CN109574917B - 一种芴酮衍生物及其制备和应用 - Google Patents

一种芴酮衍生物及其制备和应用 Download PDF

Info

Publication number
CN109574917B
CN109574917B CN201811466313.0A CN201811466313A CN109574917B CN 109574917 B CN109574917 B CN 109574917B CN 201811466313 A CN201811466313 A CN 201811466313A CN 109574917 B CN109574917 B CN 109574917B
Authority
CN
China
Prior art keywords
fluorenone
reactants
derivative
yield
prepared
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
CN201811466313.0A
Other languages
English (en)
Other versions
CN109574917A (zh
Inventor
穆广园
庄少卿
任春婷
徐鹏
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.)
Wuhan Shangsai Optoelectronics Technology Co ltd
Original Assignee
Wuhan Shangsai Optoelectronics 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 Wuhan Shangsai Optoelectronics Technology Co ltd filed Critical Wuhan Shangsai Optoelectronics Technology Co ltd
Priority to CN201811466313.0A priority Critical patent/CN109574917B/zh
Publication of CN109574917A publication Critical patent/CN109574917A/zh
Application granted granted Critical
Publication of CN109574917B publication Critical patent/CN109574917B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/20—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/22—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to two ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C07D263/57—Aryl or substituted aryl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • 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
    • C07D405/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D405/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—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
    • H10K85/649—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Abstract

本发明公开了一种芴酮衍生物及其制备和应用。该芴酮衍生物以芴酮为核心，通过杂环桥接受体基团从而形成一类具有新的特性的化合物，作为OLED器件发光层主体材料和电子传输材料，可显著提高器件的启动电压、发光强度、外量子效率、色度、半衰期等方面的性能，提高器件工作稳定性。

Description

一种芴酮衍生物及其制备和应用
技术领域
本发明属于光电材料应用科技领域，具体涉及一种芴酮衍生物及其制备和应用。
背景技术
OLED，即有机发光二极管，又称为有机电激光显示(OLED)。OLED 具有自发光的特性，采用非常薄的有机材料涂层和玻璃基板，当电流通过时，有机材料就会发光，而且OLED显示屏幕可视角度大，并且能够显著节省电能，因此OLED被视为21世纪最具前途的产品之一。
芴作为一种具有刚性平面联苯结构的化合物，由于其宽的能隙、高的发光效率和结构上易于修饰等特点，受到光电材料应用科技领域的广泛关注。芴类材料的缺点之一是薄膜在空气中退火或器件在长时间运行后会出现长波发射，严重影响其发射光的色纯度、效率和稳定性，目前认为是芴的刚性平面联苯结构使材料在发光时容易形成分子间激基缔合物、芴酮或者两者共同作用引起了该长波发射。国内外的学者针对此问题提出了不同的解决方案，包括支化聚合物压制芴类材料的长波发射、结构明确的寡聚物压制芴类材料的长波发射、芴的9位杂原子化压制芴类材料的长波发射、不同封端基压制聚芴类材料的长波发射、芴的9位烷基化等，规避芴类材料在光、热、电、残留的催化剂或器件电极的作用下被氧气氧化产生芴酮，影响芴类半导体的光谱稳定性。然而，稳定化策略虽然可以提高发光效率，但只能一定程度上抑制链间作用导致的激基缔合物的产生，没有完全去除长波发射，螺类化合物在有氧的情况下依然表现出明显的氧气猝灭，因此，芴类衍生物材料的光谱稳定性方面有待进一步提升。
发明内容
为进一步解决上述技术问题，在本发明的一个方面，本发明提出了一种芴酮化合物。根据本发明的实施例，
其结构通式如下化学式1所示：
化学式1
Figure BDA0001889897160000011
其中，R1和R2分别独立地为氢、氰基、硝基、取代或未取代的亚磺酸酯基、取代或未取代的C1～20的烷基、取代或未取代的C1～20的烷氧基、取代或未取代的C1～20的烷硫基、取代或未取代的C1～20硅烷基、取代或未取代的C6～45的芳基、取代或未取代的C6～45的芳氧基、取代或未取代的C6～45的芳硫基、取代或未取代的C6～45的芳胺基、取代或未取代的C6～45芳硅基、或者取代或未取代的C2～45的杂环基(优选取代或未取代的C3～45的杂芳基)。
在本发明的一些实施例中，R1、R2中的至少之一为：
Figure BDA0001889897160000021
其中，各X分别独立的选自CH、C(R5)、N；
各Y分别独立的选自N(R6)、O、S、S(＝O)、S(＝O)2；
Ar为取代或未取代的C6～42的芳基、取代或未取代的C3～42的杂芳基、取代或未取代的C6～42的芳氧基、取代或未取代的C6～42的芳硫基、取代或未取代的C6～42的芳胺基、取代或未取代的C6～42的芳硅基。
进一步的，R5、R6分别独立的为：取代或未取代的C1～20的烷基、取代或未取代的C1～20的烷氧基、取代或未取代的C1～20的烷硫基、取代或未取代的C1～20硅烷基、取代或未取代的C6～39的芳基、取代或未取代的C6～39的芳氧基、取代或未取代的C6～39的芳硫基、取代或未取代的C6～39的芳胺基、取代或未取代的C6～39芳硅基或者取代或未取代的C2～39的杂环基(优选取代或未取代的C3～45的杂芳基)。
在本发明的一些实施例中，当R1、R2中的
Figure BDA0001889897160000022
至少一个为时，R1和R2分别独立的选自下列基团：
Figure BDA0001889897160000023
Figure BDA0001889897160000024
当R1、R2中的至少一个为
Figure BDA0001889897160000025
时，R1和R2分别独立的选自下列基团：
Figure BDA0001889897160000026
其中，R7-R17分别独立的选自：取代或未取代的C6～35的芳基、取代或未取代的C3～35的杂芳基、取代或未取代的C6～35的芳氧基、取代或未取代的C6～35的芳硫基、取代或未取代的C6～35的芳胺基、取代或未取代的C6～35芳硅基或者取代或未取代的C2～35的杂环基。
其中，需要说明的是：*为取代位点。所述杂环基是指杂原子取代五元/ 六元环上的C形成的基团，例如杂芳基。所述芳氧基、芳硫基、芳胺基和芳硅基是先连接一个X再连接芳基，X是O、S、N、Si。
进一步的，在本发明的一些实施例中，R7-R17分别独立的选自下列基团：
Figure BDA0001889897160000031
在本发明的一些实施例中，所述芴酮衍生物具有以下其中之一的结构：
Figure BDA0001889897160000041
Figure BDA0001889897160000051
Figure BDA0001889897160000061
Figure BDA0001889897160000071
Figure BDA0001889897160000081
Figure BDA0001889897160000091
Figure BDA0001889897160000101
Figure BDA0001889897160000111
Figure BDA0001889897160000121
Figure BDA0001889897160000131
Figure BDA0001889897160000141
Figure BDA0001889897160000151
Figure BDA0001889897160000161
Figure BDA0001889897160000171
Figure BDA0001889897160000181
Figure BDA0001889897160000191
在本发明的另一个方面，本发明提出了一种制备上述实施例的芴酮衍生物的方法，包括如下步骤：
芴酮的卤代衍生物与R1对应的硼酸衍生物、R2对应的硼酸衍生物、碱按照摩尔比1:0-3:0-3:1-4投料，按照芴酮的溴代衍生物：混合溶剂为 1mmol:0.5-10mL的比例加入混合溶剂，在氮气氛围下，按照芴酮的卤代衍生物的物质的量计，加入5‰-5％的钯催化剂，升温至65-120℃反应6-30h，液相监测反应完成，冷却至室温，过滤，母液浓缩与滤渣混合，柱色谱分离，即可得到芴酮衍生物。
根据本发明的优选实施例，上述碱为碳酸铯、氟化铯、氟化钾、碳酸钾、磷酸钾、磷酸锂、碳酸钠、氟化四丁基铵和叔丁醇钠中的至少之一。
进一步的，根据本发明的优选实施例，上述碱为碳酸铯。
根据本发明的优选实施例，上述钯催化剂为[1,1’-双(二苯基膦基)二茂铁] 二氯化钯与二氯甲烷的复合物(PdCl2(dppf)-CH2Cl2)、四三苯基膦钯 (Pd(PPh3)4)、三(二亚苄基丙酮)二钯(Pd2(dba)3)和醋酸钯(Pd(OAc)2)中的至少之一。
进一步的，根据本发明的优选实施例，上述钯催化剂为 PdCl2(dppf)-CH2Cl2。
根据本发明的优选实施例，上述混合溶剂包括甲苯、二甲苯、乙醇、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和水中的至少之一。
进一步的，根据本发明的优选实施例，上述混合溶剂为四氢呋喃、乙醇、水中的至少之一。
在本发明的再一方面，本发明提出了一种电子元件。根据本发明的实施例，该电子元件包括依次层叠的出光层、阴极、有机层和阳极，所述出光层或所述有机层包含所述芴酮衍生物。
进一步的，所述有机层至少由电子注入层、电子传输层、发光层、空穴传输层、空穴注入层组成，所述电子传输层或所述发光层包含所述芴酮衍生物。
本发明提出的芴酮衍生物充分考虑到电子元件在电流作用下氧气对其稳定性的影响，以芴酮为核心，通过杂环桥接受体基团从而形成一类具有新的特性的化合物。一方面，该类化合物具有芴所特有的较宽的能隙和高的发光效率特点，电负性大的芴酮单元作为电子受体(A)，与强给电子基团的杂环基团及芳香基团单键连接，形成受体-给体-受体的推拉电子结构，有效平衡材料中的空穴与电子迁移速率，使其在发光主体材料中展现出较强的电荷转移吸收和荧光发射强度，密集的电子给受体也在一定程度上增大了分子的刚性，降低非辐射跃迁，是一种优良的发光层材料。另一方面，该类化合物还是一种优良的电子传输材料，具有强给电子特性的杂环基团赋予了材料以优良的电子传输特性，芴酮基团的协同配合使得HOMO(最高已占轨道)、 LUMO(最低未占轨道)实现了大的空间分离，提高了器件在电流效率、功率效率等等方面的性能，并显著降低器件应用时的启动电压，降低能耗。
专利CN107987084也公开了一种芴酮化合物及其在有机电致发光器件中的应用，但是该化合物的母环与申请大为不同，其化合物母环是将芴酮的两个苯环与吲哚并联形成，该芴酮衍生物是对吲哚的各个位置进行修饰得到，解决无合适主体材料与掺杂材料组合，以改善OLED器件颜色纯度、发光效率以及稳定性的问题，作为主体材料应用至OLED器件，具有电流效率高、驱动电压低的优点。相对而言，本申请设计的芴酮化合物直接以更为简单的芴酮为母环，对芴酮的各个位置进行修饰得到，合成步骤更简单，综合产率更高，并且，以空间位阻较大的母核结构与分子扭曲结构相结合，避免了母核结构过大，凝集结晶和分子间堆积造成的载流子猝灭，从而提高器件的稳定性，提升器件的启动电压、发光强度、外量子效率、电流效率、功率效率、色度、半衰期等方面的综合性能。
附图说明
本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1是18号器件的能级结构图；
图2是18、32、42号器件的波长-发光强度特性曲线图；
图3是18、32号器件的电压-电流密度-亮度特性曲线图；
图4是18、32号器件的亮度-外量子效率特性曲线图；
具体实施方式
为了更好地理解本发明，下面结合附图及具体实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。
实施例1
Figure 1
(1)在250mL的三口瓶中，投入3-联苯硼酸(9.90g，50mmol)、4- 溴吡啶-2-硼酸(10.09g，50mmol)、碳酸钾(13.82g，100mmol)，加入100 mL甲苯，在氮气氛围下，加入Pd(PPh3)4(0.17g，0.15mmol)，升温至85℃反应6～24h，液相监测反应完成，冷却至室温，水洗，过滤，滤液分液，有机层萃取浓缩，即可得到粗中间体(4-([1,1'-联苯-3-基)吡啶-2-基)硼酸13.20g，收率96％；
(2)在100mL的三口瓶中，投入2-溴芴酮(2.59g，10mmol)、中间体(4.13g，15mmol)、碳酸铯(13.82g，30mmol)，加入40mL四氢呋喃和20mL水，在氮气氛围下，加入PdCl2(dppf)-CH2Cl2(0.16g，0.2mmol)，升温至65℃反应6-24h，液相监测反应完成，冷却至室温，过滤，浓缩，柱色谱分离，即可得到目标化合物3.44g，收率84％。
质谱仪MALDI-TOF-MS(m/z)＝409.4872，理论分子量：409.4880； Anal.Calcd forC30H19N(％):C 88.00,H 4.68,N 3.42,Found:C 88.00,H 4.69,N 3.40。
Figure BDA0001889897160000221
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.11g，收率81％。质谱仪MALDI-TOF-MS(m/z)＝383.4504，理论分子量：383.4500；Anal.Calcd forC28H17N(％):C 87.71,H 4.47,N 3.65, Found:C 87.70，H 4.48，N 3，65。
Figure BDA0001889897160000222
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.47g，收率82％。质谱仪MALDI-TOF-MS(m/z)＝423.4706，理论分子量：423.4710；Anal.Calcd forC30H17N(％):C 85.09,H 4.05,N 3.31, Found:C 85.10,H 4.05,N 3.30。
Figure BDA0001889897160000223
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物4.57g，收率80％。质谱仪MALDI-TOF-MS(m/z)＝571.6795，理论分子量：571.6790；Anal.Calcd forC43H25N(％):C 90.34,H 4.41,N 2.45, Found:C 90.36，H 4.40，N 2.45。
Figure BDA0001889897160000224
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物4.19g，收率84％。质谱仪MALDI-TOF-MS(m/z)＝498.5855，理论分子量：498.5850；Anal.Calcd forC36H22N2(％):C 86.72,H 4.45,N 5.62, Found:C 86.72,H 4.44,N 5.62。
实施例6
Figure BDA0001889897160000225
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.81 g，收率83％。质谱仪MALDI-TOF-MS(m/z)＝459.5487，理论分子量：459.5480；Anal.Calcd forC34H21N(％):C 88.86,H 4.61,N 3.05, Fnd：C86.85，H 4.60，N 3.05
Figure BDA0001889897160000231
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.51 g，收率81％。质谱仪MALDI-TOF-MS(m/z)＝433.5105，理论分子量：433.5100；Anal.Calcd forC32H19N(％):C 88.66,H 4.42,N 3.23, Found:C 88.65，H 4.43，N 3.23。
Figure BDA0001889897160000232
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.70 g，收率85％。质谱仪MALDI-TOF-MS(m/z)＝435.4816，理论分子量：435.4820；Anal.Calcd forC31H17N(％):C 85.50,H 3.93,N 3.22, Found:C 85.50,H 3.94,N 3.21。
Figure BDA0001889897160000233
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物4.00 g，收率80％。质谱仪MALDI-TOF-MS(m/z)＝498.5847，理论分子量：498.5850；Anal.Calcd forC36H22N2(％):C 86.72,H 4.45,N 5.62, Found:C 86.72，H 4.44，N 5.62。
Figure BDA0001889897160000234
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.22 g，收率84％。质谱仪MALDI-TOF-MS(m/z)＝383.4506，理论分子量：383.4500；Anal.Calcd forC28H17N(％):C 87.71,H 4.47,N 3.65, Found:C 87.70,H 4.48,N 3.65。
实施例11
Figure BDA0001889897160000241
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物4.53g，收率79％。质谱仪MALDI-TOF-MS(m/z)＝573.6954，理论分子量：573.6950；Anal.Calcd forC43H27N(％):C 90.03,H 4.74,N 2.44, Found:C 90.02,H 4.75,N 2.44。
Figure BDA0001889897160000242
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.99g，收率82％。质谱仪MALDI-TOF-MS(m/z)＝486.5735，理论分子量：486.5740；Anal.Calcd forC35H22N2(％):C 86.40,H 4.56,N 5.76, Found:C 86.42，H 4.55，N 5.76。
Figure BDA0001889897160000243
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物4.08g，收率80％。质谱仪MALDI-TOF-MS(m/z)＝510.5967，理论分子量：510.5960；Anal.Calcd forC37H22N2(％):C 87.04,H 4.34,N 5.49, Found:C 87.04,H 4.35,N 5.50。
Figure BDA0001889897160000244
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.57g，收率81％。质谱仪MALDI-TOF-MS(m/z)＝440.5204，理论分子量：440.5200；Anal.Calcd forC29H16N2(％):C 79.07,H 3.66,N 6.36, Found:C 79.08,H 3.66,N 6.35。
Figure BDA0001889897160000245
(1)在250mL的三口瓶中，投入二苯基胺(8.46g，50mmol)、5-溴嘧啶-2-硼酸(10.14g，50mmol)、三叔丁基膦四氟硼酸盐(0.15g，0.5mmol)、叔丁醇钠(9.61g，100mmol)，加入100mL甲苯，在氮气氛围下，加入三 (二亚苄基丙酮)二钯(0.23g，0.25mmol)，升温至110℃反应6～24h，液相监测反应完成，冷却至室温，水洗，过滤，滤液分液，有机层萃取浓缩，即可得到粗中间体N,N-二苯基嘧啶-5-胺-2-硼酸13.54g，收率93％；
(2)在100mL的三口瓶中，投入2-溴芴酮(2.59g，10mmol)、中间体(4.37g，15mmol)、碳酸铯(13.82g，30mmol)，加入40mL四氢呋喃和20mL水，在氮气氛围下，加入PdCl2(dppf)-CH2Cl(0.16g，0.2mmol)，升温至65℃反应6-24h，液相监测反应完成，冷却至室温，过滤，浓缩，柱色谱分离，即可得到目标化合物3.32g，收率78％。
质谱仪MALDI-TOF-MS(m/z)＝425.4912，理论分子量：425.4910； Anal.Calcd forC29H19N3(％):C 81.86,H 4.50,N 9.88,Found:C 81.85,H 4.50,N 9.88。
Figure 2
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.43g，收率79％。质谱仪MALDI-TOF-MS(m/z)＝434.4977，理论分子量：434.4980；Anal.Calcd forC31H18N2(％):C 85.69,H 4.18,N 6.45, Found:C 85.69,H 4.18,N 6.45。
实施例17
Figure 3
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.54g，收率81％。质谱仪MALDI-TOF-MS(m/z)＝436.4694，理论分子量：436.4700；Anal.Calcd forC30H16N2(％):C 82.56,H 3.70,N 6.42, Found:C 82.55,H 3.70,N 6.42。
Figure BDA0001889897160000253
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.78g，收率82％。质谱仪MALDI-TOF-MS(m/z)＝460.5363，理论分子量：460.5360；Anal.Calcd forC33H20N2(％):C 86.07,H 4.38,N 6.08, Found:C 86.06,H 4.38,N 6.09。
Figure BDA0001889897160000261
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.35g，收率79％。质谱仪MALDI-TOF-MS(m/z)＝424.4596，理论分子量：424.4590；Anal.Calcd forC29H16N2(％):C 82.05,H 3.80,N 6.60, Found:C 82.06,H 3.80,N 6.60。
Figure BDA0001889897160000262
将3-联苯硼酸(9.90g，50mmol)替换为苯硼酸(13.41g，110mmol)， 4-溴吡啶-2-硼酸(10.09g，50mmol)替换为4,6-二溴三嗪-2-硼酸(14.13g， 50mmol)，其他按照与实施例1以基本相同的方法制备上式中的目标化合物 (反应物摩尔比、反应条件相同)，即可得到目标化合物3.09g，收率75％。质谱仪MALDI-TOF-MS(m/z)＝411.4642，理论分子量：411.4640；Anal.Calcd for C28H17N3(％):C 81.73,H 4.16,N 10.21,Found:C 81.74,H 4.16,N10.20。
Figure BDA0001889897160000263
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物2.93g，收率76％。质谱仪MALDI-TOF-MS(m/z)＝385.4266，理论分子量：385.4260；Anal.Calcd forC26H15N3(％):C 81.02,H 3.92,N 10.90, Found:C 81.02,H 3.91,N 10.90。
Figure BDA0001889897160000264
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.35g，收率73％。质谱仪MALDI-TOF-MS(m/z)＝459.5077，理论分子量：459.5080；Anal.Calcd forC32H17N3(％):C 83.64,H 3.73,N 9.14, Found:C 83.65,H 3.72,N 9.14。
实施例23
Figure BDA0001889897160000271
将3-联苯硼酸(9.90g，50mmol)替换为2-芴酮硼酸(24.64g，110mmol)， 4-溴吡啶-2-硼酸(10.09g，50mmol)替换为4,6-二溴三嗪-2-硼酸(14.13g， 50mmol)，其他按照与实施例1以基本相同的方法制备上式中的目标化合物 (反应物摩尔比、反应条件相同)，即可得到目标化合物4.55g，收率74％。质谱仪MALDI-TOF-MS(m/z)＝615.6484，理论分子量：615.6480；Anal.Calcd for C42H21N3(％):C 81.94,H 3.44,N 6.83,Found:C,81.94；H,3.45；N,6.83。
实施例24
Figure BDA0001889897160000272
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.85g，收率77％。质谱仪MALDI-TOF-MS(m/z)＝500.5608，理论分子量：500.5610；Anal.Calcd forC34H20N4(％):C 81.58,H 4.03,N 11.19, Found:C 81.58,H 4.05,N 11.18。
实施例25
Figure BDA0001889897160000273
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.70g，收率74％。质谱仪MALDI-TOF-MS(m/z)＝500.5605，理论分子量：500.5610；Anal.Calcd forC34H20N4(％):C 81.58,H 4.03,N 11.19, Found:C 81.58,H 4.02,N 11.20。
实施例26
Figure BDA0001889897160000274
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.77g，收率75％。质谱仪MALDI-TOF-MS(m/z)＝502.5769，理论分子量：502.5770；Anal.Calcd forC34H22N4(％):C 81.26,H 4.41,N 11.15, Found:C 81.25,H 4.40,N 11.15。
Figure BDA0001889897160000281
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.42g，收率79％。质谱仪MALDI-TOF-MS(m/z)＝433.5100，理论分子量：433.5100；Anal.Calcd forC32H19N(％):C 88.66,H 4.42,N 3.23, Found:C 88.68,H 4.42,N 3.22。
实施例28
Figure BDA0001889897160000282
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.84g，收率77％。质谱仪MALDI-TOF-MS(m/z)＝498.5858，理论分子量：498.5850；Anal.Calcd forC36H22N2(％):C 86.72,H 4.45,N 5.62, Found:C 86.70,H 4.46,N 5.62。
实施例29
Figure BDA0001889897160000283
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.84g，收率77％。质谱仪MALDI-TOF-MS(m/z)＝440.5206，理论分子量：440.5200；Anal.Calcd forC29H16N2(％):C 79.07,H 3.66,N 6.36, Found:C 79.06,H 3.65,N 6.36。
实施例30
Figure 4
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.32g，收率76％。质谱仪MALDI-TOF-MS(m/z)＝437.4574，理论分子量：437.4580；Anal.Calcd forC29H15N3(％):C 79.62,H 3.46,N 9.61, Found:C 79.61,H 3.47,N 9.60。
Figure BDA0001889897160000291
按照与实施例1相同的方法制备上式中的目标化合物(相比较于实施例 1，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.80g，收率76％。质谱仪MALDI-TOF-MS(m/z)＝500.5604，理论分子量：500.5610；Anal.Calcd forC34H20N4(％):C 81.58,H 4.03,N 11.19, Found:C 81.58,H 4.02,N 11.20。
实施例32
Figure BDA0001889897160000292
按照与实施例15相同的方法制备上式中的目标化合物(相比较于实施例15，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.43g，收率72％。质谱仪MALDI-TOF-MS(m/z)＝476.5388，理论分子量：476.5390；Anal.Calcd forC32H20N4(％):C 80.65,H 4.23,N 11.76, Found:C,80.66；H,4.24；N,11.75。
实施例33
Figure BDA0001889897160000293
(1)在250mL的三口瓶中，投入4-叔丁基苯硼酸(8.90g，50mmol)、 4-溴吡啶-2-硼酸(10.09g，50mmol)、碳酸钾(13.82g，100mmol)，加入 100mL甲苯，在氮气氛围下，加入Pd(PPh3)4(0.17g，0.15mmol)，升温至 85℃反应6～24h，液相监测反应完成，冷却至室温，水洗，过滤，滤液分液，有机层萃取浓缩，即可得到粗中间体(5-(4-叔丁基苯基)吡啶-2-基)硼酸12.37 g，收率97％；
(2)在100mL的三口瓶中，投入2,7-二溴芴酮(3.38g，10mmol)、中间体(6.38g，25mmol)、碳酸铯(13.82g，30mmol)，加入40mL四氢呋喃和20mL水，在氮气氛围下，加入PdCl2(dppf)-CH2Cl2(0.16g，0.2mmol)，升温至65℃反应6-24h，液相监测反应完成，冷却至室温，过滤，浓缩，柱色谱分离，即可得到目标化合物4.49g，收率75％。
质谱仪MALDI-TOF-MS(m/z)＝598.7900，理论分子量：598.7900； Anal.Calcd forC43H38N2(％):C 86.25,H 6.40,N 4.68,Found:C 86.26,H 6.40,N 4.66。
Figure BDA0001889897160000301
按照与实施例33相同的方法制备上式中的目标化合物(相比较于实施例33，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物4.53g，收率68％。质谱仪MALDI-TOF-MS(m/z)＝666.7367，理论分子量：666.7360；Anal.Calcd forC47H26N2(％):C 84.67,H 3.93,N 4.20, Found:C 84.66,H 3.94,N 4.20。
Figure BDA0001889897160000302
按照与实施例33相同的方法制备上式中的目标化合物(相比较于实施例33，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物4.11g，收率70％。质谱仪MALDI-TOF-MS(m/z)＝586.6936，理论分子量：586.6940；Anal.Calcd forC43H26N2(％):C 88.03,H 4.47,N 2.73, Found:C 88.02,H 4.46,N 2.76。
实施例36
Figure BDA0001889897160000303
(1)在250mL的三口瓶中，投入9H-咔唑(8.11g，50mmol)、2-溴吡啶-4-硼酸(10.09g，50mmol)、三叔丁基膦四氟硼酸盐(0.15g，0.5mmol)、叔丁醇钠(9.61g，100mmol)，加入100mL甲苯，在氮气氛围下，加入三 (二亚苄基丙酮)二钯(0.23g，0.25mmol)，升温至110℃反应6～24h，液相监测反应完成，冷却至室温，水洗，过滤，滤液分液，有机层萃取浓缩，即可得到粗中间体N,N-二苯基嘧啶-5-胺-2-硼酸12.96g，收率90％；
(2)在100mL的三口瓶中，投入2,7-二溴芴酮(3.38g，10mmol)、中间体(7.20g，25mmol)、碳酸铯(13.82g，30mmol)，加入40mL四氢呋喃和20mL水，在氮气氛围下，加入PdCl2(dppf)-CH2Cl2(0.16g，0.2mmol)，升温至65℃反应6-24h，液相监测反应完成，冷却至室温，过滤，浓缩，柱色谱分离，即可得到目标化合物4.85g，收率73％。
质谱仪MALDI-TOF-MS(m/z)＝664.7685，理论分子量：664.7680； Anal.Calcd forC47H28N4(％):C 84.92,H 4.25,N 8.43,Found:C 84.92,H 4.24,N 8.45。
实施例37
Figure BDA0001889897160000311
按照与实施例33相同的方法制备上式中的目标化合物(相比较于实施例33，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物4.11g，收率70％。质谱仪MALDI-TOF-MS(m/z)＝688.7896，理论分子量：688.7900；Anal.Calcd forC49H28N4(％):C 85.45,H 4.10,N 8.13, Found:C 85.44,H 4.10,N 8.15。
实施例38
Figure BDA0001889897160000312
按照与实施例33相同的方法制备上式中的目标化合物(相比较于实施例33，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物4.71g，收率68％。质谱仪MALDI-TOF-MS(m/z)＝692.7333，理论分子量：692.7340；Anal.Calcd forC47H24N4(％):C 81.49,H 3.49,N 8.09, Found:C 81.50,H 3.48,N 8.10。
实施例39
Figure BDA0001889897160000313
将4-叔丁基苯硼酸(8.90g，50mmol)替换为苯硼酸(13.41g，110mmol)， 4-溴吡啶-2-硼酸(10.09g，50mmol)替换为4,6-二溴三嗪-2-硼酸(14.13g， 50mmol)，其他按照与实施例33以基本相同的方法制备上式中的目标化合物(反应物摩尔比、反应条件相同)，即可得到目标化合物4.31g，收率67％。质谱仪MALDI-TOF-MS(m/z)＝642.7228，理论分子量：642.7220；Anal.Calcd for C43H26N6(％):C 80.36,H 4.08,N 13.08,Found:C 80.35,H4.08,N 13.10。
实施例40
Figure BDA0001889897160000314
按照与实施例33相同的方法制备上式中的目标化合物(相比较于实施例33，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.84g，收率65％。质谱仪MALDI-TOF-MS(m/z)＝590.6467，理论分子量：590.6460；Anal.Calcd forC39H22N6(％):C 79.31,H 3.75,N 14.23, Found:C 79.30，H 3.75，N 14.25。
实施例41
Figure BDA0001889897160000321
按照与实施例33相同的方法制备上式中的目标化合物(相比较于实施例33，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物5.25g，收率64％。质谱仪MALDI-TOF-MS(m/z)＝820.9164，理论分子量：820.9160；Anal.Calcd forC55H32N8(％):C 80.47,H 3.93,N 13.65, Found:C 80.46,H 3.95,N 13.65。
实施例42
Figure BDA0001889897160000322
按照与实施例15相同的方法制备上式中的目标化合物(相比较于实施例15，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.27g，收率73％。质谱仪MALDI-TOF-MS(m/z)＝448.5247，理论分子量：448.5250；Anal.Calcd forC32H20N2(％):C 85.69,H 4.49,N 6.25, Found:C 85.70,H 4.50,N 6.25。
实施例43
Figure BDA0001889897160000323
按照与实施例15相同的方法制备上式中的目标化合物(相比较于实施例15，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物2.96g，收率70％。质谱仪MALDI-TOF-MS(m/z)＝422.4866，理论分子量：422.4870；Anal.Calcd forC30H18N2(％):C 85.29,H 4.29,N 6.63, Found:C 85.29,H 4.29,N 6.63。
实施例44
Figure BDA0001889897160000324
按照与实施例36相同的方法制备上式中的目标化合物(相比较于实施例36，每一对应步骤的反应物可不同，但反应物摩尔比、反应条件相同)，即可得到终产物3.67g，收率65％。质谱仪MALDI-TOF-MS(m/z)＝564.6477，理论分子量：564.6480；Anal.Calcd forC39H24N4(％):C 82.96,H 4.28,N 9.92, Found:C 82.95,H 4.28,N 9.94。
Figure BDA0001889897160000331
在100mL的三口瓶中，投入2,7-二溴芴酮(3.38g，10mmol)、苯并噁唑-2-硼酸(4.07g，25mmol)、碳酸铯(13.82g，30mmol)，加入40mL四氢呋喃和20mL水，在氮气氛围下，加入PdCl2(dppf)-CH2Cl2(0.16g，0.2 mmol)，升温至65℃反应6-24h，液相监测反应完成，冷却至室温，过滤，浓缩，柱色谱分离，即可得到目标化合物2.78g，收率67％。
质谱仪MALDI-TOF-MS(m/z)＝414.4200，理论分子量：414.4200； Anal.Calcd forC27H14N2(％):C 78.26,H 3.40,N 6.75,Found:C 78.25,H 3.41,N 6.76。
器件实施例1(电子元件的制造)
将氧化铟锡(ITO)玻璃基板相继在清洗剂和去离子水中以超声波清洗 1h，之后先后用丙酮和异丙醇继续超声清洗15min，真空干燥2h(105℃)，其后进行15min的UV臭氧处理，将ITO玻璃基板传送至真空蒸镀机。
将三氧化钼(MoO3)真空沉积在ITO玻璃基板上至10nm的厚度形成空穴注入层。
将N,N′-二苯基-N,N′-(1-萘基)-1,1′-联苯-4,4′-二胺(NPB)真空沉积在空穴注入层上至60nm的厚度形成空穴传输层。
将实施例1-45制备得到的化合物或1,3-二(9H-咔唑-9-基)苯(mCP)(作为发光层主体材料)和三(2-苯基吡啶)合铱(Ir(ppy)3)(作为发光层客体材料)以95:5的重量比共同真空沉积在空穴传输层上至20nm的厚度形成发光层。
将1,3,5-三[(3-吡啶基)-3-苯基]苯(TmPyPB)真空沉积在发光层上至30 nm的厚度形成电子传输层材料。
将氟化锂(LiF)真空沉积在电子传输层上至1nm的厚度形成电子注入层。
将铝(Al)真空沉积在电子注入层上至100nm的厚度形成阴极,从而形成电子元件。
对制备的电子元件测定其启动电压和发光亮度，观察发光颜色，并且对 10000nit下器件的T95寿命进行测定，具有代表性的器件性能测定结果示于表1中。
表1有机电致发光器件性能表征
Figure BDA0001889897160000341
检测结果表明，采用本发明提供的芴酮衍生物作为发光层主体材料制备得到的发光元件在启动电压、发光亮度、外量子效率和色度、玻璃化转变温度、半衰期等方面具有优异的性能，并显著优于现有技术中常用的mCP作为发光层主体材料制备的发光元件。
器件实施例2(电子元件的制造)
将氧化铟锡(ITO)玻璃基板相继在清洗剂和去离子水中以超声波清洗 1h，之后先后用丙酮和异丙醇继续超声清洗15min，真空干燥2h(105℃)，其后进行15min的UV臭氧处理，将ITO玻璃基板传送至真空蒸镀机。
将三氧化钼(MoO3)真空沉积在ITO玻璃基板上至10nm的厚度形成空穴注入层。
将N,N′-二苯基-N,N′-(1-萘基)-1,1′-联苯-4,4′-二胺(NPB)真空沉积在空穴注入层上至60nm的厚度形成空穴传输层。
将1,3-二(9H-咔唑-9-基)苯(mCP)(作为发光层主体材料)和三(2-苯基吡啶)合铱(Ir(ppy)3)(作为发光层客体材料)以95:5的重量比共同真空沉积在空穴传输层上至20nm的厚度形成发光层。
将实施例1-45制备得到的化合物或1,3,5-三[(3-吡啶基)-3-苯基]苯 (TmPyPB)真空沉积在发光层上至30nm的厚度形成电子传输层材料。
将氟化锂(LiF)真空沉积在电子传输层上至1nm的厚度形成电子注入层。
将铝(Al)真空沉积在电子注入层上至100nm的厚度形成阴极,从而形成电子元件。
对制备的电子元件测定其启动电压和发光亮度，观察发光颜色，并且对 10000nit下器件的T95寿命进行测定，具有代表性的器件性能测定结果示于表2中。
表2有机电致发光器件性能表征
Figure BDA0001889897160000351
Figure BDA0001889897160000361
检测结果表明，采用本发明提供的芴酮衍生物作为电子传输材料制备得到的发光元件在启动电压、电流效率、功率效率和色度、玻璃化转变温度、半衰期等方面具有优异的性能，并显著优于现有技术中常用的TmPyPB作为电子传输材料制备的发光元件。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (6)

1.一种芴酮衍生物，其特征在于，其结构通式如下化学式1所示：
化学式1
Figure FDA0002723544420000011
其中，
R1、R2中的至少之一为：
Figure FDA0002723544420000012
其余的R1、R2为H；
当R1、R2中的至少一个为
Figure FDA0002723544420000013
时，R1和R2分别独立选自下列基团：
Figure FDA0002723544420000014
当R1、R2中的至少一个为
Figure FDA0002723544420000015
时，R1和R2分别独立选自下列基团：
Figure FDA0002723544420000016
所述R10-R16分别独立的选自下列基团：
Figure FDA0002723544420000017
Figure FDA0002723544420000021
*为取代位点；
所述R17分别独立的选自下列基团：
Figure FDA0002723544420000022
2.根据权利要求1所述的芴酮衍生物，其特征在于，包括以下化合物：
Figure FDA0002723544420000031
Figure FDA0002723544420000041
Figure FDA0002723544420000051
Figure FDA0002723544420000061
Figure FDA0002723544420000071
Figure FDA0002723544420000081
Figure FDA0002723544420000091
Figure FDA0002723544420000101
Figure FDA0002723544420000111
Figure FDA0002723544420000121
3.一种权利要求1-2任一项所述的芴酮衍生物的制备方法，其特征在于，包括如下步骤：
将芴酮的卤代衍生物与R1对应的硼酸衍生物、R2对应的硼酸衍生物、碱按照摩尔比1:0-3:0-3:1-4投料，按照芴酮的溴代衍生物：混合溶剂为1mmol:0.5-10mL的比例加入混合溶剂，在氮气氛围下，按照芴酮的卤代衍生物的物质的量计，加入5‰-5％的钯催化剂，升温至65-120℃反应6-30h，液相监测反应完成，冷却至室温，过滤，母液浓缩与滤渣混合，柱色谱分离，即可得到芴酮衍生物。
4.根据权利要求3所述的芴酮衍生物的制备方法，其特征在于，所述钯催化剂为[1,1’-双(二苯基膦基)二茂铁]二氯化钯、[1,1’-双(二苯基膦基)二茂铁]二氯化钯与二氯甲烷的复合物、四三苯基膦钯、三(二亚苄基丙酮)二钯和醋酸钯中的至少之一；
所述碱为碳酸铯、氟化铯、氟化钾、碳酸钾、磷酸钾、磷酸锂、碳酸钠、氟化四丁基铵和叔丁醇钠中的至少之一；
所述混合溶剂包括甲苯、二甲苯、乙醇、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和水中的至少之一。
5.一种电子元件，其特征在于，包括依次层叠的出光层、阴极、有机层和阳极，所述出光层或所述有机层包含由权利要求1～2任一项所述的化合物。
6.根据权利要求5所述的电子元件，其特征在于，所述有机层至少由电子注入层、电子传输层、发光层、空穴传输层、空穴注入层组成，所述电子传输层或所述发光层包含由权利要求1～2任一项所述的化合物。
CN201811466313.0A 2018-12-03 2018-12-03 一种芴酮衍生物及其制备和应用 Active CN109574917B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811466313.0A CN109574917B (zh) 2018-12-03 2018-12-03 一种芴酮衍生物及其制备和应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811466313.0A CN109574917B (zh) 2018-12-03 2018-12-03 一种芴酮衍生物及其制备和应用

Publications (2)

Publication Number Publication Date
CN109574917A CN109574917A (zh) 2019-04-05
CN109574917B true CN109574917B (zh) 2020-12-08

Family

ID=65926966

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811466313.0A Active CN109574917B (zh) 2018-12-03 2018-12-03 一种芴酮衍生物及其制备和应用

Country Status (1)

Country Link
CN (1) CN109574917B (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110746406A (zh) * 2019-11-19 2020-02-04 苏州久显新材料有限公司 3,4-二氮杂芴酮衍生物及其合成方法和含有3,4-二氮杂芴酮衍生物的电子器件
CN114621193B (zh) * 2020-12-14 2023-11-03 上海和辉光电股份有限公司 有机发光材料及其制造方法和oled器件

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101203518A (zh) * 2005-05-19 2008-06-18 艾文蒂斯药品公司 新芴衍生物，含有它的组合物及用途
CN102126963A (zh) * 2011-01-11 2011-07-20 上海师范大学 一类螺二芴胺基化合物及其制备方法
CN105418356A (zh) * 2014-08-11 2016-03-23 上海和辉光电有限公司 有机铱配合物、其制备方法及包含该配合物的发光材料、有机电致发光器件

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63180961A (ja) * 1987-01-22 1988-07-26 Canon Inc 電子写真感光体
KR101815653B1 (ko) * 2015-10-16 2018-01-08 주식회사 스킨앤스킨 아자보라디벤조크라이센 유도체 유기 발광 화합물, 잉크 조성물 및 유기 발광 소자
CN107068878B (zh) * 2016-04-25 2019-02-22 中节能万润股份有限公司 一种含单取代基-9-芴酮化合物的有机电致发光器件及其应用
CN107046100B (zh) * 2016-04-25 2018-12-28 中节能万润股份有限公司 一种含双取代基-9-芴酮化合物的有机电致发光器件及其应用
CN106467529B (zh) * 2016-08-24 2019-06-14 江苏三月光电科技有限公司 一种以9-芴酮为核心的有机电致发光材料及其应用
CN106467484B (zh) * 2016-08-24 2020-04-03 中节能万润股份有限公司 一种以9-芴酮为核心的化合物及其在oled器件上的应用
CN107721806A (zh) * 2017-11-08 2018-02-23 长春海谱润斯科技有限公司 一种有机电致发光材料及其有机发光器件
CN108178750A (zh) * 2017-12-05 2018-06-19 烟台九目化学制品有限公司 一种苯并[g]喹唑啉类衍生物的制备及其应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101203518A (zh) * 2005-05-19 2008-06-18 艾文蒂斯药品公司 新芴衍生物，含有它的组合物及用途
CN102126963A (zh) * 2011-01-11 2011-07-20 上海师范大学 一类螺二芴胺基化合物及其制备方法
CN105418356A (zh) * 2014-08-11 2016-03-23 上海和辉光电有限公司 有机铱配合物、其制备方法及包含该配合物的发光材料、有机电致发光器件

Also Published As

Publication number Publication date
CN109574917A (zh) 2019-04-05

Similar Documents

Publication Publication Date Title
CN110862381B (zh) 一种有机电致发光化合物及其制备方法和应用
TWI651312B (zh) 有機化合物及有機光電裝置和顯示裝置
TWI640513B (zh) 咪唑雜菲化合物以及包含其的有機發光二極體
TW201042001A (en) Organic electronic device
Sun et al. Novel carbazolyl-substituted spiro [acridine-9, 9′-fluorene] derivatives as deep-blue emitting materials for OLED applications
TWI564272B (zh) 用於有機電激發光裝置中的化合物及使用該化合物之有機電激發光裝置
TWI564290B (zh) 有機材料及使用此材料之有機電激發光裝置
KR101912951B1 (ko) 유기발광 화합물 및 이를 이용한 유기 전계 발광 소자
CN112778343A (zh) 一种硼基有机电致发光材料及其制备方法和应用
KR20150012974A (ko) 새로운 유기전계발광소자용 화합물 및 그를 포함하는 유기전계발광소자
KR20130121597A (ko) 트리페닐아민을 사용한 정공 수송 물질 및 이를 포함한 유기 전계 발광 소자
KR101334204B1 (ko) 신규한 파이렌 화합물과, 상기 파이렌 화합물의 제조방법 및 상기 파이렌 화합물을 이용한 유기발광소자
CN111675693A (zh) 一类含吖啶和菲并咪唑的d-a型发光小分子及其在电致发光器件中的应用
TWI756542B (zh) 有機化合物及使用其的有機電激發光元件
KR20130121516A (ko) 신규한 아릴아민을 사용한 정공 수송 물질 및 이를 포함한 유기 전계 발광 소자
CN110835351A (zh) 一种以吡咯亚甲基硼络合物为核心的有机化合物及其制备和应用
CN109574917B (zh) 一种芴酮衍生物及其制备和应用
TW201806937A (zh) 化合物及其有機電子裝置
Wang et al. Excellent deep-blue emitting materials based on anthracene derivatives for non-doped organic light-emitting diodes
CN109574908B (zh) 一种含螺二甲基蒽芴的化合物及其在有机电致发光器件上的应用
TW201945515A (zh) 雜芳族化合物及使用該雜芳族化合物的有機電激發光組件
TWI804701B (zh) 化合物、有機光電二極體以及顯示裝置
TW201718446A (zh) 有機化合物及使用其的有機電激發光元件
KR20130086757A (ko) 아민계 정공 수송 물질 및 이를 포함한 유기 전계 발광 소자
CN113321649B (zh) 一种化合物、电子传输材料和有机电致发光器件

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