CN109575001A - 3- dibenzofurans based triazine derivative organic compound and the organic electroluminescence device comprising it - Google Patents

3- dibenzofurans based triazine derivative organic compound and the organic electroluminescence device comprising it Download PDF

Info

Publication number
CN109575001A
CN109575001A CN201711318649.8A CN201711318649A CN109575001A CN 109575001 A CN109575001 A CN 109575001A CN 201711318649 A CN201711318649 A CN 201711318649A CN 109575001 A CN109575001 A CN 109575001A
Authority
CN
China
Prior art keywords
layer
mentioned
compound
dibenzofurans
triazine derivative
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
CN201711318649.8A
Other languages
Chinese (zh)
Inventor
徐荷娜
林炫彻
李大均
安重福
裵镐基
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.)
Cmdl Ltd
Original Assignee
Cmdl 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 Cmdl Ltd filed Critical Cmdl Ltd
Publication of CN109575001A publication Critical patent/CN109575001A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D405/00Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D251/00Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D307/00Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91Dibenzofurans; Hydrogenated dibenzofurans
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D409/00Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/16Electron transporting layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17Carrier injection layers
    • H10K50/171Electron injection layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18Carrier blocking layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/615Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/615Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/654Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/657Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/657Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00Constructional details relating to the organic devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301Details of OLEDs

Landscapes

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

Abstract

The present invention provides the 3- dibenzofurans based triazine derivative organic compound comprising heteroaryl connexon indicated by following chemical formula a: chemical formula a:.In above-mentioned chemical formula a, Ar1To Ar3And L is as invented defined in claimed range.

Description

3- dibenzofurans based triazine derivative organic compound and the organic electroluminescence comprising it Luminescent device
Technical field
The present invention relates to 3- dibenzofurans based triazine derivative organic compound and include its organic electroluminescence Part.
Background technique
Electroluminescent device (electroluminescence device:EL device) is shown as self light-generating type Device has the advantages that fast response time, visual angle are broad.1987 Eastman Kodak Co (Eastman Kodak) open for the first time The organic electroluminescence device using low molecule aromatic diamine and aluminium complex as emitting layer material is sent out [Appl.Phys.Lett.51,913,1987].
In organic electroluminescence device, determines that the most important factor of luminous efficiency is luminescent material, but shine material Phosphor material in material is compared with fluorescent material, and theoretically amendatory luminous efficiency reaches 4 times.So far, well-known Phosphorescent light-emitting materials have iridium (III) complexing species and carbazoles material, studying novel phosphor material recently.
The principle of organic electroluminescent phenomenon is, when between cathode and anode there are when organic thin film layer, if to two Apply voltage between electrode, then injects electrons and holes from cathode and anode to organic thin film layer respectively.To organic thin film layer Injected electrons and hole recombination are simultaneously formed exciton (exciton), and exciton falls to ground state again and shines.Utilize this original The organic electroluminescence device of reason can usually be constituted by being located at cathode and anode and the organic thin film layer between them, for example, by Organic thin film layer including hole injection layer, hole transmission layer, luminescent layer, electron transfer layer is constituted.
As the material used in organic electroluminescence device, most of is to make pure organic matter or by organic matter and metal The complex compound for forming complexing, can be divided into hole-injecting material, hole mobile material, luminescent material, electron-transport material depending on the application Material, electron injection material etc..Wherein, hole-injecting material or hole mobile material be as the organic material with p-type property, That is, main use is easy to oxidation and the organic matter with electrochemically stable state in oxidation.On the other hand, electron injection material Or electron transport material is as the organic material with n-type property, that is, main use is easy to restore and has electricity in reduction The organic matter of chemically stable state.Emitting layer material is as the material simultaneously with p-type property and n-type property, that is, preferably To be preferably converted into the tool of light when forming exciton in the material for aoxidizing with all having stable state under reducing condition There is the material of high-luminous-efficiency.Therefore, the art needs to develop the new organic materials for having condition as described above.
Summary of the invention
The technical problem to be solved in the present invention
An example of the invention, which provides, to be had energy level appropriate, electrochemical stability and thermal stability and is included in 3- hexichol And the compound of the connexon between furans and triazine with heteroaryl substituent.
It includes upper with heteroaryl substituent between 3- dibenzofurans and triazine that another example of the invention, which provides, State the organic electroluminescence device of connexon.
Technical solution
In an example of the invention, the 3- dibenzofurans based triazine derivative that providing is indicated by following chemical formula a has Machine compound:
Chemical formula a:
In above-mentioned chemical formula a, L is singly-bound or phenylene, Ar1For the heteroaryl of substituted or unsubstituted C3-C60, Above-mentioned Ar1Substituent group in substituted situation is selected from by the alkyl of C1~C30, the aryl of C6~C30 and their combination One of group of composition, Ar2And Ar3It is separately the aryl of substituted or unsubstituted C6-C60, substituted or unsubstituted The heteroaryl of C3-C60, in above-mentioned Ar1And Ar2Substituent group in substituted situation be selected from by C1~C30 alkyl, C6~ One of the aryl of C30, the heteroaryl of C5~C30 and group of their combination composition.
Specifically, above-mentioned Ar1It can be selected from one of pyridine, quinoline, isoquinolin or phenanthridinyl.
Specifically, above-mentioned Ar2And above-mentioned Ar3It can separately be phenyl, naphthalene, xenyl, phenanthryl, fluorenyl, spiro fluorene Base, benzothienyl, benzofuranyl, dibenzofuran group, dibenzothiophene, terphenyl, pyridyl group, phenylpyridyl Or pyrimidine radicals.
Above-mentioned organic compound can be used as luminescent layer, hole blocking layer, electronics in material for organic electroluminescent device The substance of transport layer or electron injecting layer.
In another example of the invention, following organic electroluminescence device is provided, that is, press from both sides between cathode and anode There is at least one organic thin film layer, above-mentioned organic thin film layer has the multilayered structure including at least one luminescent layer, above-mentioned to shine At least one layer in layer or the above-mentioned organic thin film layer other than above-mentioned luminescent layer includes above-mentioned 3- dibenzofuran group three One of oxazine derivatives organic compound or two or more mixtures.
Also, provide following device, that is, above-mentioned organic thin film layer is between cathode and luminescent layer, including has electricity The electron transporting zone of at least one of sub- implanted layer, electron transfer layer, functional layer, buffer layer and hole blocking layer, it is above-mentioned Functional layer has the function of electronics injecting function and electron-transport simultaneously.
Beneficial effect
Above-mentioned 3- dibenzofurans based triazine derivative compound can first-class meet in organic electroluminescence device In condition, such as energy level appropriate, electrochemical stability and thermal stability needed for the substance that can be used etc., according to substituent group It can play the role of a variety of needed for the organic electroluminescence device.
Detailed description of the invention
Fig. 1 and Fig. 2 be show it is related with the organic electroluminescence device prepared in embodiment 1~11 and the Comparative Examples 1 to 5 The life characteristic appraisal curve figure of measurement result.
Fig. 3 is survey related with the organic electroluminescence device prepared in embodiment 12~14 and comparative example 2 and comparative example 6 Determine the life characteristic appraisal curve figure of result.
Specific embodiment
Hereinafter, the example that the present invention will be described in detail.But these examples only propose that the present invention is simultaneously unlimited as illustrating Due to this, the range of range should be claimed based on aftermentioned invention to define in the present invention.
In the present specification, unless otherwise defined, the case where " substitution " include the alkyl of selected free C1-C12, amino, Itrile group, the naphthenic base of C3-C7, the alkenyl of C2-C12, the cycloalkenyl of C3-C7, the alkynyl of C2-C50, the cycloalkynyl radical of C5-C50, cyanogen Base, the alkoxy of C1-C12, the aryl of C6-C60 and C7-C60 aralkyl and their combination composition group in substituent group The case where substitution.
In the present specification, unless otherwise defined, " their combination " refer to more than two substituent groups by linker come It combines, or more than two substituent groups are by being condensed the state combined.
In the present specification, unless otherwise defined, " miscellaneous " refers to that a compound or substituent group include hetero atom, above-mentioned miscellaneous Atom can be for selected from one of the group being made of N, O, S, P and their combination.For example, can refer to following situation, that is, on It states a compound or substituent group includes 1 to 3 hetero atom, and remaining is carbon.
In an example of the invention, the novel 3- dibenzofuran group triazine derivatives indicated by following chemical formula a are provided Object organic compound:
Chemical formula a:
In above-mentioned chemical formula a, L is singly-bound or phenylene, Ar1For the heteroaryl of substituted or unsubstituted C3-C60, Above-mentioned Ar1Substituent group in substituted situation is selected from by the alkyl of C1~C30, the aryl of C6~C30 and their combination One of group of composition, Ar2And Ar3It is separately the aryl of substituted or unsubstituted C6-C60, substituted or unsubstituted The heteroaryl of C3-C60, in above-mentioned Ar1And Ar2Substituent group in substituted situation be selected from by C1~C30 alkyl, C6~ One of the aryl of C30, the heteroaryl of C5~C30 and group of their combination composition.
Specifically, Ar1It can be pyridine, quinoline, isoquinolin or phenanthridinyl.
Specifically, Ar2To Ar3It can separately be phenyl, naphthalene, xenyl, phenanthryl, fluorenyl, Spirofluorene-based, benzo Thienyl, benzofuranyl, dibenzofuran group, dibenzothiophene, terphenyl, pyridyl group, phenylpyridyl or pyrimidine Base.
For example, above-mentioned 3- dibenzofurans based triazine derivative organic compound can for recorded in following table 11 to One of 130 compounds.
Table 1
Above-mentioned 3- dibenzofurans based triazine derivative compound is in the case where being used as organic electroluminescence device, equal energy Condition needed for enough first-class meeting the substance that can be used in organic electroluminescence device, such as energy level appropriate, electrification Learn stability and thermal stability etc., according to substituent group can play the role of in organic electroluminescence device needed for it is a variety of.
In another example of the invention, following organic electroluminescence device is provided, that is, press from both sides between cathode and anode There is at least one organic thin film layer, above-mentioned organic thin film layer has the multilayered structure including at least one luminescent layer, above-mentioned to shine At least one layer in layer or the above-mentioned organic thin film layer other than above-mentioned luminescent layer includes above-mentioned 3- dibenzofuran group three One of oxazine derivatives organic compound or two or more mixtures.
Included in the above-mentioned 3- dibenzofurans based triazine derivative of the organic thin film layer of above-mentioned organic electroluminescence device Compound is the compound indicated by above-mentioned chemical formula a, and relative detailed description is as described above.
In one example, according to required purposes, above-mentioned organic thin film layer can be uitably included selected from by hole blocking layer, hair One or more of photosphere, electron transfer layer and group of electron injecting layer composition.
In another example, above-mentioned organic thin film layer is between cathode and luminescent layer, it may include have electron injecting layer, The electron transporting zone of at least one of electron transfer layer, functional layer, buffer layer and hole blocking layer, above-mentioned functional layer is simultaneously Have the function of electronics injecting function and electron-transport.
Above-mentioned hole injection layer, hole transmission layer, functional layer, buffer layer, electronic barrier layer, luminescent layer, hole blocking layer, Electron transfer layer, electron injecting layer etc. can be formed respectively using well known substance or they one or more of may include More than one 3- dibenzofurans based triazine derivative compounds indicated by above-mentioned chemical formula a.
With the 3- dibenzofuran group triazine derivatives indicated by above-mentioned chemical formula a for being included in above-mentioned organic thin film layer The relevant detailed description of compounds is as described above.
Hereinafter, being recorded to the embodiment of the present invention and comparative example.These following embodiments are only a realities of the invention Example is applied, the present invention is not limited to following embodiments.
Embodiment
Hereinafter, particular instantiation is carried out to reaction example and comparative example, but the present invention is not limited to following reaction examples and realities Apply example.In following reaction examples, to mark midbody compound in such a way that the number of final product adds sequence number.For example, Compound 1 is labeled as compound [1], and by the midbody compound of above compound labeled as [1-1] etc..In this specification In, the number of compound is recorded in the number of the chemical formula of above-mentioned table 1.For example, the change that will be indicated by 1 in table 1 Conjunction substance markers are compound 1.
Reaction equation 1
The preparation of midbody compound [6-1]
Into the reaction flask of 3L put into 100g (542.27mmol, 1.0eq) 2,4,6- tri- chloro-1,3,5-triazines, The anhydrous tetrahydro furan of 800ml (8ml/g) is stirred under nitrogen atmosphere with 0 DEG C of temperature.It is slowly added 97.93ml (1M Solution in THF, 1.0eq) phenyl-magnesium-bromide and warm naturally to room temperature, stir 1 hour.To 2N- hydrochloride water After adding reaction solution in solution, cleaned using methylene chloride, distilled water.It is filtered using anhydrous magnesium sulfate drying and by silica gel, It after filtered fluid is concentrated under reduced pressure, is recrystallized using methylene chloride, hexane, to be prepared for the rice of 98g (80%) The midbody compound [6-1] of color solid.
The preparation of midbody compound [6-2]
Compound [6-1], the 90.14g of 98g (433.51mmol, 1.0eq) are put into the reaction flask of 3L The anhydrous tetrahydro furan of [1,1 '-the biphenyl] -4- base-boric acid of (455.19mmol, 1.05eq), 785ml (8ml/g), in nitrogen Under atmosphere, stirred with 50 DEG C of temperature.50 DEG C at a temperature of, be added 10g (8.67mmol, 0.02eq) tetrakis triphenylphosphine palladium (0), after potassium carbonate and addition that 119.83g (867.03mmol, 2.0eq) is dissolved in the distilled water of 200ml, return stirring mistake Night.Reaction solution is cooled to room temperature and is filtered.Solid is cleaned using methanol, distilled water.It is recrystallized using toluene, thus It is prepared for the midbody compound [6-2] of the beige solid of 96g (65%).
The preparation of midbody compound [6-3]
Compound [6-2], the 98.54g of 96g (279.22mmol, 1.0eq) are put into the reaction flask of 3L Isosorbide-5-Nitrae-the dioxane of (the bromo- 5- chlorphenyl of the 3-) boric acid of (418.84mmol, 1.5eq), 770ml (8ml/g), in nitrogen atmosphere Under, it is stirred with 60 DEG C of temperature.60 DEG C at a temperature of, be added 6.45g (5.58mmol, 0.02eq) tetrakis triphenylphosphine palladium (0), after potassium carbonate and addition that 57.89g (418.84mmol, 1.5eq) is dissolved in the distilled water of 150ml, return stirring mistake Night.Reaction solution is cooled to room temperature and is filtered.Solid is cleaned using methanol, distilled water.It is recrystallized using toluene, thus It is prepared for the midbody compound [6-3] of the beige solid of 83g (60%).
The preparation of midbody compound [6-4]
Compound [6-3], the 78.53g of 83g (352.79mmol, 1.0eq) are put into the reaction flask of 3L Dibenzo [b, the d] furans -3- base of (370.43mmol, 1.05eq)] boric acid, 800ml (10ml/g) anhydrous tetrahydro furan, Under nitrogen atmosphere, stirred with 50 DEG C of temperature.50 DEG C at a temperature of, be added 8.15g (7.06mmol, 0.02eq) four (triphens Base phosphine) palladium (0), after the sodium hydroxide of 42.33g (1058.36mmol, 3.0eq) and addition are dissolved in the distilled water of 160ml, Return stirring is stayed overnight.Reaction solution is cooled to room temperature and is filtered.Solid is cleaned using methanol, distilled water.It is carried out again using toluene Crystallization, to be prepared for the midbody compound [6-4] of the beige solid of 124g (60%).
The preparation of midbody compound [6-5]
The compound [6-4] of investment 124g (211.58mmol, 1.0eq), 4,4,4 ', 4 ', 5 into the reaction flask of 3L, 5,5 ', 5 '-prestox -2, anhydrous tetrahydro furan, the 1.43g of 2 '-bis- (1,3,2- bis- evil borines), 1000ml (8ml/g) The 2- dicyclohexyl phosphorus -2 ' of the acid chloride of (6.35mmol, 0.03eq), 6.05g (12.69mmol, 0.06eq), 4 ', 6 '-three is different The potassium acetate of pentylbiphenyl (trade name Xphos), 62.3g (634.73mmol, 3.0eq), under nitrogen atmosphere, return stirring 2 Hour.Reaction solution is cooled to room temperature, and is cleaned using chloromethanes, distilled water.Using anhydrous magnesium sulfate drying and pass through silica gel Filtering, after filtered fluid is concentrated under reduced pressure, is recrystallized using acetone, hexane, to be prepared for the rice of 98g (80%) The midbody compound [6-5] of color solid.
The preparation of compound [6]
Compound [6-5], the 2.32ml of 15g (22.14mmol, 1.0eq) are put into the reaction flask of 1L The 2- bromopyridine of (24.35mmol, 1.1eq), the anhydrous tetrahydro furan of 450ml (30ml/g), 0.1g (0.44mmol, 0.02eq) Palladium (2) acetate, 0.42g (0.89mmol, 0.04eq) 2- dicyclohexyl phosphorus -2 ', 4 ', 6 '-tri isopropyl biphenyls, in nitrogen Under atmosphere, stirred with 50 DEG C of temperature.50 DEG C at a temperature of, in the distilled water of 90ml dissolve 14.1g (66.41mmol, After potassium phosphate 3.0eq) and addition, return stirring 2 hours.Reaction solution is cooled to room temperature and is filtered.Utilize methanol, distilled water Clean solid.It is recrystallized using anhydrous tetrahydro furan, to be prepared for the target of the white solid of 11.13g (80%) Compound [6].
The preparation of compound [86]
Into the reaction flask of 1L put into 15g (22.14mmol, 1.0eq) compound [6-5], (24.35mmol, Palladium (2) second of the anhydrous tetrahydro furan of 4- bromo-isoquinoline, 450ml (30ml/g) 1.1eq), 0.1g (0.44mmol, 0.02eq) The 2- dicyclohexyl phosphorus -2 ' of hydrochlorate, 0.42g (0.89mmol, 0.04eq), 4 ', 6 '-tri isopropyl biphenyls, under nitrogen atmosphere, with 50 DEG C of temperature stirring.50 DEG C at a temperature of, in the distilled water of 90ml dissolve 14.1g (66.41mmol, 3.0eq) phosphorus After sour potassium and addition, return stirring 2 hours.Reaction solution is cooled to room temperature and is filtered.Solid is cleaned using methanol, distilled water. It is recrystallized using toluene, to be prepared for the target compound [86] of the white solid of 11.26g (75%).
The preparation of compound [96]
Compound [6-5], the 5.07g of 15g (22.14mmol, 1.0eq) are put into the reaction flask of 1L The 2- bromoquinoline of (24.35mmol, 1.1eq), 450ml (30ml/g) anhydrous tetrahydro furan, 0.1g (0.44mmol, 0.02eq) The 2- dicyclohexyl phosphorus -2 ' of palladium (2) acetate, 0.42g (0.89mmol, 0.04eq), 4 ', 6 '-tri isopropyl biphenyls, in nitrogen Under atmosphere, stirred with 50 DEG C of temperature.50 DEG C at a temperature of, in the distilled water of 90ml dissolve 14.1g (66.41mmol, After potassium phosphate 3.0eq) and addition, return stirring 2 hours.Reaction solution is cooled to room temperature and is filtered.Utilize methanol, distilled water Clean solid.It is recrystallized using toluene, to be prepared for the target compound of the white solid of 10.52g (70%) [96]。
Reaction equation 2
The preparation of compound [77]
Pass through method identical with reaction equation 1 and utilizes with 2- naphthalene vinyl boric acid instead of using [1,1 '-biphenyl] -4- Base-boric acid is come the compound [77-5] of the 10g (15.35mmol, 1.0eq) prepared, the 3- of 3.51g (16.88mmol, 1.1eq) Bromo-isoquinoline is prepared for the target compound [77] of the white solid of 7.9g (79%).
Reaction equation 3
The preparation of compound [1]
As starting material and pass through method identical with reaction equation 1 using using the chloro- 4,6- diphenyl -1,3,5- triazine of 2- The 2- bromine pyrrole of the midbody compound [1-3] of the 10g (16.62mmol, 1.0eq) of preparation, 1.74ml (18.29mmol, 1.1eq) Pyridine is prepared for the target compound [1] of 7.26g (79%) white solid.
The preparation of compound [21]
Utilize the midbody compound of the 10g (16.62mmol, 1.0eq) prepared by method identical with reaction equation 3 The 3- bromopyridine of [1-3], 1.79ml (18.29mmol, 1.1eq) are prepared for the target chemical combination of the white solid of 7.35g (80%) Object [21].
The preparation of compound [61]
Utilize the midbody compound of the 10g (16.62mmol, 1.0eq) prepared by method identical with reaction equation 3 The 1- bromo-isoquinoline of [1-3], 3.8g (18.29mmol, 1.1eq) are prepared for the target chemical combination of the white solid of 7.61g (76%) Object [61].
The preparation of compound [81]
Utilize the midbody compound of the 10g (16.62mmol, 1.0eq) prepared by method identical with reaction equation 3 The 4- bromo-isoquinoline of [1-3], 3.8g (18.29mmol, 1.1eq) (18.29mmol, 1.1eq) are prepared for the white of 7.51g (75%) The target compound [81] of color solid.
The preparation of compound [121]
Utilize the midbody compound of the 10g (16.62mmol, 1.0eq) prepared by method identical with reaction equation 3 The 6- bromine phenanthridines of [1-3], 4.72g (18.29mmol, 1.1eq) are prepared for the target compound of the white solid of 7.05g (65%) [121]。
The preparation of compound [127]
Utilize the midbody compound of the 10g (16.62mmol, 1.0eq) prepared by method identical with reaction equation 3 The 7- bromoquinoline of [1-3], 3.8g (18.29mmol, 1.1eq) are prepared for the target compound of the white solid of 7.01g (70%) [127]。
Reaction equation 4
The preparation of compound [45]
Using by 2,4- bis- ([1,1 '-biphenyl) -4- base) -6- chloro-1,3,5-triazines as starting material and by with it is anti- Midbody compound [45-3], the 1.44ml for the 10g (13.26mmol, 1.0eq) for answering the identical method of formula 1 to prepare The 4- bromopyridine of (14.59mmol, 1.1eq) is prepared for the target compound [45] of the white solid of 6.55g (70%).
Reaction equation 5
The preparation of compound [39]
Using by 2- (3- bromophenyl) -4,6- diphenyl -1,3,5-triazines as starting material and by with 1 phase of reaction equation With the midbody compound [39-3] of 10g (14.76mmol, 1.0eq) of method preparation, 1.59ml (16.23mmol, 3- bromopyridine 1.1eq) is prepared for the target compound [39] of the white solid of 7.42g (80%).
The preparation of compound [110]
Pass through method identical with reaction equation 5 and utilizes compound [39-3], the 3.38g of 10g (14.76mmol, 1.0eq) The 3- bromoquinoline of (16.23mmol, 1.1eq) is prepared for the target compound [110] of the white solid of 7.21g (72%).
The preparation of compound [120]
Pass through method identical with reaction equation 5 and utilizes compound [39-3], the 3.38g of 10g (14.76mmol, 1.0eq) The 4- bromoquinoline of (16.23mmol, 1.1eq) is prepared for the target compound [120] of the white solid of 7g (70%).
Compound 1 is prepared for the preparation method of reaction equation 5 to compound 130, in following table according to above-mentioned reaction equation 1 Its result is shown in 2.
Table 2
Comparative example compound
Chemical formula b:
Chemical formula c:
Chemical formula d:
Chemical formula e:
Comparative example 1
The compound f indicated by following chemical formula f is used as Day-Glo blue host, the chemical combination indicated by following chemical formula g Object g is used as Day-Glo blue dopant, 2-TNATA (4,4', 4 "-three (N- naphthalene -2- base)-N- phenylaminos-triphenylamine (4,4 ', 4 "-tris (N-naphthalen-2-yl)-N-phenylamino)-triphenylamine)) it is used as hole injection layer substance, By α-NPD (N, N'- bis- (naphthalene -1- base)-N, N'- diphenylbenzidine (N, N '-di (naphthalene-1-yl)-N, N ' - Diphenylbenzidine)) it is used as hole transmission layer substance, is thus prepared for the organic luminescent device having the following structure: ITO/2-TNATA (60nm)/α-NPD (30nm)/compound f+ compound g (30nm)/Alq3(25nm)/Liq(1nm)/Al (100nm)。
Use following anode, that is, by 15 Ω of Corning Incorporated (Corning)/cm2() ito glass substrate cuts It is cut into 25mm × 25mm × 0.7mm size, respectively in acetone isopropanol and pure water after ultrasonic cleaning 15 minutes, into Row 30 minutes ultraviolet (UV) ozone cleans.The sky of 60nm thickness is formed in the top vacuum evaporation 2-TNATA of aforesaid substrate Cave implanted layer.The hole transmission layer of 30nm thickness is formed in the top vacuum evaporation α-NPD of above-mentioned hole injection layer.Above-mentioned The top vacuum evaporation of hole transmission layer is by the chemical formula f compound indicated and the compound indicated by chemical formula g (doping rate: 4 Weight percent) form the luminescent layer of 30nm thickness.Then, on the top of above-mentioned luminescent layer with the thickness vacuum evaporation of 25nm Alq3Compound forms electron transfer layer.The top of above-mentioned electron transfer layer successively vacuum evaporation 1nm Liq (electronics note Enter layer) and the Al (cathode) of 100nm prepare organic luminescent device as shown in table 3.It is referred to as comparative sample 1.
Chemical formula f:
Chemical formula g:
BCP:
Alq3:
Comparative example 2~5
In above-mentioned comparative example 1, electron transfer layer compound Alq is replaced using following compound b, c, d and e respectively3, Thus it is prepared for the organic luminescent device having the following structure: ITO/2-TNATA (60nm)/α-NPD (30nm)/compound f+ization Close object g (30nm)/compound b, c, d or e (25nm)/Liq (1nm)/Al (100nm).Comparative example 2 is referred to as to comparing Example 5.
Comparative example 6
In addition to electron transfer layer use above compound b and as cave barrier layer compound vapor deposition 5nm above-mentioned BCP with Outside, organic luminescent device is prepared in method identical with above-mentioned comparative example 1.It is referred to as comparative example 6.
Embodiment 1~11
It is logical in addition to making synthesized compound 1,21,45,61,81,121,127,6,77,86,96 as shown in Table 1 above Sublimation purification process is crossed to replace Alq respectively3And be used as other than electron transfer layer, with method system identical with above-mentioned comparative example 1 Standby organic luminescent device, and be shown in table 3.Embodiment 1 is referred to as to embodiment 11.
Embodiment 12~14
In addition to making synthesized compound 39,110,120 as shown in Table 1 above by sublimation purification process come generation respectively It is used as other than hole blocking layer for compound BCP, prepares organic luminescent device in method identical with above-mentioned comparative example 6, and It is shown in table 3.Embodiment 12 is referred to as to embodiment 14.
Evaluate example 1: the characteristics of luminescence and life assessment of comparative example 1~6 and embodiment 1~14
For comparative example 1~6 and embodiment 1~14, utilize Keithley digital sourcemeter (Keithley sourcemeter) " 2400 ", Konica Minolta (KONIKA MINOLTA) " CS-2000 " have rated luminescence peak, luminous efficiency, utilize arteries and veins The M6000S biometrics device of scientific (mcscience) company and initial stage brightness (L with 1000nit0) on the basis of, it measures bright Degree (L) reaches for 97% time (LT97), its result is shown in following table 3 and Fig. 1 to Fig. 3.
Table 3
As shown in Table 3 above, compared with the Comparative Examples 1 to 5, embodiment 1~11 presents low voltage drive and is improved The characteristics of luminescence.Also, when using hole blocking layer, low voltage drive is also presented, the characteristics of luminescence that is improved and longevity Order characteristic.
Fig. 1 and Fig. 2 be show it is related with the organic electroluminescence device prepared in embodiment 1~11 and the Comparative Examples 1 to 5 The life characteristic appraisal curve figure of said determination result.
Fig. 3 is on related with the organic electroluminescence device prepared in embodiment 12~14 and comparative example 2 and comparative example 6 State the life characteristic appraisal curve figure of measurement result.
As shown in Table 3 above, compared with comparative example 1~6, embodiment 1~14 presents the life characteristic being improved.Especially It, the above compound for importing the pyrrolotriazine derivatives of the connexon in 3- dibenzofuran group with heteroaryl substituent is presented Outstanding performance and service life.
More than, multiple preferred embodiments of the invention are described in detail, but invention of the invention is claimed It's not limited to that for range, and field technical staff utilizes basic conception of the invention defined in the claimed range of invention Various deformation and improvement form to carry out also belong to invention of the invention and range are claimed.

Claims (7)

1. a kind of 3- dibenzofurans based triazine derivative organic compound, which is characterized in that indicated by following chemical formula a:
Chemical formula a:
In above-mentioned chemical formula a,
L be singly-bound or phenylene,
Ar1For the heteroaryl of substituted or unsubstituted C3-C60, in above-mentioned Ar1Substituent group in substituted situation be selected from by One of the alkyl of C1~C30, the aryl of C6~C30 and group of their combination composition,
Ar2And Ar3It is separately the heteroaryl of the aryl of substituted or unsubstituted C6-C60, substituted or unsubstituted C3-C60 Base, in above-mentioned Ar1And Ar2Substituent group in substituted situation is aryl, C5 selected from alkyl, C6~C30 by C1~C30 One of the group of heteroaryl and the their combination composition of~C30.
2. 3- dibenzofurans based triazine derivative organic compound according to claim 1, which is characterized in that Ar1For pyrrole Pyridine, quinoline, isoquinolin or phenanthridinyl.
3. 3- dibenzofurans based triazine derivative organic compound according to claim 1, which is characterized in that Ar2And Ar3It is separately phenyl, naphthalene, xenyl, phenanthryl, fluorenyl, Spirofluorene-based, benzothienyl, benzofuranyl, dibenzo Furyl, dibenzothiophene, terphenyl, pyridyl group, phenylpyridyl or pyrimidine.
4. 3- dibenzofurans based triazine derivative organic compound according to claim 1, which is characterized in that above-mentionedization Formula a is one of following 1 to 130:
5. 3- dibenzofurans based triazine derivative organic compound according to claim 1, which is characterized in that above-mentioned 3- Dibenzofurans based triazine derivative organic compound is used as luminescent layer, hole barrier in material for organic electroluminescent device The substance of layer, electron transfer layer or electron injecting layer.
6. a kind of organic electroluminescence accompanies at least one organic thin film layer, above-mentioned organic electroluminescence between cathode and anode Luminescent device is characterized in that,
Above-mentioned organic thin film layer has the multilayered structure including at least one luminescent layer,
At least one layer in above-mentioned luminescent layer or above-mentioned organic thin film layer other than above-mentioned luminescent layer includes claim 1 To one of 3- dibenzofurans based triazine derivative organic compound or two or more mixing described in any one of 5 Object.
7. organic electroluminescence device according to claim 6, which is characterized in that above-mentioned organic thin film layer between cathode with Between luminescent layer, including at least one in electron injecting layer, electron transfer layer, functional layer, buffer layer and hole blocking layer The electron transporting zone of kind, above-mentioned functional layer have the function of electronics injecting function and electron-transport simultaneously.
CN201711318649.8A 2017-09-29 2017-12-12 3- dibenzofurans based triazine derivative organic compound and the organic electroluminescence device comprising it Pending CN109575001A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020170127512A KR102001425B1 (en) 2017-09-29 2017-09-29 Dibenzofuranyl trazine derivative organic compounds and organic electroluminescent device including the same
KR10-2017-0127512 2017-09-29

Publications (1)

Publication Number Publication Date
CN109575001A true CN109575001A (en) 2019-04-05

Family

ID=65919377

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711318649.8A Pending CN109575001A (en) 2017-09-29 2017-12-12 3- dibenzofurans based triazine derivative organic compound and the organic electroluminescence device comprising it

Country Status (2)

Country Link
KR (1) KR102001425B1 (en)
CN (1) CN109575001A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112341447A (en) * 2020-09-29 2021-02-09 烟台京师材料基因组工程研究院 Electron transport material, organic electroluminescent device and display device
CN112480069A (en) * 2019-09-11 2021-03-12 Cmdl有限公司 Organic light emitting compound and organic electroluminescent device comprising the same
CN112707871A (en) * 2019-10-25 2021-04-27 常州强力昱镭光电材料有限公司 Electronic active material, exciplex, organic electroluminescent device and application
CN113004295A (en) * 2021-03-11 2021-06-22 吉林奥来德光电材料股份有限公司 Triazine electron transport material, preparation method and application thereof
CN113227078A (en) * 2018-12-21 2021-08-06 斗山索如始株式会社 Organic light-emitting compound and organic electroluminescent element using same
CN113234010A (en) * 2021-05-07 2021-08-10 烟台显华化工科技有限公司 Compound, electron transport material, organic electroluminescent device and display device
CN113402498A (en) * 2021-08-19 2021-09-17 浙江华显光电科技有限公司 Spirobifluorene compound, preparation, organic light-emitting device, and display or lighting device

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102537419B1 (en) * 2019-11-04 2023-05-25 주식회사 엘지화학 Novel compound and organic light emitting device comprising the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103764786A (en) * 2011-05-03 2014-04-30 罗门哈斯电子材料韩国有限公司 Novel organic electroluminescent compounds and an organic electroluminescent device using the same
WO2014208755A1 (en) * 2013-06-28 2014-12-31 東ソー株式会社 Cyclic azine compound, method for producing same, and organic electroluminescent element using same
US20150249221A1 (en) * 2014-03-01 2015-09-03 Universal Display Corporation Organic electroluminescent materials and devices
KR20150129282A (en) * 2014-05-09 2015-11-19 주식회사 엠비케이 Novel compoung for organic electroluminescent device, organic electroluminescent device including the same and electric apparatus
CN106883220A (en) * 2017-01-17 2017-06-23 北京大学深圳研究生院 A kind of navy blue heat lag luminous organic material and its preparation method and application
KR20170089599A (en) * 2016-01-27 2017-08-04 에스에프씨 주식회사 Novel heterocyclic compounds and organic light-emitting diode including the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102154878B1 (en) * 2014-12-02 2020-09-10 두산솔루스 주식회사 Organic compounds and organic electro luminescence device comprising the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103764786A (en) * 2011-05-03 2014-04-30 罗门哈斯电子材料韩国有限公司 Novel organic electroluminescent compounds and an organic electroluminescent device using the same
WO2014208755A1 (en) * 2013-06-28 2014-12-31 東ソー株式会社 Cyclic azine compound, method for producing same, and organic electroluminescent element using same
US20150249221A1 (en) * 2014-03-01 2015-09-03 Universal Display Corporation Organic electroluminescent materials and devices
KR20150129282A (en) * 2014-05-09 2015-11-19 주식회사 엠비케이 Novel compoung for organic electroluminescent device, organic electroluminescent device including the same and electric apparatus
KR20170089599A (en) * 2016-01-27 2017-08-04 에스에프씨 주식회사 Novel heterocyclic compounds and organic light-emitting diode including the same
CN106883220A (en) * 2017-01-17 2017-06-23 北京大学深圳研究生院 A kind of navy blue heat lag luminous organic material and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李楠主编: "《有机化学第2版》", 31 December 2007, 中国农业出版社 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113227078A (en) * 2018-12-21 2021-08-06 斗山索如始株式会社 Organic light-emitting compound and organic electroluminescent element using same
CN112480069A (en) * 2019-09-11 2021-03-12 Cmdl有限公司 Organic light emitting compound and organic electroluminescent device comprising the same
CN112707871A (en) * 2019-10-25 2021-04-27 常州强力昱镭光电材料有限公司 Electronic active material, exciplex, organic electroluminescent device and application
CN112707871B (en) * 2019-10-25 2022-08-19 常州强力昱镭光电材料有限公司 Electronic active material, exciplex, organic electroluminescent device and application
CN112341447A (en) * 2020-09-29 2021-02-09 烟台京师材料基因组工程研究院 Electron transport material, organic electroluminescent device and display device
CN112341447B (en) * 2020-09-29 2022-12-06 烟台京师材料基因组工程研究院 Electron transport material, organic electroluminescent device and display device
CN113004295A (en) * 2021-03-11 2021-06-22 吉林奥来德光电材料股份有限公司 Triazine electron transport material, preparation method and application thereof
CN113004295B (en) * 2021-03-11 2022-07-19 吉林奥来德光电材料股份有限公司 Triazine electron transport material, preparation method and application thereof
CN113234010A (en) * 2021-05-07 2021-08-10 烟台显华化工科技有限公司 Compound, electron transport material, organic electroluminescent device and display device
CN113402498A (en) * 2021-08-19 2021-09-17 浙江华显光电科技有限公司 Spirobifluorene compound, preparation, organic light-emitting device, and display or lighting device
CN113402498B (en) * 2021-08-19 2022-03-11 浙江华显光电科技有限公司 Spirobifluorene compound, preparation, organic light-emitting device, and display or lighting device

Also Published As

Publication number Publication date
KR20190037808A (en) 2019-04-08
KR102001425B1 (en) 2019-07-18

Similar Documents

Publication Publication Date Title
CN109575001A (en) 3- dibenzofurans based triazine derivative organic compound and the organic electroluminescence device comprising it
CN110615759B (en) Compound, photoelectric conversion device, and electronic device
JP5063992B2 (en) Novel di (pyridylphenyl) derivative, electron transport material comprising the same, and organic electroluminescence device including the same
CN102803437B (en) Compound for organic photoelectric device and organic photoelectric device including same
KR101787850B1 (en) Benzo-fused thiophene or benzo-fused furan compounds comprising a triphenylene group
CN105670610B (en) The compound of organic photoelectric device and organic photoelectric device comprising the compound
KR102232993B1 (en) Organic electroluminescence element
CN102482279B (en) Organic electronic device and compound thereof and terminating machine
KR101631079B1 (en) Organic electroluminescent element
EP1221434A1 (en) Hydrocarbon compound, material for organic electroluminescent element and organic electroluminescent element
CN109690804A (en) Organnic electroluminescent device including electron transfer layer and electron buffer layer
JP2010021561A (en) New blue illuminator used for organic electroluminescent element
JP2002234888A (en) Amine compound and organic electroluminescent element containing the same compound
KR20080010186A (en) Anthracene derivatives, organic electronic devices using the same and electronic apparatuses comprising the same
CN108218842A (en) Spiro fluorene xanthene derivative compound and the organic electroluminescence device for including it
CN105431424A (en) Compound, material for organic electroluminescent element, ink composition, organic electroluminescent element, electronic device, and method for producing compound
CN108003038A (en) A kind of indeno phenanthrene compound and preparation method thereof and organic electroluminescence device
CN110078755A (en) Compound, display panel and display device
JP2003151773A (en) Light emitting element
CN102099942A (en) Cyclic phosphazene compounds and use thereof in organic light emitting diodes
JP2009170814A (en) Quinoxaline derivative and organic electroluminescent element containing the same
JP2009001499A (en) Aromatic hydrocarbon compound, and organic electroluminescent device comprising the aromatic hydrocarbon compound
JP2006056841A (en) Amine compound and organic electroluminescent element containing the amine compound
JP5640460B2 (en) Light emitting device and light emitting device material
KR20140117086A (en) pyrazole derivative and organoelectroluminescent device employing the same

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20190405

RJ01 Rejection of invention patent application after publication