CN104650066B - A kind of preparation of green light material and its organic luminescent device - Google Patents
A kind of preparation of green light material and its organic luminescent device Download PDFInfo
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- CN104650066B CN104650066B CN201410379881.2A CN201410379881A CN104650066B CN 104650066 B CN104650066 B CN 104650066B CN 201410379881 A CN201410379881 A CN 201410379881A CN 104650066 B CN104650066 B CN 104650066B
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Abstract
The invention discloses a kind of preparation of green light material and its organic luminescent device.The green light material is 3,7 2（The base of 1 phenyl 1H benzos [d] imidazoles 2）‑10‑（4 (base of 1 phenyl 1H benzos [d] imidazoles 2) phenyl）10H phenthazine, its chemical structural formula is as follows：
Description
Technical field
The invention belongs to synthesize luminous organic material and its organic luminescent device field, more particularly to a kind of phenothiazines
The preparation technology of derivative.
Background technology
Organic electroluminescent（EL）Device（Hereinafter, simply referred to as " organic EL device "）.Typically by two opposed electricity
Pole and at least one layer of organic luminescent compounds composition being inserted between two electrodes.Electric charge is implanted in anode and negative electrode
Between in the organic layer that is formed, to form electronics and hole pair, generate the organic compound with fluorescence or phosphorescent characteristics
Light is launched.
Organic electroluminescence device（OLED）It is a kind of new flat panel display device, with energy-conservation, fast response time, face
Colour-stable, environmental suitability is strong, radiationless, long lifespan, light weight, thickness of thin the features such as.Due to photoelectric communication in recent years and many
Field of media is developed rapidly, and organic optoelectronic material turns into the core of modern society information and electronic industry.
Research for organic EL Material is to apply high to the macromolecule membrane containing organic pigment from nineteen fifty Bernose
Current Voltage observation starts.Nineteen sixty-five, Po petroleum ethers et al. are found that the Electroluminescence Properties of anthracene single crystal first, and this is to organise
The first electro optical phenomenon of compound.1987, Tang of Kodak et al. had found, had separation by what organic material was formed
The organic luminescent device of function lamination can also provide 1000cd/cm under 10V or smaller low-voltage2Or it is higher highlighted
Degree.
At present, the material of main part in electroluminescent device mainly has small molecule host material and polymer host material two
Class.Using small molecule host material doping phosphorescent complexes many efficient electroluminescent cells have been prepared for as luminescent layer
Part.But preparing small molecule electroluminescent device needs, using complicated technologies such as vacuum evaporations, to substantially increase preparation cost.
Meanwhile, small molecule is easy to the stability that the properties such as crystallization also significantly limit device in itself.In recent years, using polymerizeing owner
The material doped various phosphorescent complexes objects of body prepare electroluminescent device as luminescent layer and receive more concern.However,
The solubility property and filming performance for the polymer host material reported at present are relatively poor, so as to influence it as luminescent layer.
The content of the invention
For the deficiency in above-mentioned field, the invention provides a kind of synthesis side for efficiently synthesizing phenothiazines
Method, this method is improved on the basis of current method, and easy to operate, yield is high, and product purity is high, and cost for purification is low, right
The industrialization promotion of the material has great meaning.
Contain phenothiazines, the material of main part with superior luminescence performance it is an object of the invention to provide one kind.
Technical scheme is as follows：A kind of phenothiazines, it is 3,7- bis- that the phenothiazines, which derives,（1- benzene
Base -1H- benzos [d] imidazoles -2- bases）-10-（4- (1- phenyl -1H- benzos [d] imidazoles -2- bases) phenyl）- 10H- phenthazine, its
Chemical structural formula is as follows：
The preparation method of above-mentioned phenothiazines, wherein, comprise the following steps：
S100, to bromo-iodobenzene and phenthazine under the catalysis of copper powder, obtain compound 10-（4- bromophenyls）- 10H- fen thiophenes
Piperazine；
S200, by 10-（4- bromophenyls）- 10H- phenthazine is under conditions of the dissolving of glacial acetic acid and dichloromethane, frozen water
Bromine is added dropwise in bath, obtains the bromo- 10- of compound 3,7-two（4- bromophenyls）- 10H- phenthazine；
S300, by the bromo- 10- of 3,7- bis-（4- bromophenyls）- 10H- phenthazine adds n-BuLi reaction and dimethyl formyl
Amine reaction generation 10-（4- Fonnylphenyls）- 10H--3,7-dicarbaldehydes of phenthazine；
S400, by 10-（4- Fonnylphenyls）- 10H- phenthazine -3,7- dicarbaldehydes and adjacent aminodiphenylamine reaction are obtained
3,7- bis-（1- phenyl -1H- benzos [d] imidazoles -2- bases）-10-（4- (1- phenyl -1H- benzos [d] imidazoles -2- bases) phenyl）-
10H- phenthazine.
The preparation method of described phenothiazines, wherein, the S100 specifically includes following steps：
To be raw material to bromo-iodobenzene, phenthazine, copper powder is that catalyst, potassium carbonate are alkali, and dimethylformamide is solvent, instead
It is 150 DEG C ~ 160 DEG C to answer temperature, and the reaction time is 22 ~ 26 hours.Through extraction, point liquid is rotated, and 10- is obtained after recrystallization（4- bromines
Phenyl）- 10H- phenthazine.
The preparation method of described phenothiazines, wherein, the S200 specifically includes following steps：
By 10-（4- bromophenyls）- 10H- phenthazine, glacial acetic acid and dichloromethane are solvent, are placed in ice-water bath；Quickly stir
Mix down and be slowly dropped into bromine, room temperature reaction is stayed overnight, it is post-treated after obtain the bromo- 10- of 3,7- bis-（4- bromophenyls）- 10H- fen thiophenes
Piperazine.
The last handling process includes neutralizing, extraction, and point liquid is rotated, recrystallization.The recrystallization is dichloro using solvent
Methane and petroleum ether, ratio are 1:10.
The preparation method of described phenothiazines, wherein, the S300 specifically includes following steps：
Using anhydrous tetrahydro furan as solvent, under nitrogen protection, by the bromo- 10- of 3,7- bis-（4- bromophenyls）- 10H- phenthazine
Lithium reagent is prepared with n-BuLi reaction；Dimethylformamide is slowly dropped into, reaction is warmed to room temperature by completion of dropping, is heated to reflux
Reaction 20 ~ 25 hours, it is post-treated to obtain 10-（4- Fonnylphenyls）- 10H- phenthazine -3,7- dicarbaldehydes.
The last handling process includes hydrolysis, extracts, recrystallization.The recrystallization solvent be dichloromethane and petroleum ether,
Ratio is 1:4.
The preparation method of described phenothiazines, wherein, the S400 specifically includes following steps：
By 10-（4- Fonnylphenyls）- 10H- phenthazine -3,7- dicarbaldehyde and adjacent aminodiphenylamine, sodium pyrosulfite, with
Dimethylformamide is solvent, and reaction temperature is 150 ~ 160 DEG C, and reflux time is 22 ~ 26 hours.
A kind of organic luminescent device being made containing phenothiazines, it include first electrode, second electrode with
And the one or more organic compound layers being placed between the first electrode, the second electrode, it is characterised in that at least one
The individual organic compound layer includes the compound containing phenothiazines.
A class phenothiazines, preparation method and its answering in organic electroluminescence device that the present invention is provided
With.The phenothiazines have a high luminous efficiency, high luminous efficiency show the compound can as luminescent material or
Light emitting host material, especially can be as phosphorescent light body material, for showing high efficiency, height in organic electroluminescence device
Brightness, long-life, have the advantages that manufacturing cost is relatively low, reduce the manufacturing cost of organic electroluminescence device.
Beneficial effect：The invention provides a kind of preparation method of phenothiazines, the phenothiazines derivative exists
Green emitting is presented under solution solid state and with high luminous efficiency, this shows that the compound can be as green glow main body
Materials application is in electroluminescent device.
Brief description of the drawings
Fig. 1 is the figure for preparing EL device structure of the present invention.
Fig. 2 is the mass spectrogram of the prepare compound of embodiment 4.
Fig. 3 is the nuclear-magnetism figure of the prepare compound of embodiment 4.
Embodiment
The present invention provides a kind of phenothiazines, for make the purpose of the present invention, technical scheme and effect it is clearer,
Clearly, the present invention is described in more detail below.It should be appreciated that specific embodiment described herein is only to explain this
Invention, is not intended to limit the present invention.
A kind of phenothiazines that the present invention is provided, are 3,7- bis-（1- phenyl -1H- benzos [d] imidazoles -2- bases）-
10-（4- (1- phenyl -1H- benzos [d] imidazoles -2- bases) phenyl）- 10H- phenthazine, its chemical structural formula is as follows：
Above-mentioned applies in green glow material of main part containing phenothiazines, shows high efficiency, high brightness, longevity
Life, has the advantages that manufacturing cost is relatively low, reduces the manufacturing cost of organic electroluminescence device.
Present invention also offers a kind of 3,7- bis-（1- phenyl -1H- benzos [d] imidazoles -2- bases）-10-（4- (1- phenyl-
1H- benzos [d] imidazoles -2- bases) phenyl）The preparation method of -10H- phenthazine, wherein reaction scheme are as shown below, and its is specific
Step is：
S100, to bromo-iodobenzene and phenthazine under the catalysis of copper powder, obtain compound 10-（4- bromophenyls）- 10H- fen thiophenes
Piperazine（a）；
S200, by 10-（4- bromophenyls）- 10H- phenthazine is under conditions of the dissolving of glacial acetic acid and dichloromethane, frozen water
Bromine is added dropwise in bath, obtains compound 3, the bromo- 10- of 7- bis-（4- bromophenyls）- 10H- phenthazine（b）；
S300, by the bromo- 10- of 3,7- bis-（4- bromophenyls）- 10H- phenthazine adds n-BuLi reaction and dimethyl formyl
Amine reaction generation 10-（4- Fonnylphenyls）- 10H- phenthazine -3,7- dicarbaldehydes（c）；
S400, by 10-（4- Fonnylphenyls）- 10H- phenthazine -3,7- dicarbaldehydes and adjacent aminodiphenylamine reaction are obtained
3,7- bis-（1- phenyl -1H- benzos [d] imidazoles -2- bases）-10-（4- (1- phenyl -1H- benzos [d] imidazoles -2- bases) phenyl）-
10H- phenthazine（d）.
The preparation method of described phenothiazines, wherein, the S100 specifically includes following steps：
To be raw material to bromo-iodobenzene, phenthazine, copper powder is that catalyst, potassium carbonate are alkali, and dimethylformamide is solvent, instead
It is 150 DEG C ~ 160 DEG C to answer temperature, and the reaction time is 22 ~ 26 hours.Through extraction, point liquid is rotated, and 10- is obtained after recrystallization（4- bromines
Phenyl）- 10H- phenthazine.
The preparation method of described phenothiazines, wherein, the S200 specifically includes following steps：
By 10-（4- bromophenyls）- 10H- phenthazine, glacial acetic acid and dichloromethane are solvent, are placed in ice-water bath；Quickly stir
Mix down and be slowly dropped into bromine, room temperature reaction is stayed overnight, it is post-treated after obtain 3,7-two bromo- 10-（4- bromophenyls）- 10H- fen thiophenes
Piperazine.
The last handling process includes neutralizing, extraction, and point liquid is rotated, recrystallization.The recrystallization is dichloro using solvent
Methane and petroleum ether, ratio are 1:10.
The preparation method of described phenothiazines, wherein, the S300 specifically includes following steps：
Using anhydrous tetrahydro furan as solvent, under nitrogen protection, by the bromo- 10- of 3,7- bis-（4- bromophenyls）- 10H- phenthazine
Lithium reagent is prepared with n-BuLi reaction；Dimethylformamide is slowly dropped into, reaction is warmed to room temperature by completion of dropping, is heated to reflux
Reaction 20 ~ 25 hours, it is post-treated to obtain 10-（4- Fonnylphenyls）- 10H- phenthazine -3,7- dicarbaldehydes.
The last handling process includes hydrolysis, extracts, recrystallization.The recrystallization solvent be dichloromethane and petroleum ether,
Ratio is 1:4.
The preparation method of described phenothiazines, wherein, the S400 specifically includes following steps：
By 10-（4-Fonnylphenyl）- 10H- phenthazine -3,7- dicarbaldehyde and adjacent aminodiphenylamine, sodium pyrosulfite,
Using dimethylformamide as solvent, reaction temperature is 150 ~ 160 DEG C, and reflux time is 22 ~ 26 hours.
The present invention is described in detail with reference to embodiments, but is not limited only to these embodiments.
Embodiment 1：10-（4- bromophenyls）The synthesis of -10H- phenthazine
Bromo-iodobenzene 71g, phenthazine 20g, copper powder 6.44g, potassium carbonate 69.36g will be fitted into 1000ml three-necked flasks, plus
Enter the dissolving of 150ml dimethylformamides；Vacuumize-lead to nitrogen three times, be warming up to 155 DEG C, reaction is stayed overnight.By above-mentioned reaction
Reaction solution crosses silica gel funnel, is rinsed with about 1L dichloromethane to without product dissolution, is spin-dried for solvent；Dry method loading crosses silicagel column, washes
De- agent is pure petroleum ether (60 ~ 90), takes second point, product is dried in vacuo at 55 DEG C, obtains 31.77g products, yield
89.34%.The test result of products therefrom is as follows：Mass spectrum：355.10.1H NMR（DMSO, 300MHz）：7.82（D, J=8.7Hz,
2H）,7.37（D, J=8.7Hz, 2H）,7.11~7.14（M, 2H）,6.89~7.14（M, 4H）,6.26~6.29（M, 2H）.
Embodiment 2：The bromo- 10- of 3,7- bis-（4- bromophenyls）The synthesis of -10H- phenthazine
By 10-（4- bromophenyls）- 10H- phenthazine 20g is added in 1000ml three-necked flasks, with 160ml glacial acetic acid and
480ml dichloromethane dissolves, and is placed in ice-water bath；5.82ml bromines are slowly dropped under quick stirring, room temperature reaction is stayed overnight.Reaction
Liquid is with 1mol/L sodium hydrate aqueous solutions about 500ml and remaining bromine, and separatory funnel point liquid takes organic phase；Organic phase water
Washing three times, is spin-dried for, and dissolving 300ml petroleum ethers (60 ~ 90) with 20ml dichloromethane is separated out, and suction filtration is dried, 200ml petroleum ethers
（60~90）Rinse, product is dried in vacuo at 55 DEG C, obtains 24.14g products, yield 83.5%.The test result of products therefrom
It is as follows：Mass spectrum：512.08.1H NMR（DMSO, 300MHz）：7.85~7.88（M, 2H）,7.40~7.42（M, 2H）,7.32（D, J
=2.1Hz, 2H）,7.10~7.14（M, 2H）,6.06（D, J=9Hz, 2H）.
Embodiment 3：10-（4- Fonnylphenyls）The synthesis of -10H- phenthazine -3,7- dicarbaldehydes
By the bromo- 10- of 3,7- bis-（4- bromophenyls）- 10H- phenthazine 15g is fitted into 1000ml three-necked flasks, adds 300ml
THF water removal tetrahydrofuran dissolvings；Vacuumize-lead to nitrogen three times, be put into dry ice-propanone bath and cool down, be slowly dropped into 38.49ml just
Butyl lithium, low-temp reaction one hour；Be slowly dropped into 18.15ml dimethylformamides, low-temp reaction removed after one hour dry ice-
Acetone bath, room temperature reaction is stayed overnight.Reaction solution adds 20ml water terminating reactions, adds the hydrolysis of 50ml watery hydrochloric acid；Add 500ml dichloros
Methane point liquid, takes dichloromethane phase, is spin-dried for after solvent crossing silicagel column, eluant, eluent is DCM:Petroleum ether (60 ~ 90)=1：4, produced
Thing 15.1g, yield is 73.98%.The test result of products therefrom is as follows：Mass spectrum：359.40.1H NMR（DMSO, 300MHz）：
10.17（S, 1H）,9.75（S, 2H）,8.27（D, J=8.4Hz, 2H）,7.78（D, J=8.1Hz, 2H）,7.60（D, J=1.8Hz,
2H）,7.46（D, J=1.8Hz, 2H）,6.22（D, J=8.4Hz, 2H）.
Embodiment 4：3,7- bis-（1- phenyl -1H- benzos [d] imidazoles -2- bases）-10-（4- (1- phenyl -1H- benzos [d] miaows
Azoles -2- bases) phenyl）The synthesis of -10H- phenthazine
By 10-（4- Fonnylphenyls）- 10H- phenthazine -3,7- dicarbaldehydes 7.55g and adjacent aminodiphenylamine 12.37g, Jiao
Sodium sulfite 13.97g 200ml dimethylformamides dissolve；Vacuumize-lead to nitrogen three times, be warming up to 155 DEG C, back flow reaction
Overnight.500ml water is added in reaction solution has a large amount of solids to separate out, and suction filtration is dried；Flowed back, dried with 1L petroleum ethers (60 ~ 90),
13.12g products are obtained, yield is 73.30%；The test result of products therefrom is as follows：Mass spectrum：852.23, see Fig. 2.1H NMR
（DMSO, 300MHz）：7.76~7.79（M, 5H）,7.55~7.62（M, 10H）,7.42~7.47（M, 8H）,7.15~7.27（M,
6H）,7.15~7.05（M, 3H）,7.01~7.02（M, 2H）,5.97（D, J=4.35Hz, 2H）, see Fig. 3.
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 or converted according to the above description, so these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Comparing embodiment：
Using chemical formula a compound as light emitting host material, chemical formula b compound is as dopant material, and TPBI makees
For hole-injecting material, NPB has made organic luminescent device as hole mobile material.
Chemical formula a chemical formulas b
Chemical formula c chemical formulas d
By Corning（It is healthy and free from worry）15 Ω of society/cm2(1000) ITO glass substrates are cut into 50mm*50mm*0.7mm's
Size.Then in microwave, successively in acetone, isopropanol is cleaned 15 minutes in pure water respectively, cleans 30 points again in ultraviolet
Clock.In the TPBI of thereon vacuum evaporation 30nm thickness, hole injection layer is formed.Vacuum evaporation above hole injection layer
The NPB of 40nm thickness, forms hole transmission layer.The chemical formula a of vacuum evaporation 30nm thickness is represented above hole transporting layer
The compound that compound and chemical formula b are represented（Doping rate 8%）, form luminescent layer.Vacuum evaporation 10nm thickness above luminescent layer
Alq3, form electron supplying layer.Vacuum evaporation LiF 1.0nm (electron injection) and Al successively above electron supplying layer
120nm, has made organic luminescent device.In this comparing embodiment and following Application Example, using the manufacture of DOV companies
EL evaporators carry out vacuum evaporation.
Application Example：
Using the method in such as comparative example 1, the organic luminescent device with following structure is made, difference is conduct
Luminescent layer compound, the compound 1 represented in preparation example is used instead of compound a:ITO/TPBI (30nm)/α-NPB
(40nm)/compound 001 ~ 006+ compounds b] (30nm, wherein b contents be 8.0%)/Alq3 (10nm)/LiF (1.0nm)/
The organic luminescent device of Al (120nm) structure.
Measure embodiment：Comparative sample and sample formula（I）Luminescent properties
Under similarity condition, the sample and Application Example formula of comparing embodiment 1 are measured（I）Sample.Measurement is used
The type source measuring unit of KEITHLEY Keithleys 235, SpectrascanPR650 spectral scan colorimeters, to evaluate driving voltage,
Luminosity, luminous efficiency, glow color.The results are shown in Table 1：
Table 1
According to represented by table 1, above-mentioned sample wavelength is 515nm, and display glow color is green.Application Example
Sample is compared with the sample of comparing embodiment 1, can using the organic luminescent device of the organic layer of ternary imidazo carbazole derivates
Efficiency with lower driving voltage, higher brightness and Geng Gao.
Although the present invention has carried out special description and diagram with exemplary embodiment, but it is understood that without departing under
In the case of the spirit and scope of the invention that row claim is limited, those of ordinary skill in the art can carry out various to it
Change in form and details.
Claims (10)
1. a kind of phenothiazines, it is characterised in that the phenothiazines are 3,7- bis-（1- phenyl -1H- benzos
[d] imidazoles -2- bases）-10-（4- (1- phenyl -1H- benzos [d] imidazoles -2- bases) phenyl）- 10H- phenthazine, its chemical structural formula
It is as follows：
。
2. a kind of preparation method of phenothiazines as claimed in claim 1, it is characterised in that comprise the following steps：
S100, to bromo-iodobenzene and phenthazine under the catalysis of copper powder, obtain compound 10-（4- bromophenyls）- 10H- phenthazine；
S200, by 10-（4- bromophenyls）- 10H- phenthazine is under conditions of the dissolving of glacial acetic acid and dichloromethane, ice-water bath drop
Liquid feeding bromine, obtains compound 3, the bromo- 10- of 7- bis-（4- bromophenyls）- 10H- phenthazine；
S300, by the bromo- 10- of 3,7- bis-（4- bromophenyls）- 10H- phenthazine adds n-BuLi reaction and dimethylformamide is anti-
10- should be generated（4- Fonnylphenyls）- 10H- phenthazine -3,7- dicarbaldehydes；
S400, by 10-（4- Fonnylphenyls）- 10H- phenthazine -3,7- dicarbaldehydes and adjacent aminodiphenylamine reaction obtain 3,7-
Two（1- phenyl -1H- benzos [d] imidazoles -2- bases）-10-（4- (1- phenyl -1H- benzos [d] imidazoles -2- bases) phenyl）- 10H- fens
Thiazine.
3. the preparation method of phenothiazines according to claim 2, it is characterised in that the step S100 is specific
Comprise the following steps：To be raw material to bromo-iodobenzene, phenthazine, copper powder is that catalyst, potassium carbonate are alkali, and dimethylformamide is molten
Agent, reaction temperature is 150 DEG C ~ 160 DEG C, and the reaction time is 22 ~ 26 hours；
Through extraction, point liquid is rotated, and 10- is obtained after recrystallization（4- bromophenyls）- 10H- phenthazine.
4. the preparation method of phenothiazines according to claim 2, it is characterised in that the step S200 is specific
Comprise the following steps：By 10-（4- bromophenyls）- 10H- phenthazine, glacial acetic acid and dichloromethane are solvent, are placed in ice-water bath；
Be slowly dropped into bromine under quick stirring, room temperature reaction is stayed overnight, it is post-treated after obtain the bromo- 10- of 3,7- bis-（4- bromophenyls）-10H-
Phenthazine.
5. the preparation method of phenothiazines according to claim 4, it is characterised in that the last handling process bag
Neutralization is included, is extracted, point liquid is rotated, recrystallization；The recrystallization is dichloromethane and petroleum ether using solvent, and ratio is 1:10.
6. the preparation method of phenothiazines according to claim 2, it is characterised in that the step S300 is specific
Comprise the following steps：
Using anhydrous tetrahydro furan as solvent, under nitrogen protection, by the bromo- 10- of 3,7- bis-（4- bromophenyls）- 10H- phenthazine and just
Butyl lithium reaction prepares lithium reagent；Dimethylformamide is slowly dropped into, reaction is warmed to room temperature by completion of dropping, heating reflux reaction
20 ~ 25 hours, it is post-treated obtain 10-（4-Fonnylphenyl）- 10H--3,7-dicarbaldehydes of phenthazine.
7. the preparation method of phenothiazines according to claim 6, it is characterised in that described last handling process
Including hydrolysis, extract, recrystallization；
The recrystallization solvent is dichloromethane and petroleum ether, and ratio is 1:4.
8. the preparation method of phenothiazines according to claim 2, it is characterised in that the step S400 is specific
Comprise the following steps：
By 10-（4- Fonnylphenyls）- 10H- phenthazine -3,7- dicarbaldehyde and adjacent aminodiphenylamine, sodium pyrosulfite, with diformazan
Base formamide is solvent, and reaction temperature is 150 ~ 160 DEG C, and reflux time is 22 ~ 26 hours.
9. a kind of organic luminescent device, including first electrode, second electrode and it is placed in one or more between two electrode
Organic compound layer, it is characterised in that at least one organic compound layer includes at least one fen as defined in claim 1
Thiazide derivative.
10. application of the phenothiazines according to claim 1 in organic electroluminescence device, its feature exists
In described phenothiazines are used as green glow material of main part in the organic electroluminescence device.
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| KR102080737B1 (en) | 2019-05-29 | 2020-02-24 | (주)피엔에이치테크 | An electroluminescent compound and an electroluminescent device comprising the same |
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