CN107056626B - A kind of compound and its preparation method and application - Google Patents

A kind of compound and its preparation method and application Download PDF

Info

Publication number
CN107056626B
CN107056626B CN201710163955.2A CN201710163955A CN107056626B CN 107056626 B CN107056626 B CN 107056626B CN 201710163955 A CN201710163955 A CN 201710163955A CN 107056626 B CN107056626 B CN 107056626B
Authority
CN
China
Prior art keywords
formula
substituted
aryl
unsubstituted
condensed ring
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.)
Active
Application number
CN201710163955.2A
Other languages
Chinese (zh)
Other versions
CN107056626A (en
Inventor
金福荣
汪康
张成成
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.)
Jilin Optical and Electronic Materials Co Ltd
Original Assignee
Jilin Optical and Electronic Materials 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 Jilin Optical and Electronic Materials Co Ltd filed Critical Jilin Optical and Electronic Materials Co Ltd
Priority to CN201710163955.2A priority Critical patent/CN107056626B/en
Publication of CN107056626A publication Critical patent/CN107056626A/en
Application granted granted Critical
Publication of CN107056626B publication Critical patent/CN107056626B/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
    • 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
    • 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
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—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
    • H10K85/649—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

Landscapes

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

Abstract

The present invention provides a kind of compound and its preparation method and application, compound provided by the invention, by selecting specific mother nucleus structure and substituent A, B, Ar1And Ar2, so that obtained compound is applied to the luminous efficiency raising of device after organic electroluminescence device, and long service life.

Description

A kind of compound and its preparation method and application
Technical field
The present invention relates to organic electroluminescence device fields more particularly to a kind of compound and its preparation method and application.
Background technique
Organic luminescent device (OLED) is made of the organic matter layer being inserted between cathode, anode and cathode and anode, Wherein, organic layer is generally made of multilayered structure, such as include hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and Electron injecting layer etc.；Its effect is the efficiency and stability in order to improve organic electroluminescence device.
Present Portable Displays lead to the higher consumption of benchmark Portable Displays requirement with the increase of panel size Electric power.Thus, the battery of limited power supply source is difficult meet demand in Portable Displays, and uses organic electroluminescent When device, efficiency and service life are must to solve the problems, such as.Efficiency and service life, driving voltage are coherent mutually, general efficiency increases Start voltage reduction, and organic matter can be caused by starting the resistance heating (Joule heating) occurred when voltage reduction driving Crystallization, so that keep the service life long, but the efficiency of organic electroluminescence device cannot be improved by improving above-mentioned organic layer.Because respectively Energy level and T1 value between organic layer, whens optimal combination such as inherent characteristic (degree of excursion, interfacial characteristics etc.) of substance, which can be only achieved, to be prolonged Long light-emitting device life period and raising efficiency of luminescent device purpose.
Traditional hole transmission layer develops hole degree of excursion (hole mobility) fast object to reduce driving voltage Matter develops packing density (packing density) high HOMO valence to improve hole degree of excursion and connects with luminescent layer HOMO valence Close substance, but degree of excursion fast substance in hole generally results in the efficiency reduction of luminescent device.Because of organic electroluminescence device hole When degree of excursion is faster than electronics degree of excursion (electron mobility), it may appear that electronics is unbalanced (charge unbalance) Phenomenon eventually leads to the problem of luminous efficiency reduction and service life reduction.And use packing density (packing density) low Substance reduces hole degree of excursion, and then adjusts the electronic equalizing situation in luminescent layer, but will appear low packing density (packing density) and then driving voltage is improved, and the raising of driving voltage will increase electronics heating and shorten device lifetime, Therefore it provides a kind of hole transport layer material, which makes it be applied to electroluminescent device, not only increases its service life, but also improve its hair Light efficiency is current problem to be solved.
Summary of the invention
In view of this, technical problem to be solved by the present invention lies in provide a kind of compound and preparation method thereof and answer With compound of the present invention is applied to luminescent device as hole transport layer material, so that obtained device not only shines It is high-efficient, and long service life.
The present invention provides a kind of compounds, have formula (I) structure,
Wherein, the independent alkyl selected from the C1~C30 replaced of described A, B, the alkyl of unsubstituted C1~C30, substitution C3~C30 naphthenic base, the naphthenic base of unsubstituted C3~C30, the aryl of substituted C6~C60, unsubstituted C6~C60 Aryl, the condensed ring radical of substituted C8~C60 or the condensed ring radical of unsubstituted C8~C60；Or the carbon shape of described A, B and place At condensed ring；
The Ar1、Ar2The independent aryl selected from the aryl of C6~C60, unsubstituted C6~C60 that replace replaces The heterocyclic aryl of C4~C60, the heterocyclic aryl of unsubstituted C4~C60, substituted C8~C60 condensed ring radical or unsubstituted C8 The condensed ring radical of~C60.
Preferably, the A be selected from replace the alkyl of C5~C15, the alkyl of unsubstituted C5~C15, substituted C6~ The naphthenic base of C30, the naphthenic base of unsubstituted C6~C30, the aryl of substituted C12~C30, unsubstituted C12~C30 virtue The condensed ring radical of base, the condensed ring radical of substituted C13~C40 or unsubstituted C13~C40；
The B is selected from the ring of the alkyl of C5~C15 replaced, the alkyl of unsubstituted C5~C15, substituted C6~C30 Alkyl, the naphthenic base of unsubstituted C6~C30, the aryl of substituted C12~C30, the aryl of unsubstituted C12~C30, substitution C13~C40 condensed ring radical or unsubstituted C13~C40 condensed ring radical.
Preferably, the A be selected from methyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, oneself Base, 2- ethylhexyl, phenyl, xenyl, naphthalene, anthryl, phenanthryl or fluorenyl；
The B is selected from methyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, hexyl, 2- second Base hexyl, phenyl, xenyl, naphthalene, anthryl, phenanthryl or fluorenyl.
Preferably, the Ar1The aryl of aryl, unsubstituted C12~C30 selected from substituted C12~C30 replaces The heterocyclic aryl of C12~C30, the heterocyclic aryl of unsubstituted C12~C30, substituted C12~C30 condensed ring radical or unsubstituted C12~C30 condensed ring radical；
The Ar2Aryl, the substituted C12~C30 of aryl, unsubstituted C12~C30 selected from substituted C12~C30 Heterocyclic aryl, the heterocyclic aryl of unsubstituted C12~C30, the condensed ring radical of substituted C12~C30 or unsubstituted C12~ The condensed ring radical of C30.
Preferably, the hetero atom in the heterocyclic aryl is one or more of oxygen, nitrogen and sulphur.
Preferably, the Ar1、Ar2It is independent to be selected from formula (a-1), formula (a-2), formula (a-3), formula (a-4), formula (a-5), formula (a-6), formula (a-7), formula (a-8), formula (a-9), formula (a-10), formula (a-11), formula (a-12), formula (a-13), formula (a-14), formula (a-15), formula (a-16), formula (a-17), formula (a-18), formula (a-19), formula (a-20), formula (a-21), formula (a-22), formula (a- 23), formula (a-24), formula (a-25), formula (a-26), formula (a-27), formula (a-28), formula (a-29), formula (a-30), formula (a-31), Formula (a-32), formula (a-33), formula (a-34), formula (a-35), formula (a-36) or formula (a-38),
Preferably, the compound is formula (I-1), formula (I-2), formula (I-3), formula (I-4) or formula (I-5),
8, compound according to claim 1, which is characterized in that the compound is formula (P1), formula (P2), formula (P3), formula (P4), formula (P5), formula (P6), formula (P7), formula (P8), formula (P9), formula (P10), formula (P11), formula (P12), formula (P13), formula (P14), formula (P15), formula (P16), formula (P17), formula (P18), formula (P19), formula (P20), formula (P21), formula (P22), formula (P23), formula (P24), formula (P25), formula (P26), formula (P27), formula (P28), formula (P29), formula (P30), formula (P31), formula (P32), formula (P33), formula (P34), formula (P35), formula (P36), formula (P37), formula (P38), formula (P39), formula (P40), formula (P41), formula (P42), formula (P43), formula (P44), formula (P45), formula (P46), formula (P47), formula (P48), formula (P49), formula (P50), formula (P51), formula (P52), formula (P53) or formula (P54),
The present invention also provides a kind of preparation methods of compound of the present invention, comprising:
By the compound hybrid reaction of the compound of formula (II) structure and formula (III) structure, the chemical combination of formula (I) structure is obtained Object,
Wherein, the independent alkyl selected from the C1~C30 replaced of described A, B, the alkyl of unsubstituted C1~C30, substitution C3~C30 naphthenic base, the naphthenic base of unsubstituted C3~C30, the aryl of substituted C6~C60, unsubstituted C6~C60 Aryl, the condensed ring radical of substituted C8~C60 or the condensed ring radical of unsubstituted C8~C60；Or the A, the B and place Carbon forms condensed ring；
The X is halogen；
The Ar1、Ar2The independent aryl selected from the aryl of C6~C60, unsubstituted C6~C60 that replace replaces The heterocyclic aryl of C4~C60, the heterocyclic aryl of unsubstituted C4~C60, substituted C8~C60 condensed ring radical or unsubstituted C8 The condensed ring radical of~C60.
The present invention also provides a kind of compounds of the present invention as hole transport layer material is preparing organic electroluminescence Application in luminescent device.
Compared with prior art, provided by the invention the present invention provides a kind of compound and its preparation method and application Compound, by selecting specific mother nucleus structure and substituent A, B, Ar1And Ar2, so that obtained compound is applied to organic The luminous efficiency of device improves after electroluminescent device, and long service life, the experimental results showed that, chemical combination provided by the invention Object is applied to OLED, and obtained device and existing hole transport layer material are applied to luminescent device, and luminous efficiency improves 20% or more, service life improves 50% or more.
Specific embodiment
The present invention provides a kind of compounds, have formula (I) structure,
Wherein, the independent alkyl selected from the C1~C30 replaced of described A, B, the alkyl of unsubstituted C1~C30, substitution C3~C30 naphthenic base, the naphthenic base of unsubstituted C3~C30, the aryl of substituted C6~C60, unsubstituted C6~C60 Aryl, the condensed ring radical of substituted C8~C60 or the condensed ring radical of unsubstituted C8~C60；Or the carbon shape of described A, B and place At condensed ring；
The Ar1、Ar2The independent aryl selected from the aryl of C6~C60, unsubstituted C6~C60 that replace replaces The heterocyclic aryl of C4~C60, the heterocyclic aryl of unsubstituted C4~C60, substituted C8~C60 condensed ring radical or unsubstituted C8 The condensed ring radical of~C60.
According to the present invention, the A is preferably the alkyl of the C5~C15 replaced, the alkyl of unsubstituted C5~C150, substitution The naphthenic base of C6~C30, the naphthenic base of unsubstituted C6~C30, the aryl of substituted C12~C30, unsubstituted C12~ The condensed ring radical of the aryl of C30, the condensed ring radical of substituted C13~C40 or unsubstituted C13~C40；The C8 more preferably replaced~ The alkyl of C10, the alkyl of unsubstituted C8~C10, the naphthenic base of substituted C8~C15, unsubstituted C8~C15 cycloalkanes Base, the aryl of substituted C18~C25, the aryl of unsubstituted C18~C25, substituted C18~C25 condensed ring radical or unsubstituted C18~C25 condensed ring radical；Wherein, the substituted alkyl, substituted naphthenic base, substituted aryl and substituted condensed ring radical In the independent alkyl selected from C1~C10 of substituent group, the aryl of C6~C15 or the condensed ring radical of C8~C30；More specifically, institute State A be preferably methyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, hexyl, 2- ethylhexyl, Phenyl, xenyl, naphthalene, anthryl, phenanthryl or fluorenyl.
According to the present invention, the B is preferably the alkyl of the C5~C15 replaced, the alkyl of unsubstituted C5~C150, substitution The naphthenic base of C6~C30, the naphthenic base of unsubstituted C6~C30, the aryl of substituted C12~C30, unsubstituted C12~ The condensed ring radical of the aryl of C30, the condensed ring radical of substituted C13~C40 or unsubstituted C13~C40；The C8 more preferably replaced~ The alkyl of C10, the alkyl of unsubstituted C8~C10, the naphthenic base of substituted C8~C15, unsubstituted C8~C15 cycloalkanes Base, the aryl of substituted C18~C25, the aryl of unsubstituted C18~C25, substituted C18~C25 condensed ring radical or unsubstituted C18~C25 condensed ring radical；Wherein, the substituted alkyl, substituted naphthenic base, substituted aryl and substituted condensed ring radical In the independent alkyl selected from C1~C10 of substituent group, the aryl of C6~C15 or the condensed ring radical of C8~C30；More specifically, institute State A be preferably methyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, hexyl, 2- ethylhexyl, Phenyl, xenyl, naphthalene, anthryl, phenanthryl or fluorenyl.
According to the present invention, containing that can form condensed ring, the condensed ring is preferably fragrant for the A, the B and the carbon where them Condensed ring, the carbon atom number of the condensed ring are preferably C8~C30, more preferably C13~C25, and more specifically, the condensed ring is preferably Fluorenes.
According to the present invention, the Ar1The aryl of aryl, unsubstituted C12~C30 selected from substituted C12~C30 takes The heterocyclic aryl of the C12~C30 in generation, the heterocyclic aryl of unsubstituted C12~C30, the condensed ring radical of substituted C12~C30 or not The condensed ring radical of substituted C12~C30；More preferably the aryl of C18~C25, unsubstituted C18~C25 aryl, replace The heterocyclic aryl of C15~C20, the heterocyclic aryl of unsubstituted C15~C20, substituted C15~C25 condensed ring radical or unsubstituted C15~C25 condensed ring radical；Wherein, the substituent group on the substituted aryl, substituted heterocyclic aryl and substituted condensed ring radical It is preferred that the virtue of the independent selection alkyl of C1~C30, the naphthenic base of C3~C30, the aryl of C6~C60, unsubstituted C6~C60 The condensed ring radical of base or C8~C60；Preferably the alkyl of C5~C15, the naphthenic base of C6~C30, the aryl of C12~C30 or C13~ The condensed ring of C40, the more preferably alkyl of C8~C10, the naphthenic base of non-C8~C15, the aryl of C18~C25 or C18~C25 Condensed ring radical；Most preferably methyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, hexyl, 2- ethyl Hexyl, phenyl, xenyl, naphthalene, anthryl, phenanthryl or fluorenyl；Hetero atom on the heterocyclic aryl is preferably in nitrogen, oxygen and sulphur One or more；More specifically, the Ar1Selected from formula (a-1), formula (a-2), formula (a-3), formula (a-4), formula (a-5), Formula (a-6), formula (a-7), formula (a-8), formula (a-9), formula (a-10), formula (a-11), formula (a-12), formula (a-13), formula (a-14), Formula (a-15), formula (a-16), formula (a-17), formula (a-18), formula (a-19), formula (a-20), formula (a-21), formula (a-22), formula (a- 23), formula (a-24), formula (a-25), formula (a-26), formula (a-27), formula (a-28), formula (a-29), formula (a-30), formula (a-31), Formula (a-32), formula (a-33), formula (a-34), formula (a-35), formula (a-36) or formula (a-38).
According to the present invention, the Ar2The aryl of aryl, unsubstituted C12~C30 selected from substituted C12~C30 takes The heterocyclic aryl of the C12~C30 in generation, the heterocyclic aryl of unsubstituted C12~C30, the condensed ring radical of substituted C12~C30 or not The condensed ring radical of substituted C12~C30；More preferably the aryl of C18~C25, unsubstituted C18~C25 aryl, replace The heterocyclic aryl of C15~C20, the heterocyclic aryl of unsubstituted C15~C20, substituted C15~C25 condensed ring radical or unsubstituted C15~C25 condensed ring radical；Wherein, the substituent group on the substituted aryl, substituted heterocyclic aryl and substituted condensed ring radical It is preferred that the virtue of the independent selection alkyl of C1~C30, the naphthenic base of C3~C30, the aryl of C6~C60, unsubstituted C6~C60 The condensed ring radical of base or C8~C60；Preferably the alkyl of C5~C15, the naphthenic base of C6~C30, the aryl of C12~C30 or C13~ The condensed ring of C40, the more preferably alkyl of C8~C10, the naphthenic base of non-C8~C15, the aryl of C18~C25 or C18~C25 Condensed ring radical；Most preferably methyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, hexyl, 2- ethyl Hexyl, phenyl, xenyl, naphthalene, anthryl, phenanthryl or fluorenyl；Hetero atom on the heterocyclic aryl is preferably in nitrogen, oxygen and sulphur One or more；More specifically, the Ar1Selected from formula (a-1), formula (a-2), formula (a-3), formula (a-4), formula (a-5), Formula (a-6), formula (a-7), formula (a-8), formula (a-9), formula (a-10), formula (a-11), formula (a-12), formula (a-13), formula (a-14), Formula (a-15), formula (a-16), formula (a-17), formula (a-18), formula (a-19), formula (a-20), formula (a-21), formula (a-22), formula (a- 23), formula (a-24), formula (a-25), formula (a-26), formula (a-27), formula (a-28), formula (a-29), formula (a-30), formula (a-31), Formula (a-32), formula (a-33), formula (a-34), formula (a-35), formula (a-36) or formula (a-38).
In addition, it is necessary to, it is noted that in substituent groupIndicate connecting key, simultaneouslyIt is not fixed and is connected to any one Indicate that it can be in any position of place aromatic rings on carbon.
More specifically, compound of the present invention is preferably formula (I-1), formula (I-2), formula (I-3), formula (I-4) or formula (I- 5),
The more preferably described compound be formula (P1), formula (P2), formula (P3), formula (P4), formula (P5), formula (P6), formula (P7), Formula (P8), formula (P9), formula (P10), formula (P11), formula (P12), formula (P13), formula (P14), formula (P15), formula (P16), formula (P17), formula (P18), formula (P19), formula (P20), formula (P21), formula (P22), formula (P23), formula (P24), formula (P25), formula (P26), formula (P27), formula (P28), formula (P29), formula (P30), formula (P31), formula (P32), formula (P33), formula (P34), formula (P35), formula (P36), formula (P37), formula (P38), formula (P39), formula (P40), formula (P41), formula (P42), formula (P43), formula (P44), formula (P45), formula (P46), formula (P47), formula (P48), formula (P49), formula (P50), formula (P51), formula (P52), formula (P53) Or formula (P54),
The present invention also provides a kind of preparation methods of compound of the present invention, comprising:
By the compound hybrid reaction of the compound of formula (II) structure and formula (III) structure, the chemical combination of formula (I) structure is obtained Object,
Wherein, the independent alkyl selected from the C1~C30 replaced of described A, B, the alkyl of unsubstituted C1~C30, substitution C3~C30 naphthenic base, the naphthenic base of unsubstituted C3~C30, the aryl of substituted C6~C60, unsubstituted C6~C60 Aryl, the condensed ring radical of substituted C8~C60 or the condensed ring radical of unsubstituted C8~C60；Or the A, the B and place Carbon forms condensed ring；
The X is halogen；
The Ar1、Ar2The independent aryl selected from the aryl of C6~C60, unsubstituted C6~C60 that replace replaces The heterocyclic aryl of C4~C60, the heterocyclic aryl of unsubstituted C4~C60, substituted C8~C60 condensed ring radical or unsubstituted C8 The condensed ring radical of~C60.
The compound hybrid reaction of the compound of formula (II) structure and formula (III) structure is obtained into formula according to the present invention (I) compound of structure, the present invention in, in the compound of formula (II) structure in A, B, range of choice and aforesaid compound Limit identical, the X is preferably chlorine, bromine or iodine；Ar in the compound of formula (III) structure1、Ar2The selection of substituent group also with Aforesaid compound restriction is identical, and the present invention does not have particular/special requirement to the condition of the reaction, and those skilled in the art can basis The existing suitable reaction condition of selecting response.In addition, the present invention is to the compound of formula (II) structure and the change of formula (III) structure The source for closing object is not particularly limited, and is made by preparation method well known in the art.
The present invention also provides a kind of compounds of the present invention as hole transport layer material is preparing organic electroluminescence Application in luminescent device；
The present invention provides a kind of compound and its preparation method and application, compound provided by the invention passes through selection Specific mother nucleus structure and substituent A, B, Ar1And Ar2, so that after obtained compound is applied to organic electroluminescence device The luminous efficiency of device improves, and long service life.
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
The preparation of 1 substrate of embodiment
The synthesis of Sub1
In 2L two-mouth bottle plus sub 1-1 (50g) be slowly added dropwise under the conditions of 0 DEG C of methylene chloride (1L) later titanium tetrachloride (1M, 232ml), dimethylamine borane complex (28.5ml) slowly is added dropwise, 0 DEG C is neutralized with sodium carbonate (1M) for reaction 2 hours later.Reaction Liquid methylene chloride and distilled water extract organic layer.It is concentrated under reduced pressure to give red material after dry, is obtained using hexane silicagel column Product sub 1-2 (28g).
It is inner that two-mouth bottle (500ml) plus sub 1-2 (25g) and potassium tert-butoxide (34g) are dissolved in dimethyl sulfoxide (250ml), Iodomethane (43g) slowly is added dropwise after stirring 1 hour, is stirred 12 hours under the conditions of 80 DEG C.Acetone and water separate organic layer, sulfuric acid Vacuum distillation after magnesium is dry.Product sub 1 (22g) is obtained using hexane silicagel column.
The synthesis of Sub2
The synthesis of Sub 2-1
After the inner 2- bromo biphenyl (54g) of there-necked flask (1L) is dissolved with tetrahydrofuran (200L), under the conditions of -78 DEG C of low temperature slowly The butyl lithium that (2.5M, 154.4ml) is added dropwise stirs 2 hours later.Then it is dissolved in the sub 1-1 of tetrahydrofuran (300ml) (50g) is slowly added dropwise under the conditions of -78 DEG C such as above-mentioned there-necked flask, maintenance stirring at normal temperature 24 hours.Sodium carbonate after reaction terminates 1M solution neutralizes.Organic layer is separated, rotary evaporation removes tetrahydrofuran, and ethyl acetate and distilled water are extracted twice.After drying, use Hexane silicagel column obtains product sub 2-1 (42g).
The synthesis of sub 2
Add sub 2-1 (40g), hydrochloric acid (10ml), acetic acid (350ml) return stirring 24 hours later in two-mouth bottle 500ml. Filter solid is crossed after reaction solution room temperature cooling, is washed several times with methanol.Utilize the isolated product sub 2 of hexane silicagel column (28g)。
The synthesis of Sub3
The inner 2- bromobenzene (36g) of there-necked flask (1L), after tetrahydrofuran (200L) dissolution, under the conditions of -78 DEG C of low temperature slowly The butyl lithium that (2.5M, 154.4ml) is added dropwise stirs 2 hours later.Then it is dissolved in the sub1-1 of tetrahydrofuran (300ml) (50g) is slowly added dropwise under the conditions of -78 DEG C such as above-mentioned there-necked flask, maintenance stirring at normal temperature 24 hours.Sodium carbonate after reaction terminates 1M solution neutralizes.Remove tetrahydrofuran after organic layer separation, ethyl acetate and distilled water are extracted twice.After dry organic layer Product sub 3-1 (42g) is obtained using hexane silicagel column.
Add Sub3-1 (9.64g, 28.7mmol), benzene (7.4g, 30.1mmol) and dichloro in reaction vessel under condition of nitrogen gas Methane (MC) 570mL.In system slowly be added dropwise be dissolved in methylene chloride (120mL) boron trifluoride ether (3.8mL, 30.1mmol).Stirring at normal temperature 2 hours.Stop reaction with methanol and distilled water, organic matter is extracted with dichloromethane, organic layer is used Anhydrous magnesium sulfate is dry, and solvent is removed in vacuum distillation, obtains compound sub3 (9.67g, 85%) with column Chromatographic purification.
The synthesis of Sub 4 and Sub 5:
2- bromobenzene is substituted for 1- bromo pentane silane, 3- (bromomethyl) heptane and uses identical mole ratio, system according to Sub 3-1 Standby Sub 4-1 and Sub 5-1.
Benzene is substituted for pentane, 3- (methyl) heptane and uses identical mole ratio according to Sub 3, prepares Sub 4 and Sub 5。
The structure of obtained Sub1~Sub5 is as follows, detects to it, and mass spectrometry value indicates as shown in table 1:
1 sub1 of table~sub5 mass spectrometry value
Compound Mass spectrum Compound Mass spectrum
Sub-1 Theoretical value=272.02 (measured value C15H13Br=273.17) Sub-2 Theoretical value=394.04 (measured value C25H15Br=395.29)
Sub-3 Theoretical value=396.05 (measured value C25H17Br=397.31) Sub-4 Theoretical value=384.15 (measured value C23H29Br=384.17)
Sub-5 Theoretical value=468.24 (measured value C29H41Br=468.26)
The synthesis of Sub 6
The synthesis of Sub 6-3
In reaction vessel in order plus 2- bromo biphenyl (32.2g, 138mmol), 9,9 '-spiral shell, two fluorenes -2- amine (41.6g, 125.5mmol), tris(dibenzylideneacetone) dipalladium (5.74g, 6.3mmol), tri-tert-butylphosphine (2.54g, 12.5mmol), uncle After sodium butoxide (36.2g, 376.4mmol), toluene 1320mL, reacted under the conditions of 100 DEG C.React end ether and water Organic matter is extracted, organic layer is dry with anhydrous magnesium sulfate, after concentrated product, obtains 46.7g with silicagel column and recrystallization method and produces Object Sub 6-3, yield 77%.
The synthesis of Sub6-14
Add 3- (4- bromophenyl) -9- phenyl -9H- carbazole (55g, 138mmol), 9,9 '-spiral shells two in reaction vessel in order Fluorenes -2- amine (41.6g, 125.5mmol), tris(dibenzylideneacetone) dipalladium (5.74g, 6.3mmol), tri-tert-butylphosphine It is reacted under the conditions of 100 DEG C after (2.54g, 12.5mmol), sodium tert-butoxide (36.2g, 376.4mmol), toluene 1320mL. Ether and water extract organic matter, organic layer magnesium sulfate dry concentrated product silicagel column and recrystallization later after reaction terminates Method obtains 57g product Sub4-14, yield 70%.
The synthesis of Sub 6-28
In reaction vessel in order plus 4- bromine dibenzo [b, d] furans (34g, 138mmol), triphenylene -2- amine (30.5g, 125.5mmol), tris(dibenzylideneacetone) dipalladium (5.74g, 6.3mmol), tri-tert-butylphosphine (2.54g, 12.5mmol), uncle It is reacted under the conditions of 100 DEG C after sodium butoxide (36.2g, 376.4mmol), toluene 1320mL.Reaction terminate after ether with Water extracts organic matter, and organic layer obtains 41g product Sub with magnesium sulfate dry concentrated product silicagel column and recrystallization method later 4-28, yield 80%.
Similarly, belong to the compound of Sub6 type with can also prepare in aforementioned manners, but preparation method is not limited in Within the scope of this.The sub6 class compound prepared below for the present invention by above-mentioned preparation method, Mass Spectrometer Method is as a result, mass spectrum Value is shown in Table 2；
2 Sub6-1 of table~Sub6-54 mass spectrometry value
Compound Mass spectrum Compound Mass spectrum
Sub6-1 Theoretical value=321.15 (measured value C24H19N=321.41) Sub6-2 Theoretical value=361.18 (measured value C27H23N=361.48)
Sub6-3 Theoretical value=483.2 (measured value C37H25N=483.6) Sub6-4 Theoretical value=645.25 (measured value C50H31N=645.79)
Sub6-5 Theoretical value=321.15 (measured value C24H19N=321.41) Sub6-6 Theoretical value=473.21 (measured value C36H27N=473.61)
Sub6-7 Theoretical value=559.23 (measured value C43H29N=559.70) Sub6-8 Theoretical value=335.13 (measured value C24H17NO=335.40)
Sub6-9 Theoretical value=497.18 (measured value C37H23NO=497.58) Sub6-10 Theoretical value=401.21 (measured value C30H27N=401.54)
Sub6-11 Theoretical value=486.21 (measured value C36H26N2=486.61) Sub6-12 Theoretical value=486.21 (measured value C36H26N2=486.61)
Sub6-13 Theoretical value=526.24 (measured value C39H30N2=526.67) Sub6-14 Theoretical value=648.26 (measured value C49H32N2=648.79)
Sub6-15 Theoretical value=562.24 (measured value C42H30N2=562.70) Sub6-16 Theoretical value=640.29 (measured value C48H36N2=640.81)
Sub6-17 Theoretical value=720.35 (measured value C54H44N2=720.94) Sub6-18 Theoretical value=680.32 (measured value C51H40N2=680.88)
Sub6-19 Theoretical value=491.22 (measured value C36H29NO=491.62) Sub6-20 Theoretical value=639.29 (measured value C49H37N=639.82)
Sub6-21 Theoretical value=345.15 (measured value C26H19N=345.44) Sub6-22 Theoretical value=345.15 (measured value C26H19N=345.44)
Sub6-23 Theoretical value=395.17 (measured value C30H21N=395.49) Sub6-24 Theoretical value=369.15 (measured value C28H19N=369.46)
Sub6-25 Theoretical value=371.17 (measured value C28H21N=371.47) Sub6-26 Theoretical value=359.13 (measured value C26H7NO=359.42)
Sub6-27 Theoretical value=359.13 (measured value C26H17NO=359.42) Sub6-28 Theoretical value=409.15 (measured value C30H19NO=409.48)
Sub6-29 Theoretical value=471.20 (measured value C36H25N=471.59) Sub6-30 Theoretical value=473.21 (measured value C36H27N=473.61)
Sub6-31 Theoretical value=507.20 (measured value C39H25N=507.62) Sub6-32 Theoretical value=507.20 (measured value C39H25N=507.62)
Sub6-33 Theoretical value=557.21 (measured value C43H27N=557.68) Sub6-34 Theoretical value=531.20 (measured value C41H25N=531.64)
Sub6-35 Theoretical value=533.21 (measured value C41H27N=533.66) Sub6-36 Theoretical value=501.17 (measured value C36H23NO2=501.57)
Sub6-37 Theoretical value=501.17 (measured value C36H23NO2=501.57) Sub6-38 Theoretical value=653.24 (measured value C48H31NO2=653.77)
Sub6-39 Theoretical value=733.30 (measured value C54H39NO2=733.89) Sub6-40 Theoretical value=653.24 (measured value C48H31NO2=653.77)
Sub6-41 Theoretical value=562.24 (measured value C42H30N2=562.70) Sub6-42 Theoretical value=486.21 (measured value C36H26N2=486.61)
Sub6-43 Theoretical value=562.24 (measured value C42H30N2=562,70) Sub6-44 Theoretical value=500.19 (measured value C36H24N2O=500.59)
Sub6-45 Theoretical value=648.26 (measured value C49H32N2=648.79) Sub6-46 Theoretical value=562.24 (measured value C42H30N2=562.70)
Sub6-47 Theoretical value=486.21 (measured value C36H26N2=486.61) Sub6-48 Theoretical value=562.24 (measured value C42H30N2=562.70)
Sub6-49 Theoretical value=500.19 (measured value C36H24N2O=500.59) Sub6-50 Theoretical value=648.26 (measured value C49H32N2=648.79)
Sub6-51 Theoretical value=512.23 (measured value C38H28N2=512.25) Sub6-52 Theoretical value=552.26 (measured value C41H32N2=552.28)
Sub6-53 Theoretical value=804.44 (measured value C60H56N2=804.46) Sub6-54 Theoretical value=597.43 (measured value C44H55N=648.79)
The synthesis of 2 formula of embodiment (I) compound
The synthesis of P1
Amine sequence plus bromo- 1, the 1- dimethyl -1H- of 6- non-that alkene (11.6g, 42.7mmol), Sub 4-1 in reaction vessel (15g, 46.9mmol), tris(dibenzylideneacetone) dipalladium (1.95g, 2.13mmol), tri-tert-butylphosphine (0.86g, 4.3mmol), it is reacted under the conditions of 100 DEG C after sodium tert-butoxide (12.3g, 128mmol), toluene 300mL.Reaction terminate with Methylene chloride and water extract organic matter afterwards, and organic layer is obtained with the dry concentrated product later of magnesium sulfate with silicagel column and recrystallization method To product P1,13.1g (60%).
The synthesis of P7
By that non-alkene (17g, 42.9mmol) of bromo- 1, the 1- diphenyl-IH- of 6-, Sub 4-7 (26.4g, 47.2mmol), three (dibenzalacetone) two palladium (1.97g, 2.15mmol), tri-tert-butylphosphine (0.87g, 4.3mmol), sodium tert-butoxide (12.4g, 128.8mmol), toluene 450mL obtains P7, the P7 of 26.3g (70%) according to P1 synthetic method as raw material.
The synthesis of P13
By that non-alkene (7.89g, 28.9mmol) of bromo- 1, the 1- dimethyl -1H- of 6-, Sub 4-13 (16.75g, 31.8mmol), tris(dibenzylideneacetone) dipalladium (1.32g, 1.45mmol), tri-tert-butylphosphine (0.59g, 2.89mmol), uncle Sodium butoxide (8.34g, 86.8mmol), toluene 250mL obtain P13,15.1g (73%) according to P1 synthetic method as raw material.
The synthesis of P17
By that non-alkene (16.7g, 61.1mmol) of bromo- 1, the 1- dimethyl -1H- of 6-, Sub 4-17 (48.52g, 67.3mmol), tris(dibenzylideneacetone) dipalladium (2.8g, 3.06mmol), tri-tert-butylphosphine (1.24g, 6.11mmol), tertiary fourth Sodium alkoxide (17.63g, 183.4mmol), toluene 500mL obtain P17,42.4g (76%) according to P1 synthetic method as raw material.
The synthesis of P23
By 6 '-bromine spiral shells [9,1 '-Fei Na alkene of fluorenes -] (8.74g, 22.1mmol), Sub 4-23 (9.61g, 24.3mmol), three (dibenzalacetone) two palladium (1.01g, 1.10mmol), tri-tert-butylphosphine (0.45g, 2.21mmol), sodium tert-butoxide (6.37g, 66.3mmol), toluene 200mL obtains P23,11.14g (71%) according to P1 synthetic method as raw material.
The synthesis of P29
By that non-alkene (15.8g, 57.85mmol) of bromo- 1, the 1- dimethyl -1H- of 6-, Sub 4-29 (30g, 63.63mmol), Tris(dibenzylideneacetone) dipalladium (2.64g, 2.89mmol), tri-tert-butylphosphine (1.17g, 5.78mmol), sodium tert-butoxide (16.7g, 173.5mmol), toluene 600mL obtain P29,29.2g (76%) according to P1 synthetic method as raw material.
The synthesis of P33
By that non-alkene (12.6g, 46.1mmol) of bromo- 1, the 1- dimethyl -1H- of 6-, Sub 4-33 (28.3g, 50.7mmol), Tris(dibenzylideneacetone) dipalladium (2.11g, 2.3mmol), tri-tert-butylphosphine (0.93g, 4.6mmol), sodium tert-butoxide (13.3g, 138.3mmol), toluene 450mL obtains P33,23.5g (68%) according to P1 synthetic method as raw material.
The synthesis of P36
By that non-alkene (16.7g, 61.1mmol) of bromo- 1, the 1- dimethyl -1H- of 6-, Sub 4-36 (33.75g, 67.3mmol), tris(dibenzylideneacetone) dipalladium (2.8g, 3.06mmol), tri-tert-butylphosphine (1.24g, 6.11mmol), tertiary fourth Sodium alkoxide (17.63g, 183.4mmol), toluene 500mL obtain P36,25.4g (60%) according to P1 synthetic method as raw material.
The synthesis of P41
By that non-alkene (15.8g, 57.85mmol) of bromo- 1, the 1- dimethyl -1H- of 6-, Sub 4-41 (30g, 63.63mmol), Tris(dibenzylideneacetone) dipalladium (2.64g, 2.89mmol), tri-tert-butylphosphine (1.17g, 5.78mmol), sodium tert-butoxide (16.7g, 173.5mmol), toluene 600mL obtain P41,20g (46%) according to P1 synthetic method as raw material.
The synthesis of P46
By that non-alkene (12.75g, 46.7mmol) of bromo- 1, the 1- dimethyl -1H- of 6-, Sub 4-46 (29,51.3mmol), three (dibenzalacetone) two palladium (2.14g, 2.33mmol), tri-tert-butylphosphine (0.94g, 4.67mmol), sodium tert-butoxide (13.5g, 140mmol), toluene 390mL obtains P46,15.87g (45%) according to P1 synthetic method as raw material.
Equally, compound described in P1~P50 has been prepared according to the synthetic method of P1, obtained compound has been carried out Structural Identification, mass spectrum are shown in Table 3.
Table 3
Compound Mass spectrum Compound Mass spectrum
P1 Theoretical value=513.25 (C39H31N=513.67) P2 Theoretical value=553.28 (C42H35N=553.73)
P3 Theoretical value=675.29 (C52H37N=675.86) P4 Theoretical value=837.34 (C65H43N=838.04)
P5 Theoretical value=513.25 (C39H31N=513.67) P6 Theoretical value=789.34 (C61H43N=790.00)
P7 Theoretical value=875.36 (C68H45N=876.09) P8 Theoretical value=527.22 (C39H29NO=527.65)
P9 Theoretical value=689.27 (C52H35NO=689.84) P10 Theoretical value=593.31 (C45H39N=593.80)
P11 Theoretical value=678.30 (C51H38N2=678.86) P12 Theoretical value=678.30 (C51H38N2=678.86)
P13 Theoretical value=718.33 (C54H42N2=718.92) P14 Theoretical value=840.35 (C64H44N2=841.05)
P15 Theoretical value=754.33 (C57H42N2=754.96) P16 Theoretical value=832.38 (C63H48N2=833.07)
P17 Theoretical value=912.44 (C69H56N2=913.20) P18 Theoretical value=872.41 (C66H52N2=873.13)
P19 Theoretical value=683.32 (C51H41NO=683.88) P20 Theoretical value=831.39 (C64H49N=832.08)
P21 Theoretical value=659.26 (C51H33N=659.81) P22 Theoretical value=659.26 (C51H33N=659.81)
P23 Theoretical value=709.28 (C55H35N=709.87) P24 Theoretical value=683.26 (C53H33N=683.84)
P25 Theoretical value=685.28 (C53H35N=685.85) P26 Theoretical value=551.22 (C41H29NO=551.68)
P27 Theoretical value=551.22 (C41H29NO=551.68) P28 Theoretical value=601.24 (C45H31NO=601.73)
P29 Theoretical value=663.29 (C51H37N=663.85) P30 Theoretical value=665.31 (C51H39N=665.86)
P31 Theoretical value=699.29 (C54H37N=699.88) P32 Theoretical value=699.29 (C54H37N=699.88)
P33 Theoretical value=749.31 (C58H39N=749.94) P34 Theoretical value=723.29 (C56H37N=723.90)
P35 Theoretical value=725.31 (C56H39N=725.92) P36 Theoretical value=693.27 (C51H35NO2=693.83)
P37 Theoretical value=693.27 (C51H35NO2=693.83) P38 Theoretical value=845.33 (C63H43NO2=846.02)
P39 Theoretical value=925.39 (C69H51NO2=926.15) P40 Theoretical value=845.33 (C63H43NO2=846.02)
P41 Theoretical value=754.33 (C57H42N2=754.96) P42 Theoretical value=678.30 (C51H38N2=678.86)
P43 Theoretical value=754.33 (C57H42N2=754.96) P44 Theoretical value=692.28 (C51H36N2O=692.84)
P45 Theoretical value=840.35 (C64H44N2=841.05) P46 Theoretical value=754.33 (C57H42N2=754.96)
P47 Theoretical value=678.30 (C51H38N2=678.86) P48 Theoretical value=754.33 (C57H42N2=754.96)
P49 Theoretical value=692.28 (C51H36N2O=692.84) P50 Theoretical value=840.35 (C64H44N2=841.05)
P51 Theoretical value=704.32 (C53H40N2=704.31) P52 Theoretical value=704.32 (C53H40N2=704.31)
P53 Theoretical value=804.41 (C59H52N2O=804.43) P54 Theoretical value=1036.58 (C78H72N2=841.05)
Embodiment 3
Compound prepared by embodiment 2 is used to prepare green organic electrofluorescence device as hole transport layer material, It is specific the preparation method comprises the following steps:
N1- (2- naphthalene)-N4, N4- bis- (4- (2- naphthalene (phenyl) amino) phenyl)-is deposited in ITO first (anode) above And then compound P160nm, main substance that the present invention synthesizes is deposited in N1- phenyl benzene-Isosorbide-5-Nitrae-diamines (" 2-TNATA ") 60nm 4 ,-two carbazoles of 4 '-N, N '-biphenyl (" CBP ") and dopant three (2- phenylpyridine) iridium (" Ir (ppy) 3 ") 90: 10 weight Than mixing vapor deposition 30nm, vapor deposition hole blocking layer (" BAlq ") 10nm thickness, vapor deposition " Alq3 " 40nm thickness, vapor deposition electron injection Layer LiF0.2nm, evaporation cathode Al 150nm form prepare organic luminescent device.
Equally, it changes P1 into other compounds as described in example 2 of the present invention, is then prepared a series of Organic luminescent device.
Comparative example 1~3
According to the preparation method of embodiment 3, only by P1 chemical conversion formula (D-1), formula (D-2) and the formula in electroluminescent device (D-3) compound, obtains luminescent device.
Embodiment 4
The organic luminescent device biasing (bias voltage) prepared to embodiment 3 and comparative example 1~3 is used later (photoresearch) the PR-650 testing electroluminescent characteristic (EL) of company, 5000cd/m2Mcscience under Benchmark brightness The service life equipment Test T95 of preparation, measurement result are shown in Table 4.
Table 4
From table 4, it can be seen that the compound of the present invention is applied to organic luminescent device relative to existing as cavitation material Cavitation material the luminous efficiency and service life of luminescent device can be improved.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims (10)

1. a kind of compound has formula (I) structure,
Wherein, described A, B are independent selected from the alkyl of C1~C30 replaced, the alkyl of unsubstituted C1~C30, substituted C3 The naphthenic base of~C30, the naphthenic base of unsubstituted C3~C30, the aryl of substituted C6~C60, unsubstituted C6~C60 virtue The condensed ring radical of base, the condensed ring radical of substituted C8~C60 or unsubstituted C8~C60；Or described A, B and the carbon at place formed it is thick Ring；Substituent group in the substituted alkyl, substituted naphthenic base, substituted aryl and substituted condensed ring radical is independent selected from C1 The condensed ring radical of the alkyl of~C10, the aryl of C6~C15 or C8~C30；
The Ar1、Ar2The independent aryl of C6~C60 selected from substitution, the aryl of unsubstituted C6~C60, substituted C4~ The heterocyclic aryl of C60, the heterocyclic aryl of unsubstituted C4~C60, the condensed ring radical of substituted C8~C60 or unsubstituted C8~ The condensed ring radical of C60；The preferably independent choosing of substituent group on the substituted aryl, substituted heterocyclic aryl and substituted condensed ring radical Select the aryl or C8~C60 of the alkyl of C1~C30, the naphthenic base of C3~C30, the aryl of C6~C60, unsubstituted C6~C60 Condensed ring radical.
2. compound according to claim 1, which is characterized in that the A is selected from the alkyl of the C5~C15 replaced, does not take The alkyl of the C5~C15 in generation, the naphthenic base of substituted C6~C30, the naphthenic base of unsubstituted C6~C30, substituted C12~ The aryl of C30, the aryl of unsubstituted C12~C30, the condensed ring radical of substituted C13~C40 or unsubstituted C13~C40 it is thick Ring group；
The B be selected from replace the alkyl of C5~C15, the alkyl of unsubstituted C5~C15, substituted C6~C30 naphthenic base, The naphthenic base of unsubstituted C6~C30, the aryl of substituted C12~C30, the aryl of unsubstituted C12~C30, substituted C13 The condensed ring radical of the condensed ring radical of~C40 or unsubstituted C13~C40.
3. compound according to claim 1, which is characterized in that the A is selected from methyl, methyl, ethyl, propyl, isopropyl Base, butyl, isobutyl group, tert-butyl, amyl, hexyl, 2- ethylhexyl, phenyl, xenyl, naphthalene, anthryl, phenanthryl or fluorenyl；
The B is selected from methyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, hexyl, 2- ethyl hexyl Base, phenyl, xenyl, naphthalene, anthryl, phenanthryl or fluorenyl.
4. compound according to claim 1, which is characterized in that the Ar1Aryl selected from substituted C12~C30, not The aryl of substituted C12~C30, the heterocyclic aryl of substituted C12~C30, the heterocyclic aryl of unsubstituted C12~C30, substitution C12~C30 condensed ring radical or unsubstituted C12~C30 condensed ring radical；
The Ar2The aryl of aryl, unsubstituted C12~C30 selected from substituted C12~C30, substituted C12~C30 it is miscellaneous Cyclophane base, the heterocyclic aryl of unsubstituted C12~C30, the condensed ring radical of substituted C12~C30 or unsubstituted C12~C30 Condensed ring radical.
5. compound according to claim 4, which is characterized in that the hetero atom in the heterocyclic aryl is oxygen, nitrogen and sulphur One or more of.
6. compound according to claim 1, which is characterized in that the Ar1、Ar2It is independent to be selected from formula (a-1), formula (a- 2), formula (a-3), formula (a-4), formula (a-5), formula (a-6), formula (a-7), formula (a-8), formula (a-9), formula (a-10), formula (a-11), Formula (a-12), formula (a-13), formula (a-14), formula (a-15), formula (a-16), formula (a-17), formula (a-18), formula (a-19), formula (a- 20), formula (a-21), formula (a-22), formula (a-23), formula (a-24), formula (a-25), formula (a-26), formula (a-27), formula (a-28), Formula (a-29), formula (a-30), formula (a-31), formula (a-32), formula (a-33), formula (a-34), formula (a-35), formula (a-36) or formula (a-38),
7. compound according to claim 1, which is characterized in that the compound is formula (I-1), formula (I-2), formula (I- 3), formula (I-4) or formula (I-5),
8. compound according to claim 1, which is characterized in that the compound be formula (P1), formula (P2), formula (P3), Formula (P4), formula (P5), formula (P6), formula (P7), formula (P8), formula (P9), formula (P10), formula (P11), formula (P12), formula (P13), formula (P14), formula (P15), formula (P16), formula (P17), formula (P18), formula (P19), formula (P20), formula (P21), formula (P22), formula (P23), formula (P24), formula (P25), formula (P26), formula (P27), formula (P28), formula (P29), formula (P30), formula (P31), formula (P32), formula (P33), formula (P34), formula (P35), formula (P36), formula (P37), formula (P38), formula (P39), formula (P40), formula (P41), formula (P42), formula (P43), formula (P44), formula (P45), formula (P46), formula (P47), formula (P48), formula (P49), formula (P50), formula (P51), formula (P52), formula (P53) or formula (P54),
9. a kind of preparation method of compound described in claim 1, comprising:
By the compound hybrid reaction of the compound of formula (II) structure and formula (III) structure, the compound of formula (I) structure is obtained,
Wherein, described A, B are independent selected from the alkyl of C1~C30 replaced, the alkyl of unsubstituted C1~C30, substituted C3 The naphthenic base of~C30, the naphthenic base of unsubstituted C3~C30, the aryl of substituted C6~C60, unsubstituted C6~C60 virtue The condensed ring radical of base, the condensed ring radical of substituted C8~C60 or unsubstituted C8~C60；Or the carbon shape of the A, the B and place At condensed ring；The independent choosing of substituent group in the substituted alkyl, substituted naphthenic base, substituted aryl and substituted condensed ring radical From the alkyl, the aryl of C6~C15 or the condensed ring radical of C8~C30 of C1~C10；
The X is halogen；
The Ar1、Ar2The independent aryl of C6~C60 selected from substitution, the aryl of unsubstituted C6~C60, substituted C4~ The heterocyclic aryl of C60, the heterocyclic aryl of unsubstituted C4~C60, the condensed ring radical of substituted C8~C60 or unsubstituted C8~ The condensed ring radical of C60
Substituent group on the substituted aryl, substituted heterocyclic aryl and substituted condensed ring radical preferably independent selection C1~ The alkyl of C30, the naphthenic base of C3~C30, the aryl of C6~C60, the aryl of unsubstituted C6~C60 or the condensed ring of C8~C60 Base.
10. prepared by compound described in a kind of claim 1~8 any one and preparation method as claimed in claim 9 Compound is preparing the application in organic electroluminescence device as hole transport layer material.
CN201710163955.2A 2017-03-17 2017-03-17 A kind of compound and its preparation method and application Active CN107056626B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710163955.2A CN107056626B (en) 2017-03-17 2017-03-17 A kind of compound and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710163955.2A CN107056626B (en) 2017-03-17 2017-03-17 A kind of compound and its preparation method and application

Publications (2)

Publication Number Publication Date
CN107056626A CN107056626A (en) 2017-08-18
CN107056626B true CN107056626B (en) 2019-03-22

Family

ID=59620014

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710163955.2A Active CN107056626B (en) 2017-03-17 2017-03-17 A kind of compound and its preparation method and application

Country Status (1)

Country Link
CN (1) CN107056626B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018083053A1 (en) * 2016-11-02 2018-05-11 Merck Patent Gmbh Materials for electronic devices
TWI815831B (en) 2017-11-23 2023-09-21 德商麥克專利有限公司 Materials for electronic devices
WO2020130623A1 (en) * 2018-12-18 2020-06-25 주식회사 엘지화학 Polycyclic compound and organic light-emitting device comprising same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005023437A1 (en) * 2005-05-20 2006-11-30 Merck Patent Gmbh Connections for organic electronic devices
CN103805168B (en) * 2012-11-14 2015-08-26 吉林奥来德光电材料股份有限公司 Benzanthracenes electroluminescent organic material and its preparation method and application
CN103805165B (en) * 2012-11-14 2015-12-02 吉林奥来德光电材料股份有限公司 A kind of Benzanthracenes electroluminescent organic material and its preparation method and application

Also Published As

Publication number Publication date
CN107056626A (en) 2017-08-18

Similar Documents

Publication Publication Date Title
CN105051014B (en) material for electronic device
TWI611003B (en) Compounds for electronic devices
CN105378028B (en) Organic photoelectric assembly constituent, organic photoelectric assembly and display module
CN101987822B (en) Organic electroluminescent material and application thereof
CN105566200B (en) Compound for organic photoelectric device and the constituent for organic photoelectric device and organic photoelectric device and display device
CN108290836A (en) Organic electronic element compound, organic electronic element and its electronic device using the compound
CN107056844A (en) The organic luminescent device of organo-metallic compound including organo-metallic compound and the diagnosis composition including organo-metallic compound
TW201538460A (en) Compounds and organic electronic devices
CN107223122A (en) The material based on spirobifluorene derivative for electronic device
CN104628581B (en) 2,6,6,8 4 replacement 6H benzos [cd] pyrene compounds and the organic electroluminescence device containing which
TW201827386A (en) Compounds and organic electronic devices
CN106008573A (en) Organic compound, light-emitting element, light-emitting device, electronic device, and lighting device
CN108779103A (en) With the fluorene structured compound of spiral shell two
CN105849113B (en) Aromatic amine compound, light emitting element material and light-emitting component
CN107619410A (en) Compound and the organic electronic element for including it
CN108658837A (en) A kind of organic electroluminescence device
CN114394929B (en) Carbazole-based triarylamine derivative and organic electroluminescent device thereof
CN107056626B (en) A kind of compound and its preparation method and application
CN110520504A (en) Constituent, organic photoelectric device and display device for phosphorescence host
CN113735794A (en) Compound containing condensed aryl and organic electroluminescent device thereof
CN105924438A (en) Organic optoelectronic material with indeno-phenanthroline structure and preparing method and application thereof
CN107778309A (en) A kind of and quinoline and its application
CN108899431A (en) A kind of organic luminescent device
CN114249738A (en) Electroluminescent material and device
CN107629062A (en) A kind of carbazole analog derivative and its organic luminescent device

Legal Events

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