CN104650043B - Imidazoles electron transport material and its preparation method and application - Google Patents
Imidazoles electron transport material and its preparation method and application Download PDFInfo
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Abstract
The carbazole imidazoles electron transport material that the present invention provides is based on triphenylimidazolyl and carbazole, on this basis, connect the anthracene of different substituents, constitute the classical compound of a class, under conditions of electric current is constant, luminosity is compared with comparative sample and is significantly increased.Anthryl carbazole dialdehyde analog derivative using benzil/aniline and replacement is raw material, and through repeatedly verifying, its synthesis and purification comparison procedure are simple, with low cost, can meet industrialization development demand.
Description
Technical field
The present invention relates to organic photoelectrical material field is and in particular to a kind of carbazole-imidazoles electron transport material and its system
Preparation Method and application.
Background technology
Organic electroluminescence device is so that its body is thin, area big, all solidstate, flexibility the advantages of cause the extensive of people
Concern, organic electroluminescence device also becomes people with it in the great potential of the aspects such as solid-state illumination light source, liquid crystal backlight
The focus of research.
Early in the fifties, Bernanose.A et al. has begun to the research of organic electroluminescence device (OLED).Initially
The material of research is anthracene single crystal piece.Big due to there is single-chip thickness, required driving voltage is very high.Until 1987
The Deng Qingyun (C.W.Tang) of U.S.'s Eastman Kodak Company and Vanslyke reports structure and is： ITO/Diamine/
Alq3/Mg:The electroluminous organic small molecular device of Ag, device brightness under 10 volts of running voltage reaches 100cd/m2, outer amount
Sub- efficiency reaches 1.0%.Electroluminescent research causes the extensive concern of scientists, it is seen that organic electroluminescent
Device is applied to the probability showing.Open the prelude of organic electroluminescence device research and industrialization from this.
The high efficiency of organic electroluminescence device, high brightness, high color stability etc. are for its industrialization important in inhibiting.
In recent years, in organic electroluminescence device, being introduced into of phosphorescent coloring made triplet state in luminescent layer and singlet exciton all obtain
To making full use of, the brightness of device and efficiency are greatly increased.And the working life of device particularly blue-light device
And the life-span of blue light-emitting layer is the bottleneck problem of restriction organic electroluminescence device performance, people pass through to develop long-life blue light
The mode such as material and optimised devices structure extending device lifetime, in terms of structure optimization, by introduce two kinds of dopant dyes Lai
Improve the mode of device lifetime, by introducing the first dopant accepting substrate electron-hole energy and accepting the second of hole
The method to improve device lifetime for the dopant, the above-mentioned doping luminescent layer being previously mentioned, is all to be mixed in single luminescent layer
Miscellaneous, its shortcoming is that the luminosity of device is not high.
Content of the invention
The present invention is that the technology solving the use requirement that imidazoles luminescent material can not meet OLED in prior art is asked
Topic, and it is simple to provide a kind of preparation method, the high imidazoles electron transport material of luminous efficiency, electroluminescent organic material and
Its preparation method and application.
In order to solve above-mentioned technical problem, technical scheme is specific as follows：
A kind of imidazoles electron transport material, shown in the concrete structure formula such as formula (1) of this material：
Wherein, R1 ~ R9 can be identical or different, is hydrogen, and the alkyl of 1 ~ 20 carbon atom has the virtue of carbon number 1 ~ 20
Base, the heterocyclic radical of carbon atom numerical digit 1 ~ 20.
The compound of the preferably present invention is：R1 ~ R9 is independently selected from hydrogen, methyl, phenyl.
The compound of the more preferably present invention is that specific structural formula corresponds to the chemical structural formula of following 001-006 respectively：
Some of the above is exactly the specific version of this compound, but this series compound does not limit to and listed this
A little chemical constitutions.Based on every (1) by structural formula, the combination in any of the concrete structure that R1 ~ R9 group is respectively given before
All should be included.
The preparation side of the different substituted-phenyl carbazole derivative organic electroluminescent materials that bi triphenyl imidazoles replace
Method, the concrete steps of this preparation method and condition are as follows：
It is 1.1 ~ 1.6 in molar ratio:The 1 iodine anthracene weighing different substituents and carbazole, Phen, Hydro-Giene (Water Science). and carbazole
Mol ratio be 1:10 ~ 15, cesium carbonate is 1.5 ~ 2.5 with the mol ratio of carbazole:1, add solvent, reaction system is deaerated, rise
Temperature, to 150 ~ 155 DEG C, through silica gel funnel, washing, point liquid, rotary evaporation, recrystallization, is vacuum dried to gained solid, is taken
The phenyl carbazole analog derivative in generation.
It is 2 ~ 2.5 in molar ratio:1 weighs bromine and the anthryl carbazole analog derivative replacing, and adds solvent, described solvent is
Acetic acid and dichloromethane, the ratio of solvent is 1:2, reaction overnight, with alkali neutralization, point liquid extraction, washing, is spin-dried for, sucking filtration, vacuum
It is dried, obtain the anthryl carbazole dibromo analog derivative replacing.
It is 2 ~ 2.5 in molar ratio:1 weighs n-BuLi and the anthryl carbazole dibromo analog derivative replacing, and adds solvent, right
Reaction system deaerates, dry ice-propanone bath cooling, and low-temp reaction 1 ~ 1.5 hour, according to DMF and anthryl carbazole dibromo analog derivative
Mol ratio is 5.5 ~ 6:1, room temperature reaction overnight, adds water terminating reaction, hydrolysis, through a point liquid, is spin-dried for, column chromatography obtains replacement
Anthryl carbazole dialdehyde analog derivative.
It is 2.5 ~ 3 in molar ratio:2.5~3:1 weighs benzil/aniline and the anthryl carbazole dialdehyde analog derivative replacing, plus
Enter catalyst, the ratio row of ammonium acetate, sodium pyrosulfite and substituted anthryl carbazole dialdehyde analog derivative are followed successively by 7 ~ 7.5:2.5~
3:1, be warming up to 90 ~ 100 DEG C, backflow overnight, through extracting, washing, be spin-dried for, column chromatography, recrystallization, sucking filtration, vacuum drying, obtain
The different replacement anthryl carbazole derivates that bi triphenyl imidazoles replace.
The invention has the beneficial effects as follows：
1st, carbazole-imidazoles electron transport material that the present invention provides is here based on triphenylimidazolyl and carbazole
On the basis of, connect the anthracene of different substituents, constitute the classical compound of a class, the introducing of different substituents, make this material phase
There are more preferable planar structure and conjugated system than simple carbazole-glyoxaline compound.Triphenylimidazolyl is good electrophilic
Group, is to connect methyl on imidazole ring Isosorbide-5-Nitrae, 5 positions to push away electronics base, is being connected with hole mobile material carbazole, is being fine
Electron transport material.Under conditions of electric current is constant, luminosity is compared with comparative sample and is significantly increased.
2nd, the preparation method of carbazole-imidazoles electroluminescent organic material that the present invention provides, using benzil/aniline and
The anthryl carbazole dialdehyde analog derivative replacing is raw material, and through repeatedly verifying, its synthesis and purification comparison procedure are simple, low cost
Honest and clean, industrialization development demand can be met.
Specific embodiment
The present invention is the skill solving the use requirement that imidazoles-carbazoles luminescent material in prior art can not meet OLED
Art problem, and provide a kind of preparation method simply, the high imidazoles of luminous efficiency-carbazoles electron transport material, its structure is led to
Formula is：（1）
Shown in formula such as formula (1)：Wherein, R1 ~ R9 can be identical or different, is hydrogen, and the alkyl of 1 ~ 20 carbon atom has
The aryl of carbon number 1 ~ 20, the heterocyclic radical of carbon atom numerical digit 1 ~ 20.
Specifically the compound of the present invention is：R1 ~ R9 is independently selected from hydrogen, methyl, phenyl.
The compound of the more specifically present invention is that specific structural formula corresponds to the chemical constitution of following 001-006 respectively
Formula：
Present invention also offers the preparation method containing carbazole-imidazole derivative, comprise the steps：
For example, what some present invention provided is prepared by following methods containing carbazole-imidazole derivative：Make different substituents
Iodine anthracene and carbazole reaction, in molar ratio for 2 ~ 2.5:1 weighs bromine and the anthryl carbazole analog derivative replacing, and adds solvent, institute
Stating solvent is acetic acid and dichloromethane, and the ratio of solvent is 1:2, reaction overnight, with alkali neutralization, point liquid extraction, washing, is spin-dried for,
Sucking filtration, vacuum drying, obtain the anthryl carbazole dibromo analog derivative replacing.
It is 2 ~ 2.5 in molar ratio:1 weighs n-BuLi and the anthryl carbazole dibromo analog derivative replacing, and adds solvent, right
Reaction system deaerates, dry ice-propanone bath cooling, and low-temp reaction 1 ~ 1.5 hour, according to DMF and anthryl carbazole dibromo analog derivative
Mol ratio is 5.5 ~ 6:1, room temperature reaction overnight, adds water terminating reaction, hydrolysis, through a point liquid, is spin-dried for, column chromatography obtains replacement
Anthryl carbazole dialdehyde analog derivative.
It is 2.5 ~ 3 in molar ratio:2.5~3:1 weighs benzil/aniline and the anthryl carbazole dialdehyde analog derivative replacing, plus
Enter catalyst, the ratio row of ammonium acetate, sodium pyrosulfite and substituted anthryl carbazole dialdehyde analog derivative are followed successively by 7 ~ 7.5:2.5~
3:1, be warming up to 90 ~ 100 DEG C, backflow overnight, through extracting, washing, be spin-dried for, crystallize, sucking filtration, vacuum drying, obtain bi triphenyl
The different replacement anthryl carbazole derivates that imidazoles replace.
In order to solve the low technical problem of organic electroluminescence device brightness in prior art, the invention provides a kind of miaow
Azoles-carbazoles electron transport material, the concrete steps of this preparation method and condition are as follows：
Application Example：
Embodiment 1：
Double (2-1,4,5-triphenyl-1H- the imidazole radicals)-9H-carbazole of 9- (9- anthryl)-3,6-：
By 9- bromine anthracene 0.3100mol, carbazole 0.2400mol, Phen 0.0218mol, Hydro-Giene (Water Science). 0.0218mol,
Cesium carbonate 0.3600mol loads in 1000ml there-necked flask, adds 300ml DMF dissolving, evacuation-logical nitrogen three times, heats up
To 150 DEG C, reaction is overnight.Reactant liquor is crossed silica gel funnel, is rinsed to no product dissolution with dichloromethane, be threaded to about 400ml and use
500ml washes, point liquid, takes dichloromethane phase, washes with water three times, be spin-dried for, and adds 100ml dissolving, adds 500ml ethanol to have greatly
Amount solid separates out, sucking filtration, 55 DEG C of vacuum drying.Obtain the bromo- 9- phenyl -9H- carbazole 0.2168mol of 3,6- bis-, yield 88.2%.
The mass spectrum of products therefrom：Theoretical value 343.42；Test value is 343.40.Elementary analysiss：Theoretical value C:90.93；H:4.99；
N:4.08；Test value is C:90.90；H:4.95；N:4.15.
9- (9- anthryl) -9H- carbazole 0.1640mol is loaded in 2000ml there-necked flask, with 320ml acetic acid and 960ml
Dichloromethane dissolves, and is placed in ice-water bath；It is slowly dropped into 0.3280mol bromine, room temperature reaction is overnight.Reactant liquor 1mol/L hydrogen
With remaining bromine in aqueous solution of sodium oxide 1.5L；Liquid is divided to take organic faciess；Wash with water respectively three times, point liquid takes organic faciess, rotation
Dry, use 300ml petroleum ether（60~90）Washing, sucking filtration, 55 DEG C of vacuum drying.Obtain product 9- (9- anthryl) -3,6- two bromo-
9H- carbazole 0.1443mol, yield 87.9%.The mass spectrum of products therefrom：Theoretical value 501.21；Test value is 502.19.Element
Analysis：Theoretical value C:62.30；H:3.02；Br:31.88；N:2.79；Test value is C:62.28；H:3.04；Br:31.86；
N:2.81.
Upper step product 0.0996mol is loaded in there-necked flask, adds 500ml THF (eliminating water) dissolving；Evacuation-logical nitrogen
Gas three times, dry ice-propanone bath cooling, it is slowly dropped into 0.2490mol n-BuLi, low-temp reaction one hour；It is slowly dropped into
0.5478molDMF, low-temp reaction, after one hour, continues room temperature reaction overnight.Reactant liquor adds water terminating reaction, adds appropriate
2mol/L dilute hydrochloric acid 50ml hydrolyzes；Add 400ml dichloromethane to divide liquid, take dichloromethane phase, be spin-dried for silicagel column, eluant is
DCM:Petroleum ether（60~90）=2:3.Obtain 9- (9- anthryl) -9H- carbazole -3,6- diformazan aldehyde product 0.0885mol, yield
88.9%.
By upper step product 0.0287mol, ammonium acetate 0.2100mol, benzil 0.0751mol, sodium pyrosulfite
0.0752mol loads and uses 1,2- dichloroethanes 45ml to dissolve in 100ml there-necked flask, evacuation-logical nitrogen three times, injects aniline
0.0751mol, is warming up to 95 DEG C, and backflow is overnight.Reactant liquor adds 600ml water terminating reaction, adds the dissolving of 400ml dichloromethane
Product, point liquid, take dichloromethane phase, organic faciess are washed twice again；It is spin-dried for, add the dissolving of 100ml dichloromethane, use petroleum ether
（60~90）500ml separates out, sucking filtration solid, ethyl alcohol recrystallization, sucking filtration, 55 DEG C of vacuum drying.Obtain product 0.0241mol, yield
84.0%.The mass spectrum of double (2-1,4,5-triphenyl-1H- imidazole radicals)-9H-carbazole of gained 9- (9- anthryl)-3,6-：Theoretical value
For 932.12；Test value is 932.14.Elementary analysiss：Theoretical value C:87.62；H:4.78；N:7.51；Test value is C:
87.60；H:4.75；N:7.56.
Embodiment 2：
Double (1,4,5- triphenyl -2-1H- the imidazole radicals) -9H- carbazole of 9- (10- methyl anthracene -9- base) -3,6-：
By bromo- for 9- 10- methyl anthracene 0.2600mol, carbazole 0.2400mol, Phen 0.0218mol, Hydro-Giene (Water Science).
0.0218mol, cesium carbonate 0.3600mol load in 1000ml there-necked flask, add 300ml DMF dissolving, evacuation-logical nitrogen
Three times, it is warming up to 151 DEG C, reaction is overnight.Reactant liquor is crossed silica gel funnel, is rinsed to no product dissolution with dichloromethane；It is threaded to
About 400ml is washed with 500ml, point liquid, takes dichloromethane phase, washes three times with water；It is spin-dried for, add 100ml dissolving, add
500ml ethanol has a large amount of solids to separate out, sucking filtration, 55 DEG C of vacuum drying, obtains 9- (10- methyl anthracene -9- base) -9H- carbazole
0.2119mol, yield 88.30%.The mass spectrum of products therefrom：Theoretical value 357.45；Test value is 357.40.Elementary analysiss：Reason
It is C by value:90.72；H:5.36；N:3.92；Test value is C:90.70；H:5.35；N:3.95.
9- (10- methyl anthracene -9- base) -9H- carbazole 0.1640mol is loaded in 2000ml there-necked flask, uses 320ml acetic acid
With the dissolving of 960ml dichloromethane, it is placed in ice-water bath；It is slowly dropped into 0.3444mol bromine, room temperature reaction is overnight.Reactant liquor is used
With remaining bromine in 1mol/L sodium hydrate aqueous solution 1.5L；Liquid is divided to take organic faciess；Wash with water respectively three times, point liquid has taken
Machine phase, is spin-dried for, and uses 300ml petroleum ether（60~90）Washing, sucking filtration, 55 DEG C of vacuum drying.Obtain 3,6- bis- bromo- 9- (10- methyl
Anthracene -9- base) -9H- carbazole 0.1435mol, yield 87.5%.The mass spectrum of products therefrom：Theoretical value 515.24；Test value is
515.22.Elementary analysiss：Theoretical value C:62.94；H:3.33；Br:31.02；N:2.72；Test value is C:62.92；H:
3.31；Br:31.04；N:2.74.
Bromo- for 3,6- bis- 9- (10- methyl anthracene -9- base) -9H- carbazole 0.0996mol is loaded in there-necked flask, adds
500ml THF (eliminating water) dissolves；Evacuation-logical nitrogen three times, dry ice-propanone bath cooling, it is slowly dropped into 0.1992mol normal-butyl
Lithium, low-temp reaction one hour, it is slowly dropped into DMF 0.5578mol, then low-temp reaction removes dry ice-propanone bath, room after one hour
Temperature reaction is overnight.Reactant liquor adds water terminating reaction, adds appropriate 2mol/L dilute hydrochloric acid 50ml hydrolysis；Add 400ml dichloromethane
Divide liquid, take dichloromethane phase, be spin-dried for silicagel column, eluant is DCM:Petroleum ether（60~90）=2:3.Obtain 9- (10- methyl
Anthracene -9- base) -9H- carbazole -3,6- dicarbaldehyde 0.0389mol, yield 89.3%.
By upper step product 0.0287mol, ammonium acetate 0.2040mol, benzil 0.0718mol, sodium pyrosulfite
0.0718mol loads and uses 1,2- dichloroethanes 45ml to dissolve in 100ml there-necked flask, evacuation-logical nitrogen three times, injects aniline
0.0751mol, is warming up to 95 DEG C, and backflow is overnight.Reactant liquor adds 600ml water terminating reaction, adds the dissolving of 400ml dichloromethane
Product, point liquid, take dichloromethane phase, organic faciess are washed twice again；It is spin-dried for, add the dissolving of 100ml dichloromethane, use petroleum ether
（60~90）500ml separates out, sucking filtration solid, ethyl alcohol recrystallization, sucking filtration, 55 DEG C of vacuum drying.Obtain product 0.0245mol, yield
85.4%.The mass spectrum of products therefrom：Theoretical value 946.14；Test value is 946.17.Elementary analysiss：Theoretical value C:87.59；
H:5.01；N:7.40；Test value is C:87.57；H:5.04；N:7.38.
Embodiment 3：
Double (1,4,5- triphenyl -1H- imidazoles -2- the base) -9H- carbazole of 9- (3,10- dimethylanthracene -9- base) -3,6-：
Will be sub- to bromo- for 9- 2,10- dimethylanthracene 0.2880mol, carbazole 0.2400mol, Phen 0.0200mol, iodate
Copper 0.0200mol, cesium carbonate 0.3840mol load in 1000ml there-necked flask, add 300ml DMF dissolving, evacuation-logical nitrogen
Gas three times, is warming up to 152 DEG C, and reaction is overnight.Reactant liquor is crossed silica gel funnel, is rinsed to no product dissolution with dichloromethane；Rotation
Washed with 500ml to about 400ml, point liquid, take dichloromethane phase, wash three times with water；It is spin-dried for, add 100ml dissolving, add
500ml ethanol has a large amount of solids to separate out, sucking filtration, 55 DEG C of vacuum drying.Obtain 0.2126mol, yield 88.60%.Products therefrom 9-
The mass spectrum of (3,10- dimethylanthracene -9- base) -9H- carbazole：Theoretical value 371.47；Test value is 371.43.Elementary analysiss：Reason
It is C by value:90.53；H:5.70；N:3.77；Test value is C:90.51；H:5.75；N:3.74.
9- (3,10- dimethylanthracene -9- base) -9H- carbazole 0.1640mol loads in 2000ml there-necked flask, uses 320ml vinegar
Acid and the dissolving of 960ml dichloromethane, are placed in ice-water bath；It is slowly dropped into 0.3608mol bromine, room temperature reaction is overnight.Reactant liquor
With in 1mol/L sodium hydrate aqueous solution 1.5L and remaining bromine；Liquid is divided to take organic faciess；Wash with water respectively three times, point liquid takes
Organic faciess, are spin-dried for, and use 300ml petroleum ether（60~90）Washing, sucking filtration, 55 DEG C of vacuum drying.Obtain product 0.1444mol, produce
Rate 88.04%.The mass spectrum of the bromo- 9- of products therefrom 3,6- bis- (3,10- dimethylanthracene -9- base) -9H- carbazole：Theoretical value
529.27；Test value is 529.25.Elementary analysiss：Theoretical value C:63.54；H:3.62；Br:30.19；N:2.65；Test value
For C:63.52；H:3.60；Br:30.21；N:2.67.
Upper step product 0.0996mol is loaded in there-necked flask, adds 500ml THF (eliminating water) dissolving；Evacuation-logical nitrogen
Gas three times, dry ice-propanone bath cooling, it is slowly dropped into 0.2092mol n-BuLi, low-temp reaction one hour；It is slowly dropped into
0.5677mol DMF, then low-temp reaction remove after one hour dry ice-propanone bath, room temperature reaction is overnight.Reactant liquor adds water termination instead
Should, add appropriate 2mol/L dilute hydrochloric acid 50ml hydrolysis；Add 400ml dichloromethane to divide liquid, take dichloromethane phase, be spin-dried for silica gel
Post, eluant is DCM:Petroleum ether（60~90）=2:3.Obtain 9- (3,10- dimethylanthracene -9- base) -9H- carbazole -3,6- diformazan
Aldehyde 0.0888mol, yield 89.20%.
By upper step product 0.0287mol, ammonium acetate 0.2009mol, benzil 0.0775mol, sodium pyrosulfite
0.0775mol loads and uses 1,2- dichloroethanes 45ml to dissolve in 100ml there-necked flask, evacuation-logical nitrogen three times, injects aniline
0.0775mol, is warming up to 95 DEG C, and backflow is overnight.Reactant liquor adds 600ml water terminating reaction, adds the dissolving of 400ml dichloromethane
Product, point liquid, take dichloromethane phase, organic faciess are washed twice again；It is spin-dried for, add the dissolving of 100ml dichloromethane, use petroleum ether
（60~90）500ml separates out, sucking filtration solid, ethyl alcohol recrystallization, sucking filtration, 55 DEG C of vacuum drying.Obtain product 9- (3,10- dimethyl
Anthracene -9- base) double (Isosorbide-5-Nitrae, 5- triphenyl -1H- imidazoles -2- the base) -9H- carbazole 0.0237mol of -3,6-, yield 82.60%.Gained produces
The mass spectrum of thing：Theoretical value 960.17；Test value is 960.15.Elementary analysiss：Theoretical value C:87.56；H:5.14；N:
7.29；Test value is C:87.54；H:5.18；N:7.27.
Embodiment 4：
Double (1,4,5- triphenyl -1H- imidazoles -2- the base) -9H- carbazole of 9- (10- phenylanthracene -9- base) -3,6-
By bromo- for 9- 10- phenylanthracene 0.3120mol, carbazole 0.2400mol, Phen 0.0184mol, Hydro-Giene (Water Science).
0.0184mol, cesium carbonate 0.4080mol load in 1000ml there-necked flask, add 300ml DMF dissolving, evacuation-logical nitrogen
Three times, it is warming up to 153 DEG C, reaction is overnight.Reactant liquor is crossed silica gel funnel, is rinsed to no product dissolution with dichloromethane；It is threaded to
About 400ml is washed with 500ml, point liquid, takes dichloromethane phase, washes three times with water；It is spin-dried for, add 100ml dissolving, add
500ml ethanol has a large amount of solids to separate out, sucking filtration, 55 DEG C of vacuum drying.Obtain product 0.2119mol, yield 88.30%.Gained produces
The mass spectrum of thing 9- (10- phenylanthracene -9- base) -9H- carbazole：Theoretical value 419.52；Test value is 419.54.Elementary analysiss：Reason
It is C by value:91.62；H:5.05；N:3.34；Test value is C:91.64；H:5.07；N:3.30.
9- (10- phenylanthracene -9- base) -9H- carbazole 0.1640mol is loaded in 2000ml there-necked flask, uses 320ml acetic acid
With the dissolving of 960ml dichloromethane, it is placed in ice-water bath；It is slowly dropped into 0.3936mol bromine, room temperature reaction is overnight.Reactant liquor is used
With remaining bromine in 1mol/L sodium hydrate aqueous solution 1.5L；Liquid is divided to take organic faciess；Wash with water respectively three times, point liquid has taken
Machine phase, is spin-dried for, and uses 300ml petroleum ether（60~90）Washing, sucking filtration, 55 DEG C of vacuum drying.Obtain product 0.1446mol, yield
88.17%.The mass spectrum of the bromo- 9- of products therefrom 3,6- bis- (10- phenylanthracene -9- base) -9H- carbazole：Theoretical value 577.31；Test
It is worth for 577.29.Elementary analysiss：Theoretical value C:66.57；H:3.32；Br:27.68；N:2.43；Test value is C:66.53；H:
3.36；Br:27.66；N:2.45.
Bromo- for 3,6- bis- 9- (10- phenylanthracene -9- base) -9H- carbazole 0.0996mol is loaded in there-necked flask, adds
500ml THF (eliminating water) dissolves；Evacuation-logical nitrogen three times, dry ice-propanone bath cooling, it is slowly dropped into 0.2191mol normal-butyl
Lithium, low-temp reaction one hour；It is slowly dropped into 0.5777mol DMF, then low-temp reaction removes dry ice-propanone bath, room after one hour
Temperature reaction is overnight.Reactant liquor adds water terminating reaction, adds appropriate 2mol/L dilute hydrochloric acid 50ml hydrolysis, adds 400ml dichloromethane
Divide liquid, take dichloromethane phase, be spin-dried for silicagel column, eluant is DCM:Petroleum ether（60~90）=2:3, obtain product 9- (10- benzene
Base anthracene -9- base) -9H- carbazole -3,6- dicarbaldehyde 0.0868mol, yield 87.15%.
Will be even to 9- (10- phenylanthracene -9- base) -9H- carbazole -3,6- dicarbaldehyde 0.0287mol, ammonium acetate 0.2124mol, benzene
Use 1,2- dichloroethanes 45ml to dissolve in acyl 0.0804mol, sodium pyrosulfite 0.0804mol loading 100ml there-necked flask, take out true
Empty-logical nitrogen three times, injects aniline 0.0751mol, is warming up to 95 DEG C, backflow is overnight.It is anti-that reactant liquor adds 600ml water to terminate
Should, add 400ml dichloromethane lysate, point liquid, take dichloromethane phase, organic faciess are washed twice again；It is spin-dried for, add
100ml dichloromethane dissolves, and uses petroleum ether（60~90）500ml separates out, sucking filtration solid, ethyl alcohol recrystallization, sucking filtration, 55 DEG C of vacuum
It is dried.Obtain double (1,4,5- triphenyl -1H- imidazoles -2- the base) -9H- carbazole of product 9- (10- phenylanthracene -9- base) -3,6-
0.0246mol, yield 85.71%.The mass spectrum of products therefrom：Theoretical value 1008.21；Test value is 1008.18.Elementary analysiss：
Theoretical value C:88.16；H:4.90；N:6.95；Test value is C:88.12；H:4.92；N:6.97.
Embodiment 5：
Double (1,4,5- triphenyl -1H- imidazoles -2- the base) -9H- carbazole of 9- (3,10- diphenylanthrancene -9- base) -3,6-：
Will be sub- to bromo- for 9- 3,10- diphenylanthrancene 0.3360mol, carbazole 0.2400mol, Phen 0.0142mol, iodate
Copper 0.0142mol, cesium carbonate 0.4320mol load in 1000ml there-necked flask, add 300ml DMF dissolving, evacuation-logical nitrogen
Gas three times, is warming up to 154 DEG C, and reaction is overnight.Reactant liquor is crossed silica gel funnel, is rinsed to no product dissolution with dichloromethane；Rotation
Washed with 500ml to about 400ml, point liquid, take dichloromethane phase, wash three times with water；It is spin-dried for, add 100ml dissolving, add
500ml ethanol has a large amount of solids to separate out, sucking filtration, 55 DEG C of vacuum drying, obtains product 9- (3,10- diphenylanthrancene -9- base) -9H-
Carbazole 0.2931mol, yield 87.23%.The mass spectrum of products therefrom：Theoretical value 495.61；Test value is 495.59.Element divides
Analysis：Theoretical value C:92.09；H:5.08；N:2.83；Test value is C:92.07；H:5.06；N:2.85.
9- (3,10- diphenylanthrancene -9- base) -9H- carbazole 0.1640mol is loaded in 2000ml there-necked flask, uses 320ml
Acetic acid and the dissolving of 960ml dichloromethane, are placed in ice-water bath；It is slowly dropped into 0.4100mol bromine, room temperature reaction is overnight.Reaction
Liquid is with 1mol/L sodium hydrate aqueous solution 1.5L and remaining bromine；Liquid is divided to take organic faciess；Wash with water respectively three times, point liquid
Take organic faciess, be spin-dried for, use 300ml petroleum ether（60~90）Washing, sucking filtration, 55 DEG C vacuum drying, obtain the bromo- 9- of 3,6- bis- (3,
10- diphenylanthrancene -9- base) -9H- carbazole product 0.1425mol, yield 86.89%.The mass spectrum of products therefrom：Theoretical value
653.40；Test value is 653.38.Elementary analysiss：Theoretical value C:69.85；H:3.55；Br:24.46；N:2.14；Theoretical value
For C:69.87；H:3.58；Br:24.43；N:2.12.
Bromo- for 3,6- bis- 9- (3,10- diphenylanthrancene -9- base) -9H- carbazole 0.0996mol is loaded in there-necked flask, adds
500mlTHF (eliminating water) dissolves；Evacuation-logical nitrogen three times, dry ice-propanone bath cooling, it is slowly dropped into 0.21912mol normal-butyl
Lithium, low-temp reaction one hour；It is slowly dropped into 0.5876molDMF, then low-temp reaction removes dry ice-propanone bath, room temperature after one hour
Reaction is overnight.Reactant liquor adds water terminating reaction, adds appropriate 2mol/L dilute hydrochloric acid 50ml hydrolysis；400ml dichloromethane is added to divide
Liquid, takes dichloromethane phase, is spin-dried for silicagel column, and eluant is DCM:Petroleum ether（60~90）=2:3, obtain product 9- (3,10- bis-
Phenylanthracene -9- base) -9H- carbazole -3,6- dicarbaldehyde 0.0878mol, yield 88.15%.
By 9- (3,10- diphenylanthrancene -9- base) -9H- carbazole -3,6- dicarbaldehyde 0.0287mol, ammonium acetate 0.2120mol,
1,2- dichloroethanes 45ml is used to dissolve in benzil 0.0804mol, sodium pyrosulfite 0.0804mol loading 100ml there-necked flask,
Evacuation-logical nitrogen three times, injects aniline 0.0751mol, is warming up to 95 DEG C, overnight, reactant liquor adds 600ml water to terminate for backflow
Reaction, adds 400ml dichloromethane lysate, and point liquid takes dichloromethane phase, organic faciess are washed twice again；It is spin-dried for, add
100ml dichloromethane dissolves, and uses petroleum ether（60~90）500ml separates out, sucking filtration solid, ethyl alcohol recrystallization, sucking filtration, 55 DEG C of vacuum
It is dried, obtain double (Isosorbide-5-Nitrae, 5- triphenyl -1H- imidazoles -2- the base) -9H- carbazole of product 9- (3,10- diphenylanthrancene -9- base) -3,6-
0.0247mol, yield 86.06%.The mass spectrum of products therefrom：Theoretical value 1084.31；Test value is 1084.29.Elementary analysiss：
Theoretical value C:88.61；H:4.93；N:6.46；Test value is C:88.63；H:4.95；N:6.42.
Embodiment 6：
3,6- bis- (2-1,4,5- triphenyl -1H- imidazole radicals) -9- (2,6,10- triphenyl anthracene -9- base) -9H- carbazole：
By bromo- for 9- 2,6,10- triphenyl anthracene 0.3600mol, carbazole 0.2400mol, Phen 0.0160mol, iodate
Cuprous 0.0160mol, cesium carbonate 0.4560mol load in 1000ml there-necked flask, add 300ml DMF dissolving, evacuation-logical
Nitrogen three times, is warming up to 155 DEG C, and reaction is overnight.Reactant liquor is crossed silica gel funnel, is rinsed to no product dissolution with dichloromethane；
It is threaded to about 400ml 500ml washing, point liquid, take dichloromethane phase, wash three times with water；It is spin-dried for, add 100ml dissolving, add
500ml ethanol has a large amount of solids to separate out, sucking filtration, 55 DEG C of vacuum drying.Obtain product 0.2113mol, yield 88.04%.Gained produces
The mass spectrum of thing 9- (2,6,10- triphenyl anthracene -9- base) -9H- carbazole：Theoretical value 571.71；Test value is 571.73.Element divides
Analysis：Theoretical value C:92.44；H:5.11；N:2.45；Test value is C:92.41；H:5.12；N:2.47.
9- (2,6,10- triphenyl anthracene -9- base) -9H- carbazole 0.1640mol is loaded in 2000ml there-necked flask, uses
320ml acetic acid and the dissolving of 960ml dichloromethane, are placed in ice-water bath；It is slowly dropped into 0.4264mol bromine, room temperature reaction is overnight.
Reactant liquor is with 1mol/L sodium hydrate aqueous solution 1.5L and remaining bromine；Liquid is divided to take organic faciess；Wash with water respectively three times,
Divide liquid to take organic faciess, be spin-dried for, use 300ml petroleum ether（60~90）Washing, sucking filtration, 55 DEG C of vacuum drying.Obtain product
0.1428mol, yield 87.10%.The mass spectrum of the bromo- 9- of products therefrom 3,6- bis- (2,6,10- triphenyl anthracene -9- base) -9H- carbazole：
Theoretical value 679.44；Test value is 679.40.Elementary analysiss：Theoretical value C:72.44；H:3.73；Br:21.91；N:
1.92；Test value is C:72.46；H:3.75；Br:21.90；N:1.89.
Bromo- for 3,6- bis- 9- (2,6,10- triphenyl anthracene -9- base) -9H- carbazole 0.0996mol is loaded in there-necked flask, plus
Enter 500ml THF (eliminating water) dissolving；Evacuation-logical nitrogen three times, dry ice-propanone bath cooling, it is slowly dropped into the positive fourth of 0.2390mol
Base lithium, low-temp reaction one hour；It is slowly dropped into 0.5976mol DMF, then low-temp reaction removes dry ice-propanone bath after one hour,
Room temperature reaction is overnight.Reactant liquor adds water terminating reaction, adds appropriate 2mol/L dilute hydrochloric acid 50ml hydrolysis；Add 400ml dichloromethane
Alkane divides liquid, takes dichloromethane phase, is spin-dried for silicagel column, and eluant is DCM:Petroleum ether（60~90）=2:3, obtain product 9- (2,
6,10- triphenyl anthracene -9- bases) -9H- carbazole -3,6- dicarbaldehyde 0.0884mol, yield 88.76%.
By 9- (2,6,10- triphenyl anthracene -9- base) -9H- carbazole -3,6- dicarbaldehyde 0.0287mol, ammonium acetate
0.2153mol, benzil 0.0861mol, sodium pyrosulfite 0.0861mol load in 100ml there-necked flask with 1,2- bis- chloroethene
Alkane 45ml dissolves, evacuation-logical nitrogen three times, injects aniline 0.0751mol, is warming up to 95 DEG C, backflow is overnight.Reactant liquor adds
600ml water terminating reaction, adds 400ml dichloromethane lysate, and point liquid takes dichloromethane phase, organic faciess are washed twice again；
It is spin-dried for, add the dissolving of 100ml dichloromethane, use petroleum ether（60~90）500ml separates out, sucking filtration solid, ethyl alcohol recrystallization, sucking filtration,
55 DEG C of vacuum drying, obtain product 0.0241mol, yield 83.97%, products therefrom 3,6- bis- (2-1,4,5- triphenyl -1H- miaows
Oxazolyl) -9- (2,6,10- triphenyl anthracene -9- base) -9H- carbazole mass spectrum：Theoretical value 1160.41；Test value is 1160.38.
Elementary analysiss：Theoretical value C:89.01；H:4.95；N:6.04；Test value is C:89.00；H:4.98；N:6.02.
Contrast test 1
We are respectively by comparative sample 3,6- bis- (9- anthryl) -9- phenyl -9H- carbazole
, it is 1 that the triphenylimidazolyl-carbazole compound 001-006 of embodiment of the present invention 1-6 preparation is configured to concentration respectively
×10-6The solution of mol/L, using Edinburdh-FLS920 equipment, spin-coating method is fabricated to thin film, tests sending out of they respectively
Light efficiency, concrete data such as following table.
The luminous efficiency of gained compound and comparative sample in table 1 embodiment 1-6
From the data of table 1 can be seen that luminous efficiency weak solution for the comparative sample be 80.0%, in the film send out
Light efficiency is 51.0%；And carbazole-glyoxaline compound that the embodiment of the present invention prepares, the luminous efficiency in weak solution
Up to 94.5%, the luminous efficiency in thin film is up to 63.5%.Triphenylimidazolyl-carbazoles that i.e. present invention provides
The luminous efficiency of compound significantly improves, and disclosure satisfy that the requirement of OLED.Compared by data it has been found that this kind of material is performance
Excellent electroluminescent organic material, is a very promising class electroluminescent organic material.
Contrast test 2
Comparing embodiment 1
By Corning（Healthy and free from worry）Society 15 Ω/cm2(1000) ito glass substrate cut into size 3mm substrate ×
The size of 3mm, in a vacuum chamber, installation base plate pressure of foundation is 1 × 10-6, so that ito anode is sunk to hole injection layer phthalocyanine copper film
Long-pending thickness is the deposit thickness of 200, NPD transport layer is 400, and adulterates with DPBVi 200 comparative sample 1 in luminescent layer
5% concentration.Then, Alq3The thickness of the electron transfer layer constituting is 350, and LiF electron injecting layer deposit thickness is 5 Hes
The deposit thickness of Al negative electrode is that 1000 organic electroluminescence devices made are made.
Application Example 1-6：
Using the method in such as comparative example 1, change dopant comparative sample 1, made into containing compound 001-006ization
The organic luminescent device of compound structure.
The luminosity of gained compound and comparative sample in table 2 embodiment 1-6
According to represented by table 2, above-mentioned sample is blueness in place chromaticity coordinates position display glow color.Application implementation
The sample of example 001 to 006 is compared with the sample of comparing embodiment 1, and under conditions of electric current is constant, luminosity all carries
High.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved according to the above description or to convert, all these modifications and variations all should belong to the guarantor of claims of the present invention
Shield scope.
Claims (5)
1. a kind of electron transport compound being represented by formula 1,
Wherein, R1~R9Independently selected from hydrogen, methyl, phenyl.
2. the electron transport compound described in claim 1, specific structural formula corresponds to the chemistry knot of following 001-006 respectively
Structure formula：
.
3. the electron transport compound as described in a kind of any one as claim 1-2 preparation method it is characterised in that include as
Lower step：
Step S1：It is 2.5 ~ 3 in molar ratio:2.5~3:1 weighs benzil/aniline derives with the anthryl carbazole twain-aldehyde compound replacing
Thing, adds the ratio of catalyst acetic acid ammonium, sodium pyrosulfite and substituted naphthyl carbazole dialdehyde analog derivative to be followed successively by 7 ~ 7.5:
2.5~3:1；
Step S2：It is warming up to 90 ~ 100 DEG C, backflow is overnight；
Step S3：Reactant liquor adds suitable quantity of water stopped reaction, is extracted 3 times with dichloromethane；
Step S4：After being spin-dried for, using dichloromethane and petroleum ether（60~90℃）Recrystallization；
Step S5：Continue recrystallization, vacuum drying using ethanol.
4. a kind of organic luminescent device, including first electrode, second electrode be placed in one or more between described two electrodes
Organic compound layer is it is characterised in that at least one organic compound layer comprises at least one as any one of claim 1 ~ 2 institute
The electron transport compound of definition.
5. application in organic electroluminescence device for the carbazole-imidazole derivative according to any one of claim 1 ~ 2,
It is characterized in that, described electron transport compound is used as electron transport material in described organic luminescent device.
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| CN102596939A (en) * | 2009-09-16 | 2012-07-18 | 日东电工株式会社 | Compounds for organic light emitting diode emissive layers |
| CN102731406A (en) * | 2012-07-05 | 2012-10-17 | 吉林大学 | Phenanthroimidazole derivatives and application of phenanthroimidazole derivatives in preparation of electroluminescent device |
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| CN102596939A (en) * | 2009-09-16 | 2012-07-18 | 日东电工株式会社 | Compounds for organic light emitting diode emissive layers |
| CN102731406A (en) * | 2012-07-05 | 2012-10-17 | 吉林大学 | Phenanthroimidazole derivatives and application of phenanthroimidazole derivatives in preparation of electroluminescent device |
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