CN106699573A - Spiro-typed organic materials and organic electroluminescent device utilizing the same - Google Patents

Spiro-typed organic materials and organic electroluminescent device utilizing the same Download PDF

Info

Publication number
CN106699573A
CN106699573A CN201610458154.4A CN201610458154A CN106699573A CN 106699573 A CN106699573 A CN 106699573A CN 201610458154 A CN201610458154 A CN 201610458154A CN 106699573 A CN106699573 A CN 106699573A
Authority
CN
China
Prior art keywords
substituted
carbon number
substituted carbon
compound
fluorenes
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.)
Granted
Application number
CN201610458154.4A
Other languages
Chinese (zh)
Other versions
CN106699573B (en
Inventor
郑在皓
朴城珉
金俊佑
全永珉
南相镇
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.)
Continental Electronic Material Co Ltd
Dae Joo Electronic Materials Co Ltd
Material Science Co Ltd
Material Sciences Corp
Original Assignee
Continental Electronic Material Co Ltd
Material Sciences Corp
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 Continental Electronic Material Co Ltd, Material Sciences Corp filed Critical Continental Electronic Material Co Ltd
Publication of CN106699573A publication Critical patent/CN106699573A/en
Application granted granted Critical
Publication of CN106699573B publication Critical patent/CN106699573B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/58—Naphthylamines; N-substituted derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/92—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the nitrogen atom of at least one of the amino groups being further bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic 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
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • 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
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Abstract

The invention relates to an organic material containing spiro (benzo[de]anthracene-7.9'-fluorene) and an organic electroluminescent device utilizing the same, specifically to a new spiro-typed organic material used to an organic electroluminescent device and an organic electroluminescent device having excellent features of low electric power and high efficiency using the organic material.

Description

Volution type organic material and utilize its organic organic electroluminescence devices
Technical field
The present invention relates to new volution type organic compound and utilize its organic organic electroluminescence devices.
Background technology
Organic semiconductor is being researched and developed for the polytype many electronics of application.Filled with existing liquid crystal display Other flat panel displaying elements such as (LCD), plasma display panel (PDP) and Field Emission Display (FED) are put to compare, it is organic electromechanical to cause Luminescent device has many advantages, such as because of simple structure on preparation section, and with brightness high, viewing angle characteristic is outstanding, responds speed Degree is fast, and driving voltage is low and be the flat-panel monitors such as wall-mounted TV (TV) or the back of the body of display just by actively research and development The light source of light, illumination, billboard etc..
In organic organic electroluminescence devices, generally, when DC voltage is applied, from anode injected holes and Recombine to be formed as the exciton of electron-hole pair from negative electrode injected electrons, and transmit above-mentioned by luminescent material The energy of exciton is transformed to light.
In order to improve the efficiency and stability of organic organic electroluminescence devices, since by Eastman Kodak (Eastman Kodak Company) Deng Qingyun (C.W.Tang) etc. reported that cascade type organic matter is constituted between two opposite electrodes was thin The organic organic electroluminescence devices of low voltage drive (C.W.Tang, S.A.Vanslyke, the Applied Physics of film Letters, page 913,1987 of volume 51) since, just actively carrying out to the organic organic electro luminescent device of multi-layer film structure type The research of part organic material.
Generally, organic organic electroluminescence devices have negative electrode (electron injection electrode), anode (hole injection electricity Pole) and the structure including more than one organic layer between above-mentioned two electrode.Now, organic organic electroluminescence devices except Outside luminescent layer (EML, light emitting layer) can be included as organic layer, hole injection layer can also be included (HIL, hole injection layer), hole transporting layer (HTL, hole transport layer), electron supplying layer (ETL, electron transport layer) or electron injecting layer (EIL, electron injection layer) conduct Organic layer, also, in the characteristics of luminescence of luminescent layer, electron-blocking layer (EBL, electron blocking can also be included ) or hole blocking layer (HBL, hole blocking layer) layer.Organic electromechanical cause hair including these all organic layers Optical device has presses anode/hole injection layer/hole transporting layer/electron-blocking layer/luminescent layer/hole blocking layer/electron transport The structure of the order stacking of layer/electron injecting layer/negative electrode.
As the material used in organic organic electroluminescence devices, by pure organic substance or organic substance and metal shape Compound into complex accounts for major part, also, can be divided into hole injecting material, cavity conveying material according to purposes, light Material, electron transport material, electron injection material etc..Here, main use the relatively small organic matter of ionization energy as sky Cave injected material or cavity conveying material.On the other hand, the relatively large organic matter of electronegativity mainly is used as electron injection thing Matter or electron transport material.Luminescent layer includes two kinds of materials of main matter and dopant, and dopant is preferably quantum efficiency Material high, main matter is obtained more than dopant because of energy gap in the way of causing energy transfer to dopant well Design and use.
Moreover it is preferred that the material for being used in organic organic electroluminescence devices also has following property.
First, it is preferable that it is the outstanding material of heat endurance to be used in the material of organic organic electroluminescence devices.This be because It is that Joule heat (joule heating) occurs because of the movement of multiple electric charges in organic organic electroluminescence devices.Currently, mainly With the N of sufficient hole transporting layer material, N '-diphenyl-N, N '-two (3- tolyls) -1,1 '-biphenyl -4,4 '-diamines (TPD) or N, N '-diphenyl-N, N '-two (1- naphthyls) -1,1 '-biphenyl -4,4 '-diamines (NPB) is also because of glass transition temperature (Tg) point Not Wei 60 DEG C and 96 DEG C, it is relatively low, therefore, in the case of being driven in temperature environment high, crystallization can be caused, and occur Reduce the phenomenon of luminous efficiency.
Second, efficient organic organic electroluminescence devices of low voltage drive can be carried out to obtain, it is necessary to smooth Ground is transmitted to injected holes in organic organic electroluminescence devices or multiple electronics to luminescent layer, also, prevents injected sky Cave and multiple electronics depart to outside luminescent layer.Therefore, the material for being used in organic organic electroluminescence devices should have appropriate band Gap (band gap) and highest occupied molecular (HOMO) or minimum csa molecule (LUMO) energy level.
In addition, being used in the material of organic organic electroluminescence devices should have outstanding chemical stability, electric charge to move Shifting rate and with electrode or it is adjacent one layer between surface characteristic etc..Also, with appropriate hole or electron mobility, so that The density of hole and electronics is set to realize equilibrium in the luminescent layer of organic organic electroluminescence devices, such that it is able to make the formation pole of exciton Bigization.
In order that organic organic electroluminescence devices give full play to above-mentioned outstanding feature, organic matter layer is formed in device Material, for example, hole injecting material, cavity conveying material, luminescent substance, electron transport material, electron injection material etc. should be Stabilization and effective material, but up to the present, have not been sufficiently achieved stabilization and effective organic organic electroluminescence devices are with having The research and development of machine material.Therefore, in the technical field of the invention, still need research and development have low voltage drive, high efficiency and Long-life new material.
The content of the invention
It is an object of the present invention in order to provide low electric power, efficient organic organic electroluminescence devices and provide can be with It is applicable the new volution type organic compound for electronics barrier material or cavity conveying material.
First embodiment of the invention provides the compound represented by formula 1 below.
Chemical formula 1：
In above-mentioned chemical formula 1,
R1To R18Separately it is selected from by hydrogen, heavy hydrogen, the alkyl that substituted or non-substituted carbon number is 1 to 30, takes Generation or alkenyl that non-substituted carbon number is 2 to 30, the alkynyl that substituted or non-substituted carbon number is 2 to 24, substitution or Non-substituted carbon number is 3 to 12 cycloalkyl, the Heterocyclylalkyl that substituted or non-substituted carbon number is 2 to 30, substitution Or aralkyl that non-substituted carbon number is 7 to 30, the alkoxy that substituted or non-substituted carbon number is 1 to 30, halogen, Cyano group, nitro, hydroxyl, the aryl that substituted or non-substituted carbon number is 6 to 30, substitution or carbon number be 2 to 30 it is miscellaneous Aryl, the heteroarylalkyl that substituted or non-substituted carbon number is 3 to 30, substituted or non-substituted carbon number are 1 to 30 Alkylamino, the aryl amine that substituted or non-substituted carbon number is 6 to 30, substituted or non-substituted carbon number are 6 to 30 Arylalkylamino, the heteroaryl amido that substituted or non-substituted carbon number is 2 to 24, substituted or non-substituted carbon number be 1 to 30 silicyl, the aryl silane base that substituted or non-substituted carbon number is 6 to 30, substituted or non-substituted carbon number are In the group of functional group's composition that 6 to 30 aryloxy group and formula 2 below is represented,
Simply, R1To R18In it is at least one be the functional group represented by formula 2 below,
Chemical formula 2：
In above-mentioned chemical formula 2,
L is selected from former by singly-bound, the arlydene that substituted or non-substituted carbon number is 6 to 18 and substituted or non-substituted carbon Subnumber is the group of 3 to 18 heteroarylidene composition, or
The R of L and adjacent volution type core1To R18One or more of be connected to form saturation or unsaturation ring, or With adjacent nitrogen (N) atom, Ar1Or Ar2It is connected to form the heterocyclic radical that nuclear atom number is 5 to 18,
Ar1And Ar2Separately it is selected from by hydrogen, heavy hydrogen, the alkyl that substituted or non-substituted carbon number is 1 to 30, takes Generation or alkenyl that non-substituted carbon number is 2 to 30, the alkynyl that substituted or non-substituted carbon number is 2 to 24, substitution or Non-substituted carbon number is the cycloalkyl that 3 to carbon number is 12, the heterocycle that substituted or non-substituted carbon number is 2 to 30 Alkyl, the aralkyl that substituted or non-substituted carbon number is 7 to 30, the virtue that substituted or non-substituted carbon number is 6 to 30 Base, substitution or carbon number are 2 to 30 heteroaryl and heteroarylalkyl that substituted or non-substituted carbon number is 3 to 30 composition Group in,
Ar1And Ar2Separately it is connected with adjacent nitrogen (N) atom and L to form nuclear atom number be 5 to 18 Saturation or unsaturation ring, or be connected with adjacent nitrogen (N) atom and to form the saturation or insatiable hunger that nuclear atom number is 5 to 18 And ring, or in the case where L is singly-bound, Ar1And Ar2Separately it is connected to be formed with nitrogen (N) atom and volution type nuclear phase Saturation or unsaturation ring,
Above-mentioned R1To R18、L、Ar1And Ar2Substitution base can be identical or different substitution base, and be separately selected from By hydrogen, heavy hydrogen, cyano group, nitro, halogen, hydroxyl, the alkyl that substituted or non-substituted carbon number is 1 to 30, substitution or non-take The carbon number in generation be 2 to 30 alkenyl, the alkynyl that substituted or non-substituted carbon number is 2 to 24, carbon number be 3 to carbon Atomicity is 12 cycloalkyl, the Heterocyclylalkyl that substituted or non-substituted carbon number is 2 to 30, substituted or non-substituted carbon original Subnumber is 7 to 30 aralkyl, the aryl that substituted or non-substituted carbon number is 6 to 30, substituted or non-substituted carbon atom Number is 6 to 24 aralkyl, the heteroaryl that substituted or non-substituted carbon number is 2 to 30, substituted or non-substituted carbon atom Number is 3 to 30 heteroarylalkyl, the alkoxy that substituted or non-substituted carbon number is 1 to 30, substituted or non-substituted carbon original Subnumber is 1 to 30 alkylamino, the aryl amine that substituted or non-substituted carbon number is 6 to 30, substituted or non-substituted carbon original Subnumber is 7 to 30 arylalkylamino, the heteroaryl amido that substituted or non-substituted carbon number is 2 to 24, substituted or non-substituted Carbon number is 1 to 30 silicyl, the aryl silane base that substituted or non-substituted carbon number is 6 to 30 and substitution or non-takes The carbon number in generation is the substitution base of one or more of 6 to 30 group of aryloxy group composition.
In the present invention, R1To R18And Ar1To Ar2Can separately be selected from by hydrogen, heavy hydrogen, methyl, ethyl, propyl group, different Propyl alcohol, the tert-butyl group, cyclohexyl, trimethylsilyl, triphenylsilyl, substitution or unsubstituted phenyl, biphenyl, terphenyl, stretch Xenyl, Sanya phenyl, naphthyl, phenanthryl, fluorenyl, pyrenyl, dibenzofuran group, benzofuranyl, benzo thionyl, dibenzo Thiophene, carbazyl, the fluorenyl of volution spiral shell two, anthryl, acenaphthenyl, pyridine radicals, carboline base, quinolyl, isoquinolyl, thianthrene group, 9H- thiophenes Anthryl, ton base, dibenzo dioxy heterocycle hexadienyl, fen xanthyl, 9,9 dimethyl -9,10- dihydroanthracenes, tetralyl, tetramethyl In the group of base indyl and 4a, 9a- dimethyl hexahydro carbazyl composition,
L can be selected from and is made up of singly-bound, phenyl, biphenyl, terphenyl, naphthyl, carbazole, dibenzofurans and dibenzothiophenes Group in.
Second embodiment of the present invention provides organic organic electroluminescence devices, including：First electrode；Second electrode；With And at least one of which organic film, it is arranged between above-mentioned first electrode and above-mentioned second electrode, above-mentioned organic organic electroluminescence devices It is characterised by, compound of the above-mentioned organic film comprising above-mentioned first embodiment.
Preferably, above-mentioned organic film can be luminescent layer, hole injection layer, hole transporting layer or electron-blocking layer.
Hereinafter, the present invention is described in detail.
According to the present invention it is possible to between hole mobile layer and luminescent layer import using volution (benzo [de] anthracene -7.9 ' - Fluorenes) compound of MOLECULE DESIGN is carried out as parent nucleus.
When the hole flowed into luminescent layer and the ratio of electronics are 1:When 1, luminous efficiency can be made to maximize.If hole is not It is combined with electronics, then hole occurs the phenomenon to negative electrode (cathode) side shifting, electronics occurs to anode (anode) sidesway Dynamic phenomenon.From the point of view of the position in hole, occur in the case that energy barrier between luminescent layer and electron injecting layer is small this existing As, and from the point of view of the position of electronics, there is this phenomenon in the case that energy barrier between luminescent layer and hole mobile layer is small, and This problem can by adjust luminescent layer and it is adjacent one layer between energy barrier solve.Cause hole and electronics in luminescent layer The non-constant another reason of ratio be the multiple voltage distribution in organic electric field luminescence device.Just start, apply electric charge it Before, all voltages can apply between two electrodes, but with the rising of applied voltage, can inject electric charge, and hole is piled up Between hole mobile layer and luminescent layer, and electronics is piled up between electronics mobile layer and luminescent layer.Pile up by this way Multiple electric charges can form electric attraction to opposite electric charge so that play a part of to improve the mobility of electronics in hole so that electronics Play a part of the mobility in raising hole.If piling up excessive hole, improve the electron density in luminescent layer, if pile up compared with Few hole, then improve the density in the hole in luminescent layer.In the case of the density for improving electronics in luminescent layer, as solution (below, referred to as the example of scheme, the material with appropriate resistance and energy level is imported between luminescent layer and hole mobile layer " electron-blocking layer (Electron Blocking Layer-EBL) ") come with equalizing charge.It is being designed to above-mentioned electronics resistance In the case of triplet energies of the triplet energies of interlayer more than luminescent layer, with sharp in the inside of luminescent layer aggregation triplet The effect of son, therefore, it can the interaction between the triplet exciton by the inside of luminescent layer and is formed increasing single item Ratio, such that it is able to improve luminous efficiency.In the case where the density in hole is high, the side opposite with the above method can be designed to Method, such that it is able to improve luminous efficiency.
Although compound of the invention can be used in hole mobile layer or electron-blocking layer, can be by different kinds of molecules Design to be used as luminescent layer, electronics mobile layer and coating.
Compound of the invention has can be applicable volution (benzo [de] anthracene -7.9 '-fluorenes) structure and come in parent nucleus (core) Increase the advantage of band gap, especially, because the molecular weight of volution parent nucleus is big compared with other spirane structures, with can greatly improve The advantage of glass transition temperature.Therefore, two substitution amine are imported to above-mentioned parent nucleus, and makes amine replace base that various changes occur, from And can make the energy level of highest occupied molecular that various changes occur.Thus, it is possible to make tin indium oxide (ITO) and hole mobile layer There are various changes in hole injection barrier, also, have appropriate energy level between hole mobile layer and luminescent layer such that it is able to It is adjusted in the way of the exciton formation efficiency in the inside for improving luminescent layer.
Therefore, in a specific example of the present invention, be prepared for have be applicable to hole movement and electron-blocking layer material Volution mother nucleus structure compound.
The compound represented by chemical formula of the invention 1 can be used in the utilization solution operation in addition to evaporation mode Organic Light Emitting Diode (OLED) preparation, and in above-mentioned chemical formula 1, if properly select can be in R1To R18、Ar1And Ar2 In any substitution base for being replaced, then can increase the dissolubility of the compound represented by above-mentioned chemical formula 1, and improve film Machinability (film processibility).For example, the length that can adjust aliphatic (aliphatic) substitution base changes Kind solubility, it is possible thereby to be applied to the wet type extension operation such as ink-jet or spin coating.Also, in volution type core or the end of functional group In the case of importing the functional group of ultraviolet (UV) solidification or heat cure, after being coated by solution operation, pass through Producing high-molecular is realized in ultraviolet curing or heat cure.Thus, even if layer is applicable solution operation thereon, it is also possible to prevent molten Agent is washed out.
The compound represented by above-mentioned chemical formula 1 it is representational for example under.
Also, used as one of the invention, such as formulas below 1 or reaction equation 2 can be prepared by the table of above-mentioned chemical formula 1 The compound for showing, and the preparation method of the compound represented by above-mentioned chemical formula 1 is not limited thereto, and can be applicable various preparations Method.
Reaction equation 1：
Reaction equation 2：
In above-mentioned reaction equation 1 and reaction equation 2, to R1To R18、L、Ar1And Ar2Definition such as described above, R1' extremely R18' be separately selected from by hydrogen, heavy hydrogen, the alkyl that substituted or non-substituted carbon number is 1 to 30, substituted or non-substituted Carbon number is 2 to 30 alkenyl, the alkynyl that substituted or non-substituted carbon number is 2 to 24, substituted or non-substituted carbon original Subnumber is 3 to 12 cycloalkyl, the Heterocyclylalkyl that substituted or non-substituted carbon number is 2 to 30, substituted or non-substituted carbon Atomicity is 7 to 30 aralkyl, the alkoxy that substituted or non-substituted carbon number is 1 to 30, halogen, cyano group, nitro, hydroxyl Base, the aryl that substituted or non-substituted carbon number is 6 to 30, substitution or heteroaryl, substitution or non-that carbon number is 2 to 30 Substituted carbon number be 3 to 30 heteroarylalkyl, the alkylamino that substituted or non-substituted carbon number is 1 to 30, substitution or Non-substituted carbon number is 6 to 30 aryl amine, the arylalkylamino that substituted or non-substituted carbon number is 6 to 30, substitution Or heteroaryl amido that non-substituted carbon number is 2 to 24, the silicyl that substituted or non-substituted carbon number is 1 to 30, The fragrant oxygen that aryl silane base that substituted or non-substituted carbon number is 6 to 30, substituted or non-substituted carbon number are 6 to 30 Base, boronate, substituted or non-substituted boric acid ester group andIn the group of composition.
Specifically, in the case of above-mentioned reaction equation 1, in R1' to R18' at least one in the case of halogen, on The A of reaction equation 1 is stated for boronate or boric acid ester group, and in R1' to R18' in it is at least one for boronate or the feelings of boric acid ester group Under condition, the A of above-mentioned reaction equation 1 is halogen, thus, it is possible to be represented by formulas below 3 and reaction equation 4 respectively.
Reaction equation 3：
Reaction equation 4:
In above-mentioned reaction equation 2, in R1' to R18' in one kind beIn the case that A is halogen (for example, Br), Can be represented by formulas below 5, in R1' to R18' in one kind beA is halogen (for example, Br), and L is singly-bound In the case of, can be represented by formulas below 6.
Reaction equation 5：
Reaction equation 6：
In above-mentioned reaction equation 1 and reaction equation 2, halogen is preferably chlorine, bromine or iodine.
The present invention provides the preparation method of compound represented by formula 1 below, above-mentioned to be represented by formula 1 below The preparation method of the compound that compound is represented includes step 1, in above-mentioned steps 1, makes the chemical combination represented by formula 3 below Thing and reacted by the compound that formula 4 below is represented.
Chemical formula 1：
Chemical formula 3：
Chemical formula 4：
In above-mentioned chemical formula, R1To R18、L、A、Ar1And Ar2、R1' to R18' definition such as described above.
Above-mentioned steps 1 are to make the compound of the spirocyclic ring scaffold represented by chemical formula 3 and the amines represented by chemical formula 4 The step of reacting to prepare the compound represented by chemical formula 1.
Reaction dissolvent in the present invention, it is possible to use toluene is used as above-mentioned steps 1), and be not limited thereto.
In the present invention, above-mentioned steps 1) reaction temperature in 70 to 100 DEG C of scope, and can be not limited thereto. If above-mentioned reaction temperature is less than 70 DEG C, have the shortcomings that to extend the reaction time because reaction speed is slow, if above-mentioned reaction temperature Higher than 100 DEG C, then impurity is generated, and thus have the shortcomings that to reduce yield.
In the present invention, above-mentioned steps 1) reaction time in the scope of 12 to 24 hours, and can be not limited thereto. If the above-mentioned reaction time is less than 12 hours, have the shortcomings that to remain parent material because not terminating reaction, in normal conditions Under, because the reaction time terminated within 24 hours, therefore, there is no need to the reaction time more than 24 hours.
In the present invention, it is preferred to, above-mentioned steps 1) can be in three (dibenzalacetone) palladium (Pd2(dba)3), tri-tert Phosphine (t-Bu3P) and in the presence of sodium tert-butoxide (t-BuONa) perform, but be not limited thereto.
The present invention provides organic organic electroluminescence devices, and above-mentioned organic organic electroluminescence devices are included and represented by chemical formula 1 Compound, it is preferable that comprising by a kind of compound in compound 1 to compound 493.Now, above-mentioned organic electromechanical cause hair Optical device must include luminescent layer, also, in addition to this it is possible to comprising hole injection layer, hole blocking layer, electron transport Layer, electron injecting layer or combinations thereof.
Organic organic electroluminescence devices of the invention are characterised by, including first electrode, second electrode and above-mentioned first At least one of which organic film between electrode and above-mentioned second electrode, also, above-mentioned organic film includes the chemical combination represented by chemical formula 1 A kind of thing, it is preferable that the compound in inclusion compound 1 to compound 493.Preferably, above-mentioned organic film can for luminescent layer, Hole injection layer, hole transporting layer or electron-blocking layer, and choosing can also be included between above-mentioned first electrode and second electrode Free luminescent layer, hole injection layer, hole transporting layer, electron-blocking layer, hole blocking layer, electron supplying layer and electron injecting layer More than one layer in the group of composition.As an example, organic organic electroluminescence devices of the invention include anode, negative electrode, At least one luminescent layer between above-mentioned two electrode and the sandwich construction including electron-blocking layer and/or hole transporting layer have Machine layer, above-mentioned electron-blocking layer and/or hole transporting layer include the compound represented by chemical formula 1, it is preferable that inclusion compound One or more compound in 1 to compound 493.For example, the organic organic electroluminescence devices of multi-layered type are from bottom to top It is laminated for substrate, anode, hole injection layer, hole transporting layer, electron-blocking layer, luminescent layer, hole blocking layer, electron transport The sandwich construction of layer, electron injecting layer and negative electrode.
Substrate, anode, hole injection layer, luminescent layer, hole blocking layer, the electricity of organic organic electroluminescence devices of the invention Sub- transfer layer, electron injecting layer and negative electrode are by being typically used in the material composition of organic organic electroluminescence devices, electron-blocking layer And/or a layer in hole transporting layer can include the compound that is represented by chemical formula 1, it is preferable that can with inclusion compound 1 to One or more compound in 493.Also, above-mentioned electron-blocking layer and/or hole transporting layer are except by chemical formula 1 Outside the compound of expression, common electronics barrier material and/or cavity conveying material can also be included.
Especially, in the case of electron-blocking layer and/or hole transporting layer, it is possible to use of the invention by the table of chemical formula 1 The compound for showing, it is preferable that in can be used alone compound 1 to compound 493 or combination of compounds 1 to compound 493 It is two or more to use.Using the compound represented by chemical formula 1, it is preferable that using in compound 1 to compound 493 It is defeated relative to electron-blocking layer and/or hole in the case that more than one are as electronics barrier material and/or cavity conveying material The gross weight of layer is sent, 0.01 to 100 percentage by weight can be added, for example, 0.01 to 20 percentage by weight, 20 to 80 weight hundred Divide the amount of ratio, 80 to 100 percentage by weights etc..
In the present invention, the organic substance that can play hole injection effect can easily carry out hole note from anode Enter, it is preferable that there should be the appropriate ionization energy (ionization for carrying out hole injection from anode Potential) the characteristic such as the surface cohesive force high and anode between, the nonabsorbable in visible-range, for example, making For the substitution base of hole injection can be carried out, with organic matter, the nitrogen of six itrile group six that metalloporphyrin, oligo-thiophenes, arylamine are serial Miscellaneous benzophenanthrene, organic matter, the anthraquinone of organic matter, perylenes (perylene) series of quinacridone (quinacridone) series etc., But it is not limited thereto.
In the present invention, luminescent layer can use be used as lighting mainly (host) material or (dopant) material that adulterates Known luminous main matter or dopant.As luminescent substance, should preferably be such that good with the quantum efficiency to fluorescence or phosphorescence Material implement as can respectively receive hole and electronics from hole transporting layer and electron supplying layer combine, such that it is able to send out Go out the material of the light of visible rays scope.As the concrete example of luminescent substance, main matter or dopant, can enumerate anthracene, Naphthalene, phenanthrene, pyrene, four benzene, coronene, in the wrong, fluorescein, perylenes, Tai Jing perylenes, pyrene ketone, phthalophenone, naphthalene phthalophenone, diphenyl fourth Diene, tetraphenylbutadiene, cumarin, oxadiazoles, aldazine, double benzoxazoles, talan, pyrazine, cyclopentadiene, quinoline Metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imines, talan, vinyl anthracene, diamino Base carbazole, pyrans, thiapyran, polymethine, part cyanines, imidazoles chelating oxygen element compound, quinacridone, rubrene, the change of carbazole series The compound of compound, benzothiazole and benzimidazole series, volution (spiro) compound, polyfluorene, fluorchrome and theirs is mixed Compound, but be not limited thereto.In the case where dopant is selected, preferably should both have efficient fluorescence or phosphorescence, and With material of the band gap (bandgap) identical or less than the band gap of main matter with main matter.
Especially, in organic organic electroluminescence devices of the invention, above-mentioned luminescent layer can include fluorescence or phosphorus.
The organic substance of Electron Transfer can be played as the compound for possessing electronics pulling material, for example, conduct The substitution base of electron transmission can be carried out, with comprising cyano group, oxadiazoles, triazole etc electronics can be pulled by resonating The compound of functional group etc., but be not limited thereto.
Constitute each layer of organic organic electroluminescence devices, i.e. organic film can be by vacuum evaporation mode or solution work Sequence is formed.Specifically, the dry type such as vacuum evaporation, sputtering, plasma, ion plating epitaxy or radiation covering, leaching can be applicable The method of the arbitrary patency in wet type epitaxy such as stain covering, flowing covering forms above-mentioned organic film.The thickness of film is not It is particularly limited, if but film thickness it is blocked up, need applied voltage high to obtain the light output of regulation, cause efficiency Be deteriorated, and if the thickness of film is excessively thin, because occur consent (pin hole) even if etc. and apply electric field cannot also obtain sufficiently Luminosity.Generally, the thickness of film is preferably 5nm to 10 μm of scope, but the more preferably scope of 50nm to 400nm.
According to the present invention, the compound of MOLECULE DESIGN is obtained using volution (benzo [de] anthracene -7.9 '-fluorenes) not only can be with Using being hole mobile layer and/or electron-blocking layer, and it is that luminescent layer, electronics are moved that can be used by different kinds of molecules design Dynamic layer and coating.
Compound of the invention can be applicable spirane structure to increase band gap in parent nucleus, especially, because of the molecule of volution parent nucleus Amount can greatly improve glass transition temperature greatly and compared with other spirane structures.Also, import two substitutions to above-mentioned parent nucleus Amine, and make amine replace base that various changes occur, there are various changes in the energy level such that it is able to make highest occupied molecular.Thus, may be used So that there are various changes in the hole injection barrier of tin indium oxide and hole mobile layer, and it is possible to make hole mobile layer and hair There is appropriate energy level such that it is able to adjusted in the way of the exciton formation efficiency in the inside for improving luminescent layer between photosphere Section.
Specific embodiment
Hereinafter, the present invention is described in more details by embodiment.These embodiments are only used for more specifically The present invention is illustrated, the scope of the present invention is not limited to these embodiments.
Embodiment 1：The preparation of compound 1
Two ([1,1 '-biphenyl] -4- bases) amine and 4.45g of 3.21g (10mmol) are dissolved in the toluene of 30ml After 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol), sodium tert-butoxide, the 161mg of addition 2.88g (30mmol) The tri-butyl phosphine (50wt% in toluene) of (0.4mmol), double (dibenzalacetone) palladiums (0) of 115mg (0.2mmol), it Stirring, the backflow of 3 hours is carried out afterwards.After reaction is terminated, cooled down under normal temperature condition, and add the ethyl acetate of 50ml With the H of 50ml2O extracts organic layer.Using MgSO4After processing organic matter layer, filtered, dry, and using just oneself Alkane/alkyl dimethyl ammonium chloride implements post, so as to obtain compound 1 with 85% yield (5.83g).
Embodiment 2：The preparation of compound 2
Except N- phenyl volution [benzo [de] anthracene -7,9 '-fluorenes] -2 '-amine and 2.13g using 4.58g (10mmol) The bromo- 4- of 1- (tert-butyl group) benzene of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 2 is prepared in the same manner as in Example 1.
Embodiment 3：The preparation of compound 6
Use N- ([1,1 '-biphenyl] -4- bases) dibenzo [b, the d] furans -4- amine and 4.77g of 3.35g (10mmol) 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine spiral shell Outside ring [benzo [de] anthracene -7,9 '-fluorenes], compound 6 is prepared in the same manner as in Example 1.
Embodiment 4：The preparation of compound 9
Use N- phenyl dibenzo [b, the d] furans -4- amine and 2 '-bromine spiral shell of 4.45g (10mmol) of 2.59g (10mmol) Ring [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7, 9 '-fluorenes] outside, compound 9 is prepared in the same manner as in Example 1.
Embodiment 5：The preparation of compound 10
Using 3.75g (10mmol) N- (9,9- dimethyl -9H- fluorenes -2- bases) dibenzo [b, d] furans -4- amine and 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] of 4.45g (10mmol) come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 ' - Outside bromine volution [benzo [de] anthracene -7,9 '-fluorenes], compound 10 is prepared in the same manner as in Example 1.
Embodiment 6：The preparation of compound 13
Use N- phenyl volution [benzo [de] anthracene -7,9 '-fluorenes]-the 2 '-amine and 1.75g of 4.58g (10mmol) The bromo- 4- fluorobenzene of 1- of (10mmol) come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7,9 ' - Fluorenes] outside, compound 13 is prepared in the same manner as in Example 1.
Embodiment 7：The preparation of compound 15
Use N- phenyl volution [benzo [de] anthracene -7,9 '-fluorenes]-the 2 '-amine and 2.63g of 4.58g (10mmol) 4- bromines dibenzo [b, the d] thiophene of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 15 is prepared in the same manner as in Example 1.
Embodiment 8：The preparation of compound 19
Use N- phenyl dibenzo [b, the d] furans -3- amine and 2 '-bromine spiral shell of 4.45g (10mmol) of 2.59g (10mmol) Ring [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7, 9 '-fluorenes] outside, compound 19 is prepared in the same manner as in Example 1.
Embodiment 9：The preparation of compound 20
Use N- ([1,1 '-biphenyl] -4- bases) dibenzo [b, the d] furans -3- amine and 4.45g of 3.35g (10mmol) 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine spiral shell Outside ring [benzo [de] anthracene -7,9 '-fluorenes], compound 20 is prepared in the same manner as in Example 1.
Embodiment 10：The preparation of compound 29
Using the N of 3.35g (10mmol), 6- diphenyl dibenzo [b, d] furans -4- amine and 4.45g (10mmol) 2 ' - Bromine volution [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene - 7,9 '-fluorenes] outside, compound 29 is prepared in the same manner as in Example 1.
Embodiment 11：The preparation of compound 30
Use N- phenyl volution [benzo [de] anthracene -7,9 '-fluorenes]-the 2 '-amine and 3.22g of 4.58g (10mmol) The bromo- 9- phenyl -9H- carbazoles of 3- of (10mmol) replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 30 is prepared in the same manner as in Example 1.
Embodiment 12：The preparation of compound 37
Use 9, the 9- dimethyl-N-phenyl -9H- fluorenes -2- amine and the 2 '-bromine of 4.45g (10mmol) of 2.85g (10mmol) Volution [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7, 9 '-fluorenes] outside, compound 37 is prepared in the same manner as in Example 1.
Embodiment 13：The preparation of compound 38
Use N- ([1,1 '-biphenyl] -4- bases) -9, the 9- dimethyl -9H- fluorenes -2- amine and 4.45g of 3.61g (10mmol) 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine spiral shell Outside ring [benzo [de] anthracene -7,9 '-fluorenes], compound 38 is prepared in the same manner as in Example 1.
Embodiment 14：The preparation of compound 47
Use N- ([1,1 '-biphenyl] -2- bases) -9, the 9- dimethyl -9H- fluorenes -2- amine and 4.45g of 3.61g (10mmol) 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine spiral shell Outside ring [benzo [de] anthracene -7,9 '-fluorenes], compound 47 is prepared in the same manner as in Example 1.
Embodiment 15：The preparation of compound 63
Use N- ([1,1 '-biphenyl] -2- bases) dibenzo [b, the d] furans -4- amine and 4.77g of 3.35g (10mmol) The 2 ' of (10mmol)-(4- chlorobenzenes) volution [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and Outside 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes], compound 63 is prepared in the same manner as in Example 1.
Embodiment 16：The preparation of compound 64
Use N- phenyl volution [benzo [de] anthracene -7,9 '-fluorenes]-the 2 '-amine and 2.07g of 4.58g (10mmol) The 1- bromonaphthalenes of (10mmol) come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] it Outward, compound 64 is prepared in the same manner as in Example 1.
Embodiment 17：The preparation of compound 65
Use N- phenyl volution [benzo [de] anthracene -7,9 '-fluorenes]-the 2 '-amine and 2.29g of 4.58g (10mmol) (4- bromophenyls) trimethyl silane of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] outside, compound 65 is prepared in the same manner as in Example 1.
Embodiment 18：The preparation of compound 74
Use N- phenyl dibenzo [b, the d] furans -4- amine and the 2 '-(4- of 4.77g (10mmol) of 2.59g (10mmol) Chlorobenzene) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 74 is prepared in the same manner as in Example 1.
Embodiment 19：The preparation of compound 84
Use N- phenyl dibenzo [b, the d] furans -3- amine and the 2 '-(4- of 4.77g (10mmol) of 2.59g (10mmol) Chlorobenzene) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 84 is prepared in the same manner as in Example 1.
Embodiment 20：The preparation of compound 94
Using the N of 3.35g (10mmol), 6- diphenyl dibenzo [b, d] furans -4- amine and 4.77g (10mmol) 2 ' - (4- chlorobenzenes) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] outside, compound 94 is prepared in the same manner as in Example 1.
Embodiment 21：The preparation of compound 103
Use N- ([1,1 '-biphenyl] -4- bases) -9, the 9- dimethyl -9H- fluorenes -2- amine and 4.77g of 3.61g (10mmol) The 2 ' of (10mmol)-(4- chlorobenzenes) volution [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and Outside 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes], compound 103 is prepared in the same manner as in Example 1.
Embodiment 22：The preparation of compound 125
Use N- ([1,1 '-biphenyl] -2- bases) dibenzo [b, the d] furans -4- amine and 4.45g of 3.35g (10mmol) 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine spiral shell Outside ring [benzo [de] anthracene -7,9 '-fluorenes], compound 125 is prepared in the same manner as in Example 1.
Embodiment 23：The preparation of compound 128
Using 2.59g (10mmol) N- phenyl dibenzo [b, d] furans -4- amine and 5.98g (10mmol) 2 '-(4 ' - Bromo- [1,1 '-biphenyl] -4- bases) volution [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 ' - Outside bromine volution [benzo [de] anthracene -7,9 '-fluorenes], compound 128 is prepared in the same manner as in Example 1.
Embodiment 24：The preparation of compound 139
Use N- ([1,1 '-biphenyl] -4- bases) dibenzo [b, the d] furans -4- amine and 4.45g of 3.35g (10mmol) The 9- bromines volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution Outside [benzo [de] anthracene -7,9 '-fluorenes], compound 139 is prepared in the same manner as in Example 1.
Embodiment 25：The preparation of compound 142
Use N- phenyl dibenzo [b, the d] furans -4- amine and the 9- bromine spiral shells of 4.45g (10mmol) of 2.59g (10mmol) Ring [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7, 9 '-fluorenes] outside, compound 142 is prepared in the same manner as in Example 1.
Embodiment 26：The preparation of compound 143
Using 3.75g (10mmol) N- (9,9- dimethyl -9H- fluorenes -2- bases) dibenzo [b, d] furans -4- amine and The 9- bromines volution [benzo [de] anthracene -7,9 '-fluorenes] of 4.45g (10mmol) come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 ' - Outside bromine volution [benzo [de] anthracene -7,9 '-fluorenes], compound 143 is prepared in the same manner as in Example 1.
Embodiment 27：The preparation of compound 152
Use N- phenyl dibenzo [b, the d] furans -3- amine and the 9- bromine spiral shells of 4.45g (10mmol) of 2.59g (10mmol) Ring [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7, 9 '-fluorenes] outside, compound 152 is prepared in the same manner as in Example 1.
Embodiment 28：The preparation of compound 153
Use N- ([1,1 '-biphenyl] -4- bases) dibenzo [b, the d] furans -3- amine and 4.45g of 3.35g (10mmol) The 9- bromines volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution Outside [benzo [de] anthracene -7,9 '-fluorenes], compound 153 is prepared in the same manner as in Example 1.
Embodiment 29：The preparation of compound 162
Using the N of 3.35g (10mmol), the 9- of 6- diphenyl dibenzo [b, d] furans -4- amine and 4.45g (10mmol) Bromine volution [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene - 7,9 '-fluorenes] outside, compound 162 is prepared in the same manner as in Example 1.
Embodiment 30：The preparation of compound 170
Use 9, the 9- dimethyl-N-phenyl -9H- fluorenes -2- amine and the 9- bromines of 4.45g (10mmol) of 2.85g (10mmol) Volution [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7, 9 '-fluorenes] outside, compound 170 is prepared in the same manner as in Example 1.
Embodiment 31：The preparation of compound 171
Use N- ([1,1 '-biphenyl] -4- bases) -9, the 9- dimethyl -9H- fluorenes -2- amine and 4.45g of 3.61g (10mmol) The 9- bromines volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution Outside [benzo [de] anthracene -7,9 '-fluorenes], compound 171 is prepared in the same manner as in Example 1.
Embodiment 32：The preparation of compound 180
Use N- ([1,1 '-biphenyl] -2- bases) -9, the 9- dimethyl -9H- fluorenes -2- amine and 4.45g of 3.61g (10mmol) The 9- chlorine spiral shell [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution Outside [benzo [de] anthracene -7,9 '-fluorenes], compound 180 is prepared in the same manner as in Example 1.
Embodiment 33：The preparation of compound 189
Use N- ([1,1 '-biphenyl] -2- bases) dibenzo [b, the d] furans -4- amine and 4.45g of 3.35g (10mmol) The 9- chlorine spiral shell [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution Outside [benzo [de] anthracene -7,9 '-fluorenes], compound 189 is prepared in the same manner as in Example 1.
Embodiment 34：The preparation of compound 198
Use N- phenyl dibenzo [b, the d] furans -4- amine and 9- (the 4- chlorine of 4.77g (10mmol) of 2.59g (10mmol) Benzene) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 198 is prepared in the same manner as in Example 1.
Embodiment 35：The preparation of compound 208
Use N- phenyl dibenzo [b, the d] furans -3- amine and 9- (the 4- chlorine of 4.77g (10mmol) of 2.59g (10mmol) Benzene) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 208 is prepared in the same manner as in Example 1.
Embodiment 36：The preparation of compound 226
Use 9, the 9- dimethyl-N-phenyl -9H- fluorenes -2- amine and the 9- (4- of 4.77g (10mmol) of 2.85g (10mmol) Chlorobenzene) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 226. is prepared in the same manner as in Example 1
Embodiment 37：The preparation of compound 318
Use N- phenyl dibenzo [b, the d] furans -4- amine and 3- (the 4- chlorine of 4.77g (10mmol) of 2.59g (10mmol) Benzene) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 318 is prepared in the same manner as in Example 1.
Embodiment 38：The preparation of compound 328
Use N- phenyl dibenzo [b, the d] furans -3- amine and 3- (the 4- chlorine of 4.77g (10mmol) of 2.59g (10mmol) Benzene) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 328 is prepared in the same manner as in Example 1.
Embodiment 39：The preparation of compound 346
Use 9, the 9- dimethyl-N-phenyl -9H- fluorenes -2- amine and the 3- (4- of 4.77g (10mmol) of 2.85g (10mmol) Chlorobenzene) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 346 is prepared in the same manner as in Example 1.
Embodiment 40：The preparation of compound 379
Use N- ([1,1 '-biphenyl] -4- bases) dibenzo [b, the d] furans -4- amine and 4.77g of 3.35g (10mmol) 4 '-chromium volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine spiral shell Outside ring [benzo [de] anthracene -7,9 '-fluorenes], compound 379 is prepared in the same manner as in Example 1.
Embodiment 41：The preparation of compound 382
Use N- phenyl dibenzo [b, the d] furans -4- amine and 4 '-chromium spiral shell of 4.45g (10mmol) of 2.59g (10mmol) Ring [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7, 9 '-fluorenes] outside, compound 382 is prepared in the same manner as in Example 1.
Embodiment 42：The preparation of compound 383
Using 3.75g (10mmol) N- (9,9- dimethyl -9H- fluorenes -2- bases) dibenzo [b, d] furans -4- amine e and 4 '-chromium volution [benzo [de] anthracene -7,9 '-fluorenes] of 4.45g (10mmol) come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 ' - Outside bromine volution [benzo [de] anthracene -7,9 '-fluorenes], compound 383 is prepared in the same manner as in Example 1.
Embodiment 43：The preparation of compound 392
Use N- phenyl dibenzo [b, the d] furans -3- amine and 4 '-chromium spiral shell of 4.45g (10mmol) of 2.59g (10mmol) Ring [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7, 9 '-fluorenes] outside, compound 392 is prepared in the same manner as in Example 1.
Embodiment 44：The preparation of compound 393
Use N- ([1,1 '-biphenyl] -4- bases) dibenzo [b, the d] furans -3- amine and 4.45g of 3.35g (10mmol) 4 '-chromium volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine spiral shell Outside ring [benzo [de] anthracene -7,9 '-fluorenes], compound 393 is prepared in the same manner as in Example 1.
Embodiment 45：The preparation of compound 402
Using the N of 3.35g (10mmol), 6- diphenyl dibenzo [b, d] furans -4- amine and 4.45g (10mmol) 4 ' - Chromium volution [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene - 7,9 '-fluorenes] outside, compound 402 is prepared in the same manner as in Example 1.
Embodiment 46：The preparation of compound 410
Use 9, the 9- dimethyl-N-phenyl -9H- fluorenes -2- amine and the 4 '-chromium of 4.45g (10mmol) of 2.85g (10mmol) Volution [benzo [de] anthracene -7,9 '-fluorenes] come replace two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7, 9 '-fluorenes] outside, compound 410 is prepared in the same manner as in Example 1.
Embodiment 47：The preparation of compound 411
Use N- ([1,1 '-biphenyl] -4- bases) -9, the 9- dimethyl -9H- fluorenes -2- amine and 4.45g of 3.61g (10mmol) 4 '-chromium volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine spiral shell Outside ring [benzo [de] anthracene -7,9 '-fluorenes], compound 411 is prepared in the same manner as in Example 1.
Embodiment 48：The preparation of compound 420
Use N- ([1,1 '-biphenyl] -2- bases) -9, the 9- dimethyl -9H- fluorenes -2- amine and 4.45g of 3.61g (10mmol) 4 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] of (10mmol) replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine spiral shell Outside ring [benzo [de] anthracene -7,9 '-fluorenes], compound 420 is prepared in the same manner as in Example 1.
Embodiment 49：The preparation of compound 438
Use N- phenyl dibenzo [b, the d] furans -4- amine and the 4 '-(4- of 4.77g (10mmol) of 2.59g (10mmol) Chlorobenzene) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 438 is prepared in the same manner as in Example 1.
Embodiment 50：The preparation of compound 448
Use N- phenyl dibenzo [b, the d] furans -3- amine and the 4 '-(4- of 4.77g (10mmol) of 2.59g (10mmol) Chlorobenzene) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] Anthracene -7,9 '-fluorenes] outside, compound 448 is prepared in the same manner as in Example 1.
Embodiment 51：The preparation of compound 458
Using the N of 3.35g (10mmol), 6- diphenyl dibenzo [b, d] furans -4- amine and 4.77g (10mmol) 4 ' - (4- chlorobenzenes) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] outside, compound 458 is prepared in the same manner as in Example 1.
Embodiment 52：The preparation of compound 466
Using 2.85g (10mmol) 9,9- dimethyl-N-phenyl -9H- fluorenes -2- amine and 4.77g (10mmol) 4 ' - (4- chlorobenzenes) volution [benzo [de] anthracene -7,9 '-fluorenes] replaces two ([1,1 '-biphenyl] -4- bases) amine and 2 '-bromine volution [benzo [de] anthracene -7,9 '-fluorenes] outside, compound 466 is prepared in the same manner as in Example 1.
The nmR and yield data of synthesized above-mentioned multiple compounds are shown in table 1 below to table 4.
Table 1
Table 2
Table 3
Table 4
Experimental example 1：Preparation and the performance point of these devices using organic organic electroluminescence devices of embodiment compound Analysis
As shown in the following Table 5, using embodiment compound as electron-blocking layer, and organic machine is prepared for according to the following steps Electroluminescent device.
First, anode is formed using tin indium oxide on the substrate for be formed with reflecting layer, and utilizes N2Plasma is carried out Surface treatment.N4, N4, N4 are deposited with above it ', N4 '-four ([1,1 '-biphenyl] -4- bases)-[1,1 '-biphenyl] -4,4 '-two Amine as hole injection layer (HIL), and mix about 3% or so P- adulterate as dopant, be consequently formed 100 thickness. Then, in top the vacuum evaporation N4, N4, N4 of above-mentioned hole injection layer ', N4 '-four ([1,1 '-biphenyl] -4- bases)-[1,1 ' - Biphenyl] -4,4 '-diamines forms the hole transporting layer of 1000 thickness.On the top of above-mentioned hole transporting layer respectively with 150 thickness Degree forms the compound of each embodiment as electron-blocking layer, and top evaporation in above-mentioned electron-blocking layer can form blueness α β-the ADN of luminescent layer mix about 5% or so the N1, (4- (1- silicyls) of N1, N6, N6- tetra- as luminescent layer (EML) Phenyl) pyrene -1,6- diamines is used as dopant, so as to form the luminescent layer of 200 thickness.
Above it with 1:1 weight ratio mixing 2- (4- (9,10- bis- (naphthalene -2- bases) anthracene -2- bases) phenyl) -1- phenyl - 1H- benzos [d] imidazoles and 8-hydroxyquinoline lithium (LiQ), and electron supplying layer is deposited with 360 thickness, and with 9:1 ratio is steamed The magnesium (Mg) and silver-colored (Ag) of 160 thickness are plated as negative electrode, so as to form negative electrode.The N4 of 650 thickness is deposited with above-mentioned negative electrode, N4 '-diphenyl-N4, N4 '-two (4- (9- phenyl -9H- carbazole -3- bases) phenyl)-[1,1 '-biphenyl] -4,4 '-diamines is used as covering Cap rock (capping layer, CPL).Can on the cover layer be fitted closure (seal cap) conduct containing 39-30 hygroscopic agents Ultraviolet hardening binding agent, for from the O in air2Or organic organic electroluminescence devices are protected in moisture, thus it is prepared for Organic organic electroluminescence devices.
As comparative example, N, N '-bis--(1- naphthalenes) N, N '-diphenyl-(1,1 '-biphenyl are used instead of embodiment compound Base) -4,4 '-diamines (NPD；N, N '-Bis- (1-naphthalenyl)-N, N '-bis-phenyl- (1,1 '-biphenyl)- 4,4 '-diamine) as electron-blocking layer outside, be prepared for organic electromechanical causing hair using method same as mentioned above Optical device.
In 10mA/cm2Under conditions of, above-mentioned prepared organic organic electroluminescence devices are carried out with the performance point of device Analysis, and its result is shown in table 5 below.
Table 5
By the device evaluation of above-mentioned table 5, compound of the invention is applicable in organic organic electroluminescence devices as electricity In the case of sub- barrier layer, compared with comparative example, although current efficiency and CIEy values are similar, but in identical current density condition Under, voltage shows the characteristic of low about 0.9~1.2V or so, it is possible to ensure that external quantum efficiency rises to maximum 27% spy Property.Therefore, in the case of compound of the invention is used in organic organic electroluminescence devices as electron-blocking layer, it is known that energy Enough embody electrical efficiency and current efficiency high.

Claims (7)

1. a kind of compound, it is characterised in that represented by formula 1 below,
Chemical formula 1：
In above-mentioned chemical formula 1,
R1To R18Separately be selected from by hydrogen, heavy hydrogen, the alkyl that substituted or non-substituted carbon number is 1 to 30, substitution or Non-substituted carbon number is 2 to 30 alkenyl, the alkynyl that substituted or non-substituted carbon number is 2 to 24, substitution or non-takes The carbon number in generation is 3 to 12 cycloalkyl, the Heterocyclylalkyl that substituted or non-substituted carbon number is 2 to 30, substitution or non- Substituted carbon number is 7 to 30 aralkyl, the alkoxy that substituted or non-substituted carbon number is 1 to 30, halogen, cyanogen Base, nitro, hydroxyl, the aryl that substituted or non-substituted carbon number is 6 to 30, substitution or the heteroaryl that carbon number is 2 to 30 Base, the heteroarylalkyl that substituted or non-substituted carbon number is 3 to 30, the alkane that substituted or non-substituted carbon number is 1 to 30 Amino, the aryl amine that substituted or non-substituted carbon number is 6 to 30, the virtue that substituted or non-substituted carbon number is 6 to 30 Alkylamino, the heteroaryl amido that substituted or non-substituted carbon number is 2 to 24, substituted or non-substituted carbon number are 1 to 30 Silicyl, the aryl silane base that substituted or non-substituted carbon number is 6 to 30, substituted or non-substituted carbon number be 6 To 30 aryloxy group and formula 2 below represent functional group composition group in,
Simply, R1To R18In it is at least one be the functional group represented by formula 2 below,
Chemical formula 2：
In above-mentioned chemical formula 2,
L is selected from by singly-bound, the arlydene and substituted or non-substituted carbon number that substituted or non-substituted carbon number is 6 to 18 It is the group of 3 to 18 heteroarylidene composition, or
The R of L and adjacent volution type core1To R18One or more of be connected to form saturation or unsaturation ring, or with phase Adjacent nitrogen-atoms, Ar1Or Ar2It is connected to form the heterocyclic radical that nuclear atom number is 5 to 18,
Ar1And Ar2Separately be selected from by hydrogen, heavy hydrogen, the alkyl that substituted or non-substituted carbon number is 1 to 30, substitution or Non-substituted carbon number is 2 to 30 alkenyl, the alkynyl that substituted or non-substituted carbon number is 2 to 24, substitution or non-takes The carbon number in generation is the cycloalkyl that 3 to carbon number is 12, the heterocycle alkane that substituted or non-substituted carbon number is 2 to 30 Base, the aralkyl that substituted or non-substituted carbon number is 7 to 30, the aryl that substituted or non-substituted carbon number is 6 to 30, What substitution or the heteroaryl that carbon number is 2 to 30 and the heteroarylalkyl that substituted or non-substituted carbon number is 3 to 30 were constituted In group,
Ar1And Ar2Separately it is connected to form saturation that nuclear atom number is 5 to 18 or not with adjacent nitrogen-atoms and L Saturated rings, or be connected with adjacent nitrogen-atoms and form the saturation or unsaturation ring that nuclear atom number is 5 to 18, Huo Zhe In the case that L is singly-bound, Ar1And Ar2Separately it is connected to form saturation or unsaturation with nitrogen-atoms and volution type nuclear phase Ring,
Above-mentioned R1To R18、L、Ar1And Ar2Substitution base can be identical or different substitution base, and separately be selected from by It is hydrogen, heavy hydrogen, cyano group, nitro, halogen, hydroxyl, the alkyl that substituted or non-substituted carbon number is 1 to 30, substituted or non-substituted Carbon number be 2 to 30 alkenyl, the alkynyl that substituted or non-substituted carbon number is 2 to 24, carbon number be that 3 to carbon is former Subnumber is 12 cycloalkyl, the Heterocyclylalkyl that substituted or non-substituted carbon number is 2 to 30, substituted or non-substituted carbon atom Number is 7 to 30 aralkyl, the aryl that substituted or non-substituted carbon number is 6 to 30, substituted or non-substituted carbon number It is 6 to 24 aralkyl, the heteroaryl that substituted or non-substituted carbon number is 2 to 30, substituted or non-substituted carbon number It is 3 to 30 heteroarylalkyl, the alkoxy that substituted or non-substituted carbon number is 1 to 30, substituted or non-substituted carbon atom Number is 1 to 30 alkylamino, the aryl amine that substituted or non-substituted carbon number is 6 to 30, substituted or non-substituted carbon atom Number is 7 to 30 arylalkylamino, heteroaryl amido, the substituted or non-substituted carbon that substituted or non-substituted carbon number is 2 to 24 Atomicity is 1 to 30 silicyl, the aryl silane base that substituted or non-substituted carbon number is 6 to 30 and substituted or non-substituted Carbon number be 6 to 30 aryloxy group composition one or more of group substitution base.
2. compound according to claim 1, it is characterised in that
R1To R18And Ar1To Ar2Separately it is selected from by hydrogen, heavy hydrogen, methyl, ethyl, propyl group, isopropanol, the tert-butyl group, hexamethylene Base, trimethylsilyl, triphenylsilyl, substitution or unsubstituted phenyl, biphenyl, terphenyl, stretch xenyl, Sanya phenyl, Naphthyl, phenanthryl, fluorenyl, pyrenyl, dibenzofuran group, benzofuranyl, benzo thionyl, dibenzothiophenes, carbazyl, volution The fluorenyl of spiral shell two, anthryl, acenaphthenyl, pyridine radicals, carboline base, quinolyl, isoquinolyl, thianthrene group, 9H- thianthrene groups, ton base, dibenzo Dioxin base, fen xanthyl, 9,9 dimethyl -9,10- dihydroanthracenes, tetralyl, tetramethyl indyl and 4a, 9a- In the group of dimethyl hexahydro carbazyl composition,
L is selected from the group being made up of singly-bound, phenyl, biphenyl, terphenyl, naphthyl, carbazole, dibenzofurans and dibenzothiophenes.
3. compound according to claim 1, it is characterised in that the compound represented by above-mentioned chemical formula 1 be selected from by with In the group that lower structure is constituted,
4. a kind of organic organic electroluminescence devices, including：
First electrode；
Second electrode；And
At least one of which organic film, is arranged between above-mentioned first electrode and above-mentioned second electrode,
Above-mentioned organic organic electroluminescence devices are characterised by,
At least one of which in above-mentioned organic film includes the compound any one of claims 1 to 3.
5. organic organic electroluminescence devices according to claim 4, it is characterised in that above-mentioned organic film includes being selected from by sending out Photosphere, hole injection layer, hole transporting layer, electron-blocking layer, hole blocking layer, electron supplying layer and electron injecting layer composition More than one layer in group.
6. organic organic electroluminescence devices according to claim 4, it is characterised in that the organic film comprising above-claimed cpd It is hole injection layer, hole transporting layer or electron-blocking layer.
7. organic organic electroluminescence devices according to claim 4, it is characterised in that above-mentioned organic film passes through vacuum evaporation Mode or solution operation are formed.
CN201610458154.4A 2015-11-17 2016-06-22 Spiro organic material and organic electroluminescent device using the same Active CN106699573B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20150161346 2015-11-17
KR10-2015-0161346 2015-11-17
KR1020160013667A KR101695270B1 (en) 2015-11-17 2016-02-03 Spyro-typed organic materials and organic electroluminescent device utilizing the same
KR10-2016-0013667 2016-02-03

Publications (2)

Publication Number Publication Date
CN106699573A true CN106699573A (en) 2017-05-24
CN106699573B CN106699573B (en) 2020-08-11

Family

ID=57811579

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610458154.4A Active CN106699573B (en) 2015-11-17 2016-06-22 Spiro organic material and organic electroluminescent device using the same

Country Status (2)

Country Link
KR (1) KR101695270B1 (en)
CN (1) CN106699573B (en)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107892650A (en) * 2017-12-01 2018-04-10 吉林奥来德光电材料股份有限公司 A kind of benzo anthracene compound and preparation method thereof and organic electroluminescence device
CN108047130A (en) * 2017-12-05 2018-05-18 李现伟 Benzanthracenes electroluminescent organic material, luminescent device and display
TWI644886B (en) * 2017-10-27 2018-12-21 晶宜科技股份有限公司 Organic electroluminescent devices and material thereof
CN109790105A (en) * 2016-10-06 2019-05-21 默克专利有限公司 Material for organic electroluminescence device
WO2019101719A1 (en) 2017-11-23 2019-05-31 Merck Patent Gmbh Materials for electronic devices
CN110590568A (en) * 2018-06-12 2019-12-20 武汉尚赛光电科技有限公司 Amine derivative having spiro structure and electronic component using same
WO2020015675A1 (en) * 2018-07-18 2020-01-23 江苏三月光电科技有限公司 Compound having triarylamine as core and application thereof
CN110828701A (en) * 2018-08-10 2020-02-21 材料科学有限公司 Organic electroluminescent element
CN110950763A (en) * 2019-11-04 2020-04-03 苏州久显新材料有限公司 Spirobenzanthrone derivatives and electronic devices
CN111233675A (en) * 2018-11-29 2020-06-05 江苏三月光电科技有限公司 Organic compound containing benzoanthracene and application thereof
CN112447915A (en) * 2019-09-02 2021-03-05 冠能光电材料(深圳)有限责任公司 High-performance organic electron transport material and OLED device application
CN112479905A (en) * 2019-09-11 2021-03-12 江苏三月光电科技有限公司 Organic compound containing benzoanthracene fluorene and diarylamine and application thereof in organic electroluminescent device
CN112480133A (en) * 2019-09-11 2021-03-12 江苏三月光电科技有限公司 Compound with benzospiroanthracene as core and application thereof
CN112552190A (en) * 2020-07-24 2021-03-26 洛丁有限公司 Novel organic compound and organic light emitting diode including the same
CN112812024A (en) * 2020-04-02 2021-05-18 陕西莱特迈思光电材料有限公司 Organic compound, application and organic electroluminescent device using organic compound
CN113372313A (en) * 2021-07-02 2021-09-10 长春海谱润斯科技股份有限公司 Triarylamine compound and organic electroluminescent device thereof
CN113387875A (en) * 2021-06-30 2021-09-14 昆山国显光电有限公司 Multi-element condensed ring organic compound, organic electroluminescent device and display panel
CN113451522A (en) * 2021-06-28 2021-09-28 冠能光电材料(深圳)有限责任公司 Multifunctional organic arylamine semiconductor material and application of luminescent device thereof
CN114075117A (en) * 2021-06-04 2022-02-22 陕西莱特迈思光电材料有限公司 Organic compound, and electronic element and electronic device using same

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018216903A1 (en) * 2017-05-22 2018-11-29 주식회사 엘지화학 Novel compound and organic light-emitting device using same
KR102080288B1 (en) * 2017-05-22 2020-02-21 주식회사 엘지화학 Novel compound and organic light emitting device comprising the same
KR102585186B1 (en) 2017-11-24 2023-10-06 삼성디스플레이 주식회사 Amine compound and organic electroluminescence device including the same
CN113149889A (en) * 2021-02-26 2021-07-23 阜阳欣奕华材料科技有限公司 Compound and organic electroluminescent device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014058232A2 (en) * 2012-10-10 2014-04-17 대주전자재료 주식회사 Spiro-type organic material, and organic electroluminescent device using same
CN106612616A (en) * 2015-05-08 2017-05-03 陕西莱特迈思光电材料有限公司 Organic electroluminescent device

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
KR20150051831A (en) * 2013-11-05 2015-05-13 대주전자재료 주식회사 Spyro type organic material and organic electroluminescent device and organic eletroluminescent device utilizing the same
KR20150051830A (en) * 2013-11-05 2015-05-13 대주전자재료 주식회사 Spyro type organic material and organic electroluminescent device and organic eletroluminescent device utilizing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014058232A2 (en) * 2012-10-10 2014-04-17 대주전자재료 주식회사 Spiro-type organic material, and organic electroluminescent device using same
CN106612616A (en) * 2015-05-08 2017-05-03 陕西莱特迈思光电材料有限公司 Organic electroluminescent device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JAE-RYUNG CHA ET AL.: "New efficient fused-ring spiro[benzoanthracenefluorene] dopant materials for blue fluorescent organic light-emitting diodes", 《NEW J. CHEM.》 *

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109790105B (en) * 2016-10-06 2023-04-18 默克专利有限公司 Material for organic electroluminescent device
US11629126B2 (en) 2016-10-06 2023-04-18 Merck Patent Gmbh Materials for organic electroluminescent devices
CN109790105A (en) * 2016-10-06 2019-05-21 默克专利有限公司 Material for organic electroluminescence device
TWI644886B (en) * 2017-10-27 2018-12-21 晶宜科技股份有限公司 Organic electroluminescent devices and material thereof
US11832513B2 (en) 2017-11-23 2023-11-28 Merck Patent Gmbh Materials for electronic devices
WO2019101719A1 (en) 2017-11-23 2019-05-31 Merck Patent Gmbh Materials for electronic devices
CN107892650A (en) * 2017-12-01 2018-04-10 吉林奥来德光电材料股份有限公司 A kind of benzo anthracene compound and preparation method thereof and organic electroluminescence device
CN107892650B (en) * 2017-12-01 2021-01-08 吉林奥来德光电材料股份有限公司 Benzanthracene compound, preparation method thereof and organic electroluminescent device
CN108047130A (en) * 2017-12-05 2018-05-18 李现伟 Benzanthracenes electroluminescent organic material, luminescent device and display
CN110590568A (en) * 2018-06-12 2019-12-20 武汉尚赛光电科技有限公司 Amine derivative having spiro structure and electronic component using same
CN110590568B (en) * 2018-06-12 2022-08-19 武汉尚赛光电科技有限公司 Amine derivative having spiro structure and electronic device using the same
WO2020015675A1 (en) * 2018-07-18 2020-01-23 江苏三月光电科技有限公司 Compound having triarylamine as core and application thereof
CN110734381A (en) * 2018-07-18 2020-01-31 江苏三月光电科技有限公司 triarylamine-based compound, and preparation method and application thereof
CN110828701A (en) * 2018-08-10 2020-02-21 材料科学有限公司 Organic electroluminescent element
CN110828701B (en) * 2018-08-10 2022-11-01 材料科学有限公司 Organic electroluminescent element
CN111233675B (en) * 2018-11-29 2023-04-07 江苏三月科技股份有限公司 Organic compound containing benzoanthracene and application thereof
CN111233675A (en) * 2018-11-29 2020-06-05 江苏三月光电科技有限公司 Organic compound containing benzoanthracene and application thereof
CN112447915A (en) * 2019-09-02 2021-03-05 冠能光电材料(深圳)有限责任公司 High-performance organic electron transport material and OLED device application
CN112479905B (en) * 2019-09-11 2023-01-13 江苏三月科技股份有限公司 Organic compound containing benzoanthracene fluorene and diarylamine and application thereof in organic electroluminescent device
CN112480133A (en) * 2019-09-11 2021-03-12 江苏三月光电科技有限公司 Compound with benzospiroanthracene as core and application thereof
CN112480133B (en) * 2019-09-11 2023-08-08 江苏三月科技股份有限公司 Compound with benzospiroanthracene as core and application thereof
CN112479905A (en) * 2019-09-11 2021-03-12 江苏三月光电科技有限公司 Organic compound containing benzoanthracene fluorene and diarylamine and application thereof in organic electroluminescent device
CN110950763A (en) * 2019-11-04 2020-04-03 苏州久显新材料有限公司 Spirobenzanthrone derivatives and electronic devices
CN112812024B (en) * 2020-04-02 2022-03-29 陕西莱特迈思光电材料有限公司 Organic compound, application and organic electroluminescent device using organic compound
CN112812024A (en) * 2020-04-02 2021-05-18 陕西莱特迈思光电材料有限公司 Organic compound, application and organic electroluminescent device using organic compound
CN112552190A (en) * 2020-07-24 2021-03-26 洛丁有限公司 Novel organic compound and organic light emitting diode including the same
CN114075117B (en) * 2021-06-04 2023-07-21 陕西莱特迈思光电材料有限公司 Organic compound, and electronic element and electronic device using same
CN114075117A (en) * 2021-06-04 2022-02-22 陕西莱特迈思光电材料有限公司 Organic compound, and electronic element and electronic device using same
CN113451522A (en) * 2021-06-28 2021-09-28 冠能光电材料(深圳)有限责任公司 Multifunctional organic arylamine semiconductor material and application of luminescent device thereof
CN113387875A (en) * 2021-06-30 2021-09-14 昆山国显光电有限公司 Multi-element condensed ring organic compound, organic electroluminescent device and display panel
CN113387875B (en) * 2021-06-30 2024-02-27 昆山国显光电有限公司 Multi-element condensed ring organic compound, organic electroluminescent device and display panel
CN113372313A (en) * 2021-07-02 2021-09-10 长春海谱润斯科技股份有限公司 Triarylamine compound and organic electroluminescent device thereof

Also Published As

Publication number Publication date
CN106699573B (en) 2020-08-11
KR101695270B1 (en) 2017-01-12

Similar Documents

Publication Publication Date Title
CN106699573A (en) Spiro-typed organic materials and organic electroluminescent device utilizing the same
CN104871332B (en) Organic electroluminescent element and electronic device
CN103288656B (en) Pyrene-based compound, organic light emitting diode comprising the same and organic light emitting apparatus comprising the same
CN104768928B (en) Condensed fluoranthene compound, material for organic electroluminescent element using same, and organic electroluminescent element and electronic device using same
CN105283977B (en) Material for organic electroluminescent element, organic electroluminescent element using same, and electronic device
US10297761B2 (en) Organic electroluminescent element
CN103313980B (en) Biscarbazole derivative and organic electroluminescent element using same
CN103620808B (en) Organic electroluminescent element
CN103904227B (en) Organic light emitting diode
CN103304428A (en) Amine-based compound, organic light-emitting diode including the same, and organic light-emitting apparatus including the amine-based compound
CN105408310B (en) Carbazole derivates have used its material for organic electroluminescence device and have used its organic electroluminescent device and electronic equipment
CN105408311B (en) Compound, organic electroluminescent element, and electronic device
KR20190037176A (en) Compound and organic light emitting device comprising same
CN104995195B (en) Heterocyclic compound, material for organic electroluminescent element using same, and organic electroluminescent element and electronic device using same
CN106803541A (en) Organic light emitting apparatus
CN104271575B (en) Nitrogen-containing heterocycle compound and the organic electronic element including the nitrogen-containing heterocycle compound
CN110892541A (en) Light-emitting element, display including the same, lighting device, and sensor
CN107431136A (en) Organic electroluminescent element, electronic device, and compound
CN107851724A (en) Organic electric-field light-emitting element
CN102838604B (en) Heterogeneous ring compound and the organic light-emitting device comprising this heterogeneous ring compound
KR20110134201A (en) Compound containing carbazole and aromatic amine derivative compound, and organic electronic element using the same, terminal thereof
CN102598344A (en) Organic electroluminescent element
CN106796993B (en) Organic electroluminescence device
CN104230861A (en) Amine-based compound and organic light-emitting device including the same
CN103992232A (en) Compound and organic light-emitting diode including the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant