL of anhydrous diethyl ether, a dry ice bath at -77 ° C - 79 ° C, under the condition of isolating oxygen, 44 mL of 2.5 M butyl lithium was added, and the reaction was stirred for 1 hour. 0.1 mol-0.2 mol of the reactant 1 is added, and the reaction is carried out for 2 hours, and then gradually raised to 15 to 25 ° C. The reaction is terminated by adding water, and then the reaction product is separated, the aqueous layer is separated, and the aqueous layer is extracted with ethyl acetate. Drying the organic solvent, separating with a volume ratio of 9:1 dichloromethane and polyethylene = 9:1 to obtain intermediate 1;

   Step 12, preparing intermediate 2

   41 mmol-42 mmol of Intermediate 1 was dissolved in 250 mL-300 mL of tetrahydrofuran, and the temperature was lowered to 0 ° C. After the mixture was added to LTMP, the reaction was stirred at 0 ° C for 2 hours;

   Synthesis of LTMP: 500 mL of tetrahydrofuran dissolves 0.13 mol of butyllithium and 0.14 mol of 2,2,6,6-tetramethylpiperidine at 0 ° C;

   Then, 200 mL of water was added to terminate the reaction, the aqueous layer was separated, the organic layer was spun dry, and separated by a 10:1 volume ratio of dichloromethane and petroleum ether to obtain Intermediate 2;

   Step 21, intermediate 3 is obtained by displacement of a ketone group

   Accurately weigh 10g-15g of intermediate 2 into the reaction flask, add 200mL-300mL acetonitrile, and then weigh 30g-50g of phosphorus oxychloride slowly into the reaction bottle, slowly increase the temperature to 60 °C-70 after the addition is completed. °C, the reaction time is 4-6 hours, after the reaction is completed, add water carefully to remove, add a larger amount of sodium carbonate saturated solution to adjust the pH value of 7-8, then add dichloromethane, extract three times, spin dry to obtain intermediate 3;

   Step 22, preparing an aromatic amine compound by a coupling reaction

   14g-16g of intermediate 3, 17g-19g of reactant 3, tetrakistriphenylphosphine palladium 3g-5g were added to the reaction flask, and then a mixture of toluene, ethanol and water in a volume ratio of 2:1:1 was added. 500mL-600mL, nitrogen protection, stirring and heating to 110 ° C reaction 22-24 hours, after which the system is cooled, liquid separation, spinning toluene, adding dichloromethane to dissolve solids, passing the column, with a volume ratio of 2:1 petroleum ether Rinse with ethyl acetate to prepare an aromatic amine compound;

   Wherein reactant 1 is

   

   Reactant 2 is

   

   Reactant 3 is

   

   Intermediate 1 is

   

   Intermediate 2 is

   

   Intermediate 3 is

   
6. Use of a novel aromatic amine compound according to any one of claims 1 to 3, characterized in that the aromatic heterocyclic compound is used for producing an organic electrodevice.
7. An organic electrodevice produced by using the aromatic amine compound according to any one of claims 1 to 3, characterized in that the device comprises a first electrode, a second electrode and a layer between the electrodes The one or more organic compound layers, the at least one organic compound layer comprising at least one of the aromatic amine compounds.
8. The organic electro-op device according to claim 7, wherein the organic substance layer comprises a hole injection layer, a hole transport layer, a hole injection skill, a hole transport skill layer, an electron blocking layer, and an illuminating layer. The layer, the hole blocking layer, the electron injecting layer, and the electron injecting skill layer and the electron injecting skill layer.
9. The organic electro-op device according to claim 7, wherein the organic electro-optic device further comprises an organic light-emitting device, an organic solar cell, an electronic paper, an organic photoreceptor or an organic thin film transistor.