CN105198875B - A kind of new aromatic amine compound and its preparation and application - Google Patents

A kind of new aromatic amine compound and its preparation and application Download PDF

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CN105198875B
CN105198875B CN201510546022.2A CN201510546022A CN105198875B CN 105198875 B CN105198875 B CN 105198875B CN 201510546022 A CN201510546022 A CN 201510546022A CN 105198875 B CN105198875 B CN 105198875B
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aromatic amine
amine compound
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CN105198875A (en
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高春吉
王士凯
张成成
王贺
崔敦洙
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Olide (Shanghai) Photoelectric Material Technology Co., Ltd.
Shanghai Sheng Xi Photoelectric Technology Co. Ltd.
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention discloses a kind of new aromatic amine compound, its compound molecule formula is：Wherein, R1、R2、R3It is the one kind in the heterocyclic radical of aryl or carbon number 5~50 or the aromatic series amido of carbon number 6~30 of hydrogen atom or the alkyl of carbon number 1~30 or carbon number 6~50；Ar1、Ar2It is the one kind in the aryloxy group aromatic thiohydroxy of the aryloxy group or carbon number 6~50 of the aryl of the alkane aromatic thiohydroxy or carbon number 6~50 of hydrogen atom or the alkaryl of carbon number 7~50 or the aryloxy alkyl of carbon number 7~50 or carbon number 7~50 or the heterocyclic radical of carbon number 5~50 or the aromatic series amido of carbon number 6~30 or carbon number 6~50.This heteroaromatic compounds are used to make organic electroluminescence device, the features such as the device of new heterocycle derivative manufacture possesses brightness high, outstanding heat resistance, long-life and high efficiency.

Description

A kind of new aromatic amine compound and its preparation and application
Technical field
The present invention relates to electroluminescent material field, and in particular to a kind of new aromatic amine compound and its prepare with Using.
Background technology
Material of main part in electroluminescent device mainly has small molecule host material and the class of polymer host material two.Utilize Small molecule host material doping phosphorescent complexes have been prepared for many efficient electroluminescent devices as luminescent layer.In recent years Come, by the use of polymer host material adulterate various phosphorescent complexes objects as luminescent layer prepare electroluminescent device receive compared with Many concerns.Due to developing rapidly for photoelectric communication in recent years and MultiMedia Field, organic optoelectronic material has turned into modern society The core of meeting information and electronic industry.
Organic electroluminescence device (OLED) is a kind of new flat panel display device, with small molecule electroluminescent device phase Than with spies such as energy-conservation, fast response time, colour stable, strong environmental suitability, radiationless, long lifespan, light weight, thickness of thin Point.Organic electroluminescence device, it is typically organic by two opposed electrodes and at least one of which being inserted between two electrodes Luminophor is constituted.Electric charge is injected into the organic layer for being formed between the anode and cathode, to form electronics and hole pair, Make the organic compound with fluorescence or phosphorescent characteristics generate light to launch.Applied voltage between the anode and cathode, hole is just It is injected into luminescent layer by hole transmission layer from anode, meanwhile, electronics is injected into luminescent layer from negative electrode by electron transfer layer In.In light emitting layer area, carrier is reset to form exciton.Excitation state exciton is converted to ground state, causes luminescent layer mulecular luminescence, figure As therefore being formed.
The representative species of hole mobile material are as follows in current organic electroluminescence device：
The characteristic of the material for currently requiring that is that material possesses the efficient of heat endurance and swift electron degree of excursion and illuminator Rate and long-life, but existing material property is general.
The content of the invention
Present invention aim at a kind of new aromatic amine compound and its preparation and application are provided, this is a kind of luminous The good hole mobile material of efficiency, will by pyrido [3,2-g] quinoline compound, rise electronics degree of excursion, and by this Plant novel heterocyclic compound derivative and be prepared into device, there is good luminous efficiency.
The present invention is adopted the following technical scheme that：
The invention provides a kind of new aromatic amine compound, its compound molecule formula is：
Wherein, R1、R2、R3The aryl or carbon for being hydrogen atom or the alkyl of carbon number 1~30 or carbon number 6~50 are former One kind in the heterocyclic radical of subnumber 5~50 or the aromatic series amido of carbon number 6~30；
Ar1、Ar2It is the alkaryl or the aryloxy alkyl or carbon of carbon number 7~50 of hydrogen atom or carbon number 7~50 The heterocyclic radical or carbon number 6 of the alkane aromatic thiohydroxy of atomicity 7~50 or the aryl of carbon number 6~50 or carbon number 5~50 One kind in the aryloxy group aromatic thiohydroxy of~30 aromatic series amido or the aryloxy group of carbon number 6~50 or carbon number 6~50.
Preferably, in formula R1, R2, R3 in the case where above-mentioned restriction is met, it is independent selected from following chemical formula any one：
Wherein X and Y independences is 1~30 selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted carbon number Alkyl, the alkoxy that substituted or unsubstituted carbon number is 1~30, substituted or unsubstituted carbon number be 2~30 Alkenyl, the alkaryl that substituted or unsubstituted carbon number is 7~30, the alkane that substituted or unsubstituted carbon number is 7~30 Aryloxy group, the aromatic radical that substituted or unsubstituted carbon number is 6~30, substituted or unsubstituted carbon number are 6~30 Aryloxy group, the heterocyclic radical that substituted or unsubstituted carbon number is 5~30 and substituted or unsubstituted carbon number are 6~30 One kind in aromatic amine.
Further, described aromatic amine compound molecule can selected from it is following any one：
Present invention also offers a kind of preparation method of aromatic amine compound, comprise the following steps：
Step 1, carries out coupling reaction and methoxyl group disengaging obtains 2-PQDO compounds according to lower reaction equation
Step 2, such as following formula include the displacement reaction of ketone group and coupling reaction synthesis compound
The method specifically includes following steps：
Step 11, prepares intermediate 1
0.1mol-0.2mol reactants 2 are dissolved in 300mL absolute ethers, -78 DEG C of the dry ice bath, in the bar of starvation Under part, the butyl lithium of the 2.5M of 44mL is added, stirring reaction 1 hour adds 0.1mol-0.2mol reactants 1, and reaction 2 is small When, after be gradually raised to 15~25 DEG C, add water terminating reaction,
Then a point liquid is carried out to product, branch vibration layer, aqueous layer with ethyl acetate is extracted one time, is spin-dried for organic solvent, It is 9 with volume ratio:1 dichloromethane and polyethylene=9:1 crosses post separation, obtains intermediate 1；
Step 12, prepares intermediate 2
The intermediate 1 of 41mmol-42mmol is dissolved in the tetrahydrofuran of 250mL-300mL, 0 DEG C is cooled to, added After mixed liquor LTMP at 0 DEG C stirring reaction 2 hours；
The synthesis of LTMP：The tetrahydrofuran of 500mL dissolves the 2,2,6,6- of 0.13mol butyl lithiums and 0.14mol at 0 DEG C Tetramethyl piperidine；
200mL water terminating reactions are subsequently adding, be spin-dried for for organic layer by branch vibration layer, are 10 with volume ratio:1 dichloromethane Alkane and petroleum ether cross post separation, obtain intermediate 2；
Step 21, intermediate 3 is obtained by the displacement of ketone group
Accurately weigh 10g-15g intermediates 2 to be added in reaction bulb, add 200mL-300mL acetonitriles, then weigh 30g- 50g POCl3s are slowly dropped in reaction bulb, and slow after completion of dropping to be warmed up to 60 DEG C -70 DEG C, the reaction time is that 4-6 is small When, after completion of the reaction, carefully extraction is gone out to add water, then places substantial amounts of saturated solution of sodium carbonate tune pH value 7-8, adds dichloromethane Alkane, extracts three times, is spin-dried for obtaining 7g-8g intermediates 3；
Step 22, aromatic amine compound is obtained by coupling reaction
14g-16g intermediates 3, the reactant 3 of 17g-19g, tetra-triphenylphosphine palladium 3g-5g are added in reaction bulb, then It is 2 to add volume ratio:1:1 toluene, ethanol and water mixed liquid amount to 500mL-600mL, and nitrogen protection, stirring is warmed up to 110 DEG C reaction 22-24 hour, afterwards, system cooling, point liquid is spin-dried for toluene, adds dichloromethane dissolved solid, post, use volume Than being 2：1 petroleum ether and ethyl acetate rinse, is obtained aromatic amine compound；
Wherein, reactant 1 is,
Reactant 2 is,
Reactant 3 is,
Intermediate 1 is,
Intermediate 2 is,
Intermediate 3 is
Present invention also offers a kind of application of new aromatic amine compound, the heteroaromatic compounds are used to make Organic electroluminescence device.
The device includes first electrode, second electrode and one or more organic compounds being placed between two electrode Layer, at least one organic compound layer includes at least one described aromatic amine compound.
The organic matter layer includes hole injection layer, hole transmission layer and had both possessed hole injection technical ability but also with hole biography Defeated technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron injecting layer and had both possessed electric transmission technical ability but also with electricity Son injection technical ability layer.
The organic electroluminescence device also includes organic luminescent device, organic photovoltaic cell, Electronic Paper, Organophotoreceptor or has Machine thin film transistor (TFT).
Beneficial effects of the present invention：
Heterocycle derivative of the invention new is to introduce Ar in pyrido [3,2-g] quinoline1、Ar2And R1~R3Improve electron density And upward technical ability, the side chain R1 and R2 of pyrido [3,2-g] quinoline have in addition improves performance and improvement Skill and method advantage.
It is of the invention using new heterocycle derivative manufacture device possess brightness high, outstanding heat resistance, the long-life and The features such as high efficiency.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made Embodiment, belongs to the scope of protection of the invention.
This new aromatic amine compound that the present invention is provided, its compound molecule formula is：
Wherein, R1、R2、R3Can be hydrogen atom or the alkyl of carbon number 1~30 or carbon number 6~50 aryl or One kind in the heterocyclic radical of carbon number 5~50 or the aromatic series amido of carbon number 6~30；
Ar1、Ar2Can be the alkaryl or the aryloxy alkyl of carbon number 7~50 of hydrogen atom or carbon number 7~50 Or the heterocyclic radical or carbon atom of the alkane aromatic thiohydroxy of carbon number 7~50 or the aryl of carbon number 6~50 or carbon number 5~50 In the aryloxy group aromatic thiohydroxy of the aromatic series amido of number 6~30 or the aryloxy group of carbon number 6~50 or carbon number 6~50 one Kind.
This new aromatic amine compound molecule can selected from it is following any one：
The method that the present invention prepares aromatic amine compound, comprises the following steps：
Step 1, carries out coupling reaction and methoxyl group disengaging obtains 2-PQDO compounds according to lower reaction equation
Step 2, such as following formula include the displacement reaction of ketone group and coupling reaction synthesis compound
The technology specifically comprises the steps of：
Step 11, prepares intermediate 1
0.1mol-0.2mol reactants 2 are dissolved in 300mL absolute ethers, -78 DEG C of the dry ice bath, in the bar of starvation Under part, the butyl lithium of the 2.5M of 44mL is added, stirring reaction 1 hour adds 0.1mol-0.2mol reactants 1, and reaction 2 is small When, after be gradually raised to 15~25 DEG C, add water terminating reaction, a point liquid, branch vibration layer, water layer second are then carried out to product Acetoacetic ester is extracted one time, is spin-dried for organic solvent, is 9 with volume ratio:1 dichloromethane and polyethylene=9:1 crosses post separation, obtains Intermediate 1；
Step 12, prepares intermediate 2
The intermediate 1 of 41mmol-42mmol is dissolved in the tetrahydrofuran of 250mL-300mL, 0 DEG C is cooled to, added After mixed liquor LTMP at 0 DEG C stirring reaction 2 hours；
The synthesis of LTMP：The tetrahydrofuran of 500mL dissolves the 2,2,6,6- of 0.13mol butyl lithiums and 0.14mol at 0 DEG C Tetramethyl piperidine；
200mL water terminating reactions are subsequently adding, be spin-dried for for organic layer by branch vibration layer, are 10 with volume ratio:1 dichloromethane Alkane and petroleum ether cross post separation, obtain intermediate 2；
Step 21, intermediate 3 is obtained by the displacement of ketone group
Accurately weigh 10g-15g intermediates 2 to be added in reaction bulb, add 200mL-300mL acetonitriles, then weigh 30g- 50g POCl3s are slowly dropped in reaction bulb, and slow after completion of dropping to be warmed up to 60 DEG C -70 DEG C, the reaction time is that 4-6 is small When, after completion of the reaction, carefully extraction is gone out to add water, then places substantial amounts of saturated solution of sodium carbonate tune pH value 7-8, adds dichloromethane Alkane, extracts three times, is spin-dried for obtaining 7g-8g intermediates 3；
Step 22, aromatic amine compound is obtained by coupling reaction
14g-16g intermediates 3, the reactant 3 of 17g-19g, tetra-triphenylphosphine palladium 3g-5g are added in reaction bulb, then It is 2 to add volume ratio:1:1 toluene, ethanol and water mixed liquid amount to 500mL-600mL, and nitrogen protection, stirring is warmed up to 110 DEG C reaction 22-24 hour, afterwards, system cooling, point liquid is spin-dried for toluene, adds dichloromethane dissolved solid, post, use volume Than being 2：1 petroleum ether and ethyl acetate rinse, is obtained aromatic amine compound；
Wherein,
Reactant 1 is
Reactant 2 is
Reactant 3 is
Intermediate 1 is
Intermediate 2 is
Intermediate 3 is
This heteroaromatic compounds of the present invention are used to make organic electroluminescence device.
The invention provides aromatic amine compound or preparation side described in above-mentioned technical proposal described in above-mentioned technical proposal Application of the aromatic amine compound that method is obtained in organic electroluminescence device, the aromatic amine compound is used as sky Hole transport materials or hole barrier materials.
The present invention does not have particular/special requirement to the structure of the organic electroluminescence device, using conventional organic electroluminescent Device, in the present invention, the organic electroluminescence device can be specially organic photovoltaic cell, illumination OLED, flexibility OLED, Organophotoreceptor, organic transistor.In the present invention, the organic electroluminescence device preferably includes first electrode, Two electrodes and one or more organic matter layers being placed between two electrode；At least one in the preferred organic matter layer Organic matter layer is obtained comprising aromatic amine compound or preparation method as described in above-mentioned technical proposal as described in above-mentioned technical scheme Aromatic amine compound and the organic matter layer at least one organic matter layer include it is fragrant as described in above-mentioned technical scheme Aromatic amine compound and other materials that preparation method described in race's aminated compounds or above-mentioned technical proposal is obtained.
The present invention does not have particular/special requirement to the organic matter layer of the organic electroluminescence device, according to conventional organic electroluminescence The organic matter layer of luminescent device is configured.In the present invention, the organic matter layer preferably at least injects including hole Layer, hole transmission layer, both possessed hole injection but also with hole transport technical ability note pass layer, electronic barrier layer, luminescent layer, hole Barrier layer, electron transfer layer, electron injecting layer and both possessed electric transmission but also with electron injection technical ability biography note layer in one Kind；It is furthermore preferred that the hole injection layer, hole transmission layer, both possessed hole injection but also with hole transport technical ability note pass In this three layers of layer at least one of which be containing conventional hole injecting material, hole transporting material, both possessed hole inject but also with The material of material or the electron-transporting material generation of hole transport technical ability.
Further preferably, above-mentioned luminescent layer be can also red, yellow or cyan luminescent layer.On during above-mentioned luminescent layer cyan State new Hete rocyclic derivatives to use in cyan main body or cyan doping purposes, there is provided high efficiency, high brightness, high-resolution and long-life Organic luminescent device.
Embodiment：The synthesis of intermediate
The synthesis of intermediate 2- chloro-6-phenyls pyridine (1-1)
Synthetic method：The bromo- 6- chloropyridines (21.2g, 0.11mol) of 2-, phenyl boric acid (12.2g, 0.10mol), four triphenyls Phosphorus palladium 0.5g, is added in 1000ML reaction bulbs, adds toluene 400ML, the protection of aqueous sodium carbonate (2N, 150mL) nitrogen, oil 80 DEG C of bath is reacted 24 hours.Last handling process：Cooling, static 30 minutes points of liquid, retains organic layer, is spin-dried for toluene, and solid is placed Dichloromethane dissolves, and crosses post separation, PE：DCM=1：1 rushes post, obtains A-1 (9.6g, y=51%)
The synthesis of intermediate 1-2 and 1-3
Synthetic method according to above-mentioned intermediate 1-1 obtains the compound of following table：
The synthesis of intermediate 6- chloro- N, N- hexichol yl pyridines -2- amine (1-4)：
Synthetic method：Diphenylamines (16.9g, 0.10mol) and sodium tert-butoxide (28g, 0.30mol), toluene 400mL are added To in reaction bulb, stir 30 minutes, nitrogen protection, be subsequently adding the bromo- 2- chloropyridines (23.09g, 0.12mol) of 6-, three (two Asias Benzyl group acetone) two palladium 1.5g, tri-butyl phosphine 4g is eventually adding, it is warmed up to 100 DEG C and reacts 24 hours.Last handling process：System Cooling, adds water terminating reaction, and filtering, filtrate point liquid is spin-dried for toluene, adds a small amount of dichloromethane dissolved solid, petroleum ether:Two Chloromethanes=3:1 (volume ratio) crosses post separation, obtains solid (1-4) (14.03g, y=50%).
The synthesis of intermediate 1-5 and 1-6
The synthetic method of above-mentioned intermediate 1-4 obtains the compound of following table：
The synthesis of intermediate 6- phenyl -2- pyridine boronic acids (2-1)
Take 2- chloro-6-phenyls pyridine (8.04g, 42.4mmol) to be added in there-necked flask, add THF 100mL, nitrogen to protect Shield, -78 DEG C are stirred 30 minutes, are subsequently adding n-BuLi (2.5M) 21mL, are reacted 1 hour, add triisopropyl borate ester 14g, low-temp reaction 1 hour, gradually recovers room temperature.Last handling process, adds 2M hydrochloric acid to make solution pH value for 4-5 in system, quiet A point liquid is put, aqueous layer with ethyl acetate is extracted one time, merges organic layer, is spin-dried for, and obtains white solid (2-1) (6.8g, y=80%).
The synthesis of intermediate 2-2 and 2-6
The synthetic method of above-mentioned intermediate 2-1 obtains the compound of following table：
The synthesis of intermediate 2- (pyridine -2- carbonyls) pyridine carboxylic acid methyl esters (3-1)
Synthetic method：2- pyridine boronic acids (0.1mol) are dissolved in 300mL absolute ethers, -78 DEG C of the dry ice bath, in isolating oxygen Under conditions of gas, the butyl lithium (2.5M) of 44mL is added, stirring reaction 1 hour adds the bromo- pyridine carboxylic acid methyl esters of 2- (0.1mol), reacts 2 hours, after be gradually raised to 15~25 DEG C, add water terminating reaction.
Last handling process：A point liquid is carried out to product, branch vibration layer, aqueous layer with ethyl acetate is extracted one time, has been spin-dried for Machine solvent, uses dichloromethane:Polyethylene=9:1 (volume ratio) crosses post separation, obtains white solid 3-1 (yield is 51%).
The synthesis of intermediate 3-2~3-7
The synthetic method of above-mentioned intermediate 3-1 obtains the compound of following table：
The synthesis of intermediate pyridine [3,2-g] and quinoline -5,10- diketone (4-1)：
Synthetic method：3-1 (41.5mmol) is dissolved in the tetrahydrofuran of 300mL, 0 DEG C is cooled to, mixed liquor is added After LTMP at 0 DEG C stirring reaction 2 hours.
The synthesis of LTMP：The tetrahydrofuran of 500mL dissolves the 2,2,6,6- of 0.13mol butyl lithiums and 0.14mol at 0 DEG C Tetramethyl piperidine.
Last handling process：200mL water terminating reactions are added, be spin-dried for for organic layer by branch vibration layer, uses dichloromethane:Oil Ether=10:1 crosses post separation, and (4%) 3.8g, yield is to obtain solid (4-1).
The synthesis of intermediate 4-2~4-7
The synthesis of intermediate 5,10- dichloropyridines simultaneously [3,2-g] quinoline (5-1)：
Accurately weigh 4-1 (10g, 47.8mmol) to be added in reaction bulb, add 200mL acetonitriles, then weigh 30g trichlorine oxygen Phosphorus is slowly dropped in reaction bulb, and slow after completion of dropping to be warmed up to 60 DEG C, the reaction time is 5 hours.After completion of the reaction, add Water carefully go out by extraction, then places substantial amounts of saturated solution of sodium carbonate tune pH value 7-8, adds dichloromethane, extracts three times, is spin-dried for Solid (5-1) (7.5g, y=63%).The synthesis of intermediate 5-2~5-7
The synthetic method of above-mentioned intermediate 5-1 obtains the compound of following table：
Embodiment：The synthesis of aromatic amine compound
The synthesis of embodiment 5,10-diphenylpyrido [3,2-g] quinoline (6-1)
5,10- Dichloro-pendins simultaneously [g] the quinoline 5-1 (14.8g, 0.6mmol) that will be prepared, 4- pyridine borates (18g, 0.146mmol), tetra-triphenylphosphine palladium 4g is added in reaction bulb, adds toluene, second alcohol and water 2:1:1 (volume ratio) mixes Liquid amounts to 600mL, nitrogen protection, and stirring is warmed up to 110 DEG C and reacts 24 hours.Last handling process：System is lowered the temperature, point liquid, is spin-dried for Toluene.Dichloromethane dissolved solid is added, post, petroleum ether is crossed：Ethyl acetate=2：1 (volume ratio) is rinsed, and obtains solid (6-1) (13g, y=65%).
The synthesis of embodiment 6-2~6-17
Synthetic method according to above-described embodiment 6-1 obtains the compound of following table：
The synthesis of embodiment N5, N5, N10, N10- tetraphenyl pyrido [3,2-g] quinoline -5,10- diamines (6-23)：
According to the synthetic method of intermediate 1-4, with 5,10- dichloropyridines simultaneously [3,2-g] quinoline (6.0g, 24mmol), two Aniline (4.4,24mmol) is reacted for raw material, obtains N5, N5, N10, N10- tetraphenyl pyrido [3,2-g] quinoline -5,10- Diamines (6.17g, y=50%).
The synthesis of embodiment 5,10- bis- (1- naphthyls oxygen) pyrido [3,2-g] quinoline (6-24)：
Take 1- hydroxyl naphthalenes (14g, 0.1mol) to be dissolved in 100mL anhydrous tetrahydro furans, stir, precise NaH (0.96g, 0.4mol) it is added in reaction bulb in batches, should not be too fast, prevent too many bubble from producing, add rear solution and yellow is presented, add 5,10- dichloropyridines simultaneously [3,2-g] quinoline (27.50g, 0.11mol), will also be dividedly in some parts, and room temperature reaction is overnight.Post-processed Journey：Filtering, removes solid matter, and filtrate is spin-dried for, and adds dichloromethane dissolving, crosses post petroleum ether：Ethyl acetate=1：5 (bodies Product ratio) post is rushed, obtain solid (23.20g, y=50%).
The synthesis of embodiment 5,10- bis- (1- naphthyls sulphur) pyrido [3,2-g] quinoline (6-25)：
By 1- naphthyl mercaptans (1.6g, 10mmol), 5,10- dichloropyridines simultaneously [3,2-g] quinoline (2.48g, 10mmol), hydrogen-oxygen Change potassium (840mg, 15mmol), mPANI/pFe3O4 (2.5g, 5mol%) H2O (30mL) mixing is heated 8 hours.By acetic acid Ethyl ester extracts organic phase, and uses ethyl acetate：Petroleum ether=4:1 (volume ratio) crosses post separation, obtains white solid (6-25) (1.89g, y=38%).
The synthesis of embodiment 5- (1- naphthyls) -10- (2- naphthyls) pyrido [3,2-g] quinoline (6-26)：
Synthetic method：With reference to the synthesis of E-1,5,10- dichloropyridines simultaneously [3,2-g] quinoline (4.41g, 17.8mmol) is put into With 2- naphthalene boronic acids (3.4g, 19.6mmol), about (2.91g is produced to obtain the bromo- 10- of solid 5- (2- naphthyls) pyrido [3,2-g] quinoline 48%) rate is.
Synthetic method：With reference to the synthesis of E-1, input 5- bromo- 10- (2- naphthyls) pyrido [3,2-g] quinoline (2.91g, 8.5mmol) with 1- naphthalene boronic acids (1.65g, 9.6mmol), (48%) 1.76g, yield is to obtain solid E-23.
Embodiment：The preparation of organic luminescent device
It is by Fisher Co., Ltd's coating layer thicknessIto glass substrate be placed in distilled water and clean 2 times, ultrasonic wave Washing 30 minutes, is washed 30 minutes in order by isopropanol, acetone, methyl alcohol, cleans 2 times, ultrasonic washing repeatedly with distilled water 10 minutes, dry, be transferred in plasma washing machine, aforesaid substrate is washed 5 minutes, be sent in evaporator.Will be accurate Hole injection layer 2-TNATA evaporations are deposited with the ito transparent electrode got readyHole transmission layer a-NPD is deposited with The TPPDA evaporations of cyan main body A ND/ doping 5%
The material evaporation of hole blocking layer and hole transmission layer TPBi or embodiment ENegative electrode Said process organic matter vaporization plating speed is to maintainLiF is/ sec, Al are
The electron luminescence characteristic of the organic luminescent device of above method manufacture is represented in the following table.
From above-mentioned table result, it is seen that luminous efficiency in the middle common layer field of new aromatic amine derivative of the invention And life characteristic increases significantly.
The present invention is can to obtain luminous efficiency and the life-span is good using the organic luminescent device of new aromatic amine derivative Good result, so the present invention is useful in practicality OLED industries high.Organic luminescent device of the invention is plane face Plate shows, planar illuminant, illumination face illuminating OLED illuminator, flexible illuminator, duplicator, printer, LCD backlight lamp or Light source, display board, the mark of dosing machine class etc. are suitable to be used.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.

Claims (7)

1. a kind of aromatic amine compound, it is characterised in that its compound molecule formula is：
Wherein, the R1It is phenyl ring, R2It is hydrogen atom, R3It is hydrogen atom, or R1It is hydrogen atom, R2It is phenyl ring, R3It is hydrogen atom； Ar1、Ar2It is phenyl ring,
Respectively obtain compound
2. a kind of preparation method of aromatic amine compound as claimed in claim 1, it is characterised in that including following step Suddenly：
Step 1, carries out coupling reaction and methoxyl group disengaging obtains 2-PQDO compounds according to lower reaction equation
Step 2, such as following formula include the displacement reaction of ketone group and coupling reaction synthesis aromatic amine compound
3. method according to claim 2, it is characterised in that specifically include following steps：
Step 11, prepares intermediate 1
0.1mol-0.2mol reactants 2 are dissolved in 300mL absolute ethers, -78 DEG C of the dry ice bath, under conditions of starvation, The butyl lithium of the 2.5M of 44mL is added, stirring reaction 1 hour adds 0.1mol-0.2mol reactants 1, reacts 2 hours, after 15~25 DEG C are gradually raised to, water terminating reaction is added, a point liquid, branch vibration layer, water layer acetic acid second are then carried out to product Ester is extracted one time, is spin-dried for organic solvent, is 9 with volume ratio:1 dichloromethane and polyethylene=9:1 crosses post separation, obtains centre Body 1；
Step 12, prepares intermediate 2
The intermediate 1 of 41mmol-42mmol is dissolved in the tetrahydrofuran of 250mL-300mL, 0 DEG C is cooled to, mixing is added After liquid LTMP at 0 DEG C stirring reaction 2 hours；
The synthesis of LTMP：The tetrahydrofuran of 500mL dissolves the 2,2,6,6- tetramethyls of 0.13mol butyl lithiums and 0.14mol at 0 DEG C Phenylpiperidines；
200mL water terminating reactions are subsequently adding, be spin-dried for for organic layer by branch vibration layer, are 10 with volume ratio:1 dichloromethane and Petroleum ether crosses post separation, obtains intermediate 2；
Step 21, intermediate 3 is obtained by the displacement of ketone group
Accurately weigh 10g-15g intermediates 2 to be added in reaction bulb, add 200mL-300mL acetonitriles, then weigh 30g-50g tri- Chlorethoxyfos are slowly dropped in reaction bulb, and slow after completion of dropping to be warmed up to 60 DEG C -70 DEG C, the reaction time is 4-6 hours, reaction After finishing, carefully extraction is gone out to add water, then places substantial amounts of saturated solution of sodium carbonate tune pH value 7-8, adds dichloromethane, is extracted Three times, it is spin-dried for obtaining 7g-8g intermediates 3；
Step 22, aromatic amine compound is obtained by coupling reaction
14g-16g intermediates 3, the reactant 3 of 17g-19g, tetra-triphenylphosphine palladium 3g-5g are added in reaction bulb, added Volume ratio is 2:1:1 toluene, ethanol and water mixed liquid amount to 500mL-600mL, nitrogen protection, stirring be warmed up to 110 DEG C it is anti- Answer 22-24 hours, afterwards, system cooling, point liquid is spin-dried for toluene, adds dichloromethane dissolved solid, crosses post, is with volume ratio 2：1 petroleum ether and ethyl acetate rinse, is obtained aromatic amine compound；
Wherein, reactant 1 is,
Reactant 2 is,
Reactant 3 is,
Intermediate 1 is,
Intermediate 2 is,
Intermediate 3 is
4. a kind of application of new aromatic amine compound according to claim 1, it is characterised in that the heteroaromatic Compound is used to make organic electroluminescence device.
5. organic electroluminescence device obtained in the aromatic amine compound described in a kind of utilization claim 1, it is characterised in that should Device includes first electrode, second electrode and one or more organic compound layers being placed between two electrode, at least one Individual organic compound layer includes at least one described aromatic amine compound.
6. organic electroluminescence device according to claim 5, it is characterised in that the organic matter layer include hole injection layer, Hole transmission layer and both possessed hole injection technical ability but also with hole transport technical ability layer, electronic barrier layer, luminescent layer, hole barrier Layer, electron injecting layer and both possessed electric transmission technical ability but also with electron injection technical ability layer.
7. organic electroluminescence device according to claim 5, it is characterised in that the organic electroluminescence device also includes organic hair Optical device, organic photovoltaic cell, Electronic Paper, Organophotoreceptor or OTFT.
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