[go: up one dir, main page]

CN108440532A - A kind of benzopyrazines compound and application thereof and luminescent device - Google Patents

A kind of benzopyrazines compound and application thereof and luminescent device Download PDF

Info

Publication number
CN108440532A
CN108440532A CN201810258216.6A CN201810258216A CN108440532A CN 108440532 A CN108440532 A CN 108440532A CN 201810258216 A CN201810258216 A CN 201810258216A CN 108440532 A CN108440532 A CN 108440532A
Authority
CN
China
Prior art keywords
layer
compound
benzopyrazines
organic
organic electroluminescence
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810258216.6A
Other languages
Chinese (zh)
Inventor
黄锦海
苏建华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Taoe Chemical Technology Co Ltd
Original Assignee
Shanghai Taoe Chemical Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Taoe Chemical Technology Co Ltd filed Critical Shanghai Taoe Chemical Technology Co Ltd
Priority to CN201810258216.6A priority Critical patent/CN108440532A/en
Publication of CN108440532A publication Critical patent/CN108440532A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present invention provides a kind of benzopyrazines compounds, have the following structure formula：The benzopyrazines compound has preferable thermal stability, high-luminous-efficiency, high luminance purity, can be applied to organic electroluminescence device, solar cell, Organic Thin Film Transistors or organophotoreceptorswith field.The present invention also provides a kind of organic electroluminescence devices, the device includes anode, cathode and organic layer, organic layer includes at least one layer in luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, the at least one layer benzopyrazines compound containing such as structural formula I in organic layer, the organic electroluminescence device made of benzopyrazines compound have the advantages that electroluminescent efficiency is good and excitation purity is excellent and long lifespan.

Description

A kind of benzopyrazines compound and application thereof and luminescent device
Technical field
The present invention relates to field of organic electroluminescent materials, and in particular to a kind of benzopyrazines compound and application thereof, also It is related to a kind of luminescent device.
Background technology
Organic electroluminescence device (OLEDs) is between two metal electrodes by spin coating or vacuum evaporation deposition one The device that layer organic material is prepared, a classical three layer organic electroluminescence device include hole transmission layer, luminescent layer And electron transfer layer.The hole generated by anode is incorporated in the electronics generated by cathode through electron transfer layer through hole transmission layer Luminescent layer forms exciton, then shines.Organic electroluminescence device can be adjusted as desired by the material for changing luminescent layer Section emits the light of various needs.
Organic electroluminescence device has self-luminous, wide viewing angle, low energy consumption, efficiency as a kind of novel display technology High, thin, rich in color, fast response time, Applicable temperature range be wide, low driving voltage, can make flexible with it is transparent Display panel and the particular advantages such as environmental-friendly can be applied on flat-panel monitor and a new generation's illumination, be can also be used as The backlight of LCD.
Since the invention at the bottom of the 1980s, organic electroluminescence device is industrially applied, such as As screens such as camera and mobile phones, but current OLED device, since efficiency is low, it is wider that the factors such as service life is short restrict it General application, especially large screen display.And it is exactly in organic electroluminescence device to restrict one of key factor The performance of electroluminescent organic material.Additionally, due to OLED device when applying voltage-operated, Joule heat will produce so that Organic material is easy to happen crystallization, affects service life and the efficiency of device, therefore, it is also desirable to develop the organic electroluminescence of stability and high efficiency Luminescent material.
Organic electrophosphorescenpolymer phenomenon, breaches theoretical limitation of the organic electroluminescent quantum efficiency less than 25%, and promotion is arrived 100% (Baldo M.A., Forrest S.R.Et al, Nature, 1998,395,151-154), application also greatly carry The high efficiency of organic electroluminescence device.Usually, electroluminescent phosphorescence needs to use host-guest system technology, is commonly used as phosphorus The CBP (4,4'-bis (9-carbazolyl)-biphenyl) of light material of main part has efficient and high triplet energy level, when its work Based on material when, triplet energy state effectively can be transferred to object phosphorescent light-emitting materials from light emitting host material.But by In the characteristic of the hole of CBP easily transmission and the flowing of electronics difficulty so that as a result the charge unbalance of luminescent layer reduces the effect of device Rate.
Invention content
The present invention provides a kind of benzopyrazines compounds, are the compound for having the following structure Formulas I：
Wherein, R is selected from hydrogen, deuterium, fluorine, the alkyl of C1-C12, the alkoxy of C1-C8, substitution or unsubstituted C6-C30 Aryl；
Cz is independently selected from the substitution either carbazyl of unsubstituted C12-C30, substitution or unsubstituted C8-C30 Indyl；
L is selected from the singly-bound either aryl of substitution or unsubstituted C6-C30.
Optionally, R is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, cyclohexyl, phenyl, first Phenyl, xenyl, naphthalene.
Optionally, L is selected from singly-bound, phenyl, xenyl.
Further alternative, benzopyrazines compound is the compound of following structural 1-36：
The benzopyrazines compound of the present invention can be applied to organic electroluminescence device, solar cell, organic film Transistor or organophotoreceptorswith field.
The present invention also provides a kind of organic electroluminescence device, which includes anode, cathode and organic layer, organic layer Including at least one in luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer Layer, at least one layer of benzopyrazines compound containing as described in structural formula I in the organic layer.
Wherein organic layer is luminescent layer；
Or organic layer is luminescent layer and electron transfer layer；
Or organic layer is luminescent layer, electron transfer layer and electron injecting layer；
Or organic layer is hole transmission layer and luminescent layer；
Or organic layer is hole injection layer, hole transmission layer and luminescent layer；
Or organic layer is hole transmission layer, luminescent layer and electron transfer layer；
Or organic layer is hole injection layer, hole transmission layer, luminescent layer and electron transfer layer；
Or organic layer is hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer；
Or organic layer is hole injection layer, hole transmission layer, barrier layer, luminescent layer, electron transfer layer and electron injection Layer；
Or organic layer is hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and hole blocking layer；
Or organic layer is hole transmission layer, luminescent layer, electron injecting layer and hole blocking layer.
Further alternative, the layer where the benzopyrazines compound is luminescent layer.
Benzopyrazines compound as described in structural formula I is used alone, or is used in mixed way with other compounds；Such as structural formula Benzopyrazines compound described in I can be used alone one such compound, can also use two in structural formula I simultaneously Kind or two or more compounds；A kind of benzopyrazines compound selected from structural formula 1-36 is used alone, or uses two simultaneously Kind or more be selected from structural formula 1-36 benzopyrazines compound.
Still optionally further, organic electroluminescence device of the invention include anode, hole injection layer, hole transmission layer, Luminescent layer, electron transfer layer, electron injecting layer and cathode contain one or more kinds of structural formula I's wherein in luminescent layer Compound；It is further preferred that the compound containing one or more kinds of structural formula 1-36 in luminescent layer.
The overall thickness of the organic electroluminescence device organic layer of the present invention is 1-1000nm, preferably 50-500nm.
When having the compound of structural formula I using the present invention, can arrange in pairs or groups makes the organic electroluminescence device of the present invention With other materials, such as in hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and barrier layer Deng, and obtain blue and green light, yellow light, feux rouges or white light.
The hole transmission layer and hole injection layer of organic electroluminescence device of the present invention, material requested have good hole Transmission performance can effectively be transferred to hole on luminescent layer from anode.May include that other small molecules and macromolecule are organic Compound, including but not limited to carbazole compound, triaromatic amine compound, benzidine compound, compound of fluorene class, phthalocyanine Class compound, six cyano, six miscellaneous triphen (hexanitrilehexaazatriphenylene), 2,3,5,6- tetra- fluoro- 7,7', 8, Tetra- cyanogen dimethyl-parabenzoquinones (F4-TCNQ) of 8'-, polyvinyl carbazole, polythiophene, polyethylene or polyphenyl sulfonic acid.
The luminescent layer of the organic electroluminescence device of the present invention has the good characteristics of luminescence, can be adjusted according to the needs The range of visible light.In addition to the present invention is with Compounds of structural formula I, following compound can also be contained, but not limited to this, Naphthalene compounds, pyrene compound, compound of fluorene class, luxuriant and rich with fragrance class compound,Class compound, glimmering anthracene compound, anthracene class chemical combination Object, pentacene class compound, class compound, two aromatic ethylene class compounds, triphenylamine ethylene compounds, aminated compounds, Benzimidazoles compound, furfuran compound, organic metal chelate complex.
The Organic Electron Transport Material of organic electroluminescence device of the present invention requires good electronic transmission performance, energy In reaching effectively electronics from cathode transport to luminescent layer, there is prodigious electron mobility.In addition to that can use with this hair Outside bright compound, it is also an option that following compound, but not limited to this：Oxa- oxazole, thiazole compound, triazole Compound, three nitrogen piperazine class compounds, triazine class compound, quinoline class compound, phenodiazine anthracene compound, siliceous heterocyclic Compound, quinolines, ferrosin class compound, metallo-chelate (such as Alq3), fluorine substituted benzene compound, benzo miaow Azole compounds.
Electronics effectively can be injected into organic layer by the electron injecting layer of organic electroluminescence device of the present invention from cathode In, it is mainly selected from the alkali metal either compound of alkali metal or the compound selected from alkaline-earth metal or alkaline-earth metal or alkali Metal complex can select following compound, and but not limited to this：Alkali metal, alkaline-earth metal, rare earth metal, alkali metal Oxide either halide, the oxide of alkaline-earth metal or halide, the oxide of rare earth metal or halide, alkali metal Or the organic complex of alkaline-earth metal；Preferably lithium, lithium fluoride, lithia, lithium nitride, 8-hydroxyquinoline lithium, caesium, carbonic acid Caesium, 8-hydroxyquinoline caesium, calcium, calcirm-fluoride, calcium oxide, magnesium, magnesium fluoride, magnesium carbonate, magnesia, these compounds can individually make With can also mixture use, can also be used cooperatively with other electroluminescent organic materials.
Each layer of organic layer in the organic electroluminescence device of the present invention can be steamed by vacuum vapour deposition, molecular beam It is prepared by the modes such as plating method, the dip coating for being dissolved in solvent, spin-coating method, stick coating method or inkjet printing.Metal motor can be made It is prepared with vapour deposition method or sputtering method.
Device experimental shows benzopyrazines compound of the present invention as described in structural formula I, has preferable thermal stability, height Luminous efficiency, high luminance purity.It is imitated with electroluminescent using the organic electroluminescence device that the benzopyrazines compound makes The advantages of rate is good and excitation purity is excellent and long lifespan.
Description of the drawings
Fig. 1 is a kind of organic electroluminescence device structural schematic diagram of the present invention,
Wherein, 110 be glass substrate, and 120 be anode, and 130 be hole injection layer, and 140 be hole transmission layer, and 150 be resistance Barrier, 160 be luminescent layer, and 170 be electron transfer layer, and 180 be electron injecting layer, and 190 be cathode.
Specific implementation mode
In order to describe the present invention in more detail, spy lifts following example, and but not limited to this.
Embodiment 1
The synthetic route of compound 1
The synthetic method of intermediate 1-1
In flask, be separately added into the bromo- 2- fluoronitrobenzenes of 3- methyl indols (3.8g, 0.029mol), 5- (6.72g, 0.029mol), sodium hydroxide (1.2g, 0.029mol) and 100mL dimethyl sulfoxide (DMSO)s fully dissolve, and react 5 hours at room temperature. After reaction, water is added into system, red solid is precipitated, (filter cake is stirred with ethyl alcohol), filtering, drying is filtered, obtains red solid Body product 4.2g, yield 43.7%.
The synthetic method of intermediate 1-2
In flask, intermediate 1-1 (3.5g, 10.57mmol), SnCl is added2·2H2O (9.54g, 42.28mmol) and 50mL absolute ethyl alcohols are heated to flowing back under nitrogen protection, react 11 hours.It is cooled to room temperature after reaction, rotary evaporation Ethyl alcohol is removed, adds water, with potassium carbonate tune pH to 7, is extracted using ethyl acetate, washing is spin-dried for afterwards three times, obtains product 3g, Yield is 94.3%.
The synthetic method of intermediate 1-3
In flask, intermediate 1-2 (3g, 10mmol), glacial acetic acid (0.6g, 10mmol) and 20mL dimethyl sulfoxide (DMSO)s is added In seal pipe, 130 DEG C are heated to, is reacted 24 hours.It is cooled to room temperature, is extracted with ethyl acetate after reaction, wash, it is dense Contracting, crude by column chromatography purification, obtains product 1g, yield 32.3%.
The synthetic method of compound 1
In flask, be added intermediate 1-3 (0.3g, 0.96mmol), 4-9H- carbazyls phenyl boric acid (0.33g, 1.16mmol), potassium carbonate (0.27g, 1.93mmol), and 30mL tetrahydrofurans are added and 15mL water fully dissolves, it is heated to back Stream reacts 5 hours.It is cooled to room temperature after reaction, rotary evaporation removes solvent, has with dichloromethane dissolving, washing, separation Machine layer is spin-dried for, column chromatography, obtains product faint yellow solid 0.3g, yield 66%.
Embodiment 2
The synthetic route of compound 2
The synthetic method of intermediate 2-1
In flask, 3- phenyl carbazoles (2.43g, 10mmol) are added, to bromo-iodobenzene (3.1g, 11mmol), potassium hydroxide (1.1g, 20mmol), cuprous iodide (0.2g), Phen (0.2g) and ortho-xylene (50mL), are heated under nitrogen protection Reflux 10 hours, it is cooling, solvent is removed, crude by column chromatography purifies to obtain 2.5g, yield 63%.
The synthetic method of intermediate 2-2
In flask, intermediate 2-1 (2.5g, 6.3mmol), anhydrous tetrahydro furan (30mL) is added, under nitrogen protection - 78 DEG C are cooled to, the 2.5M n-butyllithium solutions (3mL, 7.5mmol) for being dissolved in n-hexane are added, reacts 2 hours, is slowly added to Triisopropyl borate ester (1.4g, 7.5mmol) reacts 1 hour, is slowly increased to room temperature, the reaction was continued 12 hours, and dilute salt of 1N is added Acid for adjusting pH is to 6, with dichloromethane extraction, dry, concentration, crude product toluene and n-hexane recrystallization, and yield 1.5g, production Rate is 63%.
The synthetic method of compound 2
As the synthetic method of compound 1, raw materials used is intermediate 1-3 and intermediate 2-2, yield 64%.
Embodiment 3
The synthetic route of compound 13
For its synthetic method as the synthetic method of compound 1, raw materials used is intermediate 1-3 and 3- carbazyl benzene boron Acid, yield 58%.
Embodiment 4
The synthetic route of compound 15
The synthetic method of intermediate 15-1
5,7- dihydros -7,7- dimethyl-indeno [2,1-b] carbazole (10g, 35.3mmol), bromine are added into reaction bulb Iodobenzene (12g, 42mmol), potassium tert-butoxide (7.9g, 70.6mmol), palladium (0.3g), tri-tert-butylphosphine tetrafluoroborate (0.8g) and toluene (150mL), is heated to reflux 24 hours under nitrogen protection, cooling, removing toluene, addition dichloromethane, water Wash, dry, crude product crosses column, obtain 11g products, yield 71%.
The synthetic method of intermediate 15-2
In single-necked flask be added compound 15-1 (4.37g, 10mmol), connection boric acid frequency receive alcohol ester (3.0g, 12mmol), Potassium acetate (3.0g), two triphenylphosphine palladium of dichloro (50mg) and dioxane (60mL) are heated to 100 DEG C of reaction 12h, while hot mistake Silica gel washs filter cake with dichloromethane, revolves solvent evaporated, and crude product is purified with column chromatography, obtains product 3.1g, yield is 70%.
The synthetic method of compound 15
For its synthetic method as the synthetic method of compound 1, raw materials used is intermediate 1-3 and intermediate 15-2, production Rate is 53%.
Embodiment 5
The synthetic route of compound 20
For its synthetic method as the synthetic method of compound 1, raw materials used is intermediate 1-3 and 3, bis- -9H- carbazoles of 5- Base phenyl boric acid, yield 71%.
Embodiment 6
The synthetic route of compound 21
For its synthetic method as the synthetic method of compound 1, raw materials used is intermediate 1-3 and 9- phenyl carbazole -3- Boric acid, yield 82%.
Embodiment 7
The synthetic route of compound 22
For its synthetic method as the synthetic method of compound 1, raw materials used is intermediate 1-3 and 9- (4- xenyls) click Azoles -3- boric acid, yield 42%.
Embodiment 8-14
The preparation of organic electroluminescence device
OLED is prepared using the compound of embodiment 1-7
First, by electrically conducting transparent ito glass substrate 110 (carrying anode 120 above) (the limited public affairs of South China glass group share Department) it passes through successively：Deionized water, ethyl alcohol, acetone and deionized water were cleaned, then with oxygen plasma treatment 30 seconds.
Then, the MnO of 3nm thickness is deposited on ITO3(molybdenum oxide) is hole injection layer 130.
Then, the TAPC that 50nm thickness is deposited on hole injection layer is hole mobile material 140.
Then, TCTA is deposited, forms the electronic barrier layer 150 of 5nm thickness.
Then, the luminescent layer 160 of 20nm thickness is deposited on electronic barrier layer, wherein shine based on the compounds of this invention Material, and the Ir (ppy) for being 3% with weight ratio3Guest materials is adulterated as phosphorescence.
Then, the BmPYPB of 40nm thickness is deposited on the light-emitting layer as electron transfer layer 170.
Finally, vapor deposition 1nm LiF are electron injecting layer 180 and 80nm Al as device cathodes 190.
Prepared device (structural schematic diagram is shown in Fig. 1) with Photo Research PR650 spectrometers measure 5000cd/m2Brightness under current efficiency be such as table 1.
Comparative example 1
Except use CBP replace the compounds of this invention as material of main part in addition to, other steps are according to the device of embodiment 8-14 Preparation method prepares device.
Table 1
Embodiment Compound Current efficiency (cd/A) Luminescent color
8 1 52 Green light
9 2 51 Green light
10 13 53 Green light
11 15 51 Green light
12 20 54 Green light
13 21 55 Green light
14 22 53 Green light
Comparative example 1 CBP 45 Green light
The structural formula of compound described in device is as follows：
From table 1 it follows that when the compounds of this invention is used for organic electroluminescence device, operating voltage can be reduced, Device efficiency is improved, is the phosphorescent light body material with excellent performance.As described above, the compound of the present invention has high stabilization Property, the organic electroluminescence device of preparation has high efficiency and optical purity.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Technical solution, all should be in the protection domain being defined in the patent claims.

Claims (10)

1. a kind of benzopyrazines compound, which is characterized in that be the compound for having the following structure Formulas I：
Wherein, R is selected from the virtue of hydrogen, deuterium, fluorine, the alkyl of C1-C12, the alkoxy of C1-C8, substitution or unsubstituted C6-C30 Base；
Cz is independently selected from the indoles for replacing the either carbazyl of unsubstituted C12-C30, substitution or unsubstituted C8-C30 Base；
L is selected from the singly-bound either aryl of substitution or unsubstituted C6-C30.
2. benzopyrazines compound as described in claim 1, which is characterized in that R is selected from hydrogen, methyl, ethyl, propyl, isopropyl Base, butyl, tertiary butyl, hexyl, cyclohexyl, phenyl, tolyl, xenyl, naphthalene.
3. benzopyrazines compound as described in claim 1, which is characterized in that L is selected from singly-bound, phenyl, xenyl.
4. benzopyrazines compound as described in claim 1, which is characterized in that be the compound of following structural 1-36：
5. application of the benzopyrazines compound described in claim 1 in organic electroluminescence device.
6. a kind of organic electroluminescence device, which includes anode, cathode and organic layer, and organic layer includes luminescent layer, hole At least one layer in implanted layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, which is characterized in that institute It states at least one layer in organic layer and contains benzopyrazines compound as described in claim 1.
7. organic electroluminescence device as claimed in claim 6, which is characterized in that benzopyrazines described in claim 1 Layer where closing object is luminescent layer.
8. organic electroluminescence device as claimed in claim 6, which is characterized in that benzopyrazines described in claim 1 It closes object to be used alone, or is used in mixed way with other compounds.
9. organic electroluminescence device as claimed in claim 6, which is characterized in that be used alone a kind of selected from such as claim The benzopyrazines compound of structural formula 1-36 described in 4, or simultaneously structure as claimed in claim 4 is selected from using two or more The benzopyrazines compound of formula 1-36.
10. organic electroluminescence device as claimed in claim 6, which is characterized in that the overall thickness of the organic layer is 1- 1000nm。
CN201810258216.6A 2018-03-27 2018-03-27 A kind of benzopyrazines compound and application thereof and luminescent device Pending CN108440532A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810258216.6A CN108440532A (en) 2018-03-27 2018-03-27 A kind of benzopyrazines compound and application thereof and luminescent device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810258216.6A CN108440532A (en) 2018-03-27 2018-03-27 A kind of benzopyrazines compound and application thereof and luminescent device

Publications (1)

Publication Number Publication Date
CN108440532A true CN108440532A (en) 2018-08-24

Family

ID=63196871

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810258216.6A Pending CN108440532A (en) 2018-03-27 2018-03-27 A kind of benzopyrazines compound and application thereof and luminescent device

Country Status (1)

Country Link
CN (1) CN108440532A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112239473A (en) * 2019-07-17 2021-01-19 百济神州(北京)生物科技有限公司 Tricyclic compounds as HPK1 inhibitors

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104073249A (en) * 2014-06-25 2014-10-01 上海道亦化工科技有限公司 Organic electronic transmission compound
CN106518882A (en) * 2016-10-25 2017-03-22 上海道亦化工科技有限公司 Helical structural organic light emitting material and organic light emitting device thereof
CN107602540A (en) * 2016-12-12 2018-01-19 吉林大学 The electroluminescent device to acceptor compound and for preparation based on dicyano pyrazine and dicyano benzo pyrazines derivatives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104073249A (en) * 2014-06-25 2014-10-01 上海道亦化工科技有限公司 Organic electronic transmission compound
CN106518882A (en) * 2016-10-25 2017-03-22 上海道亦化工科技有限公司 Helical structural organic light emitting material and organic light emitting device thereof
CN107602540A (en) * 2016-12-12 2018-01-19 吉林大学 The electroluminescent device to acceptor compound and for preparation based on dicyano pyrazine and dicyano benzo pyrazines derivatives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112239473A (en) * 2019-07-17 2021-01-19 百济神州(北京)生物科技有限公司 Tricyclic compounds as HPK1 inhibitors
CN112239473B (en) * 2019-07-17 2023-12-08 百济神州(北京)生物科技有限公司 Process for preparing tricyclic compounds as HPK1 inhibitors

Similar Documents

Publication Publication Date Title
CN105153130B (en) Triazine derivative electron transport compound and its organic electroluminescence device
CN106831313A (en) A kind of compound and its organic electroluminescence device with triaryl naphthalene
CN105294663B (en) One kind containing pyridine compounds and its organic electroluminescence device
CN109265450A (en) A kind of organic electroluminescent compounds and luminescent device of the aphthofurans containing benzo
CN109053698A (en) A kind of aromatic amine compound and luminescent device containing dibenzofurans
CN105601612B (en) Phosphorescence host compound containing indolyl radical and its organic electroluminescence device
CN109336772A (en) A kind of triaromatic amine compound containing spiro structure and application thereof and luminescent device
CN108658953A (en) A kind of compound based on dibenzofurans and carbazole and application thereof and luminescent device
CN108752221A (en) A kind of triaromatic amine compound containing fluorenes and application thereof and luminescent device
CN109535175A (en) A kind of double triaromatic amine compounds, application and the luminescent device of the spiro structure containing five-membered ring
CN105175313A (en) Hole injection compound and organic electroluminescent device
CN107382992A (en) A kind of carbazoles organic electroluminescent compounds and its organic electroluminescence device
CN106977514A (en) A kind of organic electroluminescent compounds and its luminescent device containing carbazole derivates
CN108997239A (en) A kind of compound of cyano-containing and application thereof and organic electroluminescence device
CN108912099A (en) A kind of compound containing triazine and carbazole and application thereof and organic electroluminescence device
CN108299389A (en) A kind of compound based on phenanthrene and carbazole and application thereof and organic electroluminescence device
CN106632325A (en) Azacycle-containing compound and organic electroluminescence device thereof
CN109705021A (en) A kind of organic electroluminescent compounds of the alkylnaphthalene containing cycloheptyl and application thereof and luminescent device
CN106831798B (en) Compound and its organic electroluminescence device containing five-membered ring structure
CN108358932A (en) A kind of nitrogen heterocyclic and application thereof and organic electroluminescence device
CN108017677A (en) A kind of complex of iridium and application thereof and organic electroluminescence device
CN105001229B (en) A kind of organic electroluminescent compounds and its device with spiro structure
CN109320495A (en) A kind of double triaromatic amine compounds, application and luminescent device containing spiro structure
CN106749289B (en) A kind of organic electroluminescent compounds and its luminescent device with spiro structure
CN108658789A (en) A kind of triaromatic amine compound containing fluorenes and application thereof and luminescent device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180824

WD01 Invention patent application deemed withdrawn after publication