CN105153153A - Novel aromatic amine compound and preparation and application thereof - Google Patents
Novel aromatic amine compound and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a novel aromatic amine compound. The novel aromatic amine compound is characterized in that a general molecular formula of the compound is shown in the specification, wherein each of R1, R2 and R3 refers to an alkyl group with 1-30 hydrogen atoms or carbon atoms, an aryl group with 6-50 carbon atoms, a heterocyclic group with 5-50 carbon atoms or an aromatic amine group with 6-30 carbon atoms; each of Ar1 and Ar2 refers to an alkaryl group with 7-50 hydrogen atoms or carbon atoms, an alkylaryloxy group with 7-50 parts of carbon atoms, an alkaryl sulfydryl group with 7-50 carbon atoms, an aryl group with 6-50 carbon atoms, a heterocyclic group with 5-50 carbon atoms, an aromatic amine group with 6-30 carbon atoms, an aryloxy group with 6-50 carbon atoms or an aryloxy arylsulfydryl group with 6-50 carbon atoms. The novel aromatic amine compound is used for manufacture of organic electroluminescence devices, and devices made from derivatives of the novel aromatic amine compound have the advantages of high luminance, excellent thermal resistance, long service life, high efficiency and the like.
Description
Technical field
The present invention relates to electroluminescent material field, be specifically related to a kind of new aromatic amine compounds and preparation and application thereof.
Background technology
Material of main part in electroluminescent device mainly contains small molecule host material and polymer host material two class.Small molecule host material doping phosphorescent complexes is utilized to prepare many efficient electroluminescent devices as luminescent layer.In recent years, the polymer host material various phosphorescent complexes object that adulterates is utilized to prepare electroluminescent device as luminescent layer and receive more concern.Due to developing rapidly of photoelectric communication in recent years and MultiMedia Field, organic optoelectronic material has become the core of modern society's information and electronic industry.
Organic electroluminescence device (OLED) is a kind of novel flat panel display device, has the features such as energy-conservation, fast response time, colour stable, environmental compatibility are strong, radiationless, the life-span is long, quality is light, thickness is thin compared with small molecule electroluminescent device.Organic electroluminescence device, is generally made up of two opposed electrodes and at least one deck organic luminescent compounds be inserted between these two electrodes.Electric charge is injected in the organic layer formed between the anode and cathode, to form electronics and hole pair, makes the organic compound with fluorescence or phosphorescent characteristics create light emission.Apply voltage between the anode and cathode, hole is just injected into luminescent layer from anode by hole transmission layer, and meanwhile, electronics is injected into luminescent layer from negative electrode by electron transfer layer.In light emitting layer area, current carrier is reset and is formed exciton.Excited state exciton is converted to ground state, and cause luminescent layer molecular luminescence, therefore image is formed.
In current organic electroluminescence device, the representative species of hole mobile material is as follows:
The properties of materials of current requirement is high-level efficiency and long lifetime that material possesses thermostability and high velocity electron degree of excursion and twinkler, but existing material property is general.
Summary of the invention
The object of the invention is to provide a kind of new aromatic amine compounds and preparation and application thereof, this is the good hole mobile material of a kind of luminous efficiency, will by pyrido [3,2-g] quinoline compound, rising electronics degree of excursion, and this novel heterocyclic compound derivative is prepared into device, has good luminous efficiency.
The present invention adopts following technical scheme:
The invention provides a kind of new aromatic amine compounds, its compound molecule general formula is:
Wherein, R1, R2, R3 are the one in the aromatic series amido of the aryl of hydrogen atom or carbonatoms 1 ~ 30 alkyl or carbonatoms 6 ~ 50 or the heterocyclic radical of carbonatoms 5 ~ 50 or carbonatoms 6 ~ 30;
Ar
1, Ar
2be the one in the aryloxy of the heterocyclic radical of the alkane aromatic thiohydroxy of the alkaryl of hydrogen atom or carbonatoms 7 ~ 50 or the aryloxy alkyl of carbonatoms 7 ~ 50 or carbonatoms 7 ~ 50 or the aryl of carbonatoms 6 ~ 50 or carbonatoms 5 ~ 50 or the aromatic series amido of carbonatoms 6 ~ 30 or carbonatoms 6 ~ 50 or the aryloxy aromatic thiohydroxy of carbonatoms 6 ~ 50.
Preferably, in general formula, R1, R2, R3 are meeting under above-mentioned restriction, be independently selected from below in chemical formula any one:
Wherein X and Y is independently selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted carbonatoms is the alkyl of 1 ~ 30, substituted or unsubstituted carbonatoms is the alkoxyl group of 1 ~ 30, substituted or unsubstituted carbonatoms is the thiazolinyl of 2 ~ 30, substituted or unsubstituted carbonatoms is the alkaryl of 7 ~ 30, substituted or unsubstituted carbonatoms is the aryloxy alkyl of 7 ~ 30, substituted or unsubstituted carbonatoms is the aromatic base of 6 ~ 30, substituted or unsubstituted carbonatoms is the aryloxy of 6 ~ 30, substituted or unsubstituted carbonatoms be 5 ~ 30 heterocyclic radical and substituted or unsubstituted carbonatoms be one in the aromatic amine of 6 ~ 30.
Further, described aromatic amine compound molecule can be selected from following any one:
Present invention also offers a kind of preparation method of aromatic amine compounds, comprise the following steps:
Step 1, carries out linked reaction according to lower reaction formula and methoxyl group disengaging obtains 3-PQDO compound
Step 2, as shown in the formula the chlorination replacement(metathesis)reaction and the linked reaction synthetic compound that comprise ketone group
The method specifically comprises the following steps:
Step 11, prepares intermediate 1
0.2mol-0.3mol reactant 2 is dissolved in 300mL anhydrous diethyl ether, the dry ice bath of-77 DEG C-79 DEG C, under the condition of starvation, add the butyllithium of the 2.5M of 44mL, stirring reaction 1 hour, add 0.1mol-0.2mol reactant 1 again, react 2 hours, after be raised to 15 ~ 25 DEG C gradually, add water termination reaction, then separatory is carried out to reaction product, branch vibration layer, aqueous layer with ethyl acetate extracts one time, is spin-dried for organic solvent, be that the methylene dichloride of 9:1 is crossed post be separated with polyethylene=9:1 by volume ratio, obtain intermediate 1;
Step 12, prepares intermediate 2
The intermediate 1 of 41mmol-42mmol is dissolved in the tetrahydrofuran (THF) of 250mL-300mL, is cooled to 0 DEG C, to add after mixed solution LTMP at 0 DEG C stirring reaction 2 hours;
The tetrahydrofuran (THF) of the synthesis of LTMP: 500mL dissolves 2,2,6, the 6-tetramethyl piperidines of 0.13mol butyllithium and 0.14mol at 0 DEG C;
Then add 200mL water termination reaction, branch vibration layer, is spin-dried for organic layer, is that the methylene dichloride of 10:1 is crossed post with sherwood oil and is separated, obtains intermediate 2 by volume ratio;
Step 21, obtains intermediate 3 by the displacement of ketone group
Accurately taking 10g-15g intermediate 2 joins in reaction flask, add 200mL-300mL acetonitrile, take 30g-50g phosphorus oxychloride to be more slowly added drop-wise in reaction flask, dropwise and be slowly warmed up to 60 DEG C-70 DEG C afterwards, the reaction times is 4-6 hour, after completion of the reaction, add water carefully to extract and go out, then the saturated solution of sodium carbonate adding amplification quantity adjusts pH value 7-8, then add methylene dichloride, extract three times, be spin-dried for obtain intermediate 3;
Step 22, obtains aromatic amine compounds by linked reaction
By the reactant 3 of 14g-16g intermediate 3,17g-19g, tetra-triphenylphosphine palladium 3g-5g joins in reaction flask, add toluene, ethanol and the water mixed liquid that volume ratio is 2:1:1 again and amount to 500mL-600mL, nitrogen protection, stir and be warmed up to 110 DEG C of reaction 22-24 hour, afterwards, system is lowered the temperature, and separatory, is spin-dried for toluene, add methylene dichloride dissolved solids, crossing post, is sherwood oil and the ethyl acetate rinse of 2:1 by volume ratio, obtained aromatic amine compounds;
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 compounds, described heteroaromatic compounds is for making organic electroluminescence device.
One or more organic compound layers that this device comprises the first electrode, the second electrode and is placed between described two electrodes, at least one organic compound layer comprises the aromatic amine compounds described at least one.
Described organic matter layer comprises hole injection layer, hole transmission layer and had not only possessed hole and injects technical ability but also possess hole transport technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron injecting layer and not only possess electric transmission technical ability but also possess electron injection technical ability layer.
Described organic electroluminescence device also comprises organic luminescent device, organic photovoltaic cell, Electronic Paper, Organophotoreceptor or OTFT.
Beneficial effect of the present invention:
The new heterocycle derivative of the present invention introduces Ar in pyrido [2,3-g] quinoline
1, Ar
2electron density and upwards technical ability, in addition the side chain R of pyrido [3,2-g] quinoline is improved with R1 ~ R3
1and R
2there is improving SNR and improve Skill and method advantage.
The device of use of the present invention new heterocycle derivative manufacture possesses the features such as high brightness, outstanding thermotolerance, long lifetime and high-level efficiency.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
A new aromatic amine compounds, is characterized in that, its compound molecule general formula is:
Wherein, R1, R2, R3 are the one in the aromatic series amido of the aryl of hydrogen atom or carbonatoms 1 ~ 30 alkyl or carbonatoms 6 ~ 50 or the heterocyclic radical of carbonatoms 5 ~ 50 or carbonatoms 6 ~ 30;
Ar
1, Ar
2be the one in the aryloxy of the heterocyclic radical of the alkane aromatic thiohydroxy of the alkaryl of hydrogen atom or carbonatoms 7 ~ 50 or the aryloxy alkyl of carbonatoms 7 ~ 50 or carbonatoms 7 ~ 50 or the aryl of carbonatoms 6 ~ 50 or carbonatoms 5 ~ 50 or the aromatic series amido of carbonatoms 6 ~ 30 or carbonatoms 6 ~ 50 or the aryloxy aromatic thiohydroxy of carbonatoms 6 ~ 50.
This new aromatic amine compound molecule can be selected from following any one:
The present invention prepares the method for aromatic amine compounds, comprises the following steps:
Step 1, carries out linked reaction according to lower reaction formula and methoxyl group disengaging obtains 3-PQDO compound
Step 2, as shown in the formula the chlorination replacement(metathesis)reaction and the linked reaction synthetic compound that comprise ketone group
The method specifically comprises the following steps:
Step 11, prepares intermediate 1
0.2mol-0.3mol reactant 2 is dissolved in 300mL anhydrous diethyl ether, the dry ice bath of-77 DEG C-79 DEG C, under the condition of starvation, add the butyllithium of the 2.5M of 44mL, stirring reaction 1 hour, add 0.1mol-0.2mol reactant 1 again, react 2 hours, after be raised to 15 ~ 25 DEG C gradually, add water termination reaction, then separatory is carried out to reaction product, branch vibration layer, aqueous layer with ethyl acetate extracts one time, is spin-dried for organic solvent, be that the methylene dichloride of 9:1 is crossed post be separated with polyethylene=9:1 by volume ratio, obtain intermediate 1;
Step 12, prepares intermediate 2
The intermediate 1 of 41mmol-42mmol is dissolved in the tetrahydrofuran (THF) of 250mL-300mL, is cooled to 0 DEG C, to add after mixed solution LTMP at 0 DEG C stirring reaction 2 hours;
The tetrahydrofuran (THF) of the synthesis of LTMP: 500mL dissolves 2,2,6, the 6-tetramethyl piperidines of 0.13mol butyllithium and 0.14mol at 0 DEG C;
Then add 200mL water termination reaction, branch vibration layer, is spin-dried for organic layer, is that the methylene dichloride of 10:1 is crossed post with sherwood oil and is separated, obtains intermediate 2 by volume ratio;
Step 21, obtains intermediate 3 by the displacement of ketone group
Accurately taking 10g-15g intermediate 2 joins in reaction flask, add 200mL-300mL acetonitrile, take 30g-50g phosphorus oxychloride to be more slowly added drop-wise in reaction flask, dropwise and be slowly warmed up to 60 DEG C-70 DEG C afterwards, the reaction times is 4-6 hour, after completion of the reaction, add water carefully to extract and go out, then the saturated solution of sodium carbonate adding amplification quantity adjusts pH value 7-8, then add methylene dichloride, extract three times, be spin-dried for obtain intermediate 3;
Step 22, obtains aromatic amine compounds by linked reaction
By the reactant 3 of 14g-16g intermediate 3,17g-19g, tetra-triphenylphosphine palladium 3g-5g joins in reaction flask, add toluene, ethanol and the water mixed liquid that volume ratio is 2:1:1 again and amount to 500mL-600mL, nitrogen protection, stir and be warmed up to 110 DEG C of reaction 22-24 hour, afterwards, system is lowered the temperature, and separatory, is spin-dried for toluene, add methylene dichloride dissolved solids, crossing post, is sherwood oil and the ethyl acetate rinse of 2:1 by volume ratio, obtained aromatic amine compounds;
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 is for making organic electroluminescence device.
The invention provides the application of aromatic amine compounds in organic electroluminescence device that preparation method described in aromatic amine compounds described in technique scheme or technique scheme obtains, described aromatic amine compounds is as hole mobile material or hole barrier materials.
The structure of the present invention to described organic electroluminescence device does not have particular requirement, adopt conventional organic electroluminescence device, in the present invention, described organic electroluminescence device can be specially organic photovoltaic cell, illumination OLED, flexible OLED, Organophotoreceptor, organic transistor.In the present invention, described organic electroluminescence device one or more organic matter layers of preferably including the first electrode, the second electrode and being placed between described two electrodes; In preferred described organic matter layer at least one organic matter layer comprise aromatic amine compounds that as described in as described in technique scheme aromatic amine compounds or technique scheme, preparation method obtains and as described in organic matter layer at least one organic matter layer comprise the aromatic amine compounds and other materials that as described in as described in technique scheme aromatic amine compounds or technique scheme, preparation method obtains.
The organic matter layer of the present invention to described organic electroluminescence device does not have particular requirement, and the organic matter layer of organic electroluminescence device conveniently carries out arranging.In the present invention, described organic matter layer preferably at least comprises hole injection layer, hole transmission layer, not only possesses hole and to inject but also the note possessing hole transport technical ability passes layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and not only possessed electric transmission but also possessed the one of biography note layer of electron injection technical ability; Preferred, described hole injection layer, hole transmission layer, not only possess hole inject but also the note possessing hole transport technical ability pass these three layers, layer at least one deck be containing conventional hole injecting material, hole transporting material, not only possess hole and inject but also possess the material that the material of hole transport technical ability or electron-transporting material generate.
Further preferably, above-mentioned luminescent layer is also can red, yellow or cyan luminescent layer.During above-mentioned luminescent layer cyan, above-mentioned new Hete rocyclic derivatives is used in cyan main body or cyan doping purposes, provides high-level efficiency, high brightness, high resolving power and long-life organic luminescent device.
Embodiment: the synthesis of intermediate
The synthesis of intermediate 2-chloro-6-phenyl pyridine (1-1)
The bromo-6-chloropyridine of synthetic method: 2-(21.2g; 0.11mol); phenylo boric acid (12.2g; 0.10mol), four triphenyl phosphorus palladium 0.5g, join in 1000ML reaction flask; add toluene 400ML; aqueous sodium carbonate (2N, 150mL) nitrogen protection, oil bath 80 DEG C reaction 24 hours.
Last handling process: cooling, static 30 minutes separatory, retain organic layer, are spin-dried for toluene, and solid places methylene dichloride and dissolves, and cross post and be separated, PE:DCM=1:1 rushes post, obtains 1-1 (9.6g, y=51%).
The synthesis of intermediate 1-2 and 1-3
The synthetic method of above-mentioned intermediate 1-1 obtains the compound of following table:
The synthesis of intermediate 6-chloro-N, N-phenylbenzene pyridine-2-amine (1-4):
Synthetic method: by pentanoic (16.9g; 0.10mol) with sodium tert-butoxide (28g; 0.30mol); toluene 400mL joins in reaction flask, stirs 30 minutes, nitrogen protection; then the bromo-2-chloropyridine of 6-(23.09g is added; 0.12mol), three (two sub-Bian benzylacetones) two palladium 1.5g, finally add tri-butyl phosphine 4g, be warmed up to 100 DEG C reaction 24 hours.Last handling process: system is lowered the temperature, and adds water termination reaction, filters, filtrate separatory, is spin-dried for toluene, adds a small amount of methylene dichloride dissolved solids, sherwood oil: methylene dichloride=3:1 (volume ratio) crosses post and is separated, and obtains solid (1-4) (14.03g, y=50%).
The synthesis of intermediate 1-5 and 1-6
Above-mentioned intermediate 1-4 synthetic method obtains the compound of following table:
The synthesis of intermediate 6-phenyl-2-pyridine boronic acid (2-1)
Get 2-chloro-6-phenyl pyridine (8.04g; 42.4mmol) join in there-necked flask; add THF100mL; nitrogen protection ,-78 DEG C are stirred 30 minutes, then add n-Butyl Lithium (2.5M) 21mL; react 1 hour; add triisopropyl borate ester 14g again, low-temp reaction 1 hour, recovers room temperature gradually.Last handling process, adds 2M hydrochloric acid and makes solution pH value be 4-5 in system, leave standstill separatory, aqueous layer with ethyl acetate extracts one time, merges organic layer, is spin-dried for, obtains white solid (2-1) (6.8g, y=80%).
Intermediate 2-2 ~-6 are synthesized
The synthetic method of above-mentioned intermediate 2-1 obtains the compound of following table:
The synthesis of intermediate 3-(pyridine-2-carbonyl) pyridine carboxylic acid methyl esters (3-1)
Synthetic method: 3-pyridine boronic acid (0.1mol) is dissolved in 300mL anhydrous diethyl ether, the dry ice bath-78 DEG C, under the condition of starvation, add the butyllithium (2.5M) of 44mL, stirring reaction 1 hour, then add the bromo-pyridine carboxylic acid methyl esters (0.1mol) of 2-, react 2 hours, after be raised to 15 ~ 25 DEG C gradually, add water termination reaction.
Last handling process: separatory is carried out to reaction product, branch vibration layer, aqueous layer with ethyl acetate extracts one time, is spin-dried for organic solvent, cross post with methylene dichloride: polyethylene=9:1 (volume ratio) to be separated, obtain white solid 3-1 (productive rate 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 [2,3-g] quinoline-5,10-diketone (4-1)
Synthetic method: be dissolved in the tetrahydrofuran (THF) of 300mL by 3-1 (41.5mmol), be cooled to 0 DEG C, to add after mixed solution LTMP at 0 DEG C stirring reaction 2 hours.
The tetrahydrofuran (THF) of the synthesis of LTMP: 500mL dissolves 2,2,6, the 6-tetramethyl piperidines of 0.13mol butyllithium and 0.14mol at 0 DEG C.
Last handling process: add 200mL water termination reaction, branch vibration layer, is spin-dried for organic layer, with methylene dichloride: sherwood oil=10:1 crosses post and is separated, and obtains solid (4-1) (3.8g, productive rate is 4%).
The synthesis of intermediate 4-2 ~ 4-7
Above-mentioned intermediate 4-1 synthetic method obtains the compound of following table:
The synthesis of intermediate 5,10-dichloropyridine also [2,3-g] quinoline (5-1)
Accurately taking 4-1 (10g, 47.8mmol) joins in reaction flask, adds 200mL acetonitrile, then takes 30g phosphorus oxychloride and be slowly added drop-wise in reaction flask, dropwises slowly to be warmed up to 60 DEG C afterwards, and the reaction times is 5 hours.After completion of the reaction, add water and carefully extract and go out, then the saturated solution of sodium carbonate adding amplification quantity adjusts pH value 7-8, then add methylene dichloride, extract three times, be spin-dried for obtain solid (5-1) (7.5g, y=63%).
The synthesis of intermediate 5-2 ~ 5-7
Above-mentioned intermediate 5-1 synthetic method obtains the compound of following table:
Embodiment: the synthesis of aromatic amine compounds
The synthesis of embodiment 5,10-phenylbenzene pyrido [2,3-g] quinoline (6-1)
By 5 of preparation; 10-Dichloro-pendin is [g] quinoline 5-1 (14.8g also; 0.6mmol); 4-pyridine borate (18g; 0.146mmol), tetra-triphenylphosphine palladium 4g joins in reaction flask, then add toluene, second alcohol and water 2:1:1 (volume ratio) mixed solution amounts to 600mL; nitrogen protection, stirs and is warmed up to 110 DEG C of reactions 24 hours.Last handling process: system is lowered the temperature, and separatory, is spin-dried for toluene.Add methylene dichloride dissolved solids, cross post, sherwood oil: ethyl acetate=2:1 (volume ratio) rinses, and obtains solid (6-1) (13g, y=65%).
The synthesis of embodiment 6-2 ~ 6-17
Above-described embodiment 6-1 synthetic method obtains the compound of following table:
The synthesis of embodiment N5, N5, N10, N10-tetraphenyl pyrido [2,3-g] quinoline-5,10-diamines (6-23)
According to the synthetic method of intermediate 1-4, with 5,10-dichloropyridine also [3,2-g] quinoline (6.0g, 24mmol), pentanoic (4.4,24mmol) for raw material reacts, obtain 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-naphthyloxy) pyrido [2,3-g] quinoline (6-24)
Getting 1-hydroxyl naphthalene (14g, 0.1mol) is dissolved in 100mL anhydrous tetrahydro furan, stirs, precise NaH (0.96g, 0.4mol) is added in reaction flask in batches, too not fast, prevent too many bubble from producing, add rear solution and present yellow, then add 5,10-dichloropyridine also [3,2-g] quinoline (27.50g, 0.11mol), also will add, room temperature reaction spends the night in batches.Last handling process: filter, removing solid matter, filtrate is spin-dried for, and adds methylene dichloride and dissolves, cross post sherwood oil: ethyl acetate=1:5 (volume ratio) rushes post, obtains solid (23.20g, y=50%).
The synthesis of embodiment 5,10-bis-(1-naphthyl sulphur) pyrido [2,3-g] quinoline (6-25)
By 1-naphthyl mercaptan (1.6g, 10mmol), 5,10-dichloropyridine is [3,2-g] quinoline (2.48g also, 10mmol), potassium hydroxide (840mg, 15mmol), mPANI/pFe3O4 (2.5g, 5mol%) H2O (30mL) mixing, heats 8 hours.By extraction into ethyl acetate organic phase, and adopt ethyl acetate: sherwood oil=4:1 (volume ratio) crosses post and is separated, and obtains white solid (6-25) (1.89g, y=38%).
The synthesis of embodiment 5-(1-naphthyl)-10-(2-naphthyl) pyrido [2,3-g] quinoline (6-26)
Synthetic method: with reference to the synthesis of E-1, drop into 5,10-dichloropyridine also [3,2-g] quinoline (4.41g, 17.8mmol) with 2-naphthalene boronic acids (3.4g, 19.6mmol), obtain the bromo-10-of solid 5-(2-naphthyl) pyrido [3,2-g] quinoline is about (2.91g, productive rate is 48%).
Synthetic method: with reference to the synthesis of E-1, drops into 5-bromo-10-(2-naphthyl) pyrido [3,2-g] quinoline (2.91g, 8.5mmol) with 1-naphthalene boronic acids (1.65g, 9.6mmol), solid E-23 (1.76g, productive rate is 48%) is obtained.
Experimental example: the preparation of organic luminescent device
By Fisher Co., Ltd's coat-thickness be
ito glass substrate be placed in distilled water clean 2 times, ultrasonic washing 30 minutes, 30 minutes are washed in order by Virahol, acetone, methyl alcohol, 2 times are repeatedly cleaned with distilled water, ultrasonic washing 10 minutes, dry, transfer in plasma washing machine, aforesaid substrate is washed 5 minutes, deliver in evaporator.By evaporation hole injection layer 2-TNATA evaporation on ready ito transparent electrode
hole transmission layer a-NPD evaporation
the TPPDA evaporation of cyan main body A ND/ doping 5%
The material evaporation of hole blocking layer and hole transmission layer TPBi or embodiment E
negative electrode
said process organic matter vaporization plating speed keeps
liF is
al is
The electron luminescence characteristic of the organic luminescent device of aforesaid method manufacture represents in the following table
From above-mentioned table result, in the middle common layer field finding out new aromatic amine derivative of the present invention, luminous efficiency and life characteristic increase significantly.
The present invention utilizes the organic luminescent device of new aromatic amine derivative can obtain luminous efficiency and life-span good result, so useful in the present invention's OLED industry that to be practicality high.Organic luminescent device of the present invention is the applicable use such as light source, display panel, mark of flat panel display, planar illuminant, illumination face illuminating OLED twinkler, flexible twinkler, duplicating machine, printer, LCD backlight or weigher class.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a new aromatic amine compounds, is characterized in that, its compound molecule general formula is:
Wherein, R1, R2, R3 are the one in the aromatic series amido of the aryl of hydrogen atom or carbonatoms 1 ~ 30 alkyl or carbonatoms 6 ~ 50 or the heterocyclic radical of carbonatoms 5 ~ 50 or carbonatoms 6 ~ 30;
Ar
1, Ar
2be the one in the aryloxy of the heterocyclic radical of the alkane aromatic thiohydroxy of the alkaryl of hydrogen atom or carbonatoms 7 ~ 50 or the aryloxy alkyl of carbonatoms 7 ~ 50 or carbonatoms 7 ~ 50 or the aryl of carbonatoms 6 ~ 50 or carbonatoms 5 ~ 50 or the aromatic series amido of carbonatoms 6 ~ 30 or carbonatoms 6 ~ 50 or the aryloxy aromatic thiohydroxy of carbonatoms 6 ~ 50.
2. aromatic amine compounds according to claim 1, is characterized in that, in described compound molecule general formula R1, R2, R3 be independently selected from below in chemical formula any one:
Wherein X and Y is independently selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted carbonatoms is the alkyl of 1 ~ 30, substituted or unsubstituted carbonatoms is the alkoxyl group of 1 ~ 30, substituted or unsubstituted carbonatoms is the thiazolinyl of 2 ~ 30, substituted or unsubstituted carbonatoms is the alkaryl of 7 ~ 30, substituted or unsubstituted carbonatoms is the aryloxy alkyl of 7 ~ 30, substituted or unsubstituted carbonatoms is the aromatic base of 6 ~ 30, substituted or unsubstituted carbonatoms is the aryloxy of 6 ~ 30, substituted or unsubstituted carbonatoms be 5 ~ 30 heterocyclic radical and substituted or unsubstituted carbonatoms be one in the aromatic amine of 6 ~ 30.
3., according to a kind of new aromatic amine compounds according to claim 1 or claim 2, it is characterized in that, its compound molecule be selected from following any one:
4. a preparation method for the aromatic amine compounds as described in as arbitrary in claim 1-3, is characterized in that, comprise the following steps:
Step 1, carries out linked reaction according to lower reaction formula and methoxyl group disengaging obtains 3-PQDO compound
Step 2, as shown in the formula the chlorination replacement(metathesis)reaction and the linked reaction synthetic compound that comprise ketone group
5. method according to claim 4, is characterized in that, specifically comprises the following steps:
Step 11, prepares intermediate 1
0.2mol-0.3mol reactant 2 is dissolved in 300mL anhydrous diethyl ether, the dry ice bath of-77 DEG C-79 DEG C, under the condition of starvation, add the butyllithium of the 2.5M of 44mL, stirring reaction 1 hour, add 0.1mol-0.2mol reactant 1 again, react 2 hours, after be raised to 15 ~ 25 DEG C gradually, add water termination reaction, then separatory is carried out to reaction product, branch vibration layer, aqueous layer with ethyl acetate extracts one time, is spin-dried for organic solvent, be that the methylene dichloride of 9:1 is crossed post be separated with polyethylene=9:1 by volume ratio, obtain intermediate 1;
Step 12, prepares intermediate 2
The intermediate 1 of 41mmol-42mmol is dissolved in the tetrahydrofuran (THF) of 250mL-300mL, is cooled to 0 DEG C, to add after mixed solution LTMP at 0 DEG C stirring reaction 2 hours;
The tetrahydrofuran (THF) of the synthesis of LTMP: 500mL dissolves 2,2,6, the 6-tetramethyl piperidines of 0.13mol butyllithium and 0.14mol at 0 DEG C;
Then add 200mL water termination reaction, branch vibration layer, is spin-dried for organic layer, is that the methylene dichloride of 10:1 is crossed post with sherwood oil and is separated, obtains intermediate 2 by volume ratio;
Step 21, obtains intermediate 3 by the displacement of ketone group
Accurately taking 10g-15g intermediate 2 joins in reaction flask, add 200mL-300mL acetonitrile, take 30g-50g phosphorus oxychloride to be more slowly added drop-wise in reaction flask, dropwise and be slowly warmed up to 60 DEG C-70 DEG C afterwards, the reaction times is 4-6 hour, after completion of the reaction, add water carefully to extract and go out, then the saturated solution of sodium carbonate adding amplification quantity adjusts pH value 7-8, then add methylene dichloride, extract three times, be spin-dried for obtain intermediate 3;
Step 22, obtains aromatic amine compounds by linked reaction
By the reactant 3 of 14g-16g intermediate 3,17g-19g, tetra-triphenylphosphine palladium 3g-5g joins in reaction flask, add toluene, ethanol and the water mixed liquid that volume ratio is 2:1:1 again and amount to 500mL-600mL, nitrogen protection, stir and be warmed up to 110 DEG C of reaction 22-24 hour, afterwards, system is lowered the temperature, and separatory, is spin-dried for toluene, add methylene dichloride dissolved solids, crossing post, is sherwood oil and the ethyl acetate rinse of 2:1 by volume ratio, obtained aromatic amine compounds;
Wherein, reactant 1 is
, reactant 2 is
, reactant 3 is
, intermediate 1 is
, intermediate 2 is
, intermediate 3 is
。
6., according to the application of the arbitrary described a kind of new aromatic amine compounds of claim 1-3, it is characterized in that, described heteroaromatic compounds is for making organic electroluminescence device.
7. the organic electroluminescence device utilizing the arbitrary described aromatic amine compounds of claim 1-3 obtained, it is characterized in that, one or more organic compound layers that this device comprises the first electrode, the second electrode and is placed between described two electrodes, at least one organic compound layer comprises the aromatic amine compounds described at least one.
8. organic electroluminescence device according to claim 7, it is characterized in that, described organic matter layer comprises hole injection layer, hole transmission layer and had not only possessed hole and injects technical ability but also possess hole transport technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron injecting layer and not only possess electric transmission technical ability but also possess electron injection technical ability layer.
9. organic electroluminescence device according to claim 7, is characterized in that, described organic electroluminescence device also comprises organic luminescent device, organic photovoltaic cell, Electronic Paper, Organophotoreceptor or OTFT.
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| CN105669670A (en) * | 2016-03-04 | 2016-06-15 | 吉林奥来德光电材料股份有限公司 | Heterocyclic compound and preparation method thereof as well as organic electroluminescent device |
| TWI574958B (en) * | 2016-04-27 | 2017-03-21 | 國立清華大學 | Compound, emitting layer of organic light emitting diode and organic light emitting diode device |
| CN106699780A (en) * | 2016-12-23 | 2017-05-24 | 长春海谱润斯科技有限公司 | Aromatic amine derivative as well as preparation method and application thereof |
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| PL3678668T3 (en) | 2017-09-08 | 2024-06-03 | The Board Of Trustees Of The Leland Stanford Junior University | Enpp1 inhibitors and their use for the treatment of cancer |
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| KR20100000121A (en) * | 2008-06-24 | 2010-01-06 | 다우어드밴스드디스플레이머티리얼 유한회사 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| CN103626758A (en) * | 2012-08-20 | 2014-03-12 | 海洋王照明科技股份有限公司 | Organic semiconductor material, preparation method of organic semiconductor material and electroluminescent device |
| CN103626753A (en) * | 2012-08-20 | 2014-03-12 | 海洋王照明科技股份有限公司 | Organic semiconductor material, preparation method of organic semiconductor material and electroluminescent device |
| US11611046B2 (en) * | 2014-03-13 | 2023-03-21 | Merck Patent Gmbh | Organic electroluminescent device |
| CN105085516B (en) * | 2015-06-02 | 2018-07-10 | 吉林奥来德光电材料股份有限公司 | A kind of heteroaromatic derivative and preparation method thereof and a kind of organic electroluminescence device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669670A (en) * | 2016-03-04 | 2016-06-15 | 吉林奥来德光电材料股份有限公司 | Heterocyclic compound and preparation method thereof as well as organic electroluminescent device |
| TWI574958B (en) * | 2016-04-27 | 2017-03-21 | 國立清華大學 | Compound, emitting layer of organic light emitting diode and organic light emitting diode device |
| US9853221B2 (en) | 2016-04-27 | 2017-12-26 | National Tsing Hua University | Compound, emitting layer of organic light emitting diode and organic light emitting diode device |
| CN106699780A (en) * | 2016-12-23 | 2017-05-24 | 长春海谱润斯科技有限公司 | Aromatic amine derivative as well as preparation method and application thereof |
| CN106699780B (en) * | 2016-12-23 | 2018-11-27 | 长春海谱润斯科技有限公司 | A kind of aromatic amine analog derivative and its preparation method and application |
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