CN109111461A - A kind of new compound and its application in electroluminescent device - Google Patents

A kind of new compound and its application in electroluminescent device Download PDF

Info

Publication number
CN109111461A
CN109111461A CN201710481164.4A CN201710481164A CN109111461A CN 109111461 A CN109111461 A CN 109111461A CN 201710481164 A CN201710481164 A CN 201710481164A CN 109111461 A CN109111461 A CN 109111461A
Authority
CN
China
Prior art keywords
substituted
amine
condensed
group
independently selected
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
CN201710481164.4A
Other languages
Chinese (zh)
Other versions
CN109111461B (en
Inventor
王星
范洪涛
张伟
任雪艳
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.)
Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
Original Assignee
Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Eternal Material Technology Co Ltd, Guan Eternal Material Technology Co Ltd filed Critical Beijing Eternal Material Technology Co Ltd
Priority to CN201710481164.4A priority Critical patent/CN109111461B/en
Publication of CN109111461A publication Critical patent/CN109111461A/en
Application granted granted Critical
Publication of CN109111461B publication Critical patent/CN109111461B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/20—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/20—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/20—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/20—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • 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
    • 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
    • H10K85/657—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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene

Landscapes

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

Abstract

The present invention provides a kind of general formula compounds to be indicated by such as following formula:Wherein, CY1 show the substituted or non-substituted condensed-nuclei aromatics of C6~C30, and X, Y, Z are respectively and independently selected from S, O or N (R8), n represents 0 or 1, R1To R8It is respectively and independently selected from the alkyl of hydrogen, C1~C20, the substituted or non-substituted miscellaneous amine of virtue of the substituted or non-substituted aryl or condensed-nuclei aromatics group of C6~C60, the substituted or non-substituted arylamine of C6~C60, the substituted or non-substituted heteroaryl of C4~C60 or condensed hetero ring aromatic hydrocarbon group, C4~C60.General formula compound of the present invention can be used in organic electroluminescence device.

Description

A kind of new compound and its application in electroluminescent device
Technical field
The present invention relates to a kind of novel organic compound more particularly to a kind of chemical combination for organic electroluminescence device Object further relates to application of such compound in organic electroluminescence device.
Background technique
Most of hole transport (injection) material for OLED device being currently known is aromatic triamine class compound, Including the diamine compounds being coupled in pairs, star triphenyl amine compound, spiral shell shape triphenyl amine compound, branch type triphen amination Close object, triaryl amine polymer, carbazole compound, organosilicon, organometallic complex hole mobile material.These are known empty Cave transmits (injection) material and is applied to device, and efficiency and service life are also not especially desirable, develop new hole transport (injection) Material is still very urgent.Additionally, due to OLED device when applying voltage-operated, Joule heat can be generated, so that organic material It is easy to happen crystallization, the efficiency (service life) of device has apparent reduction (shortening) in this case.
Ideal small molecule hole transport material should have high thermal stability, form small potential barrier with anode, can be true Sky vapor deposition forms pin-free film.A resolving ideas is to introduce rigid structure group in the industry, passes through effect of steric hindrance reality Existing intramolecular distortion, reduces a kind of intermolecular aggregation: spiro-compound involved in Merk patent WO2013017189A1, so that The mode of dibenzofurans (or dibenzothiophenes, carbazole) group is formed together 3 with the aryl rings of loop coil (spironane) skeleton With 4 at be substituted.A kind of spiro-compound involved in Samsung patent KR20150113642A is related to loop coil (spironane) Aromatic ring on skeleton contains the compound an of naphthalene (or luxuriant and rich with fragrance) and two dibenzofurans groups.But it is public for institute in above-mentioned patent The material molecule opened, structural design scheme does not solve the problems, such as carrier balance, and stability of material is not good enough.
Summary of the invention
To solve the problems, such as that organic material crystallizes, the present invention provides a kind of novel organic electroluminescence device that can be used for New compound.Aromatic ring on the compound spiral shell decane skeleton at least contains a condensed ring and two dibenzofurans (or hexichol Bithiophene, carbazole) group.
The compound of the present invention is indicated by following general formula (1):
Wherein, CY1 indicates that the substituted or non-substituted condensed-nuclei aromatics of C6~C30, the substituent group are selected from C1~C10's Alkyl or cycloalkyl, alkenyl, alkoxy or thio alkoxy group.
X, Y, Z are respectively and independently selected from S, O or N (R8)；N represents 0 or 1；
R1To R8It is respectively and independently selected from the alkyl of hydrogen, C1~C20, substituted or non-substituted aryl or the condensed ring virtue of C6~C60 Hydrocarbyl group, the substituted or non-substituted arylamine of C6~C60, C4~C60 substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbons The substituted or non-substituted miscellaneous amine of virtue of group, C4~C60.
Specifically, as the above-mentioned R of definition1To R8Refer to when being respectively and independently selected from aryl selected from certain amount ring skeleton carbon Aromatics ring system of atom, including single ring architecture substituent group such as phenyl etc. also include the aromatic ring substituents for being covalently attached structure Group is such as xenyl, terphenyl.
Specifically, as the above-mentioned R of definition1To R8Refer to when being respectively and independently selected from condensed-nuclei aromatics group with certain amount ring bone Aromatics ring system of frame carbon atom, including condensed cyclic structure substituent group such as naphthalene, anthryl etc. also include condensed cyclic structure substituent group Building stone being connected with single ring architecture aryl such as benzene binaphthyl, naphthalene xenyl, biphenyl dianthranide base etc., further includes covalently connecting The thick aromatic ring substituents of binding structure are rolled into a ball such as binaphthyl.
Specifically, as the above-mentioned R of definition1To R8Refer to when being respectively and independently selected from heteroaryl or condensed hetero ring aromatic hydrocarbon group comprising one It is a or it is multiple selected from B, N, O, S, P (=O), Si and P hetero atom and with ring carbon atom monocycle or fused ring aryl.
Further, CY1 preferably be selected from naphthalene, anthracene, benzanthracene, pyrene, the condensed-nuclei aromatics such as fluoranthene, benzofluoranthrene.
Further, R1To R8It is respectively and independently selected from the alkyl of hydrogen, C1~C10, the substituted or non-substituted virtue of C6~C15 Base or condensed-nuclei aromatics group, the substituted or non-substituted arylamine of C6~C15, C4~C15 substituted or non-substituted heteroaryl or The substituted or non-substituted miscellaneous amine of virtue of condensed hetero ring aromatic hydrocarbon group, C4~C15.
Further, work as R1To R8It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring virtue When hydrocarbyl group, arylamine or heteroaryl amine, the substituent group thereon preferably independently is selected from F, cyano, or the alkyl selected from C1~C10 or Naphthenic base, alkenyl, alkoxy or thio alkoxy group, or be independently selected from containing the hetero atom selected from N, O, S, Si and have The monocycle or fused ring aryl of 4~15 ring carbon atoms.
Further, work as R1To R8It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring When aromatic hydrocarbon group, arylamine or heteroaryl amine, the substituent group thereon preferably independently is selected from cyano, methyl, ethyl, isopropyl, tertiary fourth Base, alkoxy, phenyl, naphthalene, pyridyl group, pyrrole radicals.
Further, R1To R8It preferably independently is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl etc., or preferably is selected from Benzene, biphenyl, terphenyl, naphthalene, 1- phenylnaphthalene, anthracene, benzanthracene, pyrene, fluoranthene, benzofluoranthrene, two fluorenes of spiral shell, fluorenes, indenes etc. or excellent Selected from diphenylamines, two (4- xenyl) amine, N- phenyl-1-naphthylamine, triphenylamine, three (4- xenyl) amine, N- (4- [1,1 '-biphenyl Base])-[1,1 '-xenyl] -2- amine, N- (2- naphthalene)-N- phenyl napthyl -1- amine etc., or preferably be selected from pyridine, carbazole, thiophene, Benzofuran, benzothiophene, dibenzofurans, dibenzothiophenes, benzofuran [2,3-b] pyridine, N- phenyl carbazole etc..
Further, general formula compound of the present invention is preferably that formula (2) indicate:
Wherein, CY1 indicates that the substituted or non-substituted condensed-nuclei aromatics of C6~C30, the substituent group are selected from C1~C10's Alkyl or cycloalkyl, alkenyl, alkoxy or thio alkoxy group；
X and Y is respectively and independently selected from S, O or N (R8)；
R1To R3And R5To R8It is respectively and independently selected from the alkyl of hydrogen, C1~C20, the substituted or non-substituted aryl of C6~C60 Or the substituted or non-substituted heteroaryl or thick of the substituted or non-substituted arylamine of condensed-nuclei aromatics group, C6~C60, C4~C60 The substituted or non-substituted miscellaneous amine of virtue of heterocyclic arene group, C4~C60；
Work as R1To R3And R5To R8It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbons When group, arylamine or heteroaryl amine, the substituent group thereon is independently selected from F, cyano, or alkyl or cycloalkanes selected from C1~C10 Base, alkenyl, alkoxy or thio alkoxy group, or be independently selected from containing selected from N, O, S, Si hetero atom and have 4~ The monocycle or fused ring aryl of 15 ring carbon atoms.
Further, in formula (2), CY1 be selected from naphthalene, anthracene, benzanthracene, pyrene, fluoranthene or benzofluoranthrene；
R1To R3And R5To R8It is respectively and independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, or is selected from benzene, biphenyl, three Biphenyl, naphthalene, 1- phenylnaphthalene, anthracene, benzanthracene, pyrene, fluoranthene, benzofluoranthrene, two fluorenes of spiral shell, fluorenes, indenes, or be selected from diphenylamines, two (4- xenyl) amine, N- phenyl-1-naphthylamine, triphenylamine, three (4- xenyl) amine, N- (4- [1,1 '-xenyl])-[1,1 '-connection Phenyl] -2- amine, N- (2- naphthalene)-N- phenyl napthyl -1- amine, or selected from pyridine, carbazole, thiophene, benzofuran, benzothiophene, Dibenzofurans, dibenzothiophenes, benzofuran [2,3-b] pyridine, N- phenyl carbazole.
Further, in general formula of the invention (1), following specific structure compounds: M1-M25 can preferably be gone out, these Compound is only representative.
General formula compound of the invention, the aromatic ring designed on spiral shell decane skeleton at least contain a condensed ring and two hexichol And furans or dibenzothiophenes or carbazole group, in such molecular structure, the upper half is locally that carbochain hexatomic ring and condensed ring are total With three carbon atoms, condensed ring conjugation, π chain six phase of the molecular configuration close to plane, when increasing molecular stacks between molecule are formed Interaction；It is that molecular configuration is non-planar under spiral shell decane frame in overall structure, can prevents because molecular crystalline influences film forming Energy；Contain electron rich structural unit in molecule simultaneously, there is good offer electronic capability.
Most preferred structural molecule amount both ensure that compound had 1000 or so in this way in the compound of the present invention Higher glass transition temperature, good thermal stability, and be conducive to the technical process when preparing organic electroluminescence device In vacuum evaporation film forming.
Heretofore described spiral shell decane frame compound has compared with high triplet energy level and glass transition temperature, stronger Cavity transmission ability, and it is possible to prevente effectively from fluorescent quenching caused by molecule is assembled under filminess, have luminous efficiency it is high, The advantages of electron injection and transmittability, the stability of film, excellent in te pins of durability, these advantages compare the series derivates Organic luminescence function layer is properly applied to as hole mobile material and/or hole-injecting material.
The present invention also provides the above-mentioned compounds selected from general formula (1) to prepare the purposes in organic electroluminescence device. When in organic electroluminescence device, injection/conveying hole efficiency into luminescent layer can be improved in device, so that current-carrying Quantum balancing advantageously promotes material emission in turn.
Specifically, the compound in the general formula (1) is used as hole-injecting material or sky in organic electroluminescence device Hole transport materials.
The present invention also provides a kind of organic electroluminescence device, which includes first electrode, second electrode and insertion One or more layers organic layer between the first electrode and second electrode, the organic layer include in general formula of the present invention (1) Compound:
Wherein, CY1 indicates that the substituted or non-substituted condensed-nuclei aromatics of C6~C30, the substituent group are selected from C1~C10's Alkyl or cycloalkyl, alkenyl, alkoxy or thio alkoxy group.
X, Y, Z are respectively and independently selected from S, O or N (R8)；N represents 0 or 1；
R1To R8It is respectively and independently selected from the alkyl of hydrogen, C1~C20, substituted or non-substituted aryl or the condensed ring virtue of C6~C60 Hydrocarbyl group, the substituted or non-substituted arylamine of C6~C60, C4~C60 substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbons The substituted or non-substituted miscellaneous amine of virtue of group, C4~C60.
Further, CY1 preferably be selected from naphthalene, anthracene, benzanthracene, pyrene, the condensed-nuclei aromatics such as fluoranthene, benzofluoranthrene.
Further, R1To R8It is respectively and independently selected from the alkyl of hydrogen, C1~C10, the substituted or non-substituted virtue of C6~C15 Base or condensed-nuclei aromatics group, the substituted or non-substituted arylamine of C6~C15, C4~C15 substituted or non-substituted heteroaryl or The substituted or non-substituted miscellaneous amine of virtue of condensed hetero ring aromatic hydrocarbon group, C4~C15.
Further, work as R1To R8It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring virtue When hydrocarbyl group, arylamine or heteroaryl amine, the substituent group thereon preferably independently is selected from F, cyano, or the alkyl selected from C1~C10 or Naphthenic base, alkenyl, alkoxy or thio alkoxy group, or be independently selected from containing the hetero atom selected from N, O, S, Si and have The monocycle or fused ring aryl of 4~15 ring carbon atoms.
Further, work as R1To R8It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring When aromatic hydrocarbon group, arylamine or heteroaryl amine, the substituent group thereon preferably independently is selected from cyano, methyl, ethyl, isopropyl, tertiary fourth Base, alkoxy, phenyl, naphthalene, pyridyl group, pyrrole radicals.
Further, R1To R8It preferably independently is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl etc., or preferably is selected from Benzene, biphenyl, terphenyl, naphthalene, 1- phenylnaphthalene, anthracene, benzanthracene, pyrene, fluoranthene, benzofluoranthrene, two fluorenes of spiral shell, fluorenes, indenes etc. or excellent Selected from diphenylamines, two (4- xenyl) amine, N- phenyl-1-naphthylamine, triphenylamine, three (4- xenyl) amine, N- (4- [1,1 '-biphenyl Base])-[1,1 '-xenyl] -2- amine, N- (2- naphthalene)-N- phenyl napthyl -1- amine etc., or preferably be selected from pyridine, carbazole, thiophene, Benzofuran, benzothiophene, dibenzofurans, dibenzothiophenes, benzofuran [2,3-b] pyridine, N- phenyl carbazole etc..
Specific embodiment
In order to make those skilled in the art more fully understand the present invention, With reference to embodiment to the present invention make into One step is described in detail.
The compound for the synthetic method that do not mention in the present invention is all the raw produce being obtained through commercial channels.Implement The iodo- 9H- fluorenes -9- ketone of the bromo- 7- of various chemicals such as 2-, the bromo- 2- chlorophenol of 4-, cupric iodide, three (2,4- penta 2 used in example Ketone) close iron (III), potassium carbonate, N,N-dimethylformamide, sodium sulphate, the bromo- 6- chlorophenol of 2-, acid chloride, di-t-butyl (first Base) phosphine tetrafluoroborate, cesium carbonate, n-BuLi the bromo- 8- phenylnaphthalene of cyclohexane solution (2.4M), 1-, sodium bicarbonate, two Chloromethanes, silica gel, glacial acetic acid, hydrochloric acid (12N), N- ([1,1'- xenyl] -4-yl)-[1,1'- xenyl] -2- amine, three (two BENZYLIDENE ACETONE) two palladiums, tri-tert-butylphosphine (50% toluene solution), sodium tert-butoxide, ethyl acetate, 4- [naphthalene -1-yl (naphthalene -2- Yl) amine] phenyl boric acid, tetra-triphenylphosphine palladium, the bromo- 6- chlorobenzenethiol of 2-, the bromo- 6- chlorobenzenethiol of 2-, 9,9- spiral shell, two fluorenes -2- boric acid, 4- tert-butylbenzeneboronic acid, the bromo- 6- chlorophenol of 2,4- bis-, the iodo- 9H- fluorenes -9- ketone of the chloro- 7- of the bromo- 4- of 2-, diphenylamines, 2- chlorophenol, (4- ((4- methyl -5- (o- tolyl) pyridine -2-yl) (naphthalene -1-yl) amine) phenyl) boric acid, 1- (8- bromonaphthalene base -1-yl) -8- Chlorodiphenyl simultaneously [b, d] furans, N- phenyl benzofurans [2,3-b] pyridine -6- amine, 1- (3- bromine pyrene -4-yl) dibenzo [b, d] furan It mutters, (4- ((2- ethyl -6- tolyl) (6- phenylnaphthalene -2-yl) amine) phenyl) boric acid, the iodo- 9H- fluorenes -9- of the chloro- 7- of the bromo- 4- of 2- Ketone, 1- (1- bromine anthryl -9-yl) dibenzo [b, d] furans, N- ([1,1'- xenyl] -2-yl) -9,9- dimethyl -9H- fluorenes - 3- amine, 1- (10- bromine phenanthryl -1-yl) dibenzo [b, d] furans, N- (4- (naphthalene -2-yl) phenyl) -2,3- dihydro -1H- indenes - 5- amine, 1- (8- bromine phenanthryl -9-yl) dibenzo [b, d] thiophene, carbazole, 1- (8- bromine benzanthracene -7-yl) dibenzo [b, d] furan It mutters, 3,5- diphenyl benzene boric acid, the bromo- 2- chlorophenol of 3-, bromo- 9- benzo [f] benzanthracene of 10-, (3- (9H- carbazole -9-yl) benzene Base) boric acid, 2- (2- (6- bromine strategic point alkene -5-yl) phenyl) -5- tolylthiophene, the bromo- 4- phenyl fluoranthene of 3-, the bromo- 4,7,12- triphen of 3- Base benzo [k] fluoranthene, the bromo- 8- phenylnaphthalene of 1- replace with 1- (the bromo- 3-yl of 4-) dibenzo [b, d] furans, 1- (the bromo- 3- of 4- Yl) dibenzo [b, d] furans, (4'- (two ([1,1'- xenyl] -4-yl) amine)-[1,1'- xenyl] -4-yl) boric acid, 6- ([1,1'- symbasis] -4-yl) -1- (4- bromo -3-yl) dibenzo [b, d] furans, 4- (4- bromo -3-yl) -9- methyl - 9H- carbazole, sodium hydride (mineral oil mixture of net content 60%), the bromo- isopropylbenzene of 4-, the bromo- 4- phenyl fluoranthene of 3-, 1- bromonaphthalene, 1- (1- bromine anthryl -9-yl) dibenzo [b, d] furans, N- ([1,1'- xenyl] -2-yl) -9,9- dimethyl -9H- fluorenes -3- The industrial chemicals such as bromo- 9- phenyl benzo [f] triphenylene of amine, 10- or intermediate chemical products can be commercially available at home.
The analysis detection of intermediate and compound in the present invention uses AB SCIEX mass spectrograph (4000 QTRAP).
Synthetic example:
The synthesis of 1. compound M1 of synthetic example
The synthesis of 1.1 intermediate As 5
Step 1: the synthesis of intermediate A 1
Under nitrogen protection, magnetic agitation, by the iodo- 9H- fluorenes -9- ketone of the bromo- 7- of 2-: the bromo- 2- chlorobenzene of 46.8g (122mmol), 4- Phenol: 24.72g, cupric iodide: 2.29g, three (2,4- pentanediones) close iron (III): 8.47g, potassium carbonate: 33.2g, N, N- dimethyl methyl Amide: 240mL is added in flask, carries out 10 hours heating stirrings.
After being cooled to room temperature (25 DEG C), filtering reacting solution extracts reaction solution using toluene, after removing water layer, will have It is several layers of to be washed with saturated aqueous ammonium chloride.After there be several layers of dryings with sodium sulphate, it is concentrated, solvent under reduced pressure is evaporated.It will Residue silica gel chromatography obtains yellow solid 31.03g, yield 56%.
Step 2: the synthesis of intermediate A 2
Under nitrogen protection, magnetic agitation, by the bromo- 6- chlorophenol of intermediate A 1:56.3g (122mmol), 2-: 25.0g, iodine Change copper: 2.29g, three (2,4- pentanediones) close iron (III): 8.47g, potassium carbonate: 33.2g, N,N-dimethylformamide: 240mL adds Enter in flask, carries out 10 hours heating stirrings.
After being cooled to room temperature (25 DEG C), filtering reacting solution evaporates solvent under reduced pressure.Residue silica gel column chromatography is pure Change, obtains yellow solid 18.8g, yield 50%.
Step3: the synthesis of intermediate A 3
Under nitrogen protection, magnetic agitation, by intermediate A 2:20.7g (40.2mmol), acid chloride: 0.54g, di-t-butyl (methyl) phosphine tetrafluoroborate: 1.19g, cesium carbonate: 65.0g, n,N-Dimethylformamide: 200mL are added in flask, 130 DEG C carry out 17 hours heating stirrings.
After being cooled to room temperature (25 DEG C), filtering reacting solution extracts reaction solution using toluene, after removing water layer, will have It is several layers of to be washed with saturated aqueous ammonium chloride.After organic layer sodium sulphate drying, it is concentrated, solvent under reduced pressure is evaporated.It will Residue silica gel chromatography obtains yellow solid 8.3g, yield 40%.
Step4: the synthesis of intermediate A 4
Under nitrogen protection, the bromo- 8- phenylnaphthalene of 1-: 28.2g (100mmol), tetrahydrofuran 800mL is added magnetic agitation In flask, reaction solution is down to -80 DEG C by ethyl alcohol/liquid nitrogen bath, and cyclohexane solution (2.4M) 41.7mL of n-BuLi is added dropwise, and drop finishes Heat preservation 30 minutes.Intermediate A 3:51.6g is added, warms naturally to after room temperature that the reaction was continued 10 hours.
100ml sodium bicarbonate aqueous solution (10%) is quenched, and reaction solution is extracted using methylene chloride, by organic layer sodium sulphate It after drying, is concentrated, solvent under reduced pressure is evaporated.By residue silica gel chromatography, yellow solid 57.5g, yield are obtained 80%.
Step5: the synthesis of intermediate A 5
Under nitrogen protection, magnetic agitation, by intermediate A 4:57.5g (80mmol), glacial acetic acid 500ml, catalytic amount hydrochloric acid (12N) 0.3mL addition flask, back flow reaction 12 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (methylene chloride/petroleum Ether=2/1), obtain off-white powder 44.8g, yield 80%.
The synthesis of 1.2 compound M1
Step6: the synthesis of intermediate A 5
Under nitrogen protection, magnetic agitation, by intermediate A 5:44.8g (64mmol), N- ([1,1'- xenyl] -4-yl) - [1,1'- xenyl] -2- amine: 20.6g, tris(dibenzylideneacetone) dipalladium: 0.59g, tri-tert-butylphosphine (50% toluene solution): 0.13mL, sodium tert-butoxide: 12.3g, toluene: 500mL are added in flask, and 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 22.1g, yield 40%.
Step7: the synthesis of compound M1
Under nitrogen protection, magnetic agitation, by intermediate A 6:22.1g (25.6mmol), 4- [naphthalene -1-yl (naphthalene -2-yl) amine] Phenyl boric acid: 10g, tetra-triphenylphosphine palladium: 0.3g, potassium carbonate: 6.1g, toluene: 300mL, ethyl alcohol: 100mL, water: 200mL, which are added, to be burnt In bottle, 70 DEG C are reacted 18 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 24.7g, yield 80%.
Product MS (m/e): 1208.43；Elemental analysis (C91H56N2O2): theoretical value C, 90.37；H,4.67；N,2.32； O,2.65；Measured value C, 90.36；H,4.66；N,2.31.
The synthesis of 2. compound M2 of synthetic example
The synthesis of 2.1 intermediate Bs 5
Referring to B5 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced For the bromo- 6- chlorobenzenethiol of 2-；The bromo- 6- chlorophenol of 2- in Step 2 replaces with the bromo- 6- chlorobenzenethiol of 2-.
The synthesis of 2.2 compound M2
Step6: the synthesis of intermediate B 6
Under nitrogen protection, magnetic agitation, by intermediate B 5:47.0g (64mmol), 9,9- spiral shell, two fluorenes -2- boric acid: 23.0g, Tris(dibenzylideneacetone) dipalladium: 0.59g, tri-tert-butylphosphine (50% toluene solution): 0.13mL, sodium tert-butoxide: 12.3g, first Benzene: 500mL is added in flask, and 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 17.1g, yield 30%.
Step7: the synthesis of compound M2
Under nitrogen protection, magnetic agitation, by intermediate B 6:22.8g (25.6mmol), 4- tert-butylbenzeneboronic acid: 4.6g, four Triphenylphosphine palladium: 0.3g, potassium carbonate: 6.1g, toluene: 300mL, ethyl alcohol: 100mL, water: 200mL are added in flask, 70 DEG C of reactions 18 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 20.9g, yield 80%.
Product MS (m/e): 1024.32；Elemental analysis (C76H48S2): theoretical value C, 89.03；H,4.72；S,6.25；It is real Measured value C, 89.04；H,4.73；S,6.23.
The synthesis of 3. compound M3 of synthetic example
The synthesis of 3.1 intermediate C5
Reference 1 intermediate A 5 of embodiment synthesizes C5 in the present embodiment, only the bromo- 2- chlorophenol of 4- in step 1, Step 2 need to be replaced with 2, The bromo- 6- chlorophenol of 4- bis-；The iodo- 9H- fluorenes -9- ketone of the bromo- 7- of 2- in Step 1 replaces with the iodo- 9H- fluorenes -9- of the chloro- 7- of the bromo- 4- of 2- Ketone.
The synthesis of 3.2 compound M3
Step6: the synthesis of compound M3
Under nitrogen protection, magnetic agitation, by intermediate C5:10.8g (12.8mmol), diphenylamines: 10.8g, three (two benzal Benzylacetone) two palladiums: 0.59g, tri-tert-butylphosphine (50% toluene solution): 0.13mL, sodium tert-butoxide: 12.3g, toluene: 500mL adds Enter in flask, 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 10.6g, yield 60%.
Product MS (m/e): 1381.53；Elemental analysis (C101H67N5O2): theoretical value C, 87.74；H,4.88；N, 5.07；O,2.31；Measured value C, 87.75；H,4.87；N,5.06.
The synthesis of 4. compound M4 of synthetic example
The synthesis of 4.1 intermediate D5
Referring to D5 in 1 intermediate A 5 of embodiment synthesis the present embodiment, only the bromo- 2- chlorophenol of the 4- of step 1 need to be replaced with 2- chlorine Phenol.
The synthesis of 4.2 compound M4
Step6: the synthesis of compound M4
Under nitrogen protection, magnetic agitation, by intermediate D5:16.0g (25.6mmol), (4- ((4- methyl -5- (o- toluene Base) pyridine -2-yl) (naphthalene -1-yl) amine) phenyl) boric acid: 11.4g, tetra-triphenylphosphine palladium: 0.3g, potassium carbonate: 6.1g, toluene: 300mL, ethyl alcohol: 100mL, water: 200mL are added in flask, and 70 DEG C are reacted 18 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 14.5g, yield 60%.
Product MS (m/e): 944.34；Elemental analysis (C70H44N2O2): theoretical value C, 88.96；H,4.69；N,2.96； O,3.39；Measured value C, 88.95；H,4.70；N,2.97.
The synthesis of 5. compound M5 of synthetic example
The synthesis of 5.1 intermediate Es 5
It, only need to be by the bromo- 2- chlorobenzene of the 4- of step 1, step 2 referring to E5 in 1 intermediate A 5 of embodiment synthesis the present embodiment Phenol replaces with 2- chlorophenol, and the bromo- 8- phenylnaphthalene of 1- in step 4 is replaced with 1- (8- bromonaphthalene base -1-yl), and -8- chlorodiphenyl is simultaneously [b, d] furans.
The synthesis of 5.2 compound M5
Step6: the synthesis of compound M5
Under nitrogen protection, magnetic agitation, by intermediate E 5:8.6g (12.8mmol), N- phenyl benzofurans [2,3-b] pyrrole Pyridine -6- amine: 3.3g, tris(dibenzylideneacetone) dipalladium: 0.59g, tri-tert-butylphosphine (50% toluene solution): 0.13mL, tertiary fourth Sodium alkoxide: 12.3g, toluene: 500mL are added in flask, and 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 4.6g, yield 40%.
Product MS (m/e): 894.25；Elemental analysis (C64H34N2O4): theoretical value C, 85.89；H,3.83；N,3.13； O,7.15；Measured value C, 85.88；H,3.82；N,3.14.
The synthesis of 6. compound M6 of synthetic example
The synthesis of 6.1 intermediate F5
Referring to D5 in 1 intermediate A 5 of embodiment synthesis the present embodiment, only the bromo- 2- chlorophenol of the 4- of step 1 need to be replaced with 2- chlorine The bromo- 8- phenylnaphthalene of 1- in step 4 is replaced with 1- (3- bromine pyrene -4-yl) dibenzo [bd] furans by phenol.
The synthesis of 6.2 compound M6
Step6: the synthesis of compound M6
Under nitrogen protection, magnetic agitation, by intermediate F5:20.2g (25.6mmol), (4- ((2- ethyl -6- tolyl) (6- phenylnaphthalene -2-yl) amine) phenyl) boric acid: 11.7g, tetra-triphenylphosphine palladium: 0.3g, potassium carbonate: 6.1g, toluene: 300mL, second Alcohol: 100mL, water: 200mL are added in flask, and 70 DEG C are reacted 18 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 17.2g, yield 60%.
Product MS (m/e): 1121.39；Elemental analysis (C84H51NO3): theoretical value C, 89.89；H,4.58；N,1.25； O,4.28；Measured value C, 89.88；H,4.57；N,1.27.
The synthesis of 7. compound M7 of synthetic example
The synthesis of 7.1 intermediate G5
Referring to D5 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the iodo- 9H- fluorenes -9- of the bromo- 7- of 2- in Step 1 is only needed Ketone replaces with the iodo- 9H- fluorenes -9- ketone of the chloro- 7- of the bromo- 4- of 2-, and the bromo- 8- phenylnaphthalene of 1- in step 4 is replaced with 1- (1- bromine anthryl - 9-yl) dibenzo [b, d] furans.
The synthesis of 7.2 compound M7
Step6: the synthesis of compound M7
Under nitrogen protection, magnetic agitation, by intermediate G5:9.2g (12.8mmol), N- ([1,1'- xenyl] -2-yl) - 9,9- dimethyl -9H- fluorenes -3- amine: (50% toluene is molten for 4.6g, tris(dibenzylideneacetone) dipalladium: 0.59g, tri-tert-butylphosphine Liquid): 0.13mL, sodium tert-butoxide: 12.3g, toluene: 500mL are added in flask, and 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 6.7g, yield 50%.
Product MS (m/e): 1045.36；Elemental analysis (C78H47NO3): theoretical value C, 89.55；H,4.53；N,1.34； O,4.59；Measured value C, 89.55；H,4.53；N,1.34.
The synthesis of 8. compound M8 of synthetic example
The synthesis of 8.1 intermediate H5
Referring to D5 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the iodo- 9H- fluorenes -9- of the bromo- 7- of 2- in Step 1 is only needed Ketone replaces with the iodo- 9H- fluorenes -9- ketone of the chloro- 7- of the bromo- 4- of 2-, and the bromo- 8- phenylnaphthalene of 1- in step 4 is replaced with 1-, and (10- bromine is luxuriant and rich with fragrance Base -1-yl) dibenzo [b, d] furans.
The synthesis of 8.2 compound M8
Step6: the synthesis of compound M8
Under nitrogen protection, magnetic agitation, by intermediate H5:9.2g (12.8mmol), N- (4- (naphthalene -2-yl) phenyl) - 2,3- dihydro -1H- indenes -5- amine: 4.3g, tris(dibenzylideneacetone) dipalladium: 0.59g, tri-tert-butylphosphine (50% toluene solution): 0.13mL, sodium tert-butoxide: 12.3g, toluene: 500mL are added in flask, and 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 5.2g, yield 40%.
Product MS (m/e): 1019.34；Elemental analysis (C76H45NO3): theoretical value C, 89.48；H,4.45；N,1.37； O,4.70；Measured value C, 89.46；H,4.47；N,1.37.
The synthesis of 9. compound M9 of synthetic example
The synthesis of 9.1 intermediate compound Is 5
Referring to I5 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 6- chlorophenol of 2- in Step 2 need to only be replaced For 2- chlorophenol, the bromo- 8- phenylnaphthalene of 1- in step 4 is replaced with into 1- (8- bromine phenanthryl -9-yl) dibenzo [b, d] thiophene.
The synthesis of 9.2 compound M9
Step6: the synthesis of compound M9
Under nitrogen protection, magnetic agitation, by intermediate compound I 5:9.4g (12.8mmol), carbazole: 2.1g, three (dibenzylidenes third Ketone) two palladiums: 0.59g, tri-tert-butylphosphine (50% toluene solution): 0.13mL, sodium tert-butoxide: 12.3g, toluene: 500mL, which are added, to be burnt In bottle, 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 4.4g, yield 40%.
Product MS (m/e): 867.22；Elemental analysis (C63H33NO2S): theoretical value C, 87.17；H,3.83；N,1.61； O,3.69；S,3.69；Measured value C, 87.17；H,3.81；N,1.61；S,3.69.
The synthesis of 10. compound M10 of synthetic example
The synthesis of 10.1 intermediate J5
Referring to J5 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced For the bromo- 2- chlorophenol of 5-；The bromo- 6- chlorophenol of 2- in Step 2 replaces with 2- chlorophenol, by the bromo- 8- phenyl of 1- in step 4 Naphthalene replaces with 1- (8- bromine benzanthracene -7-yl) dibenzo [b, d] furans.
The synthesis of 10.2 compound M10
Step6: the synthesis of compound M10
Under nitrogen protection, magnetic agitation, by intermediate J5:20.8g (25.6mmol), 3,5- diphenyl benzene boric acid: 7.0g, Tetra-triphenylphosphine palladium: 0.3g, potassium carbonate: 6.1g, toluene: 300mL, ethyl alcohol: 100mL, water: 200mL are added in flask, and 70 DEG C anti- It answers 18 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 11.3g, yield 60%.
Product MS (m/e): 736.20；Elemental analysis (C55H28O3): theoretical value C, 89.66；H,3.83；O,6.51；It is real Measured value C, 89.64；H,3.84.
The synthesis of 11. compound M11 of synthetic example
11.1 the synthesis of intermediate K5
Referring to K5 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced For the bromo- 2- chlorophenol of 3-；The bromo- 6- chlorophenol of 2- in Step 2 replaces with 2- chlorophenol, by the bromo- 8- phenyl of 1- in step 4 Naphthalene replaces with bromo- 9- benzo [f] benzanthracene of 10-.
The synthesis of 11.2 compound M11
Step6: the synthesis of compound M11
Under nitrogen protection, magnetic agitation, by intermediate K5:19.8g (25.6mmol), (3- (9H- carbazole -9-yl) phenyl) Boric acid: 7.3g, tetra-triphenylphosphine palladium: 0.3g, potassium carbonate: 6.1g, toluene: 300mL, ethyl alcohol: 100mL, water: 200mL, which are added, to be burnt In bottle, 70 DEG C are reacted 18 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 12.0g, yield 50%.
Product MS (m/e): 937.30；Elemental analysis (C71H39NO2): theoretical value C, 90.91；H,4.19；N,1.49；O, 3.41；Measured value C, 90.90；H,4.19；N,1.49.
The synthesis of 12. compound M12 of synthetic example
Referring to M12 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced It is changed to 2- chlorophenol；The bromo- 6- chlorophenol of 2- in Step 2 replaces with 2- chlorothio-phenol, by the bromo- 8- phenyl of 1- in step 4 Naphthalene replaces with 5- (3- (6- bromo- 10- (tert-butyl) benzanthracene -7-yl) phenyl) benzofuran.
Product MS (m/e): 834.26；Elemental analysis (C61H38O2S): theoretical value C, 87.74；H,4.59；O,3.83；S, 3.84；Measured value C, 87.71；H,4.60；S,3.85.
The synthesis of 13. compound M13 of synthetic example
Referring to M13 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced It is changed to 2- chlorothio-phenol；The bromo- 6- chlorophenol of 2- in Step 2 replaces with 2- chlorothio-phenol, by the bromo- 8- benzene of 1- in step 4 Base naphthalene replaces with 2- (2- (6- bromine strategic point alkene -5-yl) phenyl) -5- tolylthiophene.
Product MS (m/e): 760.14；Elemental analysis (C53H28S3): theoretical value C, 83.65；H,3.71；S,12.64；It is real Measured value C, 83.65；H,3.71；S,12.64.
The synthesis of 14. compound M14 of synthetic example
Referring to M14 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced It is changed to 6- ethyl -2- chlorophenol；The bromo- 6- chlorophenol of 2- in Step 2 replaces with 6- methyl -2- chlorophenol, will be in step 4 The bromo- 8- phenylnaphthalene of 1- replaces with the bromo- 4- phenyl fluoranthene of 3-.
Product MS (m/e): 662.22；Elemental analysis (C50H30O2): theoretical value C, 90.61；H,4.56；O,4.83；It is real Measured value C, 90.63；H,4.55.
The synthesis of 15. compound M15 of synthetic example
Referring to M15 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced It is changed to the chloro- 4,6- diphenyl phenol of 2-；The bromo- 6- chlorophenol of 2- in Step 2 replaces with chloro- 4, the 6- diphenyl phenol of 2-, will The bromo- 8- phenylnaphthalene of 1- in step 4 replaces with bromo- 4,7,12- triphenyl benzo [k] fluoranthene of 3-.
Product MS (m/e): 1126.38；Elemental analysis (C87H50O2): theoretical value C, 92.69；H,4.47；O,2.84；It is real Measured value C, 92.60；H,4.50.
The synthesis of 16. compound M16 of synthetic example
Referring to M16 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced It is changed to the chloro- 2'- ethyl -6'- methyl-of 3- [1,1'- biphenyl] -2- mercaptan；The bromo- 6- chlorophenol of 2- in Step 2 replaces with 4'- Chloro- [1,1'- the biphenyl] -4- mercaptan of (tert-butyl) -3-, replaces with 1- (the bromo- 3- of 4- for the bromo- 8- phenylnaphthalene of 1- in step 4 Yl) dibenzo [b, d] furans.
Product MS (m/e): 1042.33；Elemental analysis (C76H50OS2): theoretical value C, 87.49；H,4.83；O,1.53； S,6.15；Measured value C, 87.49；H,4.83；S,6.15.
The synthesis of 17. compound M17 of synthetic example
The synthesis of 17.1 intermediate P5
Referring to P5 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced For the bromo- 2- chlorobenzenethiol of 3-；The bromo- 6- chlorophenol of 2- in Step 2 replaces with 2- chlorobenzenethiol mercaptan, by the 1- in step 4 Bromo- 8- phenylnaphthalene replaces with 1- (the bromo- 3-yl of 4-) dibenzo [b, d] furans.
The synthesis of 17.2 compound M17
Step6: the synthesis of compound M17
Under nitrogen protection, magnetic agitation, by intermediate P5:22.3g (25.6mmol), (4'- (two ([1,1'- xenyls]- 4-yl) amine)-[1,1'- xenyl] -4-yl) boric acid: 13.24g, tetra-triphenylphosphine palladium: 0.3g, potassium carbonate: 6.1g, toluene: 300mL, ethyl alcohol: 100mL, water: 200mL are added in flask, and 70 DEG C are reacted 18 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 6.5g, yield 20%.
Product MS (m/e): 1263.36；Elemental analysis (C93H53NOS2): theoretical value C, 88.33；H,4.22；N,1.11； O,1.27；S,5.07；Measured value C, 88.30；H,4.23；N,1.12；S,5.07.
The synthesis of 18. compound M18 of synthetic example
Referring to M18 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced It is changed to 2- chlorobenzenethiol, the iodo- 9H- fluorenes -9- ketone of the bromo- 7- of 2- replaces with the iodo- 9H- fluorenes -9- ketone of the bromo- 7- of 1- phenyl -2-；In Step 2 The bromo- 6- chlorophenol of 2- replace with 2- chlorobenzenethiol, the bromo- 8- phenylnaphthalene of 1- in step 4 is replaced with into 1- (the bromo- 3- of 4- Yl) dibenzo [b, d] furans.
Product MS (m/e): 868.19；Elemental analysis (C63H32OS2): theoretical value C, 87.07；H,3.71；O,1.84；S, 7.38；Measured value C, 87.00；H,3.73；S,7.41.
The synthesis of 19. compound M19 of synthetic example
Referring to M19 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced It is changed to 2- chlorobenzenethiol；The bromo- 6- chlorophenol of 2- in Step 2 replaces with 2- chlorobenzenethiol, by the bromo- 8- benzene of 1- in step 4 Base naphthalene replaces with 6- ([1,1'- symbasis] -4-yl) -1- (4- bromo -3-yl) dibenzo [b, d] furans.
Product MS (m/e): 944.22；Elemental analysis (C69H36OS2): theoretical value C, 87.68；H,3.84；O,1.69；S, 6.79；Measured value C, 87.66；H,3.85；S,6.80.
The synthesis of 20. compound M20 of synthetic example
The synthesis of 20.1 intermediate S5
Referring to S5 in 1 intermediate A 5 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced For 2- chlorobenzenethiol；The bromo- 6- chlorophenol of 2- in Step 2 replaces with 2- chlorobenzenethiol, by the bromo- 8- phenyl of 1- in step 4 Naphthalene replaces with 4- (the bromo- 3-yl of 4-) -9H- carbazole.
The synthesis of 20.1 compound M20
Step6: the synthesis of compound M20
Under nitrogen protection, magnetic agitation, by intermediate S5:20.2g (25.6mmol), the bromo- N of 4-, N- diphenylaniline: 8.3g, tris(dibenzylideneacetone) dipalladium: 1.2g, tri-tert-butylphosphine (50% toluene solution): 0.26mL, sodium tert-butoxide: 24.6g, toluene: 1000mL are added in flask, and 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 3.9g, yield 15%.
Product MS (m/e): 1034.28；Elemental analysis (C75H42N2S2): theoretical value C, 87.01；H,4.09；N,2.71； S,6.19；Measured value C, 87.00；H,4.10；N,2.71；S,6.19.
The synthesis of 21. compound M21 of synthetic example
The synthesis of 21.1 intermediate T5
Step 1: the synthesis of intermediate T1
Under nitrogen protection, magnetic agitation, by the iodo- 9H- fluorenes -9- ketone of the bromo- 7- of 2-: 26.0g (67.8mmol), the chloro- aniline of 2-: 8.6g, [1,1 '-bis- (diphenylphosphino) ferrocene] palladium (II) dichloride chloride dichloromethane adduct: 0.98g, sodium tert-butoxide: 19.2g, toluene: 100mL are added in flask, carry out 4 hours heating stirrings.
After being cooled to room temperature (25 DEG C), filtering reacting solution evaporates solvent under reduced pressure.Residue silica gel column chromatography is pure Change, obtains yellow solid 15.6g, yield 60%.
Step 2: the synthesis of intermediate T2
Under nitrogen protection, magnetic agitation, by intermediate T1:26.0g (67.8mmol), 2- chloroaniline: 8.6g, [1,1 '-is bis- (diphenylphosphino) ferrocene] palladium (II) dichloride chloride dichloromethane adduct: 0.98g, sodium tert-butoxide: 19.2g, toluene: 100mL is added in flask, carries out 4 hours heating stirrings.
After being cooled to room temperature (25 DEG C), filtering reacting solution evaporates solvent under reduced pressure.Residue silica gel column chromatography is pure Change, obtains yellow solid 20.4g, yield 70%.
Continue to synthesize T5 in the present embodiment referring to 1 intermediate A 5 of embodiment, only the A2 in step 3 need to be replaced with T2；It will The bromo- 8- phenylnaphthalene of 1- in step 4 replaces with 4- (4- bromo -3-yl) -9- methyl -9H- carbazole.
The synthesis of 21.2 compound M21
Step6: the synthesis of intermediate T6
Under nitrogen protection, magnetic agitation, by intermediate T5:19.7g (25.6mmol), the sodium hydride (mine of net content 60% Object oil mixture): 1g, n,N-Dimethylformamide: 200mL are added in flask, and 80 DEG C are reacted 1 hour.Iodoethane 4g is added, returns Stream reaction 12 hours.
After being cooled to room temperature (25 DEG C), add water 200mL, filtering reacting solution obtains filter cake silica gel chromatography (second Acetoacetic ester/petroleum ether=2/1), obtain off-white powder 2.4g, yield 12%.
Step7: the synthesis of compound M20
Under nitrogen protection, magnetic agitation, by intermediate T6:20.5g (25.6mmol), the bromo- isopropylbenzene of 4-: 5.4g, three (two BENZYLIDENE ACETONE) two palladiums: 1.2g, tri-tert-butylphosphine (50% toluene solution): 0.26mL, sodium tert-butoxide: 24.6g, toluene: 1000mL is added in flask, and 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 10.2g, yield 43%.
Product MS (m/e): 931.39；Elemental analysis (C70H49N3): theoretical value C, 90.19；H,5.30；N,4.51；It is real Measured value C, 90.10；H,5.35；N,4.55.
The synthesis of 22. compound M22 of synthetic example
The synthesis of 22.1 intermediate U5
Continue to synthesize U5 in the present embodiment referring to 21 intermediate T5 of embodiment, it only need to be by the 2- chlorine in step 1, step 2 Aniline replaces with the chloro- 4- of 2- (2- naphthalene) aniline；The bromo- 8- phenylnaphthalene of 1- in step 4 is replaced with into the bromo- 4- phenyl fluoranthene of 3-.
The synthesis of 22.2 compound M22
Step6: the synthesis of intermediate U6
Under nitrogen protection, magnetic agitation, by intermediate U5:22.2g (25.6mmol), bromobenzene: 4g, tetra-triphenylphosphine palladium: 0.3g, potassium carbonate: 6.1g, toluene: 300mL, ethyl alcohol: 100mL, water: 200mL are added in flask, and 70 DEG C are reacted 18 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 13.3g, yield 55%.
Step7: the synthesis of compound M22
Under nitrogen protection, magnetic agitation, by intermediate U6:24.2g (25.6mmol), 3- bromopyridine: 4g, three (two benzal Benzylacetone) two palladiums: 1.2g, tri-tert-butylphosphine (50% toluene solution): 0.26mL, sodium tert-butoxide: 24.6g, toluene: 1000mL adds Enter in flask, 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 8.6g, yield 33%.
Product MS (m/e): 1023.36；Elemental analysis (C78H45N3): theoretical value C, 91.47；H,4.43；N,4.10；It is real Measured value C, 91.46；H,4.44；N,4.10.
The synthesis of 23. compound M23 of synthetic example
The synthesis of 23.1 intermediate V5
Continue to synthesize U5 in the present embodiment referring to 21 intermediate T5 of embodiment, it only need to be by the 2- chlorine in step 1, step 2 Aniline replaces with 2,4,6- trichloroanilines；It is iodo- that the iodo- 9H- fluorenes -9- ketone of the bromo- 7- of 2- in Step 1 replaces with the chloro- 7- of the bromo- 4- of 2- 9H- fluorenes -9- ketone.
The synthesis of 23.2 compound M23
Step6: the synthesis of intermediate V6
Under nitrogen protection, magnetic agitation, by intermediate V5:18.2g (25.6mmol), the sodium hydride (mine of net content 60% Object oil mixture): 1g, n,N-Dimethylformamide: 200mL are added in flask, and 80 DEG C are reacted 1 hour.Iodomethane 3.6g is added, Back flow reaction 12 hours.
After being cooled to room temperature (25 DEG C), add water 200mL, filtering reacting solution obtains filter cake silica gel chromatography (second Acetoacetic ester/petroleum ether=2/1), obtain off-white powder 10.2g, yield 55%.
Step7: the synthesis of intermediate V7
Under nitrogen protection, magnetic agitation, by intermediate V6:18.6g (25.6mmol), 1- bromonaphthalene: 5.2g, three (two benzal Benzylacetone) two palladiums: 1.2g, tri-tert-butylphosphine (50% toluene solution): 0.26mL, sodium tert-butoxide: 24.6g, toluene: 1000mL adds Enter in flask, 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 12.0g, yield 55%.
Step8: the synthesis of compound M23
Under nitrogen protection, magnetic agitation, by intermediate V7:4.3g (5.1mmol), diphenylamines 4.3g:4g, three (two benzal Benzylacetone) two palladiums: 1.2g, tri-tert-butylphosphine (50% toluene solution): 0.26mL, sodium tert-butoxide: 24.6g, toluene: 1000mL adds Enter in flask, 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain greenish yellow solid 2.5g, yield 33%.
Product MS (m/e): 1519.62；Elemental analysis (C112H77N7): theoretical value C, 88.45；H,5.10；N,6.45； Measured value C, 88.44；H,5.11；N,6.45.
The synthesis of 24. compound M24 of synthetic example
The synthesis of 24.1 intermediate W5
Referring to W1 in 1 intermediate A 1 of embodiment synthesis the present embodiment, the bromo- 2- chlorophenol of 4- in step 1 need to only be replaced For 2- chlorophenol；The iodo- 9H- fluorenes -9- ketone of the bromo- 7- of 2- replaces with the iodo- 9H- fluorenes -9- ketone of the chloro- 7- of the bromo- 4- of 2-.
Continue to synthesize W5 in the present embodiment referring to 21 intermediate T5 of embodiment, it only need to be by the bromo- 8- phenyl of 1- in step 4 Naphthalene replaces with 1- (1- bromine anthryl -9-yl) dibenzo [b, d] furans.
The synthesis of 24.2 compound M24
Step6: the synthesis of intermediate V6
Under nitrogen protection, magnetic agitation, by intermediate W5:18.4g (25.6mmol), 3- bromine strategic point alkene: 5.8g, three (two Asias Benzylacetone) two palladiums: 1.2g, tri-tert-butylphosphine (50% toluene solution): 0.26mL, sodium tert-butoxide: 24.6g, toluene: 1000mL It is added in flask, 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 12.2g, yield 55%.
Step7: the synthesis of compound M24
Under nitrogen protection, magnetic agitation, by intermediate W6:22.2g (25.6mmol), N- ([1,1'- xenyl] -2- Yl) -9,9- dimethyl -9H- fluorenes -3- amine: 9.2g, tris(dibenzylideneacetone) dipalladium: 1.2g, tri-tert-butylphosphine (50% toluene Solution): 0.26mL, sodium tert-butoxide: 24.6g, toluene: 1000mL are added in flask, and 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain off-white powder 15.2g, yield 50%.
Product MS (m/e): 1194.42；Elemental analysis (C90H54N2O2): theoretical value C, 90.43；H,4.55；N,2.34； O,2.68；Measured value C, 90.41；H,4.56；N,2.35.
The synthesis of 25. compound M25 of synthetic example
The synthesis of 25.1 intermediate Xs 5
Continue to synthesize X5 in the present embodiment referring to 21 intermediate T5 of embodiment, the 2- chloroaniline in step 1 need to only be replaced For chloro- [1,1'- the xenyl] -2- amine of 3'- (9H- carbazole -9-yl) -3-；The bromo- 8- phenylnaphthalene of 1- in step 4 replaces with 10- Bromo- 9- phenyl benzo [f] triphenylene.
The synthesis of 25.2 compound M25
Step6: the synthesis of intermediate X 6
Under nitrogen protection, magnetic agitation, by intermediate X 5:23.9g (25.6mmol), the sodium hydride (mine of net content 60% Object oil mixture): 1g, n,N-Dimethylformamide: 200mL are added in flask, and 80 DEG C are reacted 1 hour.Iodomethane 3.6g is added, Back flow reaction 12 hours.
After being cooled to room temperature (25 DEG C), add water 200mL, filtering reacting solution obtains filter cake silica gel chromatography (second Acetoacetic ester/petroleum ether=2/1), obtain off-white powder 13.3g, yield 55%.
Step7: the synthesis of the synthesis of compound M25
Under nitrogen protection, magnetic agitation, by intermediate X 6:24.3g (25.6mmol), 9- (4- bromophenyl) -9H- carbazole: 8.2g, tris(dibenzylideneacetone) dipalladium: 1.2g, tri-tert-butylphosphine (50% toluene solution): 0.26mL, sodium tert-butoxide: 24.6g, toluene: 1000mL are added in flask, and 110 DEG C are reacted 3 hours.
After being cooled to room temperature (25 DEG C), filtering reacting solution obtains filter cake silica gel chromatography (ethyl acetate/petroleum Ether=2/1), obtain greenish yellow solid 17.6g, yield 58%.
Product MS (m/e): 1190.43；Elemental analysis (C90H54N4): theoretical value C, 90.73；H,4.57；N,4.70；It is real Measured value C, 90.71；H,4.58；N,4.71.
It is described in detail below by way of technical effect of the device embodiments to the compounds of this invention.
Device embodiments
The typical structure of the OLED organic electroluminescence device prepared in embodiment are as follows:
On substrate, according to " anode/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/yin The sequence of pole " is laminated, and above-mentioned " stating " indicates to be laminated in order between different function layer.
Several common functional material specific structures of the prior art used in device embodiments are as follows in the present invention:
It is skeletonisation using the spiral shell decyl of the invention synthesized based on above-mentioned synthetic method in device embodiments of the invention Object is closed as the hole mobile material in device.
1. the compound of the present invention M1 of device embodiments is as the hole in blue-fluorescence OLED organic electroluminescence device Transmission material:
Specific organic electroluminescence device structure is ITO (150nm)/2-TNATA (30 nm)/hole mobile material (60 Nm)/ADN:DPAVBi [5%] (30 nm)/Bphen (30 nm)/LiF (0.5nm)/Al (150nm).
Organic electroluminescence device preparation process is as follows: the glass plate for being coated with transparent conductive layer is cleaned in commercialization It is ultrasonically treated in agent, rinses in deionized water, in acetone: ultrasonic oil removing in alcohol mixed solvent (volume ratio 1: 1), in cleaning It is baked under environment and completely removes moisture content, with ultraviolet light and ozone clean, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-5~9 × 10-3Pa, above-mentioned 30 nm of film thickness is deposited as hole injection layer, evaporation rate 0.1nm/s in vacuum evaporation 2-TNATA on anode tunic；
The vacuum evaporation hole mobile material on hole injection layer, evaporation rate 0.1nm/s, vapor deposition total film thickness are 80nm；
The luminescent layer of vacuum evaporation device on hole transmission layer, luminescent layer include material of main part and dye materials, benefit The method steamed altogether with multi-source, adjusting material of main part ADN evaporation rate are 0.1nm/s, and 3% ratio of dyestuff DSA-Ph evaporation rate is set Fixed, vapor deposition total film thickness is 60nm；
The electron transport layer materials Bphen of vacuum evaporation device, evaporation rate 0.1nm/s on luminescent layer steam Plating total film thickness is 30nm；
On electron transfer layer (ETL) vacuum evaporation with a thickness of the LiF of 0.5nm as electron injecting layer, with a thickness of 150 Cathode of the Al layer of nm as device.
Device embodiments 2~10.
Device is prepared using method identical with device embodiments 1, difference is only that sets hole mobile material M1 respectively The compound being changed in the table 1 of equivalent.
Comparative device embodiment 1 uses NPB as the hole transport material in blue-fluorescence OLED organic electroluminescence device Material:
Device is prepared using method identical with device embodiments 1, the difference is that NPB is used to replace M1 as hole Transmission material.
At same brightness 1000cd/m2, the Organic Electricity being prepared in device embodiments 1-10 and comparative example is measured The driving voltage and current efficiency of electroluminescence device, the results are shown in Table 1.
Table 1:
HTL It is required that brightness cd/m2 Voltage V Current efficiency cd/A
Embodiment 1 M1 1000.00 5.1 9.0
Embodiment 2 M5 1000.00 5.2 9.2
Embodiment 3 M9 1000.00 5.0 9.3
Embodiment 4 M14 1000.00 5.3 9.1
Embodiment 5 M15 1000.00 5.1 9.5
Embodiment 6 M19 1000.00 5.2 8.9
Embodiment 7 M14 1000.00 5.4 9.3
Embodiment 8 M22 1000.00 5.2 9.1
Embodiment 9 M24 1000.00 5.3 8.8
Embodiment 10 M25 1000.00 5.2 9.4
Comparative example 1 NPB 1000.00 5.7 8.5
Seen from table 1, the present invention devises totally 10 device embodiments 1-10 for being parallel to comparative example 1.Design scheme are as follows: In the case that other function material is all the same in organic electroluminescence device structure, using this kind of spiral shell decane disclosed by the invention Typical Representative compound in base frame derivative replaces the material NPB in comparative device embodiment 1 as hole mobile material.
Specific in table 1 statistics indicate that, in device embodiments 1 to 10, the operating voltage of each device is respectively less than comparative example 1 The operating voltage 5.7V of middle device, the current efficiency of each device are all larger than the current efficiency 8.5cd/A in comparative example 1.Thus It can be proved that the Typical Representative compound in this kind of spiral shell decane base frame derivative of the present invention used with comparative example it is existing Technologic material NPB is compared, and the stability of the compounds of this invention and injecting when as hole mobile material to luminescent layer and is conveyed The performance in hole, which all has, is extremely obviously improved effect, so the compounds of this invention has ideal practical value.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.

Claims (10)

1. a kind of general formula compound is indicated by such as following formula (1):
Wherein, CY1 indicates that the substituted or non-substituted condensed-nuclei aromatics of C6~C30, the substituent group are selected from the alkyl of C1~C10 Or naphthenic base, alkenyl, alkoxy or thio alkoxy group；
X, Y, Z are respectively and independently selected from S, O or N (R8)；
N represents 0 or 1；
R1To R8It is respectively and independently selected from the alkyl of hydrogen, C1~C20, the substituted or non-substituted aryl or condensed-nuclei aromatics base of C6~C60 Group, the substituted or non-substituted arylamine of C6~C60, the substituted or non-substituted heteroaryl of C4~C60 or condensed hetero ring aromatic hydrocarbon group, The substituted or non-substituted miscellaneous amine of virtue of C4~C60；
Work as R1To R8Be respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, arylamine or When heteroaryl amine, the substituent group thereon is independently selected from F, cyano, or the alkyl or cycloalkyl selected from C1~C10, alkenyl, alcoxyl Base or thio alkoxy group, or be independently selected from containing the hetero atom selected from N, O, S, Si and there are 4~15 ring carbon atoms Monocycle or fused ring aryl.
2. general formula compound according to claim 1, in formula (1):
R1To R8It is respectively and independently selected from the alkyl of hydrogen, C1~C10, the substituted or non-substituted aryl or condensed-nuclei aromatics base of C6~C15 Group, the substituted or non-substituted arylamine of C6~C15, the substituted or non-substituted heteroaryl of C4~C15 or condensed hetero ring aromatic hydrocarbon group, The substituted or non-substituted miscellaneous amine of virtue of C4~C15；
Work as R1To R8Be respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, arylamine or When heteroaryl amine, the substituent group thereon is independently selected from cyano, methyl, ethyl, isopropyl, tert-butyl, alkoxy, phenyl, naphthalene Base, pyridyl group, pyrrole radicals.
3. general formula compound according to claim 1 or 2, in formula (1):
CY1 be selected from naphthalene, anthracene, benzanthracene, pyrene, fluoranthene or benzofluoranthrene；
R1To R8It is respectively and independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, or is selected from benzene, biphenyl, terphenyl, naphthalene, 1- benzene Base naphthalene, anthracene, benzanthracene, pyrene, fluoranthene, benzofluoranthrene, two fluorenes of spiral shell, fluorenes, indenes, or selected from diphenylamines, two (4- xenyl) amine, N- phenyl-1-naphthylamine, triphenylamine, three (4- xenyl) amine, N- (4- [1,1 '-xenyl])-[1,1 '-xenyl] -2- amine, N- (2- naphthalene)-N- phenyl napthyl -1- amine, or it is selected from pyridine, carbazole, thiophene, benzofuran, benzothiophene, dibenzofurans, two Benzothiophene, benzofuran [2,3-b] pyridine, N- phenyl carbazole.
4. general formula compound according to claim 1 is indicated by following formula (2):
Wherein, CY1 indicates that the substituted or non-substituted condensed-nuclei aromatics of C6~C30, the substituent group are selected from the alkyl of C1~C10 Or naphthenic base, alkenyl, alkoxy or thio alkoxy group；
X and Y is respectively and independently selected from S, O or N (R8)；
R1To R3And R5To R8It is respectively and independently selected from the alkyl of hydrogen, C1~C20, the substituted or non-substituted aryl or thick of C6~C60 Aromatic hydrocarbon group, the substituted or non-substituted arylamine of C6~C60, C4~C60 substituted or non-substituted heteroaryl or condensed hetero ring The substituted or non-substituted miscellaneous amine of virtue of aromatic hydrocarbon group, C4~C60；
Work as R1To R3And R5To R8Be respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, When arylamine or heteroaryl amine, the substituent group thereon is independently selected from F, cyano, or the alkyl or cycloalkyl selected from C1~C10, alkene Base, alkoxy or thio alkoxy group, or be independently selected from containing the hetero atom selected from N, O, S, Si and there are 4~15 rings The monocycle or fused ring aryl of carbon atom.
5. general formula compound according to claim 4, in formula (2):
CY1 be selected from naphthalene, anthracene, benzanthracene, pyrene, fluoranthene or benzofluoranthrene；
R1To R3And R5To R8Be respectively and independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, or selected from benzene, biphenyl, terphenyl, Naphthalene, 1- phenylnaphthalene, anthracene, benzanthracene, pyrene, fluoranthene, benzofluoranthrene, two fluorenes of spiral shell, fluorenes, indenes, or selected from diphenylamines, two (4- connection Phenyl) amine, N- phenyl-1-naphthylamine, triphenylamine, three (4- xenyl) amine, N- (4- [1,1 '-xenyl])-[1,1 '-biphenyl Base] -2- amine, N- (2- naphthalene)-N- phenyl napthyl -1- amine, or it is selected from pyridine, carbazole, thiophene, benzofuran, benzothiophene, two Benzofuran, dibenzothiophenes, benzofuran [2,3-b] pyridine, N- phenyl carbazole.
6. general formula compound according to claim 1 or 2 is selected from following concrete structure formulas:
7. application of the general formula compound according to claim 1 or 2 in organic electroluminescence device.
8. application of the structural compounds according to claim 6 in organic electroluminescence device.
9. a kind of organic electroluminescence device, including first electrode, second electrode and it is located at the first electrode and second electrode Between one or more layers organic layer, the organic layer include by following general formula (1) indicate compound:
Wherein, CY1 indicates that the substituted or non-substituted condensed-nuclei aromatics of C6~C30, the substituent group are selected from the alkyl of C1~C10 Or naphthenic base, alkenyl, alkoxy or thio alkoxy group；
X, Y, Z are respectively and independently selected from S, O or N (R8)；
N represents 0 or 1；
R1To R8It is respectively and independently selected from the alkyl of hydrogen, C1~C20, the substituted or non-substituted aryl or condensed-nuclei aromatics base of C6~C60 Group, the substituted or non-substituted arylamine of C6~C60, the substituted or non-substituted heteroaryl of C4~C60 or condensed hetero ring aromatic hydrocarbon group, The substituted or non-substituted miscellaneous amine of virtue of C4~C60；
Work as R1To R8Be respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, arylamine or When heteroaryl amine, the substituent group thereon preferably independently is selected from F, cyano, or the alkyl or cycloalkyl selected from C1~C10, alkenyl, alkane Oxygroup or thio alkoxy group, or be independently selected from containing the hetero atom selected from N, O, S, Si and there are 4~15 ring carbon originals The monocycle or fused ring aryl of son.
10. a kind of organic electroluminescence device, including first electrode, second electrode and it is located at the first electrode and second electrode Between one or more layers organic layer, include the compound selected from following specific structures in the organic layer:
CN201710481164.4A 2017-06-22 2017-06-22 Novel compound and application thereof in electroluminescent device Active CN109111461B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710481164.4A CN109111461B (en) 2017-06-22 2017-06-22 Novel compound and application thereof in electroluminescent device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710481164.4A CN109111461B (en) 2017-06-22 2017-06-22 Novel compound and application thereof in electroluminescent device

Publications (2)

Publication Number Publication Date
CN109111461A true CN109111461A (en) 2019-01-01
CN109111461B CN109111461B (en) 2021-09-10

Family

ID=64732594

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710481164.4A Active CN109111461B (en) 2017-06-22 2017-06-22 Novel compound and application thereof in electroluminescent device

Country Status (1)

Country Link
CN (1) CN109111461B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112479904A (en) * 2019-09-11 2021-03-12 江苏三月光电科技有限公司 Organic compound with indeno-anthracene derivative as core and application thereof
CN113754668A (en) * 2021-09-30 2021-12-07 武汉天马微电子有限公司 Organic compound and application thereof
CN114573592A (en) * 2022-02-06 2022-06-03 上海传勤新材料有限公司 Compound containing spiroindole and aromatic amine and preparation method and application thereof
WO2022124499A1 (en) * 2020-12-09 2022-06-16 엘티소재주식회사 Heterocyclic compound and organic light-emitting device comprising same
CN116529244A (en) * 2020-11-26 2023-08-01 Sfc株式会社 Novel organic compound and organic light-emitting element comprising same

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080099705A (en) * 2007-05-10 2008-11-13 대주전자재료 주식회사 Spiro type organic light emitting materials
WO2010038956A2 (en) * 2008-09-30 2010-04-08 Daejoo Electronic Materials Co., Ltd. Novel aromatic derivatives and organic electroluminescent device comprising same
CN104560014A (en) * 2013-10-23 2015-04-29 海洋王照明科技股份有限公司 Anthracene type blue-light organic electroluminescent material and preparation method and application thereof
CN104560011A (en) * 2013-10-23 2015-04-29 海洋王照明科技股份有限公司 Anthracene type blue-light organic electroluminescent material and preparation method and application thereof
KR20160126399A (en) * 2015-04-23 2016-11-02 주식회사 엘지화학 Compound having double spiro structure and organic light emitting device comprising the same
CN106187966A (en) * 2016-07-05 2016-12-07 中节能万润股份有限公司 A kind of electroluminescent organic material, preparation method and applications
US20170040536A1 (en) * 2015-08-07 2017-02-09 Samsung Display Co., Ltd. Dibenzoborole-based compound and organic light emitting device including the same
CN106397398A (en) * 2016-08-31 2017-02-15 北京绿人科技有限责任公司 Organic compound and application thereof to organic electroluminescent devices
CN106544009A (en) * 2016-10-18 2017-03-29 中节能万润股份有限公司 A kind of electroluminescent organic material with dibenzofuran structure and preparation method thereof and its application

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080099705A (en) * 2007-05-10 2008-11-13 대주전자재료 주식회사 Spiro type organic light emitting materials
WO2010038956A2 (en) * 2008-09-30 2010-04-08 Daejoo Electronic Materials Co., Ltd. Novel aromatic derivatives and organic electroluminescent device comprising same
CN104560014A (en) * 2013-10-23 2015-04-29 海洋王照明科技股份有限公司 Anthracene type blue-light organic electroluminescent material and preparation method and application thereof
CN104560011A (en) * 2013-10-23 2015-04-29 海洋王照明科技股份有限公司 Anthracene type blue-light organic electroluminescent material and preparation method and application thereof
KR20160126399A (en) * 2015-04-23 2016-11-02 주식회사 엘지화학 Compound having double spiro structure and organic light emitting device comprising the same
US20170040536A1 (en) * 2015-08-07 2017-02-09 Samsung Display Co., Ltd. Dibenzoborole-based compound and organic light emitting device including the same
CN106187966A (en) * 2016-07-05 2016-12-07 中节能万润股份有限公司 A kind of electroluminescent organic material, preparation method and applications
CN106397398A (en) * 2016-08-31 2017-02-15 北京绿人科技有限责任公司 Organic compound and application thereof to organic electroluminescent devices
CN106544009A (en) * 2016-10-18 2017-03-29 中节能万润股份有限公司 A kind of electroluminescent organic material with dibenzofuran structure and preparation method thereof and its application

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112479904A (en) * 2019-09-11 2021-03-12 江苏三月光电科技有限公司 Organic compound with indeno-anthracene derivative as core and application thereof
CN112479904B (en) * 2019-09-11 2023-04-07 江苏三月科技股份有限公司 Organic compound with indeno-anthracene derivative as core and application thereof
CN116529244A (en) * 2020-11-26 2023-08-01 Sfc株式会社 Novel organic compound and organic light-emitting element comprising same
WO2022124499A1 (en) * 2020-12-09 2022-06-16 엘티소재주식회사 Heterocyclic compound and organic light-emitting device comprising same
CN113754668A (en) * 2021-09-30 2021-12-07 武汉天马微电子有限公司 Organic compound and application thereof
CN113754668B (en) * 2021-09-30 2023-01-20 武汉天马微电子有限公司 Organic compound and application thereof
CN114573592A (en) * 2022-02-06 2022-06-03 上海传勤新材料有限公司 Compound containing spiroindole and aromatic amine and preparation method and application thereof
CN114573592B (en) * 2022-02-06 2023-07-18 上海传勤新材料有限公司 Compound containing spiroindole and aromatic amine, and preparation method and application thereof

Also Published As

Publication number Publication date
CN109111461B (en) 2021-09-10

Similar Documents

Publication Publication Date Title
CN109111461A (en) A kind of new compound and its application in electroluminescent device
KR101778416B1 (en) Benzothiophene derivative and use thereof in organic electroluminescent field
CN112321587B (en) Organic compound, electroluminescent material and application thereof
CN110498765B (en) Compound, organic electroluminescent material and organic electroluminescent device
CN110054644B (en) Compound, display panel and display device
CN103772263A (en) Compound and organic light emitting device comprising the same
CN109776542A (en) A kind of electroluminescent organic material and its application
CN109824522A (en) A kind of organic luminescent compounds and its preparation method and application
CN103772264A (en) Compound and organic light emitting device comprising the same
CN110003258A (en) Compound, display panel and display device
CN109553620A (en) General formula compound and organic electroluminescence device
CN110256473B (en) Compound, organic photoelectric device and electronic equipment
CN110003259B (en) Compound, display panel and display device
CN107663169B (en) 6H-naphtho [2,1,8,7-klmn ] acridine derivative and application thereof
CN103539682B (en) For the compound of organic light emitting apparatus, organic light emitting apparatus and panel display apparatus
JP2017533884A (en) Nitrogen-containing polycyclic compound and organic light-emitting device using the same
KR101324150B1 (en) Organic compounds for organic electro luminescente device and organic electro luminescent device using same
CN111808127B (en) Compound, display panel and display device
CN108299282A (en) A kind of aromatic amine compound symmetrically replaced and the application in OLED device
CN109400603A (en) Compound and its application in organic light emission field
CN111825671A (en) Compound containing carbazole ring and application thereof
CN109836421B (en) A compound of general formula and its application
CN112010761A (en) Compound, application thereof and organic electroluminescent device comprising compound
CN112745322B (en) Organic material and application thereof in organic electroluminescent device
CN111763223B (en) Organic compound, thermal activation delay fluorescent material and application thereof

Legal Events

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