CN106397110B - A kind of novel spiro organic compounds - Google Patents

A kind of novel spiro organic compounds Download PDF

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CN106397110B
CN106397110B CN201511030532.0A CN201511030532A CN106397110B CN 106397110 B CN106397110 B CN 106397110B CN 201511030532 A CN201511030532 A CN 201511030532A CN 106397110 B CN106397110 B CN 106397110B
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anthryl
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CN106397110A (en
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金振禹
钱超
许军
王德宁
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Nanjing Topto Materials Co Ltd
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Abstract

The present invention provides the spiro-compound of general formula 1 and its in the application of electronic material, precision chemical and medical domain.In addition, the present invention also provides organic electroluminescence devices made from the spiro-compound as general formula 1.The compound of general formula 1 provided by the invention in use, can reduce driving voltage, improves luminous efficiency, brightness, thermal stability, color purity and device lifetime in organic electroluminescence device.[general formula 1]

Description

A kind of novel spiro organic compounds
[technical field]
The present invention relates to a kind of novel organic compounds, and in particular to one kind can be used for field of electronic materials, precise treatment Field, medical domain spiro organic compounds.
Background technique
In recent years, spiro organic compounds are chiefly used in field of electronic materials.But spiro organic compounds not only limit the use of In field of electronic materials, the fields such as precision chemical, medicine can also be widely used for.Hereinafter, will be with field of electronic materials, especially It is to be illustrated centered on the use in organic electroluminescence device field to the prior art.
Using the organic electroluminescence device of organic electroluminescent phenomenon, usually have comprising anode and cathode and they Between organic matter layer structure.Herein, organic matter layer is more in order to improve the efficiency and stability of organic electroluminescence device Formed with the multilayered structure being made of respective different material, for example, may include hole injection layer, hole transmission layer, luminescent layer, Electron transfer layer, electron injecting layer etc..In the structure of this organic electroluminescence device, apply voltage between two electrodes When, in the anode, hole is injected into organic matter layer, and in the cathode, electron injection to organic matter layer, institute's injected holes and electricity Son meets to form exciton, and exciton falls to shine when the state of base.This organic electroluminescence device is to possess self-luminous, highlight The features such as degree, high efficiency, low driving voltage, wide viewing angle, high contrast, high speed responsiveness and it is well-known.
In organic electroluminescence device, the material as organic matter layer can be divided into luminescent material and electricity according to function Lotus transmission material, such as hole-injecting material, hole mobile material, electron transport material, electron injection material etc..Luminescent material Blue, green, red illuminating material and in order to be presented relatively better natural colour and required Huang can be divided into according to illuminant colour Color and crocus luminescent material.In addition, in order to increase color purity and increase the luminous efficiency by energy transfer, as luminous Main body/doping species can be used in material.The principle is as follows, and compared to the main body of main composition luminescent layer, band gap is small, luminous The outstanding dopant of efficiency is mixed into luminescent layer on a small quantity, and the exciton generated in main body is transmitted to dopant, issues efficient light. At this point, the wavelength of main body is mobile according to the wavelength of dopant, thus wave needed for the type according to the dopant used is available Long light.
Possess to obtain excellent characteristic to give full play to above-mentioned organic electroluminescence device, forms organic matter layer in device Substance, such as hole injecting material, hole transporting material, luminescent substance, electron-transporting material, electron injection substance etc. should first by Stable and efficient material is constituted.
For example, in high temperature or driving temperature, forming material crystallization becomes contracting when the decline of the thermal stability of material The reason of service life of short device.Representative example has, in the case where dinaphthyl anthracene compound, due to symmetrical above and below in left and right Molecular structure, therefore, with the rising of device temperature, it is easy to crystallize.Recently to prevent this crystallization, by leading Enter spirane structure, to improve thin film stability.For example, U.S. Patent No. 5840217 disclose the derivative spiral shell-of spiro-bisfluorene Benzene, the unimolecule of spiral shell-DPVBi etc..But although above-mentioned well known spiro-compound has outstanding heat resistance, exists and drive Dynamic voltage is high or cannot play efficient luminous disadvantage, therefore, the material using primary limitation in blue field.
Therefore, it is proposed to by the structure for changing the organic substance for organic electroluminescence device, it is arbitrary to obtain Illuminant colour, or the organic electroluminescence device that can get the various efficient methods by body dopants system is utilized, But it also cannot achieve satisfactory brightness, characteristic, service life and persistence at present.
[advanced technical literature]
[patent document]
U.S. Patent No. 5840217
Summary of the invention
Technical problem
The present invention is to provide the novel organic compound that can be used for the purposes such as electronic material, precision chemical, medicine as mesh 's.
In addition, the purpose of the present invention is to provide one kind can be used as hole injection layer substance, hole transmission layer substance, electronics Barrier layer substance, luminescent layer substance, hole blocking layer substance, electron transfer layer substance, electron injecting layer substance and be applied to have Organic electroluminescence devices, and driving voltage can be reduced in the case where being applied to organic electroluminescence device, improve the effect that shines Rate, luminance, thermal stability, excitation purity and the novel organic compound of device lifetime.
In addition, the present invention is for the purpose of providing the organic electroluminescence device using above-mentioned organic compound.
The means solved the problems, such as
The present invention provides a kind of novel organic compound indicated with the following general formula 1.
[general formula 1]
In above formula,
The ring that CYCLO is made of 4 or 5 carbon atoms,
In the case where the ring that above-mentioned CYCLO is made of 4 carbon atoms, 2 phenyl for forming CYCLO, which combine, forms naphthalene Base,
R1, R2, R3, R4, R5, R6, R7 and R8 are hydrogen independent, heavy hydrogen, F, Cl, Br, I, CN, Si (CH3)3、B (OH)2, the linear or branched alkyl group of carbon atom number 1 to 40, the alkoxy of carbon atom number 1 to 40, carbon atom number 1 to 40 it is thio The naphthenic base of base or carbon atom number 3 to 40,
Alternatively, with selected from by with F, Cl, Br, I, CN, Si (CH3)3、B(OH)2, carbon atom number 1 to 40 linear chain or branched chain Alkyl, the alkoxy of carbon atom number 1 to 40, the thio group of carbon atom number 1 to 40, the naphthenic base of carbon atom number 3 to 40, phenyl, Anthryl, the phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, dibenzofurans, pyrroles, three that double phenyl, naphthalene, anthryl, phenyl replace More than one substituted or non-substituted carbon atom number 6 in group that azoles, pyridine, pyrazinyl, pyrimidine bases and quinolyl form~ 60 aromatic hydrocarbyl,
Alternatively, with selected from by with F, Cl, Br, I, CN, Si (CH3)3、B(OH)2, carbon atom number 1 to 40 linear chain or branched chain Alkyl, the alkoxy of carbon atom number 1 to 40, the thio group of carbon atom number 1 to 40, the naphthenic base of carbon atom number 3 to 40, phenyl, Anthryl, the phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, dibenzofurans, pyrroles, three that double phenyl, naphthalene, anthryl, phenyl replace Azoles, pyridine, pyrazinyl, pyrimidine bases and quinolyl composition group in more than one is substituted or non-substituted, comprising selected from by S, O, the heteroaromatic alkyl of the carbon atom number 5 to 60 of more than one element in the group of N and Si composition,
Alternatively, selected from anthryl, phenanthryl, pyrenyl, 9,9- diformazan by being replaced with phenyl, double phenyl, naphthalene, anthryl, phenyl One or more of fluorenes, carbazole, quinoline, dibenzofurans, pyrroles, triazole, pyridine, pyrazinyl, the group of pyrimidine bases composition replace Amino, above-mentioned phenyl, double phenyl, naphthalene, anthryl, phenyl groups are with selected from by F, Cl, Br, I, CN, Si (CH3)3、B(OH)2, carbon The linear or branched alkyl group of atomicity 1 to 40, the alkoxy of carbon atom number 1 to 40, the thio group of carbon atom number 1 to 40, carbon are former Subnumber 3 to 40 naphthenic base composition group in a kind or more it is substituted or non-substituted.
In terms of above-mentioned organic compound can be used for electronic material, precision chemical and medicine.
The present invention provides organic electroluminescence device, and clamping has the organic electroluminescence device between a cathode and an anode One or more layers the organic thin film layer for having luminescent layer is at least closed, above-mentioned organic electroluminescence device is characterized in that, above-mentioned to have At least one laminated above-mentioned organic compound for having one or more in machine film layer.
The effect of invention
Organic compound according to the present invention can be used for the fields such as electronic material, precision chemical, medicine.
In addition, above-mentioned organic compound can be used as hole injection layer substance, hole transmission layer substance, electron-blocking layer object Matter, luminescent layer substance, hole blocking layer substance, electron transfer layer substance, electron injecting layer substance are applied to organic electroluminescent Device, and in the case where being applied to organic electroluminescence device, driving voltage can be reduced, luminous efficiency, brightness, heat are improved Stability, color purity and device lifetime.
In addition, there is high efficiency and long-life using organic electroluminescence device manufactured by organic compound of the invention Characteristic.
[specific implementation content]
The present invention provides a kind of novel organic compound that the following general formula 1 indicates.
[general formula 1]
The ring that CYCLO is made of 4 or 5 carbon atoms,
In the case where the ring that above-mentioned CYCLO is made of 4 carbon atoms, 2 phenyl for forming CYCLO, which combine, forms naphthalene Base,
R1, R2, R3, R4, R5, R6, R7 and R8 are hydrogen independent, heavy hydrogen, F, Cl, Br, I, CN, Si (CH3)3、B (OH)2, the linear or branched alkyl group of carbon atom number 1 to 40, the alkoxy of carbon atom number 1 to 40, carbon atom number 1 to 40 it is thio The naphthenic base of base or carbon atom number 3 to 40,
Alternatively, with selected from by with F, Cl, Br, I, CN, Si (CH3)3、B(OH)2, carbon atom number 1 to 40 linear chain or branched chain Alkyl, the alkoxy of carbon atom number 1 to 40, the thio group of carbon atom number 1 to 40, the naphthenic base of carbon atom number 3 to 40, phenyl, Double phenyl, naphthalene, anthryl, phenyl groups replace anthryl, phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, dibenzofurans, pyrroles, More than one substituted or non-substituted carbon atom number 6 in group that triazole, pyridine, pyrazinyl, pyrimidine bases and quinolyl form ~60 aromatic hydrocarbyl,
Alternatively, with selected from by with F, Cl, Br, I, CN, Si (CH3)3、B(OH)2, carbon atom number 1 to 40 linear chain or branched chain Alkyl, the alkoxy of carbon atom number 1 to 40, the thio group of carbon atom number 1 to 40, the naphthenic base of carbon atom number 3 to 40, phenyl, Double phenyl, naphthalene, anthryl, phenyl groups replace anthryl, phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, dibenzofurans, pyrroles, Triazole, pyridine, pyrazinyl, pyrimidine bases and quinolyl composition group in more than one is substituted or non-substituted, comprising selected from by S, the heteroaromatic alkyl of the carbon atom number 5 to 60 of more than one element in the group of O, N and Si composition,
Alternatively, selected from anthryl, phenanthryl, pyrenyl, 9,9- bis- by being replaced with phenyl, double phenyl, naphthalene, anthryl, phenyl groups One or more of first fluorenes, carbazole, quinoline, dibenzofurans, pyrroles, triazole, pyridine, pyrazinyl, the group of pyrimidine bases composition take The amino in generation, above-mentioned phenyl, double phenyl, naphthalene, anthryl, phenyl groups are selected from by F, Cl, Br, I, CN, Si (CH3)3、B(OH)2、 The linear or branched alkyl group of carbon atom number 1 to 40, the alkoxy of carbon atom number 1 to 40, carbon atom number 1 to 40 thio group, carbon Atomicity 3 to 40 naphthenic base composition group in a kind or more it is substituted or non-substituted.
It is further preferred that above-mentioned general formula (1) is indicated with the following general formula (2) or general formula (3):
[general formula 2]
[general formula 3]
R1, R2, R3, R4, R5, R6, R7 and R8 are hydrogen independent, heavy hydrogen, F, Cl, Br, I, CN, Si (CH3)3、B (OH)2, the linear or branched alkyl group of carbon atom number 1 to 40, the alkoxy of carbon atom number 1 to 40, carbon atom number 1 to 40 it is thio The naphthenic base of base or carbon atom number 3 to 40,
Alternatively, with selected from by with F, Cl, Br, I, CN, Si (CH3)3、B(OH)2, the linear chain or branched chain of carbon atom number 1 to 40 Alkyl, the alkoxy of carbon atom number 1 to 40, the thio group of carbon atom number 1 to 40, the naphthenic base of carbon atom number 3 to 40, phenyl, Double phenyl, naphthalene, anthryl, phenyl groups replace anthryl, phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, dibenzofurans, pyrroles, More than one the substituted or non-substituted carbon atom selected in the group that triazole, pyridine, pyrazinyl, pyrimidine bases and quinolyl form The aromatic hydrocarbyl of number 6~60,
Alternatively, with selected from by with F, Cl, Br, I, CN, Si (CH3)3、B(OH)2, the linear chain or branched chain of carbon atom number 1 to 40 Alkyl, the alkoxy of carbon atom number 1 to 40, the thio group of carbon atom number 1 to 40, the naphthenic base of carbon atom number 3 to 40, phenyl, Double phenyl, naphthalene, anthryl, phenyl groups replace anthryl, phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, dibenzofurans, pyrroles, Triazole, pyridine, pyrazinyl, pyrimidine bases and quinolyl composition group in more than one is substituted or non-substituted, comprising selected from by S, the heteroaromatic alkyl of the carbon atom number 5 to 60 of more than one element in the group of O, N and Si composition,
Alternatively, with selected from by with phenyl, double phenyl, naphthalene, anthryl, phenyl groups phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, The amino that one or more of quinoline, dibenzofurans, pyrroles, triazole, pyridine, pyrazinyl, the group of pyrimidine bases composition replace, Above-mentioned phenyl, double phenyl, naphthalene, anthryl, phenyl are selected from by F, Cl, Br, I, CN, Si (CH3)3、B(OH)2, carbon atom number 1 to 40 Linear or branched alkyl group, the alkoxy of carbon atom number 1 to 40, the thio group of carbon atom number 1 to 40, carbon atom number 3 to 40 One or more of the group of naphthenic base composition is substituted or non-substituted.
It is further preferred that in above formula,
R1, R2, R3, R4, R5, R6, R7 and R8 are hydrogen independent, heavy hydrogen, F, Cl, Br, I, CN, Si (CH3)3、B (OH)2, carbon atom number 1 to 40 linear or branched alkyl group,
Alternatively, with selected from by with F, Cl, Br, I, B (OH)2And the linear or branched alkyl group of carbon atom number 1 to 40, phenyl, Double phenyl, naphthalene, anthryl, phenyl groups group in more than one substituted or non-substituted phenyl, double phenyl, naphthalene, anthryl, phenanthrene Base, pyrenyl,
Alternatively, with selected from by with F, Cl, Br, I, B (OH)2With the linear or branched alkyl group of carbon atom number 1 to 10, phenyl, Double phenyl, naphthalene, anthryl, phenyl groups replace anthryl, phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, dibenzofurans, pyrroles, Triazole, pyridine, pyrazinyl, pyrimidine bases composition group in more than one substituted or non-substituted pyrroles, triazole, pyridine, pyrrole Piperazine base, pyrimidine bases, quinolyl, 9,9- diformazan fluorenes, carbazole or dibenzofurans,
Alternatively, with selected from by with F, Cl, Br, I, B (OH)2With the linear or branched alkyl group of carbon atom number 1 to 10, phenyl, Anthryl, phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, quinolyl and the dibenzo furan that double phenyl, naphthalene, anthryl, phenyl groups replace More than one amino replaced in the group of composition of muttering.
The above-mentioned compound indicated with general formula (2) or general formula (3) is any one in the compound of the following general formula:
Organic compound of the present invention can be used for the fields such as electronic material, precision chemical, medicine.
Above compound is not only final compound, can also be used as the intermediate for synthesizing other compounds.
Above-mentioned organic compound can be used as the hole injection layer substance in organic electroluminescence device material, hole transport Layer substance, electron-blocking layer substance, luminescent layer substance, hole blocking layer substance, electron transfer layer substance, electron injecting layer substance To use.
The present invention provides organic electroluminescence device, and clamping has the organic electroluminescence device between a cathode and an anode One or more layers the organic thin film layer for having luminescent layer is at least closed, above-mentioned organic electroluminescence device is characterized in that, above-mentioned to have At least one laminated above-mentioned organic compound for having one or more in machine film layer.
Above-mentioned organic electroluminescence device possesses with anode, hole injection layer, hole transmission layer, electron-blocking layer, shines Layer, electron transfer layer, electron injecting layer and cathode are the construction of sequence.
It below will be to organic electroluminescence device illustration of the invention.But following exemplary contents can not limit Fixed organic electroluminescence device of the invention.
The manufacturing method of organic electroluminescence device of the invention, comprising the following steps:
Step 1, anode material is crossed by modeling using conventional method and forms anode, used substrate selection tool in substrate surface There are the glass substrate or transparent plastic substrate of good transparency, surface smoothness, operability and waterproofness.In addition, anode material Tin indium oxide (ITO) transparent, that conductibility is outstanding, indium zinc oxide (IZO), stannic oxide (SnO can be used2), zinc oxide (ZnO) etc..
Step 2, anode surface by hole injection layer material (HIL) vacuum heat deposition or is spin-coated on using conventional method, shape At hole injection layer.Hole injection layer material can be CuPc, m-MTDATA, m-MTDAPB, the TCTA of star-like amine, 2- TNATA, or the IDE406 being commercially available from Japanese Idemitsu Kosen Co., Ltd. (Idemitsu).
Step 3, hole injection layer table by hole transport layer material (HTL) vacuum heat deposition or is spin-coated on using conventional method Face forms hole transmission layer.Hole transport layer material can be α-NPD, NPB or TPD.
Step 4, hole transport layer surface by emitting layer material (EML) vacuum heat deposition or is spin-coated on using conventional method, Form luminescent layer.Luminescent material can be light storage fluorescent material, fluorescent whitening agent, laser pigment, organic scintillator, fluorescence analysis Reagent etc..Specifically, there are carbazole compound, phosphine oxide compound, carbazole phosphine oxide compound, FCNIrpic, Alq3, anthracene, Phenanthrene, pyrene,, coronene, rubrene and the polycyclic aromatic hydrocarbon compounds as quinacridone, the Asia as quaterphenyl Phenyl compound, bis- (2-methyl styrene base) benzene of Isosorbide-5-Nitrae -, bis- (4- methyl -5- phenyl -2- oxazolyl) benzene of Isosorbide-5-Nitrae -, the bis- (5- of Isosorbide-5-Nitrae - Phenyl -2- oxazolyl) phenyl, 2,5- bis- (5-t- butyl -2- benzoxazolyl) thiophene, Isosorbide-5-Nitrae-biphenyl -1,3-butadiene, 1,6- connection Benzene -1,3,5- hexatriene, as 1, Isosorbide-5-Nitrae, 4- tetraphenyl -1,3-butadiene the same liquid scintillation scintillator, auxin spreads out The metallic carrier of biology, cumarin pigment, methylene dicyanoethyl pigment, dicyanomethylenethiopyrans pigment, polymethine pigment, hydroxyl Benzene anthracene pigment, xanthene pigment, quinolone pigment, pigment, oxazines compound, stilbene derivatives, Spiro compounds, oxadiazoles etc..
Further, electron-blocking layer (EBL) can also be added between hole transmission layer and luminescent layer.
Step 5, luminous layer surface by electron transport layer materials (ETL) vacuum heat deposition or is spin-coated on using conventional method, Form electron transfer layer.Electron transport layer materials are not particularly limited, it is preferable to use Alq3。
Further, it can also add hole blocking layer (HBL), while shine among luminescent layer and electron transfer layer Layer is used together phosphorescent dopant, and the effect for preventing triplet excitons or hole to be diffused into electron transfer layer may be implemented.
Luminous layer surface by hole blocking layer material (HBL) vacuum heat deposition or is spin-coated on using conventional method, is formed empty Cave barrier layer.Hole blocking layer material is not particularly limited, preferably Liq, and 2- methyl -8-hydroxyquinoline parazon closes Aluminium, BCP and LiF etc..
Step 6, electron transfer layer table by electron injecting layer material (EIL) vacuum heat deposition or is spin-coated on using conventional method Face forms electron injecting layer.Electron injecting layer material can be LiF, Liq, Li2O, BaO, NaCl, CsF etc..
Step 7, electron injecting layer by cathode material vacuum heat deposition or is spin-coated on using conventional method, forms cathode.Yin Pole material can be Li, Al, Al-Li, Ca, Mg, Mg-In, Mg-Ag etc..
In addition, organic electroluminescence device uses tin indium oxide (ITO) or indium zinc oxide (IZO), light transmission can be made Transparent cathode.
Further, according to above-mentioned covering layer composition, coating (CPL) can also be further formed in cathode surface.
According to the manufacturing method of above-mentioned organic electroluminescence device, can with anode/hole injection layer/hole transmission layer/ Luminescent layer/electron transfer layer/electron injecting layer/cathode sequence manufactures, equally, also can be with cathode/electron injecting layer/electronics Transport layer/luminescent layer/hole transmission layer/hole injection layer/anode sequence manufactures.
The synthetic method of 1 compound of mutual-through type is illustrated by embodiment below.But following methods enumerated are not Compound synthesis method of the present invention can be limited, compound of the present invention can be according to following methods enumerated and this Method well known to field manufactures.
The synthesis of intermediate -1
[reaction equation 1]
Under the conditions of nitrogen protection, naphthoic acid 1.72g (10mmol) is dissolved in 10mL tetrahydrofuran, in -40 DEG C and 1.4M S-butyl lithium mixing removes cold rinse bank, and reaction solution stirs 2 hours, -78 DEG C of coolings in being placed at room temperature for 30 minutes in sink, drop Add 10mL to be mixed with the tetrahydrofuran of 1.44g (15mmol) methanesulfonic acid, remove cold rinse bank, mixture is in being placed at room temperature for 30 points in sink Zhong Hou, 60 DEG C are flowed back 2 hours.
It after reaction stops, being cleaned using saturated sodium-chloride, adds 2N-HCl aqueous solution and use ether after stirring 30 minutes Extraction.
The moisture in organic layer is removed with anhydrous magnesium sulfate, is filtered, is concentrated organic solution obtains compound Hex: EA =5: 1 eluent, which is crossed, to be chromatographed, and 1 0.79g of intermediate (51%) is obtained.
Intermediate -1MS (FAB): 154 (M+)
The synthesis of compound -1
[reaction equation 2]
The bromo- 4- iodine naphthalene 3.33g (10mmol) of 1- is dissolved in 15ml tetrahydrofuran, is cooled to -78 DEG C, 2.5M normal-butyl is added dropwise Lithium 4mL, -78 DEG C are stirred 1 hour, and 1 1.54g of intermediate (10mmol) for being dissolved in tetrahydrofuran 30mL is slowly added dropwise, rises to room temperature After reaction terminating, MC and 2N HCl is added, extracts organic layer.
Anhydrous magnesium sulfate removes moisture in organic layer, filters, and is concentrated organic solution obtains compound Hex: EA=5: 1 Eluent cross chromatographic column, obtain 2 2.76g of intermediate (76%).
Above-mentioned intermediate 2 is dissolved in acetic acid, and concentrated hydrochloric acid is added dropwise, and flows back 1 hour, reaction was completed.After ether and water extraction, satisfy Organic layer, the dry organic layer of magnesium sulfate are cleaned with sodium bicarbonate water, recrystallization crosses chromatographic column with Hex: EA=4: 1 eluent, Obtain 1 2.85g of compound (83%).
2 MS of intermediate (FAB): 363 (M+)
1 MS of compound (FAB): 343 (M+)
The synthesis of compound 2
[reaction equation 3]
The bromo- 1- iodine naphthalene 3.33g (10mmol) of 3- is dissolved in 15mL tetrahydrofuran, is cooled to -78 DEG C, 2.5M normal-butyl is added dropwise Lithium 4mL, -78 DEG C are stirred 1 hour, and 1 1.54g of intermediate (10mmol) for being dissolved in tetrahydrofuran 30ml is slowly added dropwise, rises to room temperature After reaction terminating, MC and 2N HCl is added, extracts organic layer.
Anhydrous magnesium sulfate removes moisture in organic layer, filters, and is concentrated organic solution obtains compound Hex: EA=5: 1 Eluent cross chromatographic column, obtain 3 2.72g of intermediate (75%).
Above-mentioned intermediate 3 is dissolved in acetic acid, and concentrated hydrochloric acid is added dropwise, and flows back 1 hour, reaction was completed.After ether and water extraction, satisfy Organic layer, the dry organic layer of magnesium sulfate are cleaned with sodium bicarbonate water, recrystallization crosses chromatographic column with Hex: EA=4: 1 eluent, Obtain 2 2.75g of compound (80%).
3 MS of intermediate (FAB): 363 (M+)
2 MS of compound (FAB): 343 (M+)
The synthesis of compound 3
[reaction equation 4]
Under the conditions of nitrogen protection, 1 3.43g of compound (10mmol) is dissolved in anhydrous tetrahydro furan 40mL, by reactant temperature Degree is down to -78 DEG C, and 2.5M n-BuLi 4mL is slowly added dropwise, and reactant stirs 1 hour under the conditions of 0 DEG C, then by temperature of charge - 78 DEG C are down to, is added dropwise trimethylborate 12.47g (12mmol), stirring at normal temperature 12 hours.After reaction, 2N-HCl water is added Solution is stirred 30 minutes, is extracted with ether.
Anhydrous magnesium sulfate removes moisture in organic layer, filters, and is concentrated organic solution obtains compound Hex: EA=5: 1 Eluent cross chromatographic column, obtain 3 2.43g of compound (79%).
3 MS of compound (FAB): 334 (M+)
The synthesis of compound -4
[reaction equation 5]
Under the conditions of nitrogen protection, 3 3.08g of compound (10mmol) and bromo-iodobenzene 2.83g (10mmol) are dissolved in Tetrahydrofuran 40mL is separately added into Pd (PPh3)40.58g (0.5mmol) and 2M K2CO315mL (30mmol), reflux 24 are small When.
After reaction, temperature of charge is down to room temperature, and MC 200mL, H is added2O200mL extracts MC layers, with anhydrous sulphur The dry concentration of sour magnesium, crosses chromatographic column with Hex: EA=5: 1 eluent, obtains 4 2.97g of compound (71%).
1H NMR (DMSO, 300Hz): δ (ppm)=8.22-7.66 (m, 4H), 7.64-7.23 (m, 7H), 7.20-6.70 (d, 4H)
4 MS of compound (FAB): 419 (M+)
The synthesis of compound 5
[reaction equation 6]
It is under the conditions of nitrogen protection, the bromo- 4- iodobenzene 2.83g (10mmol) of 3 3.08g of compound (10mmol) and 1- is mixed It closes, is dissolved in tetrahydrofuran 40mL, is separately added into Pd (PPh3)40.58g (0.5mmol) and 2M K2CO315ml (30mmol) is returned Stream 24 hours.
After reaction, temperature of charge is down to room temperature, and MC200mL, H is added2O 200mL extracts MC layers, with anhydrous sulphur The dry concentration of sour magnesium, crosses chromatographic column with Hex: EA=4: 1 eluent, obtains 5 2.89g of compound (69%).
1H NMR (DMSO, 300Hz): δ (ppm)=8.22-7.66 (m, 4H), 7.64-7.26 (m, 7H), 7.22-6.70 (d, 4H)
5 MS of compound (FAB): 419 (M+)
The synthesis of compound 6
[reaction equation 7]
1- iodine naphthalene 2.54g (10mmol) is dissolved in 15mL tetrahydrofuran, is cooled to -78 DEG C, and 2.5M n-BuLi 4mL is added dropwise, - 78 DEG C are stirred 1 hour, and the bromo- 9-Fluorenone 2.59g (10mmol) of 2- for being dissolved in tetrahydrofuran 30ml is slowly added dropwise, rises to normal-temperature reaction After termination, MC and 2N HCl is added, extracts organic layer.
Anhydrous magnesium sulfate removes moisture in organic layer, filters, and is concentrated organic solution obtains compound Hex: EA=5: 1 Eluent cross chromatographic column, obtain 4 3.06g of intermediate (79%).
Above-mentioned intermediate 4 is dissolved in acetic acid, and concentrated hydrochloric acid is added dropwise, and flows back 1 hour, reaction was completed.After ether and water extraction, satisfy Organic layer, the dry organic layer of magnesium sulfate are cleaned with sodium bicarbonate water, recrystallization crosses chromatographic column with Hex: EA=5: 1 eluent, Obtain 6 2.99g of compound (81%).
4 MS of intermediate (FAB): 387 (M+)
6 MS of compound (FAB): 369 (M+)
The synthesis of compound 7
[reaction equation 8]
The bromo- 1- iodine naphthalene 3.33g (10mmol) of 3- is dissolved in 15mL tetrahydrofuran, is cooled to -78 DEG C, and 2.5M n-BuLi is added dropwise 4mL, -78 DEG C are stirred 1 hour, and the 9-Fluorenone 1.80g (10mmol) for being dissolved in tetrahydrofuran 30ml is slowly added dropwise, rises to normal-temperature reaction After termination, MC and 2N HCl is added, extracts organic layer.
Anhydrous magnesium sulfate removes moisture in organic layer, filters, and is concentrated organic solution obtains compound Hex: EA=5: 1 Eluent cross chromatographic column, obtain 5 2.48g of intermediate (64%).
Above-mentioned intermediate 5 is dissolved in acetic acid, and concentrated hydrochloric acid is added dropwise, and flows back 1 hour, reaction was completed.After ether and water extraction, satisfy Organic layer, the dry organic layer of magnesium sulfate are cleaned with sodium bicarbonate water, recrystallization crosses chromatographic column with Hex: EA=4: 1 eluent, Obtain 7 2.81g of compound (76%).
5 MS of intermediate (FAB): 387 (M+)
7 MS of compound (FAB): 369 (M+)
The synthesis of compound 8
[reaction equation 9]
Under the conditions of nitrogen protection, 6 3.69g of compound (10mmol) is dissolved in anhydrous tetrahydro furan 40mL, by reactant temperature Degree is down to -78 DEG C, and 2.5M n-BuLi 4mL is slowly added dropwise, and reactant stirs 1 hour under the conditions of 0 DEG C, then by temperature of charge - 78 DEG C are down to, is added dropwise trimethylborate 12.47g (12mmol), stirring at normal temperature 12 hours.After reaction, 2N-HCl water is added Solution is stirred 30 minutes, is extracted with ether.
Anhydrous magnesium sulfate removes moisture in organic layer, filters, and is concentrated organic solution obtains compound Hex: EA=5: 1 Eluent cross chromatographic column, obtain 8 2.47g of compound (74%).
8 MS of compound (FAB): 334 (M+)
The synthesis of compound 9
[reaction equation 10]
Under the conditions of nitrogen protection, by the bromo- 3- iodobenzene 2.83g of 8 3.34g of compound (10mmol) and 1- (10mm ol), It is dissolved in tetrahydrofuran 40mL, is separately added into Pd (PPh3)40.58g (0.5mmol) and 2M K2CO315mL (30mmol), reflux 24 hours.
After reaction, temperature of charge is down to room temperature, and MC 200mL, H is added2O 200mL extracts MC layers, and use is anhydrous The dry concentration of magnesium sulfate, crosses chromatographic column with Hex: EA=5: 1 eluent, obtains 9 3.25g of compound (73%).
1H NMR (DMSO, 300Hz): δ (ppm)=8.07-7.66 (m, 4H), 7.64-7.23 (m, 9H), 7.20-6.91 (m, 2H), 6.89-6.60 (d, 2H)
9 MS of compound (FAB): 445 (M+)
The synthesis of compound 10
[reaction equation 11]
It is under the conditions of nitrogen protection, the bromo- 4- iodobenzene 2.83g (10mmol) of 6 3.34g of compound (10mmol) and 1- is mixed It closes, is dissolved in tetrahydrofuran 40mL, is separately added into Pd (PPh3)40.58g (0.5mmol) and 2M K2CO315mL (30mmol) is returned Stream 24 hours.
After reaction, temperature of charge is down to room temperature, and MC 200mL, H is added2O 200mL extracts MC layers, and use is anhydrous The dry concentration of magnesium sulfate, crosses chromatographic column with Hex: EA=4: 1 eluent, obtains 10 3.34g of compound (75%).
1H NMR (DMSO, 300Hz): δ (ppm)=8.07-7.66 (m, 4H), 7.64-7.25 (m, 9H), 7.22-6.91 (m, 2H), 6.87-6.60 (d, 2H)
10 MS of compound (FAB): 445 (M+)
The synthesis of compound 11
[reaction equation 12]
1- iodine naphthalene 2.54g (10mmol) is dissolved in 15mL tetrahydrofuran, is cooled to -78 DEG C, and 2.5M n-BuLi 4mL is added dropwise, - It is stirred at 78 DEG C 1 hour, is slowly added dropwise and is dissolved in the tetrahydrofuran 30mL of the bromo- 9-Fluorenone 3.38g (10mmol) of 2,7- bis-, rise to After normal-temperature reaction terminates, MC and 2N HCl is added, extracts organic layer.
Anhydrous magnesium sulfate removes moisture in organic layer, filters, and is concentrated organic solution obtains compound Hex: EA=3: 1 Eluent cross chromatographic column, obtain 6 3.31g of intermediate (71%).
Above-mentioned intermediate 6 is dissolved in acetic acid, and concentrated hydrochloric acid is added dropwise, and flows back 1 hour, reaction was completed.After ether and water extraction, satisfy Organic layer, the dry organic layer of magnesium sulfate are cleaned with sodium bicarbonate water, recrystallization crosses chromatographic column with Hex: EA=5: 1 eluent, Obtain 11 3.45g of compound (77%).
6 MS of intermediate (FAB): 466 (M+)
11 MS of compound (FAB): 448 (M+)
The synthesis of compound 12
[reaction equation 13]
Under the conditions of nitrogen protection, 11 4.48g of compound (10mmol) and phenyl boric acid 1.22g (10mmol) is mixed, it is molten In tetrahydrofuran 40mL, it is separately added into Pd (PPh3)40.58g (0.5mmol) and 2M K2CO315ml (30mmol), reflux 24 Hour.
After reaction, temperature of charge is down to room temperature, and MC 200mL, H is added2O 200mL extracts MC layers, and use is anhydrous The dry concentration of magnesium sulfate, crosses chromatographic column with Hex: EA=4: 1 eluent, obtains 12 3.16g of compound (71%).
12 MS of compound (FAB): 445 (M+)
The synthesis of compound 13
[reaction equation 14]
Under the conditions of nitrogen protection, 12 3.69g of compound (10mmol) is dissolved in anhydrous tetrahydro furan 40mL, by reactant Temperature is down to -78 DEG C, and 2.5M n-BuLi 4mL is slowly added dropwise, and reactant stirs 1 hour under the conditions of 0 DEG C, then by reactant temperature Degree is down to -78 DEG C, is added dropwise trimethylborate 12.47g (12mmol), stirring at normal temperature 12 hours.After reaction, 2N-HCl is added Aqueous solution is stirred 30 minutes, is extracted with ether.
Anhydrous magnesium sulfate removes moisture in organic layer, filters, and is concentrated organic solution obtains compound Hex: EA=4: 1 Eluent cross chromatographic column, obtain 13 3.04g of compound (74%).
13 MS of compound (FAB): 410 (M+)
The synthesis of compound 14
[reaction equation 15]
It is under the conditions of nitrogen protection, the bromo- 3- iodobenzene 2.83g (10mmol) of 13 4.10g of compound (10mmol) and 1- is mixed It closes, is dissolved in tetrahydrofuran 40mL, is separately added into Pd (PPh3)40.58g (0.5mmol) and 2M K2CO315ml (30mmol) is returned Stream 24 hours.
After reaction, temperature of charge is down to room temperature, and MC 200mL, H is added2O 200mL extracts MC layers, and use is anhydrous The dry concentration of magnesium sulfate, crosses chromatographic column with Hex: EA=4: 1 eluent, obtains 14 3.81g of compound (73%).
1H NMR (DMSO, 300Hz): δ (ppm)=8.10-7.78 (m, 4H), 7.76-7.25 (m, 13H), 7.22-6.90 (m, 2H), 6.87-6.60 (d, 2H)
14 MS of compound (FAB): 521 (M+)
The synthesis of intermediate 7
[reaction equation 16]
Under the conditions of nitrogen protection, 2- bromopyridine 1.58g (10mmol) and aniline 2.79g (30mmol) is mixed, is dissolved in After toluene 40mL, it is added t-BuONa 2.88g (30mmol), Pd (OAc)245mg (0.2mmol), BINAP0.25g (0.4mmol) flows back 2 hours.
After reaction, temperature of charge is down to room temperature, MC 150mL is added, after H2O 150mL extracts MC layers, use is anhydrous The dry concentration of MgSO4, crosses chromatographic column with Hex: EA=4: 1 eluent, obtains 7 1.24g of intermediate (73%).
7 MS of intermediate (FAB): 170 (M+)
The synthesis of compound 15
[reaction equation 17]
Under the conditions of nitrogen protection, 2 3.43g of compound (10mmol) and 7 1.70g of intermediate (10mmol) is mixed, It is dissolved in toluene 50mL, is separately added into Pd2dba30.18g (0.2mmol), t-Bu3P 0.4ml (0.4mmol), t-BuONa 2.88g (30mmol) flows back 12 hours.
After reaction, MC 250mL, H is added2O 250mL extracts MC layers, organic layer is evaporated under reduced pressure, with Hex: EA=2 : 1 eluent crosses chromatographic column, obtains 15 3.29g of compound (76%).
1H NMR (DMSO, 300Hz): δ (ppm)=8.55-8.25 (d, 2H), 8.21-8.10 (m, 1H), 8.10-7.80 (m, 2H), 7.75-6.90 (m, 11H), 6.90-6.55 (m, 4H)
15 MS of compound (FAB): 432 (M+)
The synthesis of compound 16
[reaction equation 18]
Under the conditions of nitrogen protection, 6 3.69g of compound (10mmol) and 7 1.70g of intermediate (10mmol) is mixed, It is dissolved in toluene 50mL, is separately added into Pd2dba30.18g (0.2mmol), t-Bu3P 0.4ml (0.4mmol), t-BuONa 2.88g (30mmol) flows back 12 hours.
After reaction, MC 250mL, H is added2O 250mL extracts MC layers, organic layer is evaporated under reduced pressure, with Hex: EA=2 : 1 eluent crosses chromatographic column, obtains 16 3.58g of compound (76%).
1H NMR (DMSO, 300Hz): δ (ppm)=8.57-8.25 (d, 2H), 8.21-8.10 (m, 1H), 8.10-7.75 (m, 2H), 7.72-6.90 (m, 13H), 6.90-6.52 (m, 4H)
16 MS of compound (FAB): 458 (M+)
The present invention will be described in more detail by embodiment below.But following embodiments are intended merely to more Add specific description of the invention, the scope of the present invention can not be limited to following embodiments.Following embodiments are in this hair In bright range, practitioner can carry out amendment and change appropriate.
Embodiment 1
By 5 Ω/cm2 The glass baseplate of ito anode is cut into 45mm × 45mm × 0.7mm size, in isopropanol After five minutes with ultrasound in pure water, it is used ozone clean 30 minutes under ultraviolet light irradiation, this glass baseplate is then set to vacuum On filming equipment.
On above-mentioned ITO layer top, the CuPC successively indicated with following Ex-1 is aboutThe NPD that following Ex-2 are indicated is aboutThe substance for using Ex-4 to indicate on following DPBVi for using Ex-3 to indicate adds about 1% about as dopant About as electron transfer layer the compound of the present invention 15LiF is aboutAluminium (Al) is aboutThickness deposition.
Embodiment 2
The present embodiment the difference from embodiment 1 is that: use compound 16 to replace compound 15 as electron transfer layer, It is remaining same as Example 1.
Comparative example 1
The present embodiment the difference from embodiment 1 is that: use Ex-5 indicate Alq3It is passed instead of compound 15 as electronics Defeated layer, remaining is same as Example 1.
Experimental example: the characteristic evaluation of organic electroluminescence device
The organic electroluminescent manufactured in the organic electroluminescence device 1,2 and comparative example manufactured in above-described embodiment The characteristic of device is 10mA/cm in current density2In the case where measure, as a result such as table 1.
[table 1]
Such as above-mentioned table 1, organic electroluminescence device in the embodiment of the present invention 1 and 2 is and organic in comparing embodiment Electroluminescent device is compared, and luminous efficiency is significantly improved.
Organic compound of the invention is as electron-transporting material in use, organic it can be seen from above-mentioned experimental result The luminous efficiency of electroluminescent device is mentioned.Therefore, organic compound of the invention obtains the low voltage drive of device To realize, the effect for reducing power consumption can also be provided.In addition, being driven by electricity due to low, the hair of organic electroluminescence device The light service life is also improved.

Claims (7)

1. a kind of organic compound is organic compound shown in general formula (1):
[general formula 1]
In above formula, ring that CYCLO is made of 4 or 5 carbon atoms；Upper In the case where stating the ring that CYCLO is made of 4 carbon atoms, 2 phenyl for forming CYCLO, which combine, forms naphthalene, described organic Shown in the structural formula of compound such as general formula (2):
[general formula 2]
In the case where the ring that above-mentioned CYCLO is made of 5 carbon atoms, the structural formula of the organic compound such as general formula (3) It is shown:
[general formula 3]
R1, R2, R3, R4, R5, R6, R7 and R8 are hydrogen independent, heavy hydrogen, F, Cl, Br, I, CN, Si (CH3)3、B(OH)2、 The linear or branched alkyl group of carbon atom number 1 to 40, the alkoxy of carbon atom number 1 to 40, carbon atom number 1 to 40 thio group, or The naphthenic base of person's carbon atom number 3 to 40,
Alternatively, with selected from by with F, Cl, Br, I, CN, Si (CH3)3、B(OH)2, carbon atom number 1 to 40 linear or branched alkyl group, The alkoxy of carbon atom number 1 to 40, the thio group of carbon atom number 1 to 40, the naphthenic base of carbon atom number 3 to 40, phenyl, double benzene Base, naphthalene, anthryl, phenyl groups replace anthryl, phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, dibenzofurans, pyrroles, triazole, More than one substituted or non-substituted carbon atom number 6~60 in group that pyridine, pyrazinyl, pyrimidine bases and quinolyl form Aromatic hydrocarbyl,
Alternatively, with selected from by with F, Cl, Br, I, CN, Si (CH3)3、B(OH)2, carbon atom number 1 to 40 linear or branched alkyl group, The alkoxy of carbon atom number 1 to 40, the thio group of carbon atom number 1 to 40, the naphthenic base of carbon atom number 3 to 40, phenyl, double benzene Base, naphthalene, anthryl, phenyl groups replace anthryl, phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, dibenzofurans, pyrroles, triazole, More than one in the group that pyridine, pyrazinyl, pyrimidine bases and quinolyl form is substituted or non-substituted, comprising selected from by S, O, N The heteroaromatic alkyl of the carbon atom number 5 to 60 of more than one element in group formed with Si,
Alternatively, selected from by with phenyl, double phenyl, naphthalene, anthryl, phenyl groups replace anthryl, phenanthryl, pyrenyl, 9,9- diformazan fluorenes, What one or more of carbazole, quinoline, dibenzofurans, pyrroles, triazole, pyridine, pyrazinyl, the group of pyrimidine bases composition replaced Amino, above-mentioned phenyl, double phenyl, naphthalene, anthryl, phenyl groups are selected from by F, Cl, Br, I, CN, Si (CH3)3、B(OH)2, carbon it is former The linear or branched alkyl group of subnumber 1 to 40, the alkoxy of carbon atom number 1 to 40, carbon atom number 1 to 40 thio group, carbon atom Number 3 to 40 naphthenic base composition group in a kind or more it is substituted or non-substituted.
2. organic compound according to claim 1, it is characterised in that:
R1, R2, R3, R4, R5, R6, R7 and R8 are hydrogen independent, heavy hydrogen, F, Cl, Br, I, CN, Si (CH3)3、B(OH)2、 The linear or branched alkyl group of carbon atom number 1 to 40,
Alternatively, with selected from by with F, Cl, Br, I, B (OH)2And the linear or branched alkyl group of carbon atom number 1 to 40, phenyl, double benzene Base, naphthalene, anthryl, phenyl groups replace anthryl, phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, dibenzofurans, pyrroles, triazole, Pyridine, pyrazinyl, pyrimidine bases and quinolyl composition group in more than one substituted or non-substituted phenyl, double phenyl, naphthalene Base, anthryl, phenanthryl, pyrenyl,
Alternatively, with selected from by with F, Cl, Br, I, B (OH)2With the linear or branched alkyl group of carbon atom number 1 to 10, phenyl, double benzene Base, naphthalene, anthryl, phenyl groups replace anthryl, phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, dibenzofurans, pyrroles, triazole, Pyridine, pyrazinyl, pyrimidine bases composition group in more than one substituted or non-substituted pyrroles, triazole, pyridine, pyrazinyl, Pyrimidine bases, quinolyl, 9,9- diformazan fluorenes, carbazole or dibenzofurans,
Alternatively, with selected from by with F, Cl, Br, I, B (OH)2With the linear or branched alkyl group of carbon atom number 1 to 10, phenyl, double benzene Anthryl, phenanthryl, pyrenyl, 9,9- diformazan fluorenes, carbazole, quinolyl and the dibenzofurans group that base, naphthalene, anthryl, phenyl groups replace At group in more than one replace amino.
3. organic compound according to claim 1, it is characterised in that:
The compound that general formula (2) or general formula (3) indicate is any one in following compounds:
4. organic compound described in claim 1 is in the application of electronic material.
5. hole injection layer substance, sky of the organic compound described in claim 1 in material for organic electroluminescent device Cave transport layer substance, electron-blocking layer substance, luminescent layer substance, hole blocking layer substance, electron transfer layer substance or electronics note Enter the application in layer substance.
6. a kind of organic electroluminescence device, clamping has one or more layers at least containing luminescent layer between a cathode and an anode Organic thin film layer, it is characterised in that: in organic thin film layer described in at least one layer claim 1 containing one or more Organic compound.
7. organic electroluminescence device according to claim 6, which is characterized in that above-mentioned organic electroluminescence device has Successively press anode, hole injection layer, hole transmission layer, electron-blocking layer, luminescent layer, hole blocking layer, electron transfer layer, electronics Implanted layer and the structure of cathode stacking.
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CN106397223B (en) * 2015-08-01 2019-04-19 南京高光半导体材料有限公司 A kind of organic compound, the organic electroluminescence device material comprising the compound and the organic electroluminescence device comprising the material
CN109776468B (en) * 2019-03-14 2021-03-26 南京高光半导体材料有限公司 Organic electroluminescent compound and preparation method and application thereof
CN111748339A (en) * 2019-03-29 2020-10-09 南京高光半导体材料有限公司 Organic electroluminescent compound and manufacturing method of device thereof
KR20230052219A (en) 2021-10-11 2023-04-19 김진우 Novel organic compounds and an organic electroluminescent device comprising the same
KR20230164572A (en) 2022-05-25 2023-12-04 김진우 Novel organic compounds and an organic electroluminescent device comprising the same
KR20230164571A (en) 2022-05-25 2023-12-04 김진우 Novel organic compounds and an organic electroluminescent device comprising the same
KR20230164570A (en) 2022-05-25 2023-12-04 김진우 Novel organic compounds and an organic electroluminescent device comprising the same
KR20230171384A (en) 2022-06-11 2023-12-20 김진우 Novel organic compounds and an organic electroluminescent device comprising the same
KR20230172410A (en) 2022-06-14 2023-12-22 김진우 Novel organic compounds and an organic electroluminescent device comprising the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1787988A (en) * 2003-05-15 2006-06-14 出光兴产株式会社 Arylamine compounds and organic electroluminescent devices containing the same
CN103664644A (en) * 2012-08-31 2014-03-26 海洋王照明科技股份有限公司 Organic semiconductor material containing aniline and preparation method thereof, and organic electroluminescence device
KR20150030300A (en) * 2013-09-11 2015-03-20 엘지디스플레이 주식회사 Fluorescent compound and Organic light emitting diode device using the same
CN104628581A (en) * 2015-02-04 2015-05-20 北京鼎材科技有限公司 2,6,6,8-tetra-substituted-6H-benzo[cd]pyrene compound and organic electroluminescence device containing same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE59510315D1 (en) 1994-04-07 2002-09-19 Covion Organic Semiconductors Spiro compounds and their use as electroluminescent materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1787988A (en) * 2003-05-15 2006-06-14 出光兴产株式会社 Arylamine compounds and organic electroluminescent devices containing the same
CN103664644A (en) * 2012-08-31 2014-03-26 海洋王照明科技股份有限公司 Organic semiconductor material containing aniline and preparation method thereof, and organic electroluminescence device
KR20150030300A (en) * 2013-09-11 2015-03-20 엘지디스플레이 주식회사 Fluorescent compound and Organic light emitting diode device using the same
CN104628581A (en) * 2015-02-04 2015-05-20 北京鼎材科技有限公司 2,6,6,8-tetra-substituted-6H-benzo[cd]pyrene compound and organic electroluminescence device containing same

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