WO2023125801A1 - Fluoranthene derivative, light-emitting element, and photoelectric conversion element - Google Patents

Fluoranthene derivative, light-emitting element, and photoelectric conversion element Download PDF

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WO2023125801A1
WO2023125801A1 PCT/CN2022/143372 CN2022143372W WO2023125801A1 WO 2023125801 A1 WO2023125801 A1 WO 2023125801A1 CN 2022143372 W CN2022143372 W CN 2022143372W WO 2023125801 A1 WO2023125801 A1 WO 2023125801A1
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biphenyl
substituted
fluoranthene
light
fluoranthene derivative
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PCT/CN2022/143372
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French (fr)
Chinese (zh)
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孙枋竹
徐芳荣
藤田阳二
张劲源
长尾和真
德田贵士
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东丽先端材料研究开发（中国）有限公司
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Priority to CN202280048922.2A priority Critical patent/CN117940412A/en
Publication of WO2023125801A1 publication Critical patent/WO2023125801A1/en

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    • 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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • 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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
    • 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
    • C07D213/53—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the 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
    • C07D239/26—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
    • 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
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/04—1,2,3-Triazines
    • 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
    • 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

Definitions

  • OLEDs organic light-emitting diodes
  • OLED must meet the improvement of luminous efficiency, the reduction of driving voltage, and the improvement of durability. Among them, simultaneous realization of luminous efficiency and durable life is a major issue. However, it is difficult to sufficiently reduce the driving voltage of the device by conventional techniques (Patent Documents 1 to 6), and even if the driving voltage can be reduced, the luminous efficiency and durable life of the device are not sufficient. As described above, no technology has been found that can achieve high luminous efficiency, low driving voltage, and durable life at the same time.
  • Patent Document 1 International Publication No. 2008/059713
  • Patent Document 2 International Publication No. 2007/100010
  • Patent Document 3 International Publication No. 2012/108388
  • Patent Document 4 International Publication No. 2013/065213
  • Patent Document 5 International Publication No. 2014/057874
  • Patent Document 6 International Publication No. 2015/182547.
  • the object of the present invention is to solve the above-mentioned problems of the prior art, and provide an organic thin film light-emitting element with improved luminous efficiency, driving voltage, and durable life.
  • the control of the amount of electrons with transport ability in the molecule is realized, thereby adjusting the luminous efficiency and driving voltage and durability.
  • the present invention provides a fluoranthene derivative having a structure represented by the following general formula 1.
  • L1 is an arylene group that may be substituted;
  • L2 is a single bond, an arylene group that may be substituted or a heteroarylene group that may be substituted;
  • X1, X2, X3, X4, and X5 are the same or different, each independently Is N or C-R1;
  • R1 is independently selected from hydrogen, deuterium, alkyl that may be substituted, cycloalkyl that may be substituted, heterocyclic group that may be substituted, alkenyl that may be substituted, alkenyl that may be substituted Substituted cycloalkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryl ether, optionally substituted arylsulfide, optionally Substituted aryl, optionally substituted heteroaryl, optionally substituted carbonyl, optionally substituted carboxyl, optionally substituted oxycarbonyl,
  • the present invention provides a light-emitting device having an organic layer between an anode and a cathode, wherein the organic layer contains the above-mentioned fluoranthene derivative.
  • the present invention also discloses a photoelectric conversion element, which contains the above-mentioned fluoranthene derivatives.
  • the present invention it is possible to provide an organic thin-film light-emitting device that realizes high luminous efficiency, low driving voltage, and high durability at the same time.
  • L1 is an arylene group that may be substituted;
  • L2 is a single bond, an arylene group that may be substituted or a heteroarylene group that may be substituted;
  • X1, X2, X3, X4, and X5 are the same or different, each independently Is N or C-R1;
  • R1 is independently selected from hydrogen, deuterium, alkyl that may be substituted, cycloalkyl that may be substituted, heterocyclic group that may be substituted, alkenyl that may be substituted, alkenyl that may be substituted Substituted cycloalkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryl ether, optionally substituted arylsulfide, optionally Substituted aryl, optionally substituted heteroaryl, optionally substituted carbonyl, optionally substituted carboxyl, optionally substituted oxycarbonyl,
  • hydrogen may also be deuterium.
  • the substituent is preferably an alkyl group which may be substituted, a cycloalkyl group which may be substituted, a heterocyclic group which may be substituted, an alkenyl group which may be substituted, an alkenyl group which may be substituted, Cycloalkenyl, substituted alkynyl, substituted alkoxy, substituted alkylthio, substituted aryl ether, substituted arylsulfide, substituted Aryl, optionally substituted heteroaryl, optionally substituted carbonyl, optionally substituted carboxyl, optionally substituted oxycarbonyl, optionally substituted carbamoyl, optionally substituted silyl, optionally substituted Alkylamino or arylamino which may be substituted, halogen, cyano, carbonyl, carboxyl, oxycarbonyl, carbamoyl, phosphine oxide, condensed aromatic hydrocarbon ring, monocyclic aromatic hetero
  • alkyl means, for example, a saturated aliphatic hydrocarbon group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, which may or may not have a substituent.
  • the substituent to be added in the case of being substituted is not particularly limited, for example, an alkyl group, an aryl group, a heteroaryl group, etc. are mentioned, and this point is common also in the following description.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more and 20 or less from the viewpoint of availability of materials and cost.
  • cycloalkyl means, for example, a saturated aliphatic cycloalkyl group such as cyclopropyl, cyclohexyl, norbornyl, adamantyl, etc., which may or may not have a substituent.
  • the number of carbon atoms in the alkyl moiety is not particularly limited, but it is preferably in the range of 3 or more and 20 or less from the viewpoint of availability of materials and cost.
  • alkenyl means, for example, an unsaturated aliphatic hydrocarbon group including a double bond such as vinyl, allyl, and butadiene, which may or may not have a substituent.
  • the carbon number of the alkenyl group is not particularly limited, but it is preferably in the range of 3 or more and 20 or less from the viewpoint of availability of materials and cost.
  • cycloalkenyl means, for example, an unsaturated aliphatic hydrocarbon group containing a double bond, such as cyclopentenyl, cyclopentadienyl, and cyclohexenyl, which may or may not have a substituent.
  • the carbon number of the alkenyl group is not particularly limited, but it is preferably in the range of 3 or more and 20 or less from the viewpoint of availability of materials and cost.
  • the alkynyl group means, for example, an unsaturated aliphatic hydrocarbon group including a triple bond, such as an ethynyl group, which may or may not have a substituent.
  • the carbon number of the alkenyl group is not particularly limited, but it is preferably in the range of 3 or more and 20 or less from the viewpoint of availability of materials and cost.
  • the alkoxy group means, for example, a functional group having an aliphatic hydrocarbon group bonded via an ether bond such as methoxy, ethoxy, propoxy, etc., and the aliphatic hydrocarbon group may or may not have a substituent.
  • the number of carbon atoms in the alkoxy group is not particularly limited, but it is preferably in the range of 1 to 20 in terms of availability of materials and cost.
  • alkylthio is obtained by substituting an oxygen atom of an ether bond of an alkoxy group with a sulfur atom.
  • the hydrocarbon group of the alkylthio group may or may not have a substituent.
  • the number of carbon atoms in the alkylthio group is not particularly limited, but is preferably in the range of 1 to 20 in terms of availability of materials and cost.
  • the aryl ether group means, for example, a functional group having an aromatic hydrocarbon group bonded via an ether bond such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent.
  • the number of carbon atoms in the aryl ether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less from the viewpoint of availability of materials and cost.
  • the so-called aryl sulfide group is obtained by substituting the oxygen atom of the ether bond of the aryl ether group with a sulfur atom.
  • the aromatic hydrocarbon group in the aryl sulfide group may have a substituent or may not have a substituent.
  • the carbon number of the aryl sulfide group is not particularly limited, but it is preferably in the range of 6 or more and 40 or less from the viewpoint of availability of materials and cost.
  • aryl means, for example, aromatic hydrocarbon groups such as phenyl, naphthyl, biphenyl, phenanthrenyl, terphenyl, pyrenyl, and 1,2-benzonaphthyl.
  • the aryl group may or may not have a substituent.
  • the carbon number of the aryl group is not particularly limited, but it is preferably in the range of 6 to 40 in terms of availability of materials and cost.
  • heteroaryl refers to furyl, thiophenyl, pyridyl, quinolinyl, isoquinolyl, pyrazinyl, pyrimidyl, naphthyridyl, benzofuryl, benzophenylthio, Indolyl, dibenzofuryl, dibenzophenylthio, carbazolyl and other cyclic aromatic groups having atoms other than carbon in one or more rings, which may be unsubstituted or substituted.
  • the carbon number of the heteroaryl group is not particularly limited, and is preferably in the range of 2 or more and 30 or less from the viewpoint of availability of materials and cost.
  • halogen means an atom selected from fluorine, chlorine, bromine and iodine.
  • a carbonyl group, a carboxyl group, an oxycarbonyl group, a cyano group, a carbamoyl group, and a phosphine oxide group may or may not have a substituent.
  • substituents include alkyl groups, cycloalkyl groups, aryl groups, heteroaryl groups, and the like, and these substituents may be further substituted.
  • arylene group means a divalent or trivalent group derived from an aromatic hydrocarbon group such as phenyl, naphthyl, or biphenyl, which may or may not have a substituent.
  • L1 of the general formula 1 is an arylene group
  • the number of nuclear carbons is preferably in the range of 6 or more and 24 or less, wherein 6 or more and 12 or less are more preferred
  • the arylene group specifically includes: 1,4-ylene Phenyl, 1,3-phenylene, 1,2-phenylene, 4,4'-biphenylene, 4,3'-biphenylene, 3,3'-biphenylene, 1 , 4-naphthylene, 1,5-naphthylene, 2,5-naphthylene, 2,6-naphthylene, 2,7-naphthylene, etc. More preferred are 1,4-phenylene and 1,3-phenylene.
  • heteroarylene group means any group other than pyridyl, quinolinyl, pyrimidinyl, pyrazinyl, naphthyridinyl, dibenzofuryl, dibenzophenylthio, etc., which have carbon in one or more rings.
  • a divalent or trivalent substituent derived from an aromatic group of an atom may or may not have a substituent.
  • the carbon number of the heteroarylene group is not particularly limited, but is preferably in the range of 2-30.
  • condensed aromatic hydrocarbon rings include, for example, naphthalene rings, azulene rings, anthracene rings, phenanthrene rings, pyrene rings, 1,2-triphenylene (chrysene) rings, naphthacene rings, triphenylene rings, and acenaphthene rings.
  • ring hexabenzobenzene ring, fluorene ring, 1,2-benzoacenaphthene ring, tetracene ring, pentacene ring, perylene ring, pentaphene ring, picene ring, pyranthrene ) ring, anthraanthrene ring, etc.
  • the above-mentioned condensed aromatic hydrocarbon ring may have a substituent.
  • the monocyclic aromatic heterocycle includes furan ring, thiophene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, Thiazole ring etc.
  • the above-mentioned monocyclic aromatic heterocycle may have a substituent.
  • condensed aromatic heterocyclic rings include, for example, quinoline rings, isoquinoline rings, quinoxaline rings, benzimidazole rings, indole rings, benzimidazole rings, benzothiazole rings, benzoxazole rings, quinoline rings, Oxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, diazacarbazole ring (representing a ring in which one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom), etc.
  • the above-mentioned condensed aromatic heterocycle may have a substituent.
  • the invention provides a combined fluoranthene derivative with a fluoranthene main body and an azabenzene-based main body.
  • the structure of fluoranthene is three benzene rings surrounding a cyclopentane, and electrons can be delocalized in the entire fluoranthene structure.
  • the cyclopentane part forms an electron hole part and tends to absorb electrons.
  • the main body of the azabenzene system can be benzene or azabenzene containing multiple nitrogens. In the azabenzene system, the large ⁇ bond of benzene itself can move in the entire molecule.
  • the lone pair of electrons of nitrogen can further increase the delocalized electrons in the large ⁇ bond, thereby enhancing the electron transport ability.
  • the electrons of the main body of the azabenzene system are weakly attracted by the nucleus, and the fluoranthene part has a tendency to attract electrons, so that the electrons tend to move towards the fluoranthene part in the entire molecule (although the molecule itself is neutral), so When the molecules accumulate to form a film, it can imitate the delocalization of electrons in metal bonds to a certain extent, thereby providing electron transport capabilities.
  • the number of fluoranthene hosts and the number of azabenzene hosts need to be finely controlled on a molecular basis. Considering the energy level matching of materials, electron processing ability, synthesis difficulty and cost, it is preferred that the number of fluoranthene hosts (n1) is 1 and the number of azabenzene series hosts (n4) is 1.
  • n1 1
  • n1 ⁇ n2+n3 ⁇ n4 the number of delocalized electrons in the molecule reaches an optimal level, and the best device performance can be realized.
  • R1 is selected from substitutable phenyl, substitutable furyl (such as preferably dibenzofuryl) or substitutable carbazolyl, fluorene base, dibenzothienyl.
  • linking parts L1 and L2 are selected from phenylene, electrons can be better transferred from the azabenzene-based host to the fluoranthene host.
  • L1 and L2 are selected from m-phenylene at the same time, the transmission of electrons is hindered due to being bent. This reduces the transmission capacity. Therefore, when the fluoranthene derivative is used as an electron transport layer material, L1 and L2 are not m-phenylene at the same time.
  • o-phenylene can not only bring the azabenzene-based host close to the fluoranthene host, but also improve the molecular orientation, further realizing low-voltage and high-efficiency performance. Therefore, at least one of L1 and L2 is preferably o-phenylene.
  • the substituent of the azobenzene-based main body can have a better electrical performance than biphenyl with a biphenyl-plus-phenylene structure. This is because the steric exclusion effect of biphenyl restricts the rotation of the azabenzene host, thereby strengthening the stability of the delocalized large ⁇ bond and enhancing the electronic processing performance.
  • the invention also discloses a light-emitting element, an organic layer exists between the anode and the cathode, and the organic layer is a layer responsible for emitting light and/or a layer responsible for processing electrons or holes, wherein the organic layer contains the above-mentioned fluorescent Anthracene derivatives.
  • the organic layer has an electron transport layer in which the above-mentioned fluoranthene derivative is contained.
  • the organic layer has an electron generating layer in which the above-mentioned fluoranthene derivative is contained.
  • the organic layer has a hole blocking layer in which the above-mentioned fluoranthene derivative is contained.
  • the present invention also discloses a photoelectric conversion element, which contains the above-mentioned fluoranthene derivatives.
  • a known method can be used for the synthesis of the fluoranthene derivative of the present invention.
  • a method of introducing an azabenzene-based host into a fluoranthene derivative skeleton for example, the use of a substituted or unsubstituted halogenated fluoranthene host and a substituted or unsubstituted azabenzene under a palladium catalyst or a nickel catalyst It is a method of the coupling reaction of the subject, but it is not limited to these methods.
  • a substituted arylboronic acid or a heteroarylboronic acid may be used for the azabenzene-based host, or A fluoranthene host substituted with an aryl halide is used.
  • boric acid esters may also be used instead of the above-mentioned various boric acids.
  • the light-emitting device of the present invention includes an anode and a cathode, and an organic layer interposed between the anode and the cathode.
  • the organic layer includes at least a light-emitting layer and an electron transport layer.
  • the light-emitting layer emits light using electric energy.
  • each of the above-mentioned layers may be a single layer or a multilayer connected by an electron generating layer and a hole generating layer.
  • the fluoranthene derivative of the present invention can be used in any layer in the above-mentioned device configuration, but has high electron injection and transport capabilities, fluorescence quantum yield and film stability, so it is preferably used in the electron transport layer, the electron generation layer and in the space. Hole blocking layer.
  • the anode and the cathode function to supply sufficient current for the device to emit light, and at least one of them is preferably transparent or semi-transparent in order to emit light.
  • a transparent anode or a transparent cathode can be used.
  • the material used for the anode is not particularly limited to tin oxide, indium oxide, and indium tin oxide as long as it is a material that can efficiently inject holes into the organic layer and is transparent or translucent for light emission.
  • ITO Indium Tin Oxide
  • IZO indium zinc oxide
  • other conductive metal oxides or metals such as gold, silver, chromium, inorganic conductive substances such as copper iodide and copper sulfide, polythiophene, poly
  • conductive polymers such as pyrrole and polyaniline, it is particularly preferable to use ITO glass or Nesselt glass.
  • These electrode materials may be used alone, or a plurality of materials may be laminated or mixed for use.
  • the resistance of the transparent electrode is not limited as long as a sufficient current can be supplied for the light emission of the device, but a low resistance is preferable from the viewpoint of power consumption of the device.
  • a low resistance is preferable from the viewpoint of power consumption of the device.
  • ITO substrate of 300 ⁇ / ⁇ or less, it functions as an element electrode, but now it is also possible to supply a substrate of about 10 ⁇ / ⁇ , so it is particularly preferable to use a low resistance substrate of 20 ⁇ / ⁇ or less.
  • the thickness of ITO can be arbitrarily selected according to the resistance value, but it is usually used between 100nm and 300nm in many cases.
  • an anode may be formed on a polyimide substrate.
  • the method for forming the ITO film is an electron beam method, a sputtering method, a chemical reaction method, etc., and is not particularly limited.
  • the material used for the cathode is not particularly limited as long as it can efficiently inject electrons into the light-emitting layer.
  • metals such as platinum, gold, silver, copper, iron, tin, aluminum, indium, or alloys of these metals with lithium, sodium, potassium, calcium, magnesium and other low work function (work function) metals are preferred.
  • Multilayer cascading, etc. aluminum, silver, and magnesium are preferable as main components in view of resistance value, easiness of film formation, film stability, and luminous efficiency.
  • it is composed of magnesium and silver electron injection into the electron transport layer and the electron injection layer in the present invention becomes easy, and low-voltage driving can be realized, so it is preferable.
  • the fabrication methods of these electrodes are resistance heating, electron beam, sputtering, ion plating, coating, etc., and are not particularly limited.
  • an organic material with a high refractive index can also be used.
  • metals such as LiF
  • low-refractive-index organic small molecule compounds can be used to optically adjust and add a thin-film encapsulation (TFE) layer for flexible protection to achieve flexibility and even foldability while protecting the device from water and oxygen. Impact.
  • TFE thin-film encapsulation
  • the specific structure is not limited.
  • the fluoranthene derivative of the present invention is excellent in electron injection and transport properties, so when it is used in the electron transport layer, there is a concern that electrons are not recombined in the light emitting layer and some of them leak to the hole transport layer . Therefore, it is preferable to use a compound excellent in electron blocking properties in the hole transport layer.
  • compounds containing a carbazole skeleton are preferred because they are excellent in electron blocking properties and contribute to high efficiency of light-emitting devices.
  • the above-mentioned compound containing a carbazole skeleton preferably contains a carbazole dimer, carbazole trimer, or carbazole tetramer skeleton.
  • skeleton has 2 or more diaryl amino groups.
  • the above-mentioned carbazole skeleton-containing compound or triphenylene skeleton-containing compound may be used alone as the hole transport layer, or may be used in combination with each other. Other materials may also be mixed within the range not impairing the effect of the present invention.
  • what is necessary is just to contain the compound containing a carbazole frame
  • the fluoranthene compound of the present invention cannot be used in the light-emitting layer due to the great difference in structure from materials that transmit or block electrons or holes.
  • acceptor compounds include metal chlorides such as iron(III) chloride, aluminum chloride, gallium chloride, indium chloride, and antimony chloride, and metal chlorides such as molybdenum oxide, vanadium oxide, tungsten oxide, and ruthenium oxide. metal oxides, charge transfer complexes such as tris(4-bromophenyl)ammonium hexachloroantimonate (TBPAH).
  • TPAH tris(4-bromophenyl)ammonium hexachloroantimonate
  • an organic compound having a nitro group, a cyano group, a halogen, or a trifluoromethyl group in a molecule a quinone compound, an acid anhydride compound, a fullerene, or the like can also be suitably used.
  • these compounds include hexacyanobutadiene, hexacyanobenzene, tetracyanoethylene, tetracyanoquinodimethane (TCNQ), tetrafluorotetracyanoquinodimethane (F4-TCNQ), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN6), p-fluorobenzoquinone (p-fluoronil), p-tetrachlorobenzoquinone, p-tetrabromobenzoquinone, p-benzoquinone, 2,6-dichlorobenzoquinone, 2,5-dichlorobenzoquinone, tetramethylbenzoquinone, 1,2,4,5-tetracyanoquinone Benzene, o-dicyanobenzene, p-dicyanobenzene, 1,4-dicyanotetrafluor
  • metal oxides and cyano-group-containing compounds are easy to handle and easy to vapor-deposit, so the above-mentioned effect can be easily obtained, and are therefore preferred.
  • preferable metal oxides include molybdenum oxide, vanadium oxide, and ruthenium oxide.
  • the light-emitting layer can be a single layer or multiple layers, which are respectively formed of light-emitting materials (host material, dopant material), optionally, it can be a mixture of a host material and a dopant material, or can be independently Body material. That is, in the light-emitting device of the present invention, in each light-emitting layer, only the host material or the dopant material may emit light, or both the host material and the dopant material may emit light. From the viewpoint of efficiently utilizing electric energy and obtaining light emission with high color purity, it is preferable that the light emitting layer contains a mixture of a host material and a dopant material.
  • the host material and the dopant material can be one kind or a combination of multiple kinds.
  • the dopant material may be contained in the host material entirely or partially.
  • the dopant material can be layered or dispersed. Doping materials can control the emission color. If the amount of the dopant material is too large, concentration quenching occurs, so it is preferably used at 20% by weight or less, more preferably 10% by weight or less, based on the host material.
  • the doping method it may be formed by co-evaporation with the host material, or it may be mixed with the host material in advance and then vapor-deposited at the same time.
  • luminescent materials such as condensed ring derivatives such as anthracene and pyrene known as light emitters, metal chelate doxinoid compounds (metal chelate doxinoid compounds) headed by tris(8-hydroxyquinoline)aluminum can be used.
  • bistyryl derivatives such as bistyryl anthracene derivatives or distyrylbenzene derivatives, tetraphenylbutadiene derivatives, indene derivatives, coumarin derivatives, oxadiazole derivatives, Pyrrolopyridine derivatives, perionone derivatives, cyclopentadiene derivatives, oxadiazole derivatives, thiadiazolopyridine derivatives, dibenzofuran derivatives, carbazole derivatives, indolecarbazole derivatives products, polyphenylene vinylene derivatives, polyparaphenylene derivatives, and polythiophene derivatives in the polymer system, but are not particularly limited.
  • a phosphorescent light-emitting material may also be contained in the light-emitting layer.
  • a phosphorescent material is a material that exhibits phosphorescent emission even at room temperature. In the case of using a phosphorescent material as a dopant, it is basically necessary to obtain phosphorescent emission even at room temperature, and it is not particularly limited. It is preferable to contain a material selected from the group consisting of iridium (Ir), ruthenium (Ru), rhodium ( An organometallic complex compound of at least one metal from the group consisting of Rh), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re).
  • Ir iridium
  • Ru ruthenium
  • rhodium An organometallic complex compound of at least one metal from the group consisting of Rh), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re).
  • organometallic complexes containing iridium or platinum are more preferable from the viewpoint of high phosphorescence yield even at room temperature.
  • indole derivatives, carbazole derivatives, indolecarbazole derivatives, nitrogen-containing aromatic compounds having a pyridine, pyrimidine, or triazine skeleton can be suitably derived.
  • aromatic hydrocarbon compound derivatives such as polyarylbenzene derivatives, spirofluorene derivatives, truxene derivatives, triphenylene derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, etc.
  • Chalcogen compounds, organometallic complexes such as hydroxyquinoline beryllium complexes, etc. have higher triplet energy than dopants basically used, and electrons and holes are transported from their respective transport layers. Those that are successfully injected and transported are not limited to these compounds. Furthermore, two or more types of triplet light-emitting dopants may be contained, and two or more types of host materials may be contained. In addition, one or more triplet light-emitting dopants and one or more fluorescent light-emitting dopants may be contained.
  • the electron transport layer is a layer that injects electrons from the cathode and further transports electrons.
  • An ideal electron transport layer can achieve high electron injection efficiency and efficiently transport the injected electrons. Therefore, the electron transport layer is preferably composed of a substance having a high electron affinity, a high electron mobility, excellent stability, and less generation of impurities that become traps during production and use.
  • the electron transport layer in the present invention also includes a substance synonymous with a hole blocking layer that can efficiently prevent hole migration.
  • the electron-transporting materials used in the electron-transporting layer include condensed polycyclic aromatic derivatives such as naphthalene and anthracene, and styryl-based aromatic ring derivatives represented by 4,4'-bis(diphenylvinyl)biphenyl.
  • Quinone derivatives such as anthraquinone or di-p-benzoquinone, phosphorus oxide derivatives, hydroxyquinoline complexes such as tris(8-hydroxyquinoline)aluminum(III), benzohydroxyquinoline complexes, hydroxyquinoline complexes, oxazole
  • Various metal complexes such as complexes, azomethine complexes, tropolone metal complexes and flavonol metal complexes can automatically reduce the driving voltage and obtain high-efficiency light emission Considering this, it is preferable to use a compound having a heteroaryl ring structure composed of an element selected from carbon, hydrogen, nitrogen, oxygen, silicon, and phosphorus and containing electron-accepting nitrogen.
  • Aromatic heterocycles containing electron-accepting nitrogen have high electron affinity.
  • An electron-transporting material having electron-accepting nitrogen can easily accept electrons from a cathode having a high electron affinity, and can drive at a lower voltage.
  • the lone pair of electron-accepting nitrogen can accommodate more electrons after being integrated into the large ⁇ bond, increasing the electron transport capacity and improving the electron transport capacity. Furthermore, electron supply to the light-emitting layer increases, and the probability of recombination becomes high, thereby improving luminous efficiency.
  • heteroaryl rings containing electron-accepting nitrogen examples include pyridine rings, pyrazine rings, pyrimidine rings, quinoline rings, quinoxaline rings, naphthyridine rings, pyrimidopyrimidine rings, benzoquinoline rings, and phenanthroline rings.
  • ring imidazole ring, oxazole ring, oxadiazole ring, triazole ring, thiazole ring, thiadiazole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, phenanthromidazole ring, etc.
  • Compounds having these heteroaryl ring structures include, for example, benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazine derivatives, Derivatives, phenanthroline derivatives, quinoxaline derivatives, quinoline derivatives, benzoquinoline derivatives, bipyridine or terpyridine and other oligopyridine derivatives, quinoxaline derivatives and naphthyridine derivatives, etc. as the preferred compound.
  • imidazole derivatives such as tris(N-phenylbenzimidazol-2-yl)benzene, 1,3-bis[(4-tert-butylphenyl) Oxadiazole derivatives such as 1,3,4-oxadiazolyl]benzene, triazole derivatives such as N-naphthyl-2,5-diphenyl-1,3,4-triazole, bathocuproine ( bathocuproine) or 1,3-bis(1,10-phenanthroline-9-yl)phenanthroline derivatives such as benzene, 2,2'-bis(benzo[h]quinolin-2-yl)-9 , benzoquinoline derivatives such as 9′-spirobifluorene, 2,5-bis(6′-(2′,2′′-bipyridine))-1,1-dimethyl-3,4-diphenyl Bipyridine derivatives such as silacyclopentadiene, terpyr
  • the condensed polycyclic aromatic skeleton is particularly preferably an anthracene skeleton, a pyrene skeleton, or a phenanthroline skeleton.
  • the above electron transport materials may be used alone, or two or more of the above electron transport materials may be used in combination, or one or more of other electron transport materials may be mixed and used in the above electron transport materials.
  • the fluoranthene derivatives of the present invention also have high electron injection and transport capabilities, and therefore can be suitably used as electron transport materials.
  • fluoranthene derivatives of the present invention it is not necessary to be limited to each of them, and a plurality of fluoranthene compounds of the present invention may be mixed and used, or other electrons may be transported within the range that does not impair the effects of the present invention.
  • One or more kinds of materials are used in combination with the fluoranthene compound of the present invention.
  • the electron transport material that can be mixed is not particularly limited, and compounds having condensed aryl rings such as naphthalene, anthracene, and pyrene, or derivatives thereof, 4,4'-bis(diphenylvinyl)biphenyl Representative styryl-based aromatic ring derivatives, perylene derivatives, perylene derivatives, coumarin derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone or di-p-benzoquinone, phosphorus oxide Derivatives, carbazole derivatives and indole derivatives, hydroxyquinoline complexes such as tris(8-hydroxyquinoline)aluminum(III) or hydroxyazole complexes such as hydroxyphenyloxazole complexes, azo Methylene complexes, tropolone metal complexes and flavonol metal complexes.
  • condensed aryl rings such as naphthalene, anthracene, and pyr
  • the above-mentioned electron transport materials may be used alone, but two or more of the above-mentioned electron-transport materials may be used in combination, or one or more of other electron-transport materials may be mixed and used in the above-mentioned electron-transport materials.
  • a donor material may also be contained.
  • the so-called donor material is a compound that facilitates electron injection from the cathode or the electron injection layer to the electron transport layer by improving the electron injection barrier, and further improves the conductivity of the electron transport layer.
  • the donor material in the present invention include alkali metals, inorganic salts containing alkali metals, complexes of alkali metals and organic substances, alkaline earth metals, inorganic salts containing alkaline earth metals, or complexes of alkaline earth metals and organic substances. complexes, etc.
  • Preferable types of alkali metals and alkaline earth metals include alkali metals such as lithium, sodium, cesium, and ytterbium, and their compounds, and alkaline earth metals such as magnesium and calcium, which have a low work function and have a large effect of improving electron transport capability, and their compounds.
  • the suitable doping concentration varies depending on the material or the film thickness of the doped region.
  • the donor material is an inorganic material such as an alkali metal or an alkaline earth metal
  • Co-deposition was carried out so that the vapor deposition rate ratio was in the range of 10000:1 to 2:1 to form an electron transport layer.
  • the vapor deposition rate ratio is more preferably 100:1 to 5:1, and still more preferably 100:1 to 10:1.
  • the donor material is a complex of a metal and an organic substance, it is preferable to perform co-deposition so that the vapor deposition rate ratio of the electron transport material and the donor material is in the range of 100:1 to 1:100. Evaporated to form an electron transport layer.
  • the vapor deposition rate ratio is more preferably 10:1 to 1:10, and still more preferably 7:3 to 3:7.
  • an electron transport layer doped with a donor material in the fluoranthene derivative of the present invention as described above can be used as a charge generation layer in a tandem structure type element in which a plurality of light emitting elements are connected.
  • the method of doping the electron transport layer with a donor material to improve the electron transport capability is particularly effective when the film thickness of the thin film layer is thick. It can be used especially preferably when the total film thickness of an electron transport layer and a light emitting layer is 50 nm or more.
  • a method of utilizing an interference effect in order to improve luminous efficiency which is a method of improving light emission efficiency by aligning the phases of light directly emitted from the light emitting layer and light reflected by the cathode.
  • the optimum conditions vary depending on the emission wavelength of light, and when the total film thickness of the electron transport layer and the emission layer is 50 nm or more and long-wavelength emission such as red is emitted, it may be a thick film close to 100 nm.
  • the film thickness of the electron-transporting layer to be doped may be arbitrary for a part or the whole of the electron-transporting layer.
  • partially doping it is desirable to provide a doped region at least at the electron transport layer/cathode interface, and even if doping is performed only in the vicinity of the cathode interface, the effect of lowering the voltage can be obtained.
  • the donor material is directly in contact with the light-emitting layer, there may be adverse effects that reduce the luminous efficiency. In this case, it is preferable to set an undoped area.
  • an electron injection layer may also be provided between the cathode and the electron transport layer.
  • the electron injection layer is inserted for the purpose of facilitating electron injection from the cathode to the electron transport layer.
  • a compound having a heteroaryl ring structure containing electron-accepting nitrogen can be used, or A layer comprising the above-mentioned donor material.
  • the fluoranthene derivative of the present invention may also be contained in the electron injection layer.
  • an insulator or semiconductor inorganic substance, or a metal may be used for the electron injection layer. By using these materials, it is possible to effectively prevent short-circuiting of the light-emitting element and improve the electron injection property, which is preferable.
  • Such an insulator preferably uses at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides. If the electron injection layer is composed of these alkali metal chalcogen compounds, etc., it is more preferable at the point that the electron injection property can be further improved.
  • preferable alkali metal chalcogen compounds include Li 2 O, Na 2 S and Na 2 Se
  • preferable alkaline earth metal chalcogen compounds include CaO, BaO, SrO, BeO, BaS and CaSe.
  • preferable alkali metal halides include LiF, NaF, KF, LiCl, KCl, and NaCl.
  • preferable halides of alkaline earth metals include, for example, fluorides such as CaF 2 , BaF 2 , SrF 2 , MgF 2 , and BeF 2 , or halides other than fluorides.
  • Complexes of organic substances and metals can also be suitably used. It is more preferable to use a complex of an organic substance and a metal for the electron injection layer because it is easy to adjust the film thickness.
  • organic substances in complexes with organic substances include hydroxyquinoline, benzohydroxyquinoline, pyridylphenol, flavonol, hydroxyimidazopyridine, hydroxynitrogen Indene, Hydroxytriazole, etc.
  • metals can also be used, for example, Li, Yb, Ba, etc. are mentioned.
  • the formation method of the above-mentioned layers constituting the light-emitting element is resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, coating method, etc., and is not particularly limited. Usually, from the aspect of element characteristics, resistance Thermal evaporation or electron beam evaporation.
  • the thickness of the organic layer is determined by the resistance value of the luminescent material, so it cannot be limited, but is preferably 1 nm to 1000 nm.
  • the film thicknesses of the light-emitting layer, the electron transport layer, and the hole transport layer are preferably 1 nm to 200 nm, more preferably 5 nm to 100 nm.
  • the light-emitting element of the present invention has the function of converting electrical energy into light.
  • direct current is mainly used for electric energy, but pulse current or alternating current may also be used.
  • the current value and voltage value are not particularly limited, and should be selected in such a way as to obtain the maximum brightness with the lowest possible energy in consideration of the power consumption and lifetime of the device.
  • HAT-CN6 75nm HAT-CN6 was evaporated as the hole injection layer, and 42.5nm HT-1 was evaporated as the hole transport layer. Then, the host material H-1 and the dopant material D-1 were vapor-deposited to a thickness of 20 nm so that the doping concentration became 5% by weight to form a light-emitting layer. Then, compound [6] was vapor-deposited and laminated to a thickness of 30 nm as an electron transport layer. Then, after vapor-depositing 1 nm of Yb, 15 nm of Mg/Aa (1:9) was vapor-deposited as a cathode to fabricate a 5 mm ⁇ 5 mm square element.
  • a light-emitting device was produced in the same manner as in Example 1. After the light-emitting device was produced, Alq3 was evaporated as a charge generator layer compound, and then vapor-deposit the same light-emitting element to make a tandem device and evaluate it.
  • Example 1 By comparing Example 1, Example 21, and Example 22, it can be found that after the fluoranthene group is reduced, the energy level of the molecular orbital becomes too deep, the matching with the material of the electron injection layer is improved, the voltage is reduced, and the life is also on the rise. . In particular, when a fluoranthene group is preferred, the voltage and lifetime are greatly improved. In addition, when one fluoranthene group is preferred, the vapor deposition of the material is also easier.
  • Example 6 By comparing Example 6 and Example 23, it can be found that after reducing the azabenzene group, the energy level of the molecular orbital becomes too deep, the matching with the material of the electron injection layer is improved, the voltage is reduced, and the life span also tends to increase. In particular, when an azabenzene group is preferred, the voltage and lifetime are greatly improved. In addition, when one azabenzene-based group is preferable, vapor deposition of the material is also easier. Although the tendency is similar to the tendency reflected by the fluoranthene group, to a certain extent, the reduction of the azabenzene group can optimize the device effect more than the fluoranthene group.
  • Example 6 By comparing Example 6, Example 9, Example 10, Example 24, and Example 25, it can be seen that when the nitrogen atom is contained in the main body of the azobenzene system, due to the increase in the supply of electrons, the number of electrons in the overall molecule is increased, so that Device efficiency is improved.
  • the efficiency When there is no nitrogen in the central part of the azobenzene-based body, the efficiency is very low, and when one nitrogen is included, higher efficiencies can be obtained compared to the case of no nitrogen at all, but still at a level where there is no significant advantage. And when there are 4 nitrogens, the energy level will be too deep and the voltage will be too high.
  • the central part of the aza body contains 2 nitrogens (pyrimidine) or 3 nitrogens (triazine), while the efficiency is improved, the voltage can be kept low, so that the two can reach a good balance.
  • the central part contains 2 nitrogens, it shows higher efficiency, and when it consists of 3 nitrogens, it shows a longer lifetime. This tendency also has the same reflection in embodiment 26-31.
  • Example 6 By comparing Example 6, Example 16, and Examples 26-31, it can be seen that the introduction of ortho-benzene in the molecule can shorten the distance between the fluoranthene main body and the azabenzene-based main body, strengthen the electronic processing ability, and thereby improve its electrical performance. Reduce voltage, improve efficiency, and the effect is very significant.
  • Example 6 By comparing Example 6 and Example 16, it can be seen that when the main substituents of the azabenzene series are benzene and biphenyl, compared with two benzenes, the efficiency and life can be improved, but the voltage is slightly increased. In addition, the compound used in Example 6 is more symmetrical due to the azobenzene system, and it is easier to block holes during evaporation, resulting in a decrease in yield and a decrease in production rhythm. However, Example 16, which improved the asymmetry of the main azobenzene system, had better production performance.
  • Example 26 Example 29, Example 32, and Example 33
  • the azabenzene-based main body substituted by benzene and biphenyl further reduces the voltage and improves Efficiency, improve life, but the rise of biphenyl materials is small.
  • the steric exclusion effect of biphenyl restricts the rotation of the azobenzene-based host, thereby strengthening the stability of the delocalized large ⁇ bond and enhancing the electronic processing performance is also an important reason.
  • Example 16 By comparing Example 16, Example 18 and Comparative Example 5, it can be seen that when nitrogen-containing substituents are used to replace the azobenzene-based host, due to excessive adjustment of the energy level, it does not match the material of the surrounding layer, thereby reducing the efficiency.
  • Example 16 By comparing Example 16, Example 18 and Comparative Example 6, it can be seen that when a condensed ring is connected to the main body of the azobenzene system, the fused ring will disturb the regular electron movement brought by fluoranthene, reduce the electron processing ability of the molecule, and thereby improve voltage reduces efficiency.

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Abstract

The present invention provides a fluoranthene derivative, a photoelectric conversion element containing same, and a light-emitting element. The fluoranthene derivative of the present invention has a specific structure comprising a fluoranthene host and an azabenzene-based host. According to the present invention, an organic thin-film light-emitting element having a high luminous efficiency, a low driving voltage, and a long endurance life can be provided at the same time.

Description

荧蒽衍生物、发光元件以及光电转换元件Fluoranthene derivative, light-emitting element, and photoelectric conversion element 技术领域technical field
本发明涉及可将电能转换为光的发光元件及该发光元件中所使用的材料。本发明可在显示元件、平板显示器、背光、照明、内饰、标识、看板、电子照相机、虚拟现实、增强现实、智能手表、手机、手提电脑、平板电脑、显示器、车载显示、车载尾灯、电视及光信号产生器等领域中利用。The present invention relates to a light-emitting element capable of converting electrical energy into light and a material used in the light-emitting element. The present invention can be used in display elements, flat panel displays, backlights, lighting, interior decoration, signs, billboards, electronic cameras, virtual reality, augmented reality, smart watches, mobile phones, laptops, tablet computers, monitors, vehicle displays, vehicle taillights, televisions and optical signal generators and other fields.
背景技术Background technique
近年来关于有机薄膜发光元件，也称为有机发光二极管(OLED)技术的研究日趋活跃，上述有机薄膜发光元件在自阴极注入的电子与自阳极注入的空穴在夹持于两极中的有机发光体内再结合时发光，该发光元件的特征是厚度小，且可在低驱动电压下高亮度地发光，可通过选择发光材料而实现多色发光，因此备受关注。In recent years, research on organic thin-film light-emitting devices, also known as organic light-emitting diodes (OLEDs), has become increasingly active. It emits light when it is recombined in the body. This light-emitting device is characterized by its small thickness, high-intensity light emission at low driving voltage, and multi-color light emission by selecting a light-emitting material, so it has attracted attention.
该研究在由柯达公司的唐(C.W.Tang)等人揭示有机薄膜元件可高亮度地发光以来，进行了大量实用化研究。现如今，OLED已经在手环、手机、电视等领域得到普及。然而，技术上的课题仍然较多，其中同时实现元件的高效率化与长寿命化是大的课题之一。Since C.W.Tang et al. of Kodak Corporation revealed that organic thin film elements can emit light with high brightness, a lot of practical research has been carried out. Nowadays, OLED has been popularized in wristbands, mobile phones, TVs and other fields. However, there are still many technical issues, among which realizing both high efficiency and long life of devices is one of the major issues.
OLED必须满足发光效率的提高，驱动电压的降低，耐久性的提高。其中，发光效率与耐久寿命的同时实现是大的课题。然而，利用 现有技术(专利文献1-6)难以使元件的驱动电压充分地降低，而且即使可降低驱动电压，元件的发光效率，耐久寿命也不充分。如上所述，尚未发现可同时实现高发光效率、低驱动电压、以及耐久寿命的技术。OLED must meet the improvement of luminous efficiency, the reduction of driving voltage, and the improvement of durability. Among them, simultaneous realization of luminous efficiency and durable life is a major issue. However, it is difficult to sufficiently reduce the driving voltage of the device by conventional techniques (Patent Documents 1 to 6), and even if the driving voltage can be reduced, the luminous efficiency and durable life of the device are not sufficient. As described above, no technology has been found that can achieve high luminous efficiency, low driving voltage, and durable life at the same time.
[现有技术文献][Prior art literature]
[专利文献][Patent Document]
[专利文献1]国际公开第2008/059713号[Patent Document 1] International Publication No. 2008/059713
[专利文献2]国际公开第2007/100010号[Patent Document 2] International Publication No. 2007/100010
[专利文献3]国际公开第2012/108388号[Patent Document 3] International Publication No. 2012/108388
[专利文献4]国际公开第2013/065213号[Patent Document 4] International Publication No. 2013/065213
[专利文献5]国际公开第2014/057874号[Patent Document 5] International Publication No. 2014/057874
[专利文献6]国际公开第2015/182547号。[Patent Document 6] International Publication No. 2015/182547.
发明内容Contents of the invention
[发明要解决的课题][Problem to be solved by the invention]
本发明的目的在于解决上述现有技术的问题，提供发光效率、驱动电压、耐久寿命均得以改善的有机薄膜发光元件。The object of the present invention is to solve the above-mentioned problems of the prior art, and provide an organic thin film light-emitting element with improved luminous efficiency, driving voltage, and durable life.
[用于解决课题的手段][Means used to solve the problem]
本发明通过调整所述荧蒽衍生物中的荧蒽主体与氮杂苯系主体的数量及其含氮量，实现对分子中有传输能力的电子的量的控制，从而调节发光效率、驱动电压以及耐久寿命。In the present invention, by adjusting the quantity and nitrogen content of the fluoranthene main body and azabenzene series main body in the fluoranthene derivative, the control of the amount of electrons with transport ability in the molecule is realized, thereby adjusting the luminous efficiency and driving voltage and durability.
本发明提供一种具有下述通式1所示结构的荧蒽衍生物。The present invention provides a fluoranthene derivative having a structure represented by the following general formula 1.
【通式1】[Formula 1]
Figure PCTCN2022143372-appb-000001
Figure PCTCN2022143372-appb-000001
其中，L1为可被取代的亚芳基；L2为单键、可被取代的亚芳基或可被取代的亚杂芳基；X1、X2、X3、X4、X5相同或不同，各自独立地为N或者C-R1；其中R1各自独立地选自氢、氘、可被取代的烷基、可被取代的环烷基、可被取代的杂环基、可被取代的链烯基、可被取代的环烯基、可被取代的炔基、可被取代的烷氧基、可被取代的烷硫基、可被取代的芳基醚基、可被取代的芳基硫醚基、可被取代的芳基、可被取代的杂芳基、可被取代的羰基、可被取代的羧基、可被取代的氧羰基、可被取代的氨基甲酰基、可被取代的硅烷基、可被取代的烷氨基或可被取代的芳基氨基中的一种或多种；当X1、X3、X5均为N，X2和X4均为C-R1且R1均为苯基，L1与L2均为亚苯基时，L1和L2中至少一个选自邻亚苯基或者对亚苯基；n1,n4为1-3的整数；n2,n3为0-3的整数。Wherein, L1 is an arylene group that may be substituted; L2 is a single bond, an arylene group that may be substituted or a heteroarylene group that may be substituted; X1, X2, X3, X4, and X5 are the same or different, each independently Is N or C-R1; Wherein R1 is independently selected from hydrogen, deuterium, alkyl that may be substituted, cycloalkyl that may be substituted, heterocyclic group that may be substituted, alkenyl that may be substituted, alkenyl that may be substituted Substituted cycloalkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryl ether, optionally substituted arylsulfide, optionally Substituted aryl, optionally substituted heteroaryl, optionally substituted carbonyl, optionally substituted carboxyl, optionally substituted oxycarbonyl, optionally substituted carbamoyl, optionally substituted silyl, optionally substituted One or more of substituted alkylamino or arylamino that can be substituted; when X1, X3, and X5 are all N, X2 and X4 are both C-R1 and R1 are both phenyl, and both L1 and L2 are In the case of phenylene, at least one of L1 and L2 is selected from o-phenylene or p-phenylene; n1, n4 are integers of 1-3; n2, n3 are integers of 0-3.
另外，本发明提供一种发光元件，其在阳极与阴极之间存在有机层其中，在所述有机层中含有上述荧蒽衍生物。In addition, the present invention provides a light-emitting device having an organic layer between an anode and a cathode, wherein the organic layer contains the above-mentioned fluoranthene derivative.
另外，本发明还公开一种光电转换元件，其含有上述所述的荧蒽衍生物。In addition, the present invention also discloses a photoelectric conversion element, which contains the above-mentioned fluoranthene derivatives.
[发明的效果][Effect of the invention]
根据本发明可提供同时实现高发光效率、低驱动电压、以及高耐 久寿命的有机薄膜发光元件。According to the present invention, it is possible to provide an organic thin-film light-emitting device that realizes high luminous efficiency, low driving voltage, and high durability at the same time.
具体实施方式Detailed ways
下面对本发明的具体实施方式进行详细地说明。Specific embodiments of the present invention will be described in detail below.
首先，对本发明提供的具有通式(1)所示的结构的荧蒽衍生物加以详细说明。First, the fluoranthene derivative having the structure represented by the general formula (1) provided by the present invention will be described in detail.
【通式1】[Formula 1]
Figure PCTCN2022143372-appb-000002
Figure PCTCN2022143372-appb-000002
其中，L1为可被取代的亚芳基；L2为单键、可被取代的亚芳基或可被取代的亚杂芳基；X1、X2、X3、X4、X5相同或不同，各自独立地为N或者C-R1；其中R1各自独立地选自氢、氘、可被取代的烷基、可被取代的环烷基、可被取代的杂环基、可被取代的链烯基、可被取代的环烯基、可被取代的炔基、可被取代的烷氧基、可被取代的烷硫基、可被取代的芳基醚基、可被取代的芳基硫醚基、可被取代的芳基、可被取代的杂芳基、可被取代的羰基、可被取代的羧基、可被取代的氧羰基、可被取代的氨基甲酰基、可被取代的硅烷基、可被取代的烷氨基或可被取代的芳基氨基中的一种或多种；当X1、X3、X5均为N，X2和X4均为C-R1且R1均为苯基，L1与L2均为亚苯基时，L1和L2中至少一个选自邻亚苯基或者对亚苯基；n1,n4为1-3的整数；n2,n3为0-3的整数。Wherein, L1 is an arylene group that may be substituted; L2 is a single bond, an arylene group that may be substituted or a heteroarylene group that may be substituted; X1, X2, X3, X4, and X5 are the same or different, each independently Is N or C-R1; Wherein R1 is independently selected from hydrogen, deuterium, alkyl that may be substituted, cycloalkyl that may be substituted, heterocyclic group that may be substituted, alkenyl that may be substituted, alkenyl that may be substituted Substituted cycloalkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryl ether, optionally substituted arylsulfide, optionally Substituted aryl, optionally substituted heteroaryl, optionally substituted carbonyl, optionally substituted carboxyl, optionally substituted oxycarbonyl, optionally substituted carbamoyl, optionally substituted silyl, optionally substituted One or more of substituted alkylamino or arylamino that can be substituted; when X1, X3, and X5 are all N, X2 and X4 are both C-R1 and R1 are both phenyl, and both L1 and L2 are In the case of phenylene, at least one of L1 and L2 is selected from o-phenylene or p-phenylene; n1, n4 are integers of 1-3; n2, n3 are integers of 0-3.
在上述所有基团中，氢也可以为氘。In all of the above groups, hydrogen may also be deuterium.
本文中，“可被取代”的情况下，取代基优选为可被取代的烷基、可被取代的环烷基、可被取代的杂环基、可被取代的链烯基、可被取代的环烯基、可被取代的炔基、可被取代的烷氧基、可被取代的烷硫基、可被取代的芳基醚基、可被取代的芳基硫醚基、可被取代的芳基、可被取代的杂芳基、可被取代的羰基、可被取代的羧基、可被取代的氧羰基、可被取代的氨基甲酰基、可被取代的硅烷基、可被取代的烷氨基或可被取代的芳基氨基、卤素、氰基、羰基、羧基、氧基碳基、氨甲酰基、氧化膦基、缩合芳香族烃环，单环芳香族杂环及缩合芳香族杂环中的一种或多种，进一步优选在针对各取代基的说明中列为优选的具体取代基。而且这些取代基也可进一步被上述取代基所取代。Herein, in the case of "may be substituted", the substituent is preferably an alkyl group which may be substituted, a cycloalkyl group which may be substituted, a heterocyclic group which may be substituted, an alkenyl group which may be substituted, an alkenyl group which may be substituted, Cycloalkenyl, substituted alkynyl, substituted alkoxy, substituted alkylthio, substituted aryl ether, substituted arylsulfide, substituted Aryl, optionally substituted heteroaryl, optionally substituted carbonyl, optionally substituted carboxyl, optionally substituted oxycarbonyl, optionally substituted carbamoyl, optionally substituted silyl, optionally substituted Alkylamino or arylamino which may be substituted, halogen, cyano, carbonyl, carboxyl, oxycarbonyl, carbamoyl, phosphine oxide, condensed aromatic hydrocarbon ring, monocyclic aromatic heterocycle and condensed aromatic heterocycle One or more of the rings are further preferably listed as preferred specific substituents in the description for each substituent. Also, these substituents may be further substituted with the above-mentioned substituents.
“可被取代”的情况下的“未被取代”的情况是表示由氢原子取代。The case of "unsubstituted" in the case of "may be substituted" means substitution with a hydrogen atom.
在以下所说明的化合物或其部分结构中，关于“可被取代”的情况，也与上述相同。In the compounds described below or their partial structures, "may be substituted" is also the same as above.
所谓烷基，表示例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基等饱和脂肪族烃基，其可具有取代基也可不具有取代基。在被取代的情况下的追加的取代基并无特别限制，例如可列举烷基、芳基、杂芳基等，此方面在以下的记载中也通用。而且，烷基的碳数并无特别限定，从材料获取是否容易以及成本的方面考虑，优选的是1以上、20以下。The term "alkyl" means, for example, a saturated aliphatic hydrocarbon group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, which may or may not have a substituent. The substituent to be added in the case of being substituted is not particularly limited, for example, an alkyl group, an aryl group, a heteroaryl group, etc. are mentioned, and this point is common also in the following description. Furthermore, the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more and 20 or less from the viewpoint of availability of materials and cost.
所谓环烷基，表示例如环丙基、环己基、降冰片基、金刚烷基等 饱和脂肪族环烷基，其可具有取代基也可不具有取代基。烷基部分的碳数并无特别限定，从材料获取是否容易以及成本的方面考虑，优选的是3以上、20以下的范围。The term "cycloalkyl" means, for example, a saturated aliphatic cycloalkyl group such as cyclopropyl, cyclohexyl, norbornyl, adamantyl, etc., which may or may not have a substituent. The number of carbon atoms in the alkyl moiety is not particularly limited, but it is preferably in the range of 3 or more and 20 or less from the viewpoint of availability of materials and cost.
所谓链烯基，表示例如乙烯基、烯丙基、丁二烯等包含双键的不饱和脂肪族烃基，其可具有取代基也可不具有取代基。烯基的碳数并无特别限定，从材料获取是否容易以及成本的方面考虑，优选的是3以上、20以下的范围。The term "alkenyl" means, for example, an unsaturated aliphatic hydrocarbon group including a double bond such as vinyl, allyl, and butadiene, which may or may not have a substituent. The carbon number of the alkenyl group is not particularly limited, but it is preferably in the range of 3 or more and 20 or less from the viewpoint of availability of materials and cost.
所谓环烯基，表示例如环戊烯基、环戊二烯基、环己烯基等包含包含双键的不饱和脂肪族烃基，其可具有取代基也可不具有取代基。烯基的碳数并无特别限定，从材料获取是否容易以及成本的方面考虑，优选的是3以上、20以下的范围。The term "cycloalkenyl" means, for example, an unsaturated aliphatic hydrocarbon group containing a double bond, such as cyclopentenyl, cyclopentadienyl, and cyclohexenyl, which may or may not have a substituent. The carbon number of the alkenyl group is not particularly limited, but it is preferably in the range of 3 or more and 20 or less from the viewpoint of availability of materials and cost.
所谓炔基，表示例如乙炔基等包含三键的不饱和脂肪族烃基，其可具有取代基也可不具有取代基。烯基的碳数并无特别限定，从材料获取是否容易以及成本的方面考虑，优选的是3以上、20以下的范围。The alkynyl group means, for example, an unsaturated aliphatic hydrocarbon group including a triple bond, such as an ethynyl group, which may or may not have a substituent. The carbon number of the alkenyl group is not particularly limited, but it is preferably in the range of 3 or more and 20 or less from the viewpoint of availability of materials and cost.
所谓烷氧基，表示例如甲氧基、乙氧基、丙氧基等经由醚键键合而成的有脂肪族烃基的官能基，该脂肪族烃基可具有取代基也可不具有取代基。烷氧基的碳数并无特别限定，从材料获取是否容易以及成本的方面考虑，优选的是1以上、20以下的范围。The alkoxy group means, for example, a functional group having an aliphatic hydrocarbon group bonded via an ether bond such as methoxy, ethoxy, propoxy, etc., and the aliphatic hydrocarbon group may or may not have a substituent. The number of carbon atoms in the alkoxy group is not particularly limited, but it is preferably in the range of 1 to 20 in terms of availability of materials and cost.
所谓烷硫基是将烷氧基的醚键的氧原子取代为硫原子而成的。烷硫基的烃基可具有取代基也可不具有取代基。烷硫基的碳数并无特别限定，从材料获取是否容易以及成本的方面考虑，优选的是1以上、 20以下的范围。The term "alkylthio" is obtained by substituting an oxygen atom of an ether bond of an alkoxy group with a sulfur atom. The hydrocarbon group of the alkylthio group may or may not have a substituent. The number of carbon atoms in the alkylthio group is not particularly limited, but is preferably in the range of 1 to 20 in terms of availability of materials and cost.
所谓芳基醚基，表示例如苯氧基等经由醚键键合而成的有芳香族烃基的官能基，芳香族烃基可具有取代基也可不具有取代基。芳基醚基的碳数并无特别限定，从材料获取是否容易以及成本的方面考虑，优选的是6以上、40以下的范围。The aryl ether group means, for example, a functional group having an aromatic hydrocarbon group bonded via an ether bond such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. The number of carbon atoms in the aryl ether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less from the viewpoint of availability of materials and cost.
所谓芳基硫醚基是将芳基醚基的醚键的氧原子取代为硫原子而成的。芳基硫醚基中的芳香族烃基可具有取代基也可不具有取代基。芳基硫醚基的碳数并无特别限定，从材料获取是否容易以及成本的方面考虑，优选的是6以上、40以下的范围。The so-called aryl sulfide group is obtained by substituting the oxygen atom of the ether bond of the aryl ether group with a sulfur atom. The aromatic hydrocarbon group in the aryl sulfide group may have a substituent or may not have a substituent. The carbon number of the aryl sulfide group is not particularly limited, but it is preferably in the range of 6 or more and 40 or less from the viewpoint of availability of materials and cost.
所谓芳基表示例如苯基、萘基、联苯基、菲基、联三苯基、芘基、1，2-苯并苊基等芳香族烃基。芳基可具有取代基也可不具有取代基。芳基的碳数并无特别限定，从材料获取是否容易以及成本的方面考虑，优选的是6以上、40以下的范围。The term "aryl" means, for example, aromatic hydrocarbon groups such as phenyl, naphthyl, biphenyl, phenanthrenyl, terphenyl, pyrenyl, and 1,2-benzonaphthyl. The aryl group may or may not have a substituent. The carbon number of the aryl group is not particularly limited, but it is preferably in the range of 6 to 40 in terms of availability of materials and cost.
所谓杂芳基是表示呋喃基、苯硫基(thiophenyl)、吡啶基、喹啉基、异喹啉基、吡嗪基、嘧啶基、萘啶基、苯并呋喃基、苯并苯硫基、吲哚基、二苯并呋喃基、二苯并苯硫基、咔唑基等在一个或多个环内具有碳以外的原子的环状芳香族基，其可未经取代也可经取代。杂芳基的碳数并无特别限定，从材料获取是否容易以及成本的方面考虑，优选的是2以上、30以下的范围。The so-called heteroaryl refers to furyl, thiophenyl, pyridyl, quinolinyl, isoquinolyl, pyrazinyl, pyrimidyl, naphthyridyl, benzofuryl, benzophenylthio, Indolyl, dibenzofuryl, dibenzophenylthio, carbazolyl and other cyclic aromatic groups having atoms other than carbon in one or more rings, which may be unsubstituted or substituted. The carbon number of the heteroaryl group is not particularly limited, and is preferably in the range of 2 or more and 30 or less from the viewpoint of availability of materials and cost.
所谓卤素是表示选自氟、氯、溴及碘的原子。The term "halogen" means an atom selected from fluorine, chlorine, bromine and iodine.
羰基、羧基、氧基羰基、氰基、氨甲酰基及氧化膦基可具有取代基也可不具取代基。此处，取代基可列举烷基、环烷基、芳基、杂芳 基等，这些取代基也可被进一步取代。A carbonyl group, a carboxyl group, an oxycarbonyl group, a cyano group, a carbamoyl group, and a phosphine oxide group may or may not have a substituent. Here, examples of substituents include alkyl groups, cycloalkyl groups, aryl groups, heteroaryl groups, and the like, and these substituents may be further substituted.
所谓亚芳基是表示自苯基、萘基、联苯基等芳香族烃基导出的2价或3价的基，其可具有取代基也可不具有取代基。The term "arylene group" means a divalent or trivalent group derived from an aromatic hydrocarbon group such as phenyl, naphthyl, or biphenyl, which may or may not have a substituent.
在通式1的L1为亚芳基的情况下，核碳数优选的是6以上、24以下的范围，其中6以上、12以下的更优选，亚芳基具体可列举：1，4-亚苯基、1，3-亚苯基、1，2-亚苯基、4，4′-亚联苯基、4，3′-亚联苯基、3，3′-亚联苯基、1，4-亚萘基、1，5-亚萘基、2，5-亚萘基、2，6-亚萘基、2，7-亚萘基等。更优选的是1，4-亚苯基、1，3-亚苯基。In the case where L1 of the general formula 1 is an arylene group, the number of nuclear carbons is preferably in the range of 6 or more and 24 or less, wherein 6 or more and 12 or less are more preferred, and the arylene group specifically includes: 1,4-ylene Phenyl, 1,3-phenylene, 1,2-phenylene, 4,4'-biphenylene, 4,3'-biphenylene, 3,3'-biphenylene, 1 , 4-naphthylene, 1,5-naphthylene, 2,5-naphthylene, 2,6-naphthylene, 2,7-naphthylene, etc. More preferred are 1,4-phenylene and 1,3-phenylene.
所谓亚杂芳基是表示自吡啶基、喹啉基、嘧啶基、吡嗪基、萘啶基、二苯并呋喃基、二苯并苯硫基等在一个或多个环内具有碳以外的原子的芳香族基导出的2价或3价的取代基，其可具有取代基也可不具有取代基。亚杂芳基的碳数并无特别限定，优选的是2～30的范围。The so-called heteroarylene group means any group other than pyridyl, quinolinyl, pyrimidinyl, pyrazinyl, naphthyridinyl, dibenzofuryl, dibenzophenylthio, etc., which have carbon in one or more rings. A divalent or trivalent substituent derived from an aromatic group of an atom may or may not have a substituent. The carbon number of the heteroarylene group is not particularly limited, but is preferably in the range of 2-30.
所谓缩合芳香族烃环，例如可列举萘环、薁环、蒽环、菲环、芘环、1，2-苯并菲(chrysene)环、并四苯环、三亚苯环、苊(acenaphthene)环、六苯并苯环、芴环、1，2-苯并苊环、并四苯环、并五苯环、苝环、五苯(pentaphene)环、苉(picene)环、吡蒽(pyranthrene)环、蒽并蒽烯(anthraanthrene)环等。另外，上述缩合芳香族烃环也可具有取代基。The so-called condensed aromatic hydrocarbon rings include, for example, naphthalene rings, azulene rings, anthracene rings, phenanthrene rings, pyrene rings, 1,2-triphenylene (chrysene) rings, naphthacene rings, triphenylene rings, and acenaphthene rings. ring, hexabenzobenzene ring, fluorene ring, 1,2-benzoacenaphthene ring, tetracene ring, pentacene ring, perylene ring, pentaphene ring, picene ring, pyranthrene ) ring, anthraanthrene ring, etc. In addition, the above-mentioned condensed aromatic hydrocarbon ring may have a substituent.
所谓单环芳香族杂环，可列举呋喃环、噻吩环、吡啶环、哒嗪环、嘧啶环、吡嗪环、三嗪环、噁二唑环、三唑环、咪唑环、吡唑环、噻唑环等。另外，上述单环芳香族杂环也可具有取代基。The monocyclic aromatic heterocycle includes furan ring, thiophene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, Thiazole ring etc. In addition, the above-mentioned monocyclic aromatic heterocycle may have a substituent.
所谓缩合芳香族杂环，例如可列举喹啉环、异喹啉环、喹噁啉环、苯并咪唑环、吲哚环、苯并咪唑环、苯并噻唑环、苯并噁唑环、喹噁啉环、喹唑啉环、酞嗪环、咔唑环、咔啉环、二氮杂咔唑环(表示构成咔啉环的烃环的碳原子的一个进一步被氮原子取代的环)等。另外，上述缩合芳香族杂环也可具有取代基。The so-called condensed aromatic heterocyclic rings include, for example, quinoline rings, isoquinoline rings, quinoxaline rings, benzimidazole rings, indole rings, benzimidazole rings, benzothiazole rings, benzoxazole rings, quinoline rings, Oxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, diazacarbazole ring (representing a ring in which one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom), etc. . In addition, the above-mentioned condensed aromatic heterocycle may have a substituent.
本发明提供的是一种荧蒽主体与氮杂苯系主体的组合型荧蒽衍生物，荧蒽的结构为三个苯环围绕一个环戊烷，电子可以在整个荧蒽结构中离域，另一方面环戊烷部分形成电子空洞部分，对电子产生吸收的倾向。氮杂苯系主体可以为苯或者含有多个氮的氮杂苯，氮杂苯系中苯本身的大Π键可以在分子全域移动，氮杂苯系主体中增加氮时，氮的孤对电子对能够进一步增加大Π键中的离域电子，从而加强电子的传输能力。氮杂苯系主体的电子受原子核吸引的能力较弱，同时荧蒽部分有吸引电子的倾向，使得电子在整个分子中产生向着荧蒽部分移动的倾向(尽管分子本身是中性的)，这样的分子积累成膜时一定程度上可以模仿金属键中的电子离域，从而提供电子的传输能力。另一方面，过多的荧蒽主体会扰乱电子的走向，并降低电子有效传输能力，而过多的氮会过度地降低LUMO，使得电子处理材料的能级与周边材料不匹配。因此荧蒽主体的数量及氮杂苯系主体的数量需要针对分子进行精细的控制。考虑到材料的能级匹配，电子处理能力，合成难度，成本，优选荧蒽主体数量(n1)为1，氮杂苯系主体数量(n4)为1的情况。The invention provides a combined fluoranthene derivative with a fluoranthene main body and an azabenzene-based main body. The structure of fluoranthene is three benzene rings surrounding a cyclopentane, and electrons can be delocalized in the entire fluoranthene structure. On the other hand, the cyclopentane part forms an electron hole part and tends to absorb electrons. The main body of the azabenzene system can be benzene or azabenzene containing multiple nitrogens. In the azabenzene system, the large Π bond of benzene itself can move in the entire molecule. When nitrogen is added to the main body of the azabenzene system, the lone pair of electrons of nitrogen It can further increase the delocalized electrons in the large Π bond, thereby enhancing the electron transport ability. The electrons of the main body of the azabenzene system are weakly attracted by the nucleus, and the fluoranthene part has a tendency to attract electrons, so that the electrons tend to move towards the fluoranthene part in the entire molecule (although the molecule itself is neutral), so When the molecules accumulate to form a film, it can imitate the delocalization of electrons in metal bonds to a certain extent, thereby providing electron transport capabilities. On the other hand, too much fluoranthene host will disturb the orientation of electrons and reduce the effective electron transport ability, while too much nitrogen will excessively reduce the LUMO, making the energy level of the electron-handling material mismatch with the surrounding materials. Therefore, the number of fluoranthene hosts and the number of azabenzene hosts need to be finely controlled on a molecular basis. Considering the energy level matching of materials, electron processing ability, synthesis difficulty and cost, it is preferred that the number of fluoranthene hosts (n1) is 1 and the number of azabenzene series hosts (n4) is 1.
通过研究发现，直接连接氮杂苯系主体处(即L2位置)如果使 用萘等稠环化合物，容易扰乱从氮杂苯系主体提供的电子，从而降低分子的电子处理性能。因此L2位置使用非稠环的亚苯基。It has been found through research that if condensed ring compounds such as naphthalene are used at the place directly connected to the main body of the azobenzene system (i.e. the L2 position), it is easy to disturb the electrons provided from the main body of the azobenzene system, thereby reducing the electron processing performance of the molecule. Therefore a non-fused phenylene ring is used at the L2 position.
通过研究发现，n1＝1，n1×n2+n3×n4的值在1-5内时，分子的能级可以匹配大多数市面上常见的OLED体系。It is found through research that when n1=1, and the value of n1×n2+n3×n4 is within 1-5, the energy level of the molecule can match most common OLED systems on the market.
进一步地，当n1＝1，n1×n2+n3×n4的值在2-3内时，分子内的离域电子数量达到最佳的水准，可以实现最佳的器件性能。Further, when n1=1, and the value of n1×n2+n3×n4 is within 2-3, the number of delocalized electrons in the molecule reaches an optimal level, and the best device performance can be realized.
如上所述，氮杂苯系主体的氮数需要精细控制。考虑到常见的与电子处理材料邻接的材料的能级，以及实际的测试结果，X1、X2、X3、X4、X5中有0-3个N时能有较好的电子处理表现。As mentioned above, the nitrogen number of the azobenzene-based host requires fine control. Considering the energy levels of common materials adjacent to electronic processing materials, as well as actual test results, when there are 0-3 N in X1, X2, X3, X4, and X5, better electronic processing performance can be achieved.
特别地，当X1、X2、X3、X4、X5中有2个N的时候，可以有更好的效率。Especially, when there are 2 Ns in X1, X2, X3, X4, and X5, better efficiency can be achieved.
特别地，当X1、X2、X3、X4、X5中有3个N的时候，可以有更长的寿命。In particular, when there are 3 Ns in X1, X2, X3, X4, and X5, it can have a longer lifetime.
通过在氮杂苯系主体的取代基上增加苯系芳香基取代基，可以对氮杂苯系主体整体的能级及电子提供能力进行微调，从而实现更精细的控制。因此，优选X1、X2、X3、X4、X5为C-R1时，R1选自可取代的苯基、可取代的呋喃基(例如优选二苯并呋喃基)或者可取代的咔唑基、芴基、二苯并噻吩基。By adding benzene-based aromatic substituents to the substituents of the azobenzene-based main body, the overall energy level and electron-donating ability of the azabenzene-based main body can be fine-tuned, thereby achieving finer control. Therefore, when X1, X2, X3, X4, and X5 are preferably C-R1, R1 is selected from substitutable phenyl, substitutable furyl (such as preferably dibenzofuryl) or substitutable carbazolyl, fluorene base, dibenzothienyl.
特别地，当X2为C-(Ph)n5，X4为C-(Ph)n6，Ph为苯基，n5+n6>2时，可以最广泛地适配更多周边层材料，达到最好的效果。In particular, when X2 is C-(Ph)n5, X4 is C-(Ph)n6, Ph is phenyl, n5+n6>2, more peripheral layer materials can be most widely adapted to achieve the best Effect.
当n5与n6不同时，可以提高分子的生产性和蒸镀性能。When n5 is different from n6, the productivity and vapor deposition performance of molecules can be improved.
通过研究发现，氮杂苯系主体为三嗪且取代基为两个苯时，根据 其提供电子的能力，更适合通过对位或者邻位的L1和L2传递到荧蒽本体。因此，当氮杂苯系主体中X1、X3、X5均为N，X2和X4均为C-R1且R1为苯基，L1与L2为亚苯基时，L1与L2中至少一个选自邻亚苯基或者对亚苯基。It has been found through research that when the main body of the azabenzene system is triazine and the substituents are two benzenes, according to its ability to provide electrons, it is more suitable to transfer to the fluoranthene body through the para-position or ortho-position L1 and L2. Therefore, when X1, X3, and X5 are all N in the main body of the azobenzene system, X2 and X4 are both C-R1 and R1 is phenyl, and L1 and L2 are phenylene, at least one of L1 and L2 is selected from phenylene or p-phenylene.
应当明确，连接部分L1和L2选自亚苯基时，电子可以更好地从氮杂苯系主体转移到荧蒽主体。但是当L1和L2同时选自间亚苯基时，电子的传送由于被弯曲，从而受到阻挠，另一方面氮杂苯系主体与荧蒽主体之间又离得太远，没有空间作用，整体上使得传送能力下降。因此该荧蒽衍生物作为电子传输层材料使用时，L1和L2不同时为间亚苯基。It should be clear that when the linking parts L1 and L2 are selected from phenylene, electrons can be better transferred from the azabenzene-based host to the fluoranthene host. However, when L1 and L2 are selected from m-phenylene at the same time, the transmission of electrons is hindered due to being bent. This reduces the transmission capacity. Therefore, when the fluoranthene derivative is used as an electron transport layer material, L1 and L2 are not m-phenylene at the same time.
特别地，邻亚苯基除了能够让氮杂苯系主体靠近荧蒽主体，还能改善分子的取向，进一步实现低电压高效率的性能。因此优选L1与L2中至少有一个为邻亚苯基。In particular, o-phenylene can not only bring the azabenzene-based host close to the fluoranthene host, but also improve the molecular orientation, further realizing low-voltage and high-efficiency performance. Therefore, at least one of L1 and L2 is preferably o-phenylene.
特别地，当L1与L2中至少有一个为邻亚苯基时，氮杂苯系主体的取代基使用联苯加苯的结构能够比双苯有更好的电学表现。这是由于联苯的空间排阻效应限制了氮杂苯系主体的旋转，从而加固了离域大Π键的稳定性，强化了电子处理性能。In particular, when at least one of L1 and L2 is an o-phenylene group, the substituent of the azobenzene-based main body can have a better electrical performance than biphenyl with a biphenyl-plus-phenylene structure. This is because the steric exclusion effect of biphenyl restricts the rotation of the azabenzene host, thereby strengthening the stability of the delocalized large Π bond and enhancing the electronic processing performance.
值得指出的是，氮杂苯系主体的取代基上增加含有氮的取代基(比如吡啶、嘧啶等)时，两个氮杂苯系主体会使得能级过低，从而与周边材料不匹配。另一方面，氮杂苯系主体被含氮取代基取代时，其之间的化学键由于电子被两个氮杂苯系主体各自抽走，从而电子云密度很低，容易发生裂解。所以不建议氮杂苯系主体的取代基选自含 有氮的取代基。It is worth pointing out that when nitrogen-containing substituents (such as pyridine, pyrimidine, etc.) are added to the substituents of the azabenzene series main body, the two azabenzene series main bodies will make the energy level too low, which will not match the surrounding materials. On the other hand, when the azobenzene-based host is substituted by a nitrogen-containing substituent, the chemical bond between them is easily cleaved due to the electrons being drawn away by the two azabenzene-based hosts, so that the electron cloud density is very low. It is therefore not recommended that the substituents of the azobenzene-based host be selected from nitrogen-containing substituents.
通过实践，我们认为以下的分子结构及其衍生结构可以视具体的器件结构以及器件用途，得到效率，电压，寿命三项综合优秀的表现，因此优选以下化合物：Through practice, we believe that the following molecular structures and their derivative structures can be used to obtain three comprehensive performances of efficiency, voltage, and life depending on the specific device structure and device application. Therefore, the following compounds are preferred:
Figure PCTCN2022143372-appb-000003
Figure PCTCN2022143372-appb-000003
Figure PCTCN2022143372-appb-000004
Figure PCTCN2022143372-appb-000004
Figure PCTCN2022143372-appb-000005
Figure PCTCN2022143372-appb-000005
Figure PCTCN2022143372-appb-000006
Figure PCTCN2022143372-appb-000006
Figure PCTCN2022143372-appb-000007
Figure PCTCN2022143372-appb-000007
Figure PCTCN2022143372-appb-000008
Figure PCTCN2022143372-appb-000008
Figure PCTCN2022143372-appb-000009
Figure PCTCN2022143372-appb-000009
Figure PCTCN2022143372-appb-000010
Figure PCTCN2022143372-appb-000010
Figure PCTCN2022143372-appb-000011
Figure PCTCN2022143372-appb-000011
Figure PCTCN2022143372-appb-000012
Figure PCTCN2022143372-appb-000012
Figure PCTCN2022143372-appb-000013
Figure PCTCN2022143372-appb-000013
本发明还公开了一种发光元件，其阳极与阴极之间存在有机层，有机层为负责发光的层和/或负责处理电子或者空穴的层，其中，在 所述有机层中含有上述荧蒽衍生物。The invention also discloses a light-emitting element, an organic layer exists between the anode and the cathode, and the organic layer is a layer responsible for emitting light and/or a layer responsible for processing electrons or holes, wherein the organic layer contains the above-mentioned fluorescent Anthracene derivatives.
考虑到该类型材料处理电子的能力，优选所述有机层具有电子传输层，在所述电子传输层中含有上述所述的荧蒽衍生物。In consideration of the ability of this type of material to handle electrons, it is preferable that the organic layer has an electron transport layer in which the above-mentioned fluoranthene derivative is contained.
考虑到该类型材料中大量的超过原子核束缚能力的电子，优选所述有机层具有电子产生层，在所述电子产生层中含有上述所述的荧蒽衍生物。In consideration of a large amount of electrons exceeding the binding capacity of atomic nuclei in this type of material, it is preferable that the organic layer has an electron generating layer in which the above-mentioned fluoranthene derivative is contained.
考虑到该类型材料专精于处理电子，其能级不适合空穴的传输，优选所述有机层具有空穴阻止层，在所述空穴阻止层中含有上述所述的荧蒽衍生物。Considering that this type of material is specialized in handling electrons and its energy level is not suitable for transport of holes, it is preferable that the organic layer has a hole blocking layer in which the above-mentioned fluoranthene derivative is contained.
另外，本发明还公开一种光电转换元件，其含有上述所述的荧蒽衍生物。In addition, the present invention also discloses a photoelectric conversion element, which contains the above-mentioned fluoranthene derivatives.
在本发明的荧蒽衍生物的合成中可使用公知的方法。作为在荧蒽衍生物骨架中导入氮杂苯系主体的方法，例如可列举在钯催化剂或镍催化剂下使用经取代或未经取代的卤化荧蒽主体与经取代或未经取代的氮杂苯系主体的偶合反应的方法，但并不限定于这些方法。另外，在经由亚芳基或亚杂芳基将氮杂苯系主体导入至该荧蒽衍生物的情况下，氮杂苯系主体使用经取代的芳基硼酸或杂芳基硼酸，或者也可使用取代有卤化芳基的荧蒽主体。而且，也可使用硼酸酯代替上述各种硼酸。A known method can be used for the synthesis of the fluoranthene derivative of the present invention. As a method of introducing an azabenzene-based host into a fluoranthene derivative skeleton, for example, the use of a substituted or unsubstituted halogenated fluoranthene host and a substituted or unsubstituted azabenzene under a palladium catalyst or a nickel catalyst It is a method of the coupling reaction of the subject, but it is not limited to these methods. In addition, when introducing an azabenzene-based host into the fluoranthene derivative via an arylene group or a heteroarylene group, a substituted arylboronic acid or a heteroarylboronic acid may be used for the azabenzene-based host, or A fluoranthene host substituted with an aryl halide is used. Furthermore, boric acid esters may also be used instead of the above-mentioned various boric acids.
其次，对本发明的发光元件的实施方式加以详细说明。本发明的发光元件包含阳极与阴极、及插入至这些阳极与阴极之间的有机层，该有机层至少包含发光层与电子传输层，该发光层利用电能而发光。Next, embodiments of the light-emitting element of the present invention will be described in detail. The light-emitting device of the present invention includes an anode and a cathode, and an organic layer interposed between the anode and the cathode. The organic layer includes at least a light-emitting layer and an electron transport layer. The light-emitting layer emits light using electric energy.
有机层除了仅仅包含发光层/电子传输层的构成以外，也可列举：1)空穴传输层/发光层/电子传输层及2)空穴传输层/发光层/电子传输层/电子注入层、3)空穴注入层/空穴传输层/发光层/电子传输层/电子注入、4)空穴注入层/空穴传输层/电子阻挡层/发光层/空穴阻挡层/电子传输层/电子注入层等层叠构成。而且，上述各层可分别为单层或者用电子产生层及空穴产生层连接起来的多层的。In addition to the composition of the organic layer including only the light emitting layer/electron transport layer, 1) hole transport layer/light emitting layer/electron transport layer and 2) hole transport layer/light emitting layer/electron transport layer/electron injection layer , 3) hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection, 4) hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer /Electron injection layer and other stacked structures. Furthermore, each of the above-mentioned layers may be a single layer or a multilayer connected by an electron generating layer and a hole generating layer.
本发明的荧蒽衍生物在上述元件构成中可用于任意层中，但具有高的电子注入传输能力、荧光量子产率及薄膜稳定性，因此优选的是电子传输层、电子产生层中以及空穴阻挡层。The fluoranthene derivative of the present invention can be used in any layer in the above-mentioned device configuration, but has high electron injection and transport capabilities, fluorescence quantum yield and film stability, so it is preferably used in the electron transport layer, the electron generation layer and in the space. Hole blocking layer.
在本发明的发光元件中，阳极与阴极具有为了元件发光而用以供给充分的电流的作用，为了使光出射，优选的是至少一个为透明或半透明。根据实际的应用及器件设计，可以使用透明阳极或者透明阴极。In the light-emitting device of the present invention, the anode and the cathode function to supply sufficient current for the device to emit light, and at least one of them is preferably transparent or semi-transparent in order to emit light. Depending on the actual application and device design, a transparent anode or a transparent cathode can be used.
阳极中所使用的材料若为可将空穴效率良好地注入至有机层中的材料、且为了使光出射而为透明或半透明，则并不特别限定为氧化锡、氧化铟、氧化铟锡(Indium Tin Oxide，ITO)、氧化铟锌(Indium Zinc Oxide，IZO)等导电性金属氧化物，或金、银、铬等金属，碘化铜、硫化铜等无机导电性物质，聚噻吩、聚吡咯、聚苯胺等导电性聚合物等，特别优选的是使用ITO玻璃或奈塞玻璃。这些电极材料可单独使用，也可将多种材料层叠或混合使用。透明电极的电阻若可对元件的发光供给充分的电流即可，因此并无限定，自元件的电力消耗的观点考虑，优选的是低电阻。例如若为300Ω/□以下的ITO基板，则作为元件电极而发挥功能，但现在变得也可供给10Ω/□左右的基 板，因此特别优选的是使用20Ω/□以下的低电阻的基板。ITO的厚度可根据电阻值而任意选择，但通常在100nm～300nm之间使用的情况较多。The material used for the anode is not particularly limited to tin oxide, indium oxide, and indium tin oxide as long as it is a material that can efficiently inject holes into the organic layer and is transparent or translucent for light emission. (Indium Tin Oxide, ITO), indium zinc oxide (Indium Zinc Oxide, IZO) and other conductive metal oxides, or metals such as gold, silver, chromium, inorganic conductive substances such as copper iodide and copper sulfide, polythiophene, poly For conductive polymers such as pyrrole and polyaniline, it is particularly preferable to use ITO glass or Nesselt glass. These electrode materials may be used alone, or a plurality of materials may be laminated or mixed for use. The resistance of the transparent electrode is not limited as long as a sufficient current can be supplied for the light emission of the device, but a low resistance is preferable from the viewpoint of power consumption of the device. For example, if it is an ITO substrate of 300Ω/□ or less, it functions as an element electrode, but now it is also possible to supply a substrate of about 10Ω/□, so it is particularly preferable to use a low resistance substrate of 20Ω/□ or less. The thickness of ITO can be arbitrarily selected according to the resistance value, but it is usually used between 100nm and 300nm in many cases.
而且，为了保持发光元件的机械强度，优选的是在基板上形成发光元件。基板可适宜地使用钠玻璃或无碱玻璃等玻璃基板也可以使用高分子成分的柔性基板。基板的厚度只要为充分地保持机械强度的厚度即可，因此若为0.5mm以上便足够。关于玻璃的材质，宜为自玻璃的溶出离子较少的材质，因此优选的是无碱玻璃。或者也市售有实施了SiO2等阻挡涂层(barrier coat)的钠钙玻璃，因此也可使用该钠钙玻璃。另外，若第一电极可稳定地发挥功能，例如也可在聚酰亚胺基板上形成阳极。ITO膜形成方法为电子束法、溅镀法及化学反应法等，并不受到特别限制。Also, in order to maintain the mechanical strength of the light emitting element, it is preferable to form the light emitting element on the substrate. As the substrate, glass substrates such as soda glass and non-alkali glass may be used suitably, and flexible substrates composed of polymer components may also be used. Since the thickness of a board|substrate should just be enough to maintain mechanical strength, it is sufficient if it is 0.5 mm or more. The material of the glass is preferably a material with few ions eluted from the glass, and therefore an alkali-free glass is preferable. Alternatively, soda lime glass coated with a barrier coat (barrier coat) such as SiO2 is also commercially available, so this soda lime glass can also be used. In addition, if the first electrode can function stably, for example, an anode may be formed on a polyimide substrate. The method for forming the ITO film is an electron beam method, a sputtering method, a chemical reaction method, etc., and is not particularly limited.
阴极中所使用的材料若为可将电子效率良好地注入至发光层中的物质，则并无特别限定。一般情况下优选的是铂、金、银、铜、铁、锡、铝、铟等金属，或者这些金属与锂、钠、钾、钙、镁等低逸出功(work function)金属的合金或多层层叠等。其中，自电阻值或成膜容易性、膜的稳定性、发光效率等方面考虑，主成分优选的是铝、银、镁。特别是若由镁与银构成，则本发明中的电子传输层及电子注入层的电子注入变容易，可实现低电压驱动，因此优选。The material used for the cathode is not particularly limited as long as it can efficiently inject electrons into the light-emitting layer. In general, metals such as platinum, gold, silver, copper, iron, tin, aluminum, indium, or alloys of these metals with lithium, sodium, potassium, calcium, magnesium and other low work function (work function) metals are preferred. Multilayer cascading, etc. Among them, aluminum, silver, and magnesium are preferable as main components in view of resistance value, easiness of film formation, film stability, and luminous efficiency. In particular, if it is composed of magnesium and silver, electron injection into the electron transport layer and the electron injection layer in the present invention becomes easy, and low-voltage driving can be realized, so it is preferable.
另外，为了保护阴极，可列举如下方法作为优选例：将铂、金、银、铜、铁、锡、铝及铟等金属，或使用这些金属的合金，二氧化硅、二氧化钛及氮化硅等无机物，聚乙烯醇、聚氯乙烯、烃系高分子化合 物等有机高分子化合物层叠于阴极上作为保护膜层。而且，本发明的荧蒽衍生物也可用作该保护膜层。然而，在使光自阴极侧出射的元件结构(顶部发光结构)的情况下，保护膜层可选自在可见光区域具有透光性的材料。这些电极的制作法为电阻加热、电子束、溅镀、离子镀及涂布等，并无特别限制。为了进一步提高光的取出效率，从而减少透明阴极的透明度不足造成的出光效率降低，也可以使用高折射率的有机材料。在这之上也可以使用金属(例如LiF)或者低折射率有机小分子化合物进行光学调整后增加薄膜封装(TFE)层，进行柔性保护，以实现柔性甚至可折叠的同时保护器件不受水氧的影响。具体的结构不做限制。In addition, in order to protect the cathode, the following method can be cited as a preferred example: metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys of these metals, silicon dioxide, titanium dioxide and silicon nitride, etc. Inorganic substances, organic polymer compounds such as polyvinyl alcohol, polyvinyl chloride, and hydrocarbon-based polymer compounds are laminated on the cathode as a protective film layer. Furthermore, the fluoranthene derivative of the present invention can also be used as the protective film layer. However, in the case of an element structure (top emission structure) in which light is emitted from the cathode side, the protective film layer may be selected from materials having light transmittance in the visible light region. The fabrication methods of these electrodes are resistance heating, electron beam, sputtering, ion plating, coating, etc., and are not particularly limited. In order to further improve the light extraction efficiency, thereby reducing the decrease in light extraction efficiency caused by insufficient transparency of the transparent cathode, an organic material with a high refractive index can also be used. On top of this, metals (such as LiF) or low-refractive-index organic small molecule compounds can be used to optically adjust and add a thin-film encapsulation (TFE) layer for flexible protection to achieve flexibility and even foldability while protecting the device from water and oxygen. Impact. The specific structure is not limited.
空穴传输层可通过如下方法而形成：将空穴传输材料的一种或两种以上加以层叠或混合的方法、或使用空穴传输材料与高分子粘合剂的混合物的方法。而且，空穴传输材料必须在赋予电场的电极间效率良好地传输来自正极的空穴，优选的是空穴注入效率高，且效率良好地传输所注入的空穴。因此，要求为具有适宜的电离电位(ionization potential)，且空穴迁移率大，另外稳定性优异，在制造时及使用时难以产生成为陷阱(trap)的杂质的物质。作为满足此种条件的物质，并无特别限定，例如优选的是4，4′-双(N-(3-甲基苯基)-N-苯基氨基)联苯(TPD)、4，4′-双(N-(1-萘基)-N-苯基氨基)联苯(NPD)、4，4′-双(N，N-双(4-联苯基)氨基)联苯(TBDB)、双(N，N′-二苯基-4-氨基苯基)-N，N-二苯基-4，4′-二氨基-1，1′-联苯(TPD232)等联苯胺衍生物，4，4′，4″-三(3-甲基苯基(苯基)氨基)三苯基胺 (m-MTDATA)、4，4′，4″-三(1-萘基(苯基)氨基)三苯基胺(1-TNATA)等被称为星爆芳基胺的材料群组，具有咔唑骨架的材料(其中咔唑多聚体，具体而言为双(N-芳基咔唑)或双(N-烷基咔唑)等咔唑2聚体的衍生物、咔唑3聚体的衍生物、咔唑4聚体的衍生物)、三亚苯化合物、吡唑啉衍生物、芪(stilbene)系化合物、腙系化合物、苯并呋喃衍生物或噻吩衍生物、噁二唑衍生物、酞菁衍生物、卟啉衍生物等杂环化合物，富勒烯衍生物、聚合物系中的在侧链具有上述单体的聚碳酸酯或苯乙烯衍生物、聚噻吩、聚苯胺、聚芴、聚乙烯咔唑及聚硅烷等。另外，也可使用p型Si、p型SiC等无机化合物。The hole transport layer can be formed by a method of laminating or mixing one or more types of hole transport materials, or a method of using a mixture of a hole transport material and a polymer binder. Furthermore, the hole transport material must efficiently transport holes from the positive electrode between the electrodes to which an electric field is applied, and it is preferable that the hole injection efficiency is high and the injected holes be efficiently transported. Therefore, it is required to have a suitable ionization potential, high hole mobility, excellent stability, and a substance that is less likely to generate impurities that become traps during manufacture and use. There are no particular limitations on the substance that satisfies such conditions, for example, 4,4'-bis(N-(3-methylphenyl)-N-phenylamino)biphenyl (TPD), 4,4 '-bis(N-(1-naphthyl)-N-phenylamino)biphenyl (NPD), 4,4'-bis(N,N-bis(4-biphenyl)amino)biphenyl (TBDB ), bis(N,N'-diphenyl-4-aminophenyl)-N,N-diphenyl-4,4'-diamino-1,1'-biphenyl (TPD232) and other benzidine derivatives 4,4′,4″-tris(3-methylphenyl(phenyl)amino)triphenylamine (m-MTDATA), 4,4′,4″-tris(1-naphthyl(phenyl) Base) amino) triphenylamine (1-TNATA) and other material groups known as starburst arylamines, materials with carbazole skeletons (wherein carbazole polymers, specifically bis(N-aryl carbazole) or bis(N-alkylcarbazole) and other carbazole 2-mer derivatives, carbazole 3-mer derivatives, carbazole 4-mer derivatives), triphenylene compounds, pyrazoline derivatives, stilbene-based compounds, hydrazone-based compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, phthalocyanine derivatives, porphyrin derivatives and other heterocyclic compounds, fullerene derivatives, Polycarbonate or styrene derivatives, polythiophene, polyaniline, polyfluorene, polyvinylcarbazole, polysilane, etc. having the above-mentioned monomers in the side chain in the polymer system. In addition, inorganic compounds such as p-type Si and p-type SiC can also be used.
本发明的荧蒽衍生物的电子注入传输特性优异，因此在将其用于电子传输层中的情况下，存在如下的担忧：电子在发光层中并不再结合，部分漏出至空穴传输层。因此，优选的是在空穴传输层中使用电子阻断性优异的化合物。其中，含有咔唑骨架的化合物的电子阻断性优异，可有助于发光元件的高效率化，因此优选。另外，上述含有咔唑骨架的化合物优选的是含有咔唑2聚体、咔唑3聚体、或咔唑4聚体骨架。其原因在于这些化合物兼具良好的电子阻断性与空穴注入传输特性。另外，在空穴传输层中使用含有咔唑骨架的化合物的情况下，更优选的是组合的发光层包含后述的磷光发光材料。其原因在于：具有上述咔唑骨架的化合物也具有高的三重态激子阻断功能，在与磷光发光材料组合的情况下可实现高发光效率化。而且，若将在具有高的空穴迁移率的方面而言优异的含有三亚苯骨架的化合物用于空穴传输层中，则获得载子平衡提高、发光效率提高、耐久寿命提高等效果， 因此优选。若含有三亚苯骨架的化合物具有2个以上二芳基氨基，则更优选。上述含有咔唑骨架的化合物、或含有三亚苯骨架的化合物可分别单独地用作空穴传输层，也可相互混合而使用。也可在不损及本发明的效果的范围内混合其他材料。而且，在以多层构成空穴传输层的情况下，只要在任意1层中包含含有咔唑骨架的化合物、或含有三亚苯骨架的化合物即可。但是值得注意的是，由于发光的原理是一个材料同时接收电子和空穴，形成激子后回归基态释放能量发光，所以发光材层材料需要设计成接受电子和空穴并且不传递的结构。因此与传递或者阻挡电子或者空穴的材料在结构上有很大差异，本发明的荧蒽类化合物无法用于发光层。The fluoranthene derivative of the present invention is excellent in electron injection and transport properties, so when it is used in the electron transport layer, there is a concern that electrons are not recombined in the light emitting layer and some of them leak to the hole transport layer . Therefore, it is preferable to use a compound excellent in electron blocking properties in the hole transport layer. Among them, compounds containing a carbazole skeleton are preferred because they are excellent in electron blocking properties and contribute to high efficiency of light-emitting devices. In addition, the above-mentioned compound containing a carbazole skeleton preferably contains a carbazole dimer, carbazole trimer, or carbazole tetramer skeleton. The reason is that these compounds have both good electron blocking properties and hole injection and transport properties. In addition, when a compound containing a carbazole skeleton is used in the hole transport layer, it is more preferable that the combined light emitting layer contains a phosphorescent light emitting material described later. The reason for this is that the compound having the above-mentioned carbazole skeleton also has a high triplet exciton blocking function, and when combined with a phosphorescent material, high luminous efficiency can be achieved. Moreover, if a compound containing a triphenylene skeleton, which is excellent in terms of high hole mobility, is used in the hole transport layer, effects such as improvement in carrier balance, improvement in luminous efficiency, and improvement in durability life are obtained. preferred. It is more preferable that the compound containing a triphenylene frame|skeleton has 2 or more diaryl amino groups. The above-mentioned carbazole skeleton-containing compound or triphenylene skeleton-containing compound may be used alone as the hole transport layer, or may be used in combination with each other. Other materials may also be mixed within the range not impairing the effect of the present invention. Moreover, what is necessary is just to contain the compound containing a carbazole frame|skeleton or the compound containing a triphenylene frame|skeleton in any one layer, when comprising a hole transport layer in multiple layers. However, it is worth noting that since the principle of luminescence is that a material accepts electrons and holes at the same time, and then returns to the ground state to release energy to emit light after forming excitons, so the material of the luminescent material layer needs to be designed to accept electrons and holes without transferring them. Therefore, the fluoranthene compound of the present invention cannot be used in the light-emitting layer due to the great difference in structure from materials that transmit or block electrons or holes.
也可在阳极与空穴传输层之间设置空穴注入层。通过设置空穴注入层，发光元件的驱动电压降低，耐久寿命也提高。在空穴注入层中可优选地使用电离电位比通常在空穴传输层中使用的材料小的材料。具体而言，除了列举上述的如TPD232这样的联苯胺衍生物、星爆芳基胺材料群组以外，也可使用酞菁衍生物等。而且，也优选的是空穴注入层由受体性化合物单独构成，或者将受体性化合物掺杂在其他的空穴传输材料中而使用。受体性化合物的例子可列举如氯化铁(III)、氯化铝、氯化镓、氯化铟、氯化锑这样的金属氯化物，如氧化钼、氧化钒、氧化钨、氧化钌这样的金属氧化物，如三(4-溴苯基)六氯锑酸铵(TBPAH)这样的电荷迁移络合物。而且，也可适宜地使用在分子内具有硝基、氰基、卤素或三氟甲基的有机化合物或醌系化合物、酸酐系化合物、富勒烯等。这些化合物的具体例可列举六氰基丁二烯、六 氰基苯、四氰基乙烯、四氰基对醌二甲烷(TCNQ)、四氟四氰基对醌二甲烷(F4-TCNQ)、2，3，6，7，10，11-六氰基-1，4，5，8，9，12-六氮杂三亚苯(HAT-CN6)、对四氟苯醌(p-fluoranil)、对四氯苯醌、对四溴苯醌、对苯醌、2，6-二氯苯醌、2，5-二氯苯醌、四甲基苯醌、1，2，4，5-四氰基苯、邻二氰基苯、对二氰基苯、1，4-二氰基四氟苯、2，3-二氯-5，6-二氰基苯醌、对二硝基苯、间二硝基苯、邻二硝基苯、对氰基硝基苯、间氰基硝基苯、邻氰基硝基苯、1，4-萘醌、2，3-二氯萘醌、1-硝基萘、2-硝基萘、1，3-二硝基萘、1，5-二硝基萘、9-氰基蒽、9-硝基蒽、9，10-蒽醌、1，3，6，8-四硝基咔唑、2，4，7-三硝基-9-芴酮、2，3，5，6-四氰基吡啶、马来酸酐、邻苯二甲酸酐、C60、或C70等。A hole injection layer may also be provided between the anode and the hole transport layer. By providing the hole injection layer, the driving voltage of the light-emitting element is reduced, and the durability life is also improved. A material having a lower ionization potential than a material generally used in a hole transport layer can be preferably used in the hole injection layer. Specifically, in addition to the aforementioned benzidine derivatives such as TPD232 and the starburst arylamine material group, phthalocyanine derivatives and the like can also be used. Furthermore, it is also preferable that the hole injection layer is composed of an accepting compound alone, or that the accepting compound is doped with another hole transporting material. Examples of acceptor compounds include metal chlorides such as iron(III) chloride, aluminum chloride, gallium chloride, indium chloride, and antimony chloride, and metal chlorides such as molybdenum oxide, vanadium oxide, tungsten oxide, and ruthenium oxide. metal oxides, charge transfer complexes such as tris(4-bromophenyl)ammonium hexachloroantimonate (TBPAH). Furthermore, an organic compound having a nitro group, a cyano group, a halogen, or a trifluoromethyl group in a molecule, a quinone compound, an acid anhydride compound, a fullerene, or the like can also be suitably used. Specific examples of these compounds include hexacyanobutadiene, hexacyanobenzene, tetracyanoethylene, tetracyanoquinodimethane (TCNQ), tetrafluorotetracyanoquinodimethane (F4-TCNQ), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN6), p-fluorobenzoquinone (p-fluoronil), p-tetrachlorobenzoquinone, p-tetrabromobenzoquinone, p-benzoquinone, 2,6-dichlorobenzoquinone, 2,5-dichlorobenzoquinone, tetramethylbenzoquinone, 1,2,4,5-tetracyanoquinone Benzene, o-dicyanobenzene, p-dicyanobenzene, 1,4-dicyanotetrafluorobenzene, 2,3-dichloro-5,6-dicyanobenzoquinone, p-dinitrobenzene, m- Dinitrobenzene, o-dinitrobenzene, p-cyanonitrobenzene, m-cyanonitrobenzene, o-cyanonitrobenzene, 1,4-naphthoquinone, 2,3-dichloronaphthoquinone, 1- Nitronaphthalene, 2-nitronaphthalene, 1,3-dinitronaphthalene, 1,5-dinitronaphthalene, 9-cyanoanthracene, 9-nitroanthracene, 9,10-anthraquinone, 1,3 , 6,8-tetranitrocarbazole, 2,4,7-trinitro-9-fluorenone, 2,3,5,6-tetracyanopyridine, maleic anhydride, phthalic anhydride, C60 , or C70, etc.
在这些化合物中，金属氧化物或含氰基化合物容易操作且也容易蒸镀，因此可容易地获得上述效果，因此优选。优选的金属氧化物的例子可列举氧化钼、氧化钒、或氧化钌。在含氰基化合物中，(a)在分子内，除了氰基的氮原子以外也具有至少1个电子接受性氮的化合物，(b)在分子内具有卤素与氰基两者的化合物，(c)在分子内具有羰基与氰基两者的化合物，或(d)在分子内具有卤素与氰基两者，另外除了氰基的氮原子以外也具有至少1个电子接受性氮的化合物成为强的电子受体，因此更优选。此种化合物具体而言可列举如下所述的化合物。Among these compounds, metal oxides and cyano-group-containing compounds are easy to handle and easy to vapor-deposit, so the above-mentioned effect can be easily obtained, and are therefore preferred. Examples of preferable metal oxides include molybdenum oxide, vanadium oxide, and ruthenium oxide. Among the cyano group-containing compounds, (a) compounds having at least one electron-accepting nitrogen in addition to the nitrogen atom of the cyano group in the molecule, (b) compounds having both halogen and cyano groups in the molecule, ( c) a compound having both a carbonyl group and a cyano group in the molecule, or (d) a compound having both a halogen and a cyano group in the molecule, and at least one electron-accepting nitrogen in addition to the nitrogen atom of the cyano group becomes Strong electron acceptor and therefore more preferred. Specific examples of such compounds include the compounds described below.
Figure PCTCN2022143372-appb-000014
Figure PCTCN2022143372-appb-000014
Figure PCTCN2022143372-appb-000015
Figure PCTCN2022143372-appb-000015
在空穴注入层由受体性化合物单独构成的情况、或者在空穴注入层中掺杂受体性化合物的情况的任意情况下，均是空穴注入层可为1层，也可层叠多层。而且，在掺杂受体化合物的情况下，自可缓和向空穴传输层注入空穴的障壁的观点考虑，所组合使用的空穴注入材料更优选的是与在空穴传输层中使用的化合物相同的化合物。In either case where the hole injection layer is composed of an accepting compound alone, or when the hole injection layer is doped with an accepting compound, the hole injection layer may be one layer or may be stacked in multiple layers. layer. Moreover, in the case of doping an acceptor compound, the hole injection material used in combination is more preferably the same as that used in the hole transport layer from the viewpoint of relaxing the barrier for injecting holes into the hole transport layer. Compounds of the same compound.
任选地，发光层可为单层或多层，其分别由发光材料(主体材料、掺杂材料)而形成，任选地，其可为主体材料与掺杂材料的混合物，也可单独为主体材料。亦即，在本发明的发光元件中，在各发光层中，可以是仅仅主体材料或掺杂材料发光，也可为主体材料与掺杂材料均发光。自效率良好地利用电能、获得高色纯度的发光的观点考虑，优 选的是发光层包含主体材料与掺杂材料的混合物。而且，任选地，主体材料与掺杂材料分别可为一种，也可为多种的组合。任选地，掺杂材料可在主体材料的全体中包含，也可部分地包含。任选地，掺杂材料可层叠，也可分散。掺杂材料可控制发光色。掺杂材料的量若过多，则产生浓度猝灭现象，因此优选的是相对于主体材料而言在20重量％以下使用，更优选的是10重量％以下。作为掺杂方法，可通过与主体材料的共蒸镀法而形成，也可在预先与主体材料混合后同时进行蒸镀。Optionally, the light-emitting layer can be a single layer or multiple layers, which are respectively formed of light-emitting materials (host material, dopant material), optionally, it can be a mixture of a host material and a dopant material, or can be independently Body material. That is, in the light-emitting device of the present invention, in each light-emitting layer, only the host material or the dopant material may emit light, or both the host material and the dopant material may emit light. From the viewpoint of efficiently utilizing electric energy and obtaining light emission with high color purity, it is preferable that the light emitting layer contains a mixture of a host material and a dopant material. Moreover, optionally, the host material and the dopant material can be one kind or a combination of multiple kinds. Optionally, the dopant material may be contained in the host material entirely or partially. Optionally, the dopant material can be layered or dispersed. Doping materials can control the emission color. If the amount of the dopant material is too large, concentration quenching occurs, so it is preferably used at 20% by weight or less, more preferably 10% by weight or less, based on the host material. As the doping method, it may be formed by co-evaporation with the host material, or it may be mixed with the host material in advance and then vapor-deposited at the same time.
发光材料具体而言可使用自以前起已知为发光体的蒽或芘等缩合环衍生物，以三(8-羟基喹啉)铝为首的金属螯合化类喔星化合物(metal chelate doxinoid compounds)，双苯乙烯基蒽衍生物或二苯乙烯基苯衍生物等双苯乙烯基衍生物，四苯基丁二烯衍生物、茚衍生物、香豆素衍生物、噁二唑衍生物、吡咯并吡啶衍生物、紫环酮衍生物、环戊二烯衍生物、噁二唑衍生物、噻二唑并吡啶衍生物、二苯并呋喃衍生物、咔唑衍生物、吲哚咔唑衍生物，聚合系中的聚苯乙炔衍生物、聚对苯衍生物，以及聚噻吩衍生物等，但并无特别限定。Concretely, luminescent materials such as condensed ring derivatives such as anthracene and pyrene known as light emitters, metal chelate doxinoid compounds (metal chelate doxinoid compounds) headed by tris(8-hydroxyquinoline)aluminum can be used. ), bistyryl derivatives such as bistyryl anthracene derivatives or distyrylbenzene derivatives, tetraphenylbutadiene derivatives, indene derivatives, coumarin derivatives, oxadiazole derivatives, Pyrrolopyridine derivatives, perionone derivatives, cyclopentadiene derivatives, oxadiazole derivatives, thiadiazolopyridine derivatives, dibenzofuran derivatives, carbazole derivatives, indolecarbazole derivatives products, polyphenylene vinylene derivatives, polyparaphenylene derivatives, and polythiophene derivatives in the polymer system, but are not particularly limited.
发光材料中所含有的主体材料并无特别限定，可使用萘、蒽、菲、芘、1，2-苯并菲、并四苯、三亚苯、苝、1，2-苯并苊、芴、茚等具有缩合芳基环的化合物或其衍生物，N，N′-二萘基-N，N′-二苯基-4，4′-二苯基-1，1′-二胺等芳香族胺衍生物，以三(8-羟基喹啉)铝(III)为代表的金属螯合物化类喔星化合物，二苯乙烯基苯衍生物等双苯乙烯基衍生物、四苯基丁二烯衍生物、茚衍生物、香豆素衍生 物、噁二唑衍生物、吡咯并吡啶衍生物、紫环酮衍生物、环戊二烯衍生物、吡咯并吡咯衍生物、噻二唑并吡啶衍生物、二苯并呋喃衍生物、咔唑衍生物、吲哚咔唑衍生物、三嗪衍生物，聚合物系中的聚苯乙炔衍生物、聚对苯衍生物、聚芴衍生物、聚乙烯咔唑衍生物、聚噻吩衍生物等，并无特别限定。而且，掺杂材料并无特别限定，可使用萘、蒽、菲、芘、1，2-苯并菲、三亚苯、苝、1，2-苯并苊、芴、茚等具有缩合芳基环的化合物或其衍生物(例如2-(苯并噻唑-2-基)-9，10-二苯基蒽或5，6，11，12-四苯基并四苯等)、呋喃、吡咯、噻吩、硅杂环戊二烯、9-硅芴(9-silafluorene)、9，9′-螺环二硅芴(9，9′-spirobisilafluorene)、苯并噻吩、苯并呋喃、吲哚、二苯并噻吩、二苯并呋喃、咪唑并吡啶、菲咯啉、吡啶、吡嗪、萘啶、喹噁啉、吡咯并吡啶、硫杂蒽(thioxanthene)等具有杂芳基环的化合物或其衍生物，硼烷衍生物、二苯乙烯基苯衍生物、4，4′-双(2-(4-二苯基氨基苯基)乙烯基)联苯、4，4′-双(N-(芪-4-基)-N-苯基氨基)芪等氨基苯乙烯基衍生物、芳香族乙炔衍生物、四苯基丁二烯衍生物、芪衍生物、醛连氮衍生物、吡咯亚甲基(pyrromethene)衍生物、二酮基吡咯并[3，4-c]吡咯衍生物、2，3，5，6-1H，4H-四氢-9-(2′-苯并噻唑基)喹嗪基[9，9a，1-gh]香豆素等香豆素衍生物咪唑、噻唑、噻二唑、咔唑、噁唑、噁二唑、三唑等唑衍生物及其金属络合物及以N，N′-二苯基-N，N′-二(3-甲基苯基)-4，4′-二苯基-1，1′-二胺为代表的芳香族胺衍生物等。The host material contained in the luminescent material is not particularly limited, naphthalene, anthracene, phenanthrene, pyrene, 1,2-triphenylene, tetracene, triphenylene, perylene, 1,2-benzoacenaphthylene, fluorene, Indene and other compounds with condensed aryl rings or their derivatives, N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl-1,1'-diamine and other aromatic Amine derivatives, metal chelated oxinoid compounds represented by tris(8-hydroxyquinoline)aluminum(III), bistyryl derivatives such as distyrylbenzene derivatives, tetraphenylbutadiene ene derivatives, indene derivatives, coumarin derivatives, oxadiazole derivatives, pyrrolopyridine derivatives, perionone derivatives, cyclopentadiene derivatives, pyrrolopyrrole derivatives, thiadiazolopyridine derivatives Derivatives, dibenzofuran derivatives, carbazole derivatives, indolecarbazole derivatives, triazine derivatives, polyphenylene vinylene derivatives, polyparaphenylene derivatives, polyfluorene derivatives, poly Vinylcarbazole derivatives, polythiophene derivatives, and the like are not particularly limited. Moreover, the dopant material is not particularly limited, and naphthalene, anthracene, phenanthrene, pyrene, 1,2-triphenylene, triphenylene, perylene, 1,2-benzoacenaphthylene, fluorene, indene, etc. can be used. Compounds or derivatives thereof (such as 2-(benzothiazol-2-yl)-9,10-diphenylanthracene or 5,6,11,12-tetraphenyltetracene, etc.), furan, pyrrole, Thiophene, silacyclopentadiene, 9-silafluorene (9-silafluorene), 9,9'-spiro disilafluorene (9,9'-spirobisilafluorene), benzothiophene, benzofuran, indole, di Compounds with heteroaryl rings such as benzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyridine, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene, or derivatives thereof substances, borane derivatives, distyrylbenzene derivatives, 4,4'-bis(2-(4-diphenylaminophenyl)vinyl)biphenyl, 4,4'-bis(N-( Stilbene-4-yl)-N-phenylamino)stilbene and other aminostyryl derivatives, aromatic acetylene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, pyrromethene Base (pyrromethene) derivatives, diketopyrrolo[3,4-c]pyrrole derivatives, 2,3,5,6-1H,4H-tetrahydro-9-(2′-benzothiazolyl)quinone Coumarin derivatives such as azinyl[9,9a,1-gh]coumarin, imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, triazole and other azole derivatives and their metal complexes And aromatic amine derivatives represented by N,N'-diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine wait.
而且，在发光层中也可包含磷光发光材料。所谓磷光发光材料是 即使在室温下也显示磷光发光的材料。在作为掺杂剂而使用磷光发光材料的情况下，基本上需要即使在室温下也可获得磷光发光，并无特别限定，优选的是包含选自由铱(Ir)、钌(Ru)、铑(Rh)、钯(Pd)、铂(Pt)、锇(Os)、及铼(Re)所构成的群组的至少一种金属的有机金属络合化合物。其中，自即使在室温下也具有高的磷光发光产率的观点考虑，更优选的是具有铱、或铂的有机金属络合物。作为与磷光发光性的掺杂剂组合使用的主体，可适宜地使用吲哚衍生物、咔唑衍生物、吲哚咔唑衍生物、具有吡啶、嘧啶、三嗪骨架的含氮芳香族化合物衍生物、多芳基苯衍生物、螺芴衍生物、三聚茚(truxene)衍生物、三亚苯衍生物等芳香族烃化合物衍生物、二苯并呋喃衍生物、二苯并噻吩衍生物等含有硫属元素的化合物、羟基喹啉铍络合物等有机金属络合物等，若与基本上使用的掺杂剂相比而言，为三重态能量大，电子、空穴自各自的传输层顺利地注入且进行传输的，则并不限定于这些化合物。而且，也可含有2种以上的三重态发光掺杂剂，也可含有2种以上的主体材料。另外，也可含有1种以上的三重态发光掺杂剂与1种以上的荧光发光掺杂剂。Furthermore, a phosphorescent light-emitting material may also be contained in the light-emitting layer. A phosphorescent material is a material that exhibits phosphorescent emission even at room temperature. In the case of using a phosphorescent material as a dopant, it is basically necessary to obtain phosphorescent emission even at room temperature, and it is not particularly limited. It is preferable to contain a material selected from the group consisting of iridium (Ir), ruthenium (Ru), rhodium ( An organometallic complex compound of at least one metal from the group consisting of Rh), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re). Among them, organometallic complexes containing iridium or platinum are more preferable from the viewpoint of high phosphorescence yield even at room temperature. As a host used in combination with a phosphorescent dopant, indole derivatives, carbazole derivatives, indolecarbazole derivatives, nitrogen-containing aromatic compounds having a pyridine, pyrimidine, or triazine skeleton can be suitably derived. aromatic hydrocarbon compound derivatives such as polyarylbenzene derivatives, spirofluorene derivatives, truxene derivatives, triphenylene derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, etc. Chalcogen compounds, organometallic complexes such as hydroxyquinoline beryllium complexes, etc., have higher triplet energy than dopants basically used, and electrons and holes are transported from their respective transport layers. Those that are successfully injected and transported are not limited to these compounds. Furthermore, two or more types of triplet light-emitting dopants may be contained, and two or more types of host materials may be contained. In addition, one or more triplet light-emitting dopants and one or more fluorescent light-emitting dopants may be contained.
作为优选的磷光发光性主体或掺杂剂，并无特别限定，具体而言可列举如下所示的例子。There are no particular limitations on the preferred phosphorescent host or dopant, but specific examples include the following.
Figure PCTCN2022143372-appb-000016
Figure PCTCN2022143372-appb-000016
Figure PCTCN2022143372-appb-000017
Figure PCTCN2022143372-appb-000017
在本发明中，所谓电子传输层是自阴极注入电子，进一步传输电子的层。理想的电子传输层可以做到电子注入效率高且效率良好地传输所注入的电子。因此，电子传输层优选的是由具有如下性质的物质而构成：电子亲和力大，且电子迁移率大，另外稳定性优异，在制造时及使用时难以产生成为陷阱的杂质。然而，在考虑空穴与电子的传输平衡的情况下，电子传输层若主要起到可效率良好地对来自阳极的 空穴不再结合而流向阴极侧的情况进行阻止的作用，则即使由电子传输能力并不那么高的材料构成，使发光效率提高的效果也变得与由电子传输能力高的材料构成的情况同等。因此，本发明中的电子传输层也包含与可效率良好地阻止空穴迁移的空穴阻挡层同义的物质。In the present invention, the electron transport layer is a layer that injects electrons from the cathode and further transports electrons. An ideal electron transport layer can achieve high electron injection efficiency and efficiently transport the injected electrons. Therefore, the electron transport layer is preferably composed of a substance having a high electron affinity, a high electron mobility, excellent stability, and less generation of impurities that become traps during production and use. However, in consideration of the transport balance between holes and electrons, if the electron transport layer mainly plays the role of effectively preventing the holes from the anode from being recombined and flowing to the cathode side, even if the electrons are transported The composition of a material whose transport ability is not so high also has the same effect of improving the luminous efficiency as that of a material with a high electron transport ability. Therefore, the electron transport layer in the present invention also includes a substance synonymous with a hole blocking layer that can efficiently prevent hole migration.
电子传输层中所使用的电子传输材料可列举萘、蒽等缩合多环芳香族衍生物，以4，4′-双(二苯基乙烯基)联苯为代表的苯乙烯基系芳香环衍生物，蒽醌或联对苯醌等醌衍生物，氧化磷衍生物，三(8-羟基喹啉)铝(III)等羟基喹啉络合物、苯并羟基喹啉络合物、羟基唑络合物、偶氮次甲基络合物、托酚酮(tropolone)金属络合物及黄酮醇(flavonol)金属络合物等各种金属络合物，自减低驱动电压、获得高效率发光考虑，优选的是使用具有杂芳基环结构的化合物，上述杂芳基环结构由选自碳、氢、氮、氧、硅、磷中的元素构成，且包含电子接受性氮。The electron-transporting materials used in the electron-transporting layer include condensed polycyclic aromatic derivatives such as naphthalene and anthracene, and styryl-based aromatic ring derivatives represented by 4,4'-bis(diphenylvinyl)biphenyl. Quinone derivatives such as anthraquinone or di-p-benzoquinone, phosphorus oxide derivatives, hydroxyquinoline complexes such as tris(8-hydroxyquinoline)aluminum(III), benzohydroxyquinoline complexes, hydroxyquinoline complexes, oxazole Various metal complexes such as complexes, azomethine complexes, tropolone metal complexes and flavonol metal complexes can automatically reduce the driving voltage and obtain high-efficiency light emission Considering this, it is preferable to use a compound having a heteroaryl ring structure composed of an element selected from carbon, hydrogen, nitrogen, oxygen, silicon, and phosphorus and containing electron-accepting nitrogen.
包含电子接受性氮的芳香族杂环具有高的电子亲和性。具有电子接受性氮的电子传输材料容易接收来自具有高的电子亲和力的阴极的电子，可实现更低电压的驱动。另一方面，电子接受性氮的孤对电子对融入大Π键中后可以容纳更多的电子，提高电子传输的载量，提高电子传输能力。而且，向发光层的电子供给变多，再结合概率变高，因此发光效率提高。Aromatic heterocycles containing electron-accepting nitrogen have high electron affinity. An electron-transporting material having electron-accepting nitrogen can easily accept electrons from a cathode having a high electron affinity, and can drive at a lower voltage. On the other hand, the lone pair of electron-accepting nitrogen can accommodate more electrons after being integrated into the large Π bond, increasing the electron transport capacity and improving the electron transport capacity. Furthermore, electron supply to the light-emitting layer increases, and the probability of recombination becomes high, thereby improving luminous efficiency.
包含电子接受性氮的杂芳基环例如可列举吡啶环、吡嗪环、嘧啶环、喹啉环、喹噁啉环、萘啶环、嘧啶并嘧啶环、苯并喹啉环、菲咯啉环、咪唑环、噁唑环、噁二唑环、三唑环、噻唑环、噻二唑环、苯 并噁唑环、苯并噻唑环、苯并咪唑环、菲并咪唑环等。Examples of heteroaryl rings containing electron-accepting nitrogen include pyridine rings, pyrazine rings, pyrimidine rings, quinoline rings, quinoxaline rings, naphthyridine rings, pyrimidopyrimidine rings, benzoquinoline rings, and phenanthroline rings. ring, imidazole ring, oxazole ring, oxadiazole ring, triazole ring, thiazole ring, thiadiazole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, phenanthromidazole ring, etc.
具有这些杂芳基环结构的化合物例如可列举苯并咪唑衍生物、苯并噁唑衍生物、苯并噻唑衍生物、噁二唑衍生物、噻二唑衍生物、三唑衍生物、吡嗪衍生物、菲咯啉衍生物、喹噁啉衍生物、喹啉衍生物、苯并喹啉衍生物、联吡啶或三联吡啶等寡聚吡啶衍生物、喹噁啉衍生物及萘啶衍生物等作为优选的化合物。其中，自电子传输能力的观点考虑，可优选地使用三(N-苯基苯并咪唑-2-基)苯等咪唑衍生物、1，3-双[(4-第三丁基苯基)1，3，4-噁二唑基]苯等噁二唑衍生物、N-萘基-2，5-二苯基-1，3，4-三唑等三唑衍生物、浴铜灵(bathocuproine)或1，3-双(1，10-菲咯啉-9-基)苯等菲咯啉衍生物、2，2′-双(苯并[h]喹啉-2-基)-9，9′-螺二芴等苯并喹啉衍生物、2，5-双(6′-(2′，2″-联吡啶))-1，1-二甲基-3，4-二苯基硅杂环戊二烯等联吡啶衍生物、1，3-双(4′-(2，2′：6′2″-三联吡啶基))苯等三联吡啶衍生物、双(1-萘基)-4-(1，8-萘啶-2-基)苯基氧化膦等萘啶衍生物。而且，这些衍生物若具有缩合多环芳香族骨架，则玻璃转移温度提高，且电子迁移率也变大，且发光元件的低电压化效果大，因此更优选。另外，若考虑提高元件耐久寿命、合成的容易性、原料获得容易，则缩合多环芳香族骨架特别优选的是蒽骨架、芘骨架或菲咯啉骨架。上述电子传输材料可单独使用，也可将上述电子传输材料的2种以上混合使用、或者将其他电子传输材料的一种以上混合于上述电子传输材料中而使用。本发明的荧蒽衍生物也具有高的电子注入传输能力，因此可适宜地用作电子传输材料。Compounds having these heteroaryl ring structures include, for example, benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazine derivatives, Derivatives, phenanthroline derivatives, quinoxaline derivatives, quinoline derivatives, benzoquinoline derivatives, bipyridine or terpyridine and other oligopyridine derivatives, quinoxaline derivatives and naphthyridine derivatives, etc. as the preferred compound. Among them, from the viewpoint of electron transport capability, imidazole derivatives such as tris(N-phenylbenzimidazol-2-yl)benzene, 1,3-bis[(4-tert-butylphenyl) Oxadiazole derivatives such as 1,3,4-oxadiazolyl]benzene, triazole derivatives such as N-naphthyl-2,5-diphenyl-1,3,4-triazole, bathocuproine ( bathocuproine) or 1,3-bis(1,10-phenanthroline-9-yl)phenanthroline derivatives such as benzene, 2,2'-bis(benzo[h]quinolin-2-yl)-9 , benzoquinoline derivatives such as 9′-spirobifluorene, 2,5-bis(6′-(2′,2″-bipyridine))-1,1-dimethyl-3,4-diphenyl Bipyridine derivatives such as silacyclopentadiene, terpyridine derivatives such as 1,3-bis(4′-(2,2′:6′2″-terpyridyl))benzene, bis(1-naphthalene yl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide and other naphthyridine derivatives. Furthermore, if these derivatives have a condensed polycyclic aromatic skeleton, the glass transition temperature will increase, the electron mobility will also increase, and the effect of lowering the voltage of the light-emitting device will be large, so it is more preferable. In addition, in consideration of improvement in device durability, ease of synthesis, and ease of raw material acquisition, the condensed polycyclic aromatic skeleton is particularly preferably an anthracene skeleton, a pyrene skeleton, or a phenanthroline skeleton. The above electron transport materials may be used alone, or two or more of the above electron transport materials may be used in combination, or one or more of other electron transport materials may be mixed and used in the above electron transport materials. The fluoranthene derivatives of the present invention also have high electron injection and transport capabilities, and therefore can be suitably used as electron transport materials.
在使用本发明的荧蒽衍生物的情况下，无需限于其各一种，也可将本发明的多种荧蒽化合物混合使用，或者在不损及本发明的效果的范围内将其他电子传输材料的一种以上与本发明的荧蒽化合物混合使用。作为可混合的电子传输材料，并无特别限定，可列举具有萘、蒽、芘等缩合芳基环的化合物或其衍生物、以4，4′-双(二苯基乙烯基)联苯为代表的苯乙烯基系芳香环衍生物、苝衍生物、紫环酮衍生物、香豆素衍生物、萘二甲酰亚胺衍生物、蒽醌或联对苯醌等醌衍生物、氧化磷衍生物、咔唑衍生物及吲哚衍生物、三(8-羟基喹啉)铝(III)等羟基喹啉络合物或羟基苯基噁唑络合物等羟基唑络合物、偶氮次甲基络合物、托酚酮金属络合物及黄酮醇金属络合物。In the case of using the fluoranthene derivatives of the present invention, it is not necessary to be limited to each of them, and a plurality of fluoranthene compounds of the present invention may be mixed and used, or other electrons may be transported within the range that does not impair the effects of the present invention. One or more kinds of materials are used in combination with the fluoranthene compound of the present invention. The electron transport material that can be mixed is not particularly limited, and compounds having condensed aryl rings such as naphthalene, anthracene, and pyrene, or derivatives thereof, 4,4'-bis(diphenylvinyl)biphenyl Representative styryl-based aromatic ring derivatives, perylene derivatives, perylene derivatives, coumarin derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone or di-p-benzoquinone, phosphorus oxide Derivatives, carbazole derivatives and indole derivatives, hydroxyquinoline complexes such as tris(8-hydroxyquinoline)aluminum(III) or hydroxyazole complexes such as hydroxyphenyloxazole complexes, azo Methylene complexes, tropolone metal complexes and flavonol metal complexes.
上述电子传输材料可单独使用，但也可将上述电子传输材料的2种以上混合使用，或者将其他电子传输材料的一种以上混合于上述电子传输材料中而使用。而且，也可含有施体性材料。此处，所谓施体性材料是通过改善电子注入障壁，使自阴极或电子注入层向电子传输层的电子注入变容易，进一步使电子传输层的导电性提高的化合物。The above-mentioned electron transport materials may be used alone, but two or more of the above-mentioned electron-transport materials may be used in combination, or one or more of other electron-transport materials may be mixed and used in the above-mentioned electron-transport materials. Furthermore, a donor material may also be contained. Here, the so-called donor material is a compound that facilitates electron injection from the cathode or the electron injection layer to the electron transport layer by improving the electron injection barrier, and further improves the conductivity of the electron transport layer.
本发明中的施体性材料的优选例可列举碱金属、含有碱金属的无机盐、碱金属与有机物的络合物、碱土类金属、含有碱土类金属的无机盐或碱土类金属与有机物的络合物等。碱金属、碱土类金属的优选的种类可列举逸出功低且电子传输能力提高效果大的锂、钠、铯、镱等碱金属及其化合物或镁、钙等碱土类金属及其化合物。Preferable examples of the donor material in the present invention include alkali metals, inorganic salts containing alkali metals, complexes of alkali metals and organic substances, alkaline earth metals, inorganic salts containing alkaline earth metals, or complexes of alkaline earth metals and organic substances. complexes, etc. Preferable types of alkali metals and alkaline earth metals include alkali metals such as lithium, sodium, cesium, and ytterbium, and their compounds, and alkaline earth metals such as magnesium and calcium, which have a low work function and have a large effect of improving electron transport capability, and their compounds.
适宜的掺杂浓度因材料或掺杂区域的膜厚而不同，例如在施体性材料为碱金属、碱土类金属等无机材料的情况下，优选的是以电子传 输材料与施体性材料的蒸镀速度比成为10000∶1～2∶1的范围的方式进行共蒸镀而制成电子传输层。蒸镀速度比更优选的是100∶1～5∶1，进一步更优选的是100∶1～10∶1。而且，在施体性材料为金属与有机物的络合物的情况下，优选的是以电子传输材料与施体性材料的蒸镀速度比成为100∶1～1∶100的范围的方式进行共蒸镀而制成电子传输层。蒸镀速度比更优选的是10∶1～1∶10，进一步更优选的是7∶3～3∶7。The suitable doping concentration varies depending on the material or the film thickness of the doped region. For example, when the donor material is an inorganic material such as an alkali metal or an alkaline earth metal, it is preferable to use the ratio of the electron transport material and the donor material. Co-deposition was carried out so that the vapor deposition rate ratio was in the range of 10000:1 to 2:1 to form an electron transport layer. The vapor deposition rate ratio is more preferably 100:1 to 5:1, and still more preferably 100:1 to 10:1. Furthermore, when the donor material is a complex of a metal and an organic substance, it is preferable to perform co-deposition so that the vapor deposition rate ratio of the electron transport material and the donor material is in the range of 100:1 to 1:100. Evaporated to form an electron transport layer. The vapor deposition rate ratio is more preferably 10:1 to 1:10, and still more preferably 7:3 to 3:7.
而且，在如上所述的本发明的荧蒽衍生物中掺杂有施体性材料的电子传输层可用作连结多个发光元件的串联结构型元件中的电荷产生层。Furthermore, an electron transport layer doped with a donor material in the fluoranthene derivative of the present invention as described above can be used as a charge generation layer in a tandem structure type element in which a plurality of light emitting elements are connected.
在电子传输层中掺杂施体性材料而使电子传输能力提高的方法在薄膜层的膜厚较厚的情况下特别发挥出效果。在电子传输层及发光层的合计膜厚为50nm以上的情况下可特别优选地使用。例如存在有为了使发光效率提高而利用干涉效应的方法，其是使自发光层直接放射的光与被阴极反射的光的相位对准而使光的出射效率提高的方法。其最佳条件根据光的发光波长而变化，在电子传输层及发光层的合计膜厚成为50nm以上，且为红色等长波长发光的情况下，存在成为接近100nm的厚膜的情况。The method of doping the electron transport layer with a donor material to improve the electron transport capability is particularly effective when the film thickness of the thin film layer is thick. It can be used especially preferably when the total film thickness of an electron transport layer and a light emitting layer is 50 nm or more. For example, there is a method of utilizing an interference effect in order to improve luminous efficiency, which is a method of improving light emission efficiency by aligning the phases of light directly emitted from the light emitting layer and light reflected by the cathode. The optimum conditions vary depending on the emission wavelength of light, and when the total film thickness of the electron transport layer and the emission layer is 50 nm or more and long-wavelength emission such as red is emitted, it may be a thick film close to 100 nm.
进行掺杂的电子传输层的膜厚可为电子传输层的一部分或全部的任意的。在对一部分进行掺杂的情况下，理想的是至少在电子传输层/阴极界面设置掺杂区域，即使仅仅在阴极界面附近进行掺杂也可获得低电压化的效果。另一方面，若施体性材料直接与发光层相接， 则存在产生使发光效率降低的不良影响的情况，在这种情况下，优选的是在发光层/电子传输层界面设置未掺杂区域。The film thickness of the electron-transporting layer to be doped may be arbitrary for a part or the whole of the electron-transporting layer. In the case of partially doping, it is desirable to provide a doped region at least at the electron transport layer/cathode interface, and even if doping is performed only in the vicinity of the cathode interface, the effect of lowering the voltage can be obtained. On the other hand, if the donor material is directly in contact with the light-emitting layer, there may be adverse effects that reduce the luminous efficiency. In this case, it is preferable to set an undoped area.
在本发明中，也可在阴极与电子传输层之间设置电子注入层。一般情况下，以有助于自阴极向电子传输层注入电子的目的而插入电子注入层，在插入的情况下，可使用具有包含电子接受性氮的杂芳基环结构的化合物，也可使用含有上述施体性材料的层。电子注入层中也可包含本发明的荧蒽衍生物。而且，在电子注入层中也可使用绝缘体或半导体的无机物，或者金属。通过使用这些材料，可有效地防止发光元件的短路，且可使电子注入性提高，因此优选。此种绝缘体优选的是使用选自由碱金属硫属化合物、碱土类金属硫属化合物、碱金属的卤化物及碱土类金属的卤化物所构成的群组的至少一种金属化合物。电子注入层若由这些碱金属硫属化合物等而构成，则就可使电子注入性进一步提高的方面而言更优选。具体而言，优选的碱金属硫属化合物，例如可列举Li 2O、Na 2S及Na 2Se，优选的碱土类金属硫属化合物例如可列举CaO、BaO、SrO、BeO、BaS及CaSe。而且，优选的碱金属的卤化物例如可列举LiF、NaF、KF、LiCl、KCl及NaCl等。而且，优选的碱土类金属的卤化物例如可列举CaF 2、BaF 2、SrF 2、MgF 2及BeF 2等氟化物或氟化物以外的卤化物。也可适宜地使用有机物与金属的络合物。在电子注入层中使用有机物与金属的络合物的情况下，容易调整膜厚，因此更优选。至于此种有机金属络合物的例子，作为与有机物的络合物中的有机物的优选例可列举羟基喹啉、苯并羟基喹啉、吡啶基苯酚、黄酮醇、羟基咪唑并吡啶、羟基氮茚、羟基三唑等。 另外，也可以使用金属，例如可列举Li,Yb,Ba等。 In the present invention, an electron injection layer may also be provided between the cathode and the electron transport layer. Generally, the electron injection layer is inserted for the purpose of facilitating electron injection from the cathode to the electron transport layer. In the case of insertion, a compound having a heteroaryl ring structure containing electron-accepting nitrogen can be used, or A layer comprising the above-mentioned donor material. The fluoranthene derivative of the present invention may also be contained in the electron injection layer. Furthermore, an insulator or semiconductor inorganic substance, or a metal may be used for the electron injection layer. By using these materials, it is possible to effectively prevent short-circuiting of the light-emitting element and improve the electron injection property, which is preferable. Such an insulator preferably uses at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides. If the electron injection layer is composed of these alkali metal chalcogen compounds, etc., it is more preferable at the point that the electron injection property can be further improved. Specifically, preferable alkali metal chalcogen compounds include Li 2 O, Na 2 S and Na 2 Se, and preferable alkaline earth metal chalcogen compounds include CaO, BaO, SrO, BeO, BaS and CaSe. Furthermore, examples of preferable alkali metal halides include LiF, NaF, KF, LiCl, KCl, and NaCl. Further, preferable halides of alkaline earth metals include, for example, fluorides such as CaF 2 , BaF 2 , SrF 2 , MgF 2 , and BeF 2 , or halides other than fluorides. Complexes of organic substances and metals can also be suitably used. It is more preferable to use a complex of an organic substance and a metal for the electron injection layer because it is easy to adjust the film thickness. As examples of such organometallic complexes, preferred examples of organic substances in complexes with organic substances include hydroxyquinoline, benzohydroxyquinoline, pyridylphenol, flavonol, hydroxyimidazopyridine, hydroxynitrogen Indene, Hydroxytriazole, etc. In addition, metals can also be used, for example, Li, Yb, Ba, etc. are mentioned.
构成发光元件的上述各层的形成方法为电阻加热蒸镀、电子束蒸镀、溅镀、分子层叠法、涂布法等，并无特别限定，通常自元件特性的方面考虑，优选的是电阻加热蒸镀或电子束蒸镀。The formation method of the above-mentioned layers constituting the light-emitting element is resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, coating method, etc., and is not particularly limited. Usually, from the aspect of element characteristics, resistance Thermal evaporation or electron beam evaporation.
有机层的厚度由发光物质的电阻值而定，因此无法进行限定，优选的是1nm～1000nm。发光层、电子传输层、空穴传输层的膜厚分别优选的是1nm以上、200nm以下，更优选的是5nm以上、100nm以下。The thickness of the organic layer is determined by the resistance value of the luminescent material, so it cannot be limited, but is preferably 1 nm to 1000 nm. The film thicknesses of the light-emitting layer, the electron transport layer, and the hole transport layer are preferably 1 nm to 200 nm, more preferably 5 nm to 100 nm.
本发明的发光元件具有可将电能转换为光的功能。此处，电能主要使用直流电流，也可使用脉冲电流或交流电流。电流值及电压值并无特别限制，若考虑元件的电力消耗或寿命，则应以利用尽可能低的能量获得最大亮度的方式进行选择。The light-emitting element of the present invention has the function of converting electrical energy into light. Here, direct current is mainly used for electric energy, but pulse current or alternating current may also be used. The current value and voltage value are not particularly limited, and should be selected in such a way as to obtain the maximum brightness with the lowest possible energy in consideration of the power consumption and lifetime of the device.
本发明的发光元件也可优选地用作各种设备等的背光。背光主要是用以提高并不自发光的显示装置的可见性，在液晶显示装置、时钟、声频装置、汽车面板、显示板及标识等中使用。特别是在液晶显示装置(其中特别是对薄型化进行了研究的个人计算机用途)的背光中优选地使用本发明的发光元件，可提供较现有的背光更薄型、轻量的背光。The light-emitting element of the present invention can also be preferably used as a backlight for various devices and the like. Backlights are mainly used to improve the visibility of display devices that do not emit light by themselves, and are used in liquid crystal display devices, clocks, audio devices, automotive panels, display panels, and signs. In particular, the light-emitting element of the present invention is preferably used in a backlight of a liquid crystal display device (in particular, a personal computer application in which thickness reduction has been studied), and a thinner and lighter backlight than conventional backlights can be provided.
[实施例][Example]
以下，列举实施例对本发明加以说明，但本发明并不限定于这些实施例。Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to these Examples.
实施例与对比例中所使用的材料如下所示：The materials used in Examples and Comparative Examples are as follows:
甲苯、二甲苯、甲醇等购于国药公司；三嗪类化合物购于TCI； 荧蒽类化合物购于alfa-aeser；各种催化剂等购于Aldrich公司。Toluene, xylene, methanol, etc. were purchased from Sinopharm; triazine compounds were purchased from TCI; fluoranthene compounds were purchased from alfa-aeser; various catalysts were purchased from Aldrich Company.
合成例1Synthesis Example 1
化合物[6]的合成Synthesis of Compound [6]
Figure PCTCN2022143372-appb-000018
Figure PCTCN2022143372-appb-000018
将2-氯-4,6-二苯基-1,3,5-三嗪2.67g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-(4-氯苯基)-4,6-二苯基-1,3,5-三嗪3.5g。Add 2.67g of 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, and 3.60g of potassium carbonate into the flask , replaced with argon three times and then injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5- Triazine 3.5g.
将2-(4-氯苯基)-4,6-二苯基-1,3,5-三嗪3.5g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应7小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯100ml重结晶，得到黄色固体化合物[6]4.68g(纯度99.9％)。3.5g of 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine, 2.2g of fluoranthene boronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, potassium carbonate 3.6 g was added to the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 7 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 100 ml of o-xylene to obtain 4.68 g of yellow solid compound [6] (purity 99.9%).
合成例2Synthesis example 2
化合物[7]的合成Synthesis of Compound [7]
Figure PCTCN2022143372-appb-000019
Figure PCTCN2022143372-appb-000019
将2-(4-对联苯基)-4,6-二氯-1,3,5-三嗪3.00g，盐酸活性化后的镁块0.24g，放入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯，并搅拌20分钟。加入用甲苯溶解的溴苯1.22g，并升温至120℃。4小时后冷却至室温后，加入冷水淬灭反应。之后用甲苯萃取反应物，再用水萃取反应物中的盐。将有机相旋干后得到固体。使用硅胶柱分离(PE：EA＝1：10)得到3.2g的白色固体2-(4-对联苯基)-4-氯-6-苯基-1,3,5三嗪。Put 3.00g of 2-(4-p-biphenyl)-4,6-dichloro-1,3,5-triazine and 0.24g of magnesium block activated by hydrochloric acid into the flask, and replace it with argon three times Dehydrated and deoxygenated toluene was injected and stirred for 20 minutes. 1.22 g of bromobenzene dissolved in toluene was added, and the temperature was raised to 120°C. After cooling to room temperature after 4 hours, cold water was added to quench the reaction. Then the reactant was extracted with toluene, and the salt in the reactant was extracted with water. The organic phase was spin-dried to give a solid. A silica gel column separation (PE:EA=1:10) was used to obtain 3.2 g of white solid 2-(4-p-biphenyl)-4-chloro-6-phenyl-1,3,5-triazine.
将2-(4-对联苯基)-4-氯-6-苯基-1,3,5三嗪3.2g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应3小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯100ml重结晶，得到白色固体2-(4-对联苯基)-4-(4-氯苯基)-6-苯基-1,3,5三嗪3.82g。3.2g of 2-(4-p-biphenyl)-4-chloro-6-phenyl-1,3,5 triazine, 1.56g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, carbonic acid Add 3.60 g of potassium into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 3 hours. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 100ml of o-xylene to obtain a white solid 2-(4-p-biphenyl)-4-(4-chlorophenyl)-6-phenyl -1,3,5 Triazine 3.82g.
将2-(4-对联苯基)-4-(4-氯苯基)-6-苯基-1,3,5三嗪3.82g，荧蒽硼酸2.3g，二三苯基膦二氯化钯0.12g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和50ml甲醇分别清洗3次，使用邻二甲苯100ml重结晶，得到淡黄色固体化合物[7]5.21g(纯度 99.9％)。2-(4-p-biphenyl)-4-(4-chlorophenyl)-6-phenyl-1,3,5 triazine 3.82g, fluoranthene boronic acid 2.3g, ditriphenylphosphine dichloride 0.12 g of palladium and 3.6 g of potassium carbonate were added to the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 50 ml of methanol, and recrystallized with 100 ml of o-xylene to obtain 5.21 g of light yellow solid compound [7] (purity 99.9%).
合成例3Synthesis example 3
化合物[8]的合成Synthesis of compound [8]
Figure PCTCN2022143372-appb-000020
Figure PCTCN2022143372-appb-000020
将2-(4-联苯基)-4,6-二氯-1,3,5-三嗪3.00g，盐酸活性化后的镁块0.24g，放入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯，并搅拌20分钟。加入用甲苯溶解的溴苯1.22g，并升温至120℃。4小时后冷却至室温后，加入冷水淬灭反应。之后用甲苯萃取反应物，再用水萃取反应物中的盐。将有机相旋干后得到固体。使用硅胶柱分离(PE：EA＝1：10)得到3.2g的白色固体2-(4-联苯基)-4-氯-6-苯基-1,3,5三嗪。Put 3.00 g of 2-(4-biphenyl)-4,6-dichloro-1,3,5-triazine and 0.24 g of magnesium block activated by hydrochloric acid into the flask, and replace it with argon three times Dehydrated and deoxygenated toluene was injected and stirred for 20 minutes. 1.22 g of bromobenzene dissolved in toluene was added, and the temperature was raised to 120°C. After cooling to room temperature after 4 hours, cold water was added to quench the reaction. Then the reactant was extracted with toluene, and the salt in the reactant was extracted with water. The organic phase was spin-dried to give a solid. Silica gel column separation (PE:EA=1:10) was used to obtain 3.2 g of white solid 2-(4-biphenyl)-4-chloro-6-phenyl-1,3,5-triazine.
将2-(4-联苯基)-4-氯-6-苯基-1,3,5三嗪3.2g，间氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应3小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯80ml重结晶，得到白色固体2-(4-联苯基)-4-(3-氯苯基)-6-苯基-1,3,5三嗪3.78g。3.2g of 2-(4-biphenyl)-4-chloro-6-phenyl-1,3,5 triazine, 1.56g of m-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, carbonic acid Add 3.60 g of potassium into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 3 hours. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 80ml of o-xylene to obtain a white solid 2-(4-biphenyl)-4-(3-chlorophenyl)-6-phenyl -1,3,5 Triazine 3.78g.
将2-(4-联苯基)-4-(3-氯苯基)-6-苯基-1,3,5三嗪3.78g，荧 蒽硼酸2.3g，二三苯基膦二氯化钯0.12g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和50ml甲醇分别清洗3次，使用邻二甲苯80ml重结晶，得到淡黄色固体化合物[8]5.00g(纯度99.9％)。2-(4-biphenyl)-4-(3-chlorophenyl)-6-phenyl-1,3,5 triazine 3.78g, fluoranthene boronic acid 2.3g, ditriphenylphosphine dichloride 0.12 g of palladium and 3.6 g of potassium carbonate were added to the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 50 ml of methanol, and recrystallized with 80 ml of o-xylene to obtain 5.00 g of light yellow solid compound [8] (purity 99.9%).
合成例4Synthesis Example 4
化合物[9]的合成Synthesis of Compound [9]
Figure PCTCN2022143372-appb-000021
Figure PCTCN2022143372-appb-000021
将2-苯基-4,6-二氯-1,3,5-三嗪2.55g，盐酸活性化后的镁块0.24g，放入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯，并搅拌20分钟。加入用甲苯溶解的间溴联苯2.00g，并升温至120℃。4小时后冷却至室温后，加入冷水淬灭反应。之后用甲苯萃取反应物，再用水萃取反应物中的盐。将有机相旋干后得到固体。使用硅胶柱分离(PE：EA＝1：10)得到3.1g的白色固体2-(4-苯基)-4-氯-6-间联苯基-1,3,5三嗪。Put 2.55g of 2-phenyl-4,6-dichloro-1,3,5-triazine and 0.24g of magnesium block activated by hydrochloric acid into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene , and stirred for 20 minutes. 2.00 g of m-bromobiphenyl dissolved in toluene was added, and the temperature was raised to 120°C. After cooling to room temperature after 4 hours, cold water was added to quench the reaction. Then the reactant was extracted with toluene, and the salt in the reactant was extracted with water. The organic phase was spin-dried to give a solid. A silica gel column separation (PE:EA=1:10) was used to obtain 3.1 g of white solid 2-(4-phenyl)-4-chloro-6-m-biphenyl-1,3,5-triazine.
将2-(4-苯基)-4-氯-6-间联苯基-1,3,5三嗪三嗪3.1g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应3小时。 降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯100ml重结晶，得到白色固体2-(4-苯基)-4-(4-氯苯基)-6-间联苯基-1,3,5三嗪3.75g。3.1 g of 2-(4-phenyl)-4-chloro-6-m-biphenyl-1,3,5 triazine triazine, 1.56 g of p-chlorophenylboronic acid, and 0.06 g of ditriphenylphosphine palladium dichloride g, 3.60 g of potassium carbonate was added into the flask, replaced with argon for three times, and injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 3 hours. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 100ml of o-xylene to obtain a white solid 2-(4-phenyl)-4-(4-chlorophenyl)-6-m-diphenyl Base-1,3,5 triazine 3.75g.
将2-(4-苯基)-4-(4-氯苯基)-6-间联苯基-1,3,5三嗪3.75g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯100ml重结晶，得到淡黄色固体化合物[9]4.94g(纯度99.9％)。2-(4-phenyl)-4-(4-chlorophenyl)-6-biphenyl-1,3,5 triazine 3.75g, fluoranthene boronic acid 2.2g, ditriphenylphosphine dichloro Add 0.06 g of palladium chloride and 3.6 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 100 ml of o-xylene to obtain 4.94 g of light yellow solid compound [9] (purity 99.9%).
合成例5Synthesis Example 5
化合物[10]的合成Synthesis of compound [10]
Figure PCTCN2022143372-appb-000022
Figure PCTCN2022143372-appb-000022
将2-苯基-4,6-二氯-1,3,5-三嗪2.55g，盐酸活性化后的镁块0.24g，放入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯，并搅拌20分钟。加入用甲苯溶解的间溴联苯2.00g，并升温至120℃。4小时后冷却至室温后，加入冷水淬灭反应。之后用甲苯萃取反应物，再用水萃取反应物中的盐。将有机相旋干后得到固体。使用硅胶柱分离(PE：EA＝1：10)得到3.1g的白色固体2-(4-苯基)-4-氯-6-间联 苯基-1,3,5三嗪。Put 2.55g of 2-phenyl-4,6-dichloro-1,3,5-triazine and 0.24g of magnesium block activated by hydrochloric acid into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene , and stirred for 20 minutes. 2.00 g of m-bromobiphenyl dissolved in toluene was added, and the temperature was raised to 120°C. After cooling to room temperature after 4 hours, cold water was added to quench the reaction. Then the reactant was extracted with toluene, and the salt in the reactant was extracted with water. The organic phase was spin-dried to give a solid. Separation on a silica gel column (PE:EA=1:10) gave 3.1 g of white solid 2-(4-phenyl)-4-chloro-6-m-biphenyl-1,3,5-triazine.
将2-(4-苯基)-4-氯-6-间联苯基-1,3,5三嗪三嗪3.1g，间氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应3小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯80ml重结晶，得到白色固体2-(4-苯基)-4-(3-氯苯基)-6-间联苯基-1,3,5三嗪3.83g。2-(4-phenyl)-4-chloro-6-m-biphenyl-1,3,5 triazine triazine 3.1g, m-chlorophenylboronic acid 1.56g, ditriphenylphosphine palladium dichloride 0.06 g, 3.60 g of potassium carbonate was added into the flask, replaced with argon for three times, and injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 3 hours. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 80ml of o-xylene to obtain a white solid 2-(4-phenyl)-4-(3-chlorophenyl)-6-m-biphenyl Base-1,3,5 triazine 3.83g.
将2-(4-苯基)-4-(3-氯苯基)-6-间联苯基-1,3,5三嗪3.83g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应8小时。降至室温后旋干溶剂，用100ml水和50ml甲醇分别清洗3次，使用邻二甲苯80ml重结晶，得到淡黄色固体化合物[10]5.11g(纯度99.9％)。2-(4-phenyl)-4-(3-chlorophenyl)-6-biphenyl-1,3,5 triazine 3.83g, fluoranthene boronic acid 2.2g, ditriphenylphosphine dichloro Add 0.06 g of palladium chloride and 3.6 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 8 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 50 ml of methanol, and recrystallized with 80 ml of o-xylene to obtain 5.11 g of light yellow solid compound [10] (purity 99.9%).
合成例6Synthesis Example 6
化合物[18]的合成Synthesis of compound [18]
Figure PCTCN2022143372-appb-000023
Figure PCTCN2022143372-appb-000023
将2-氯-4,6-二苯基-1,3,5-三嗪2.67g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-(4-氯苯基)-4,6-二苯基-1,3,5-三嗪3.5g。Add 2.67g of 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, and 3.60g of potassium carbonate into the flask , replaced with argon three times and then injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5- Triazine 3.5g.
将2-(4-氯苯基)-4,6-二苯基-1,3,5-三嗪3.5g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-4’-(4,6-二苯基-1,3,5-三嗪基)联苯4.1g。3.5g of 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine, 1.56g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, carbonic acid Add 3.60 g of potassium into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 4-chloro-4'-(4,6-diphenyl-1,3,5-triazine base) biphenyl 4.1g.
将4-氯-4’-(4,6-二苯基-1,3,5-三嗪基)联苯4.1g，荧蒽硼酸2.1g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。 降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[18]5.82g(纯度99.9％)。4.1g of 4-chloro-4'-(4,6-diphenyl-1,3,5-triazinyl)biphenyl, 2.1g of fluoranthene boronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.6 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 5.82 g of light yellow solid compound [18] (purity 99.9%).
合成例7Synthesis Example 7
化合物[22]的合成Synthesis of compound [22]
Figure PCTCN2022143372-appb-000024
Figure PCTCN2022143372-appb-000024
将2-氯-4,6-二苯基-1,3,5-三嗪2.67g，2-二苯并呋喃硼酸2.12g，二三苯基膦二氯化钯0.06g，碳酸钾5.20g加入烧瓶中，用氩气置换三次后注入脱水脱氧的二甲苯。冰水反应1小时。升至室温后继续反应3小时。然后旋干溶剂，用100ml水清洗3次，使用邻二甲苯100ml重结晶，得到白色固体2-(4,6-二苯基-1,3,5-三嗪基)-二苯并呋喃3.8g。2.67g of 2-chloro-4,6-diphenyl-1,3,5-triazine, 2.12g of 2-dibenzofuran boronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, and 5.20g of potassium carbonate Add to the flask, replace with argon three times, and inject dehydrated and deoxygenated xylene. Ice water was reacted for 1 hour. After rising to room temperature, the reaction was continued for 3 hours. Then the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 100ml of o-xylene to obtain a white solid 2-(4,6-diphenyl-1,3,5-triazinyl)-dibenzofuran 3.8 g.
将2-(4,6-二苯基-1,3,5-三嗪基)-二苯并呋喃3.8g，N-溴代琥珀酰亚胺3.4g，三水合磷酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋 干溶剂，使用硅胶柱分离(PE：EA＝1：20)得到4.2g的白色固体2-(4,6-二苯基-1,3,5-三嗪基)-8-溴二苯并呋喃。Add 3.8g of 2-(4,6-diphenyl-1,3,5-triazinyl)-dibenzofuran, 3.4g of N-bromosuccinimide, and 3.60g of potassium phosphate trihydrate into the flask , replaced with argon three times and then injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried and separated on a silica gel column (PE:EA=1:20) to obtain 4.2 g of white solid 2-(4,6-diphenyl-1,3,5-triazinyl)-8 -Bromodibenzofuran.
将2-(4,6-二苯基-1,3,5-三嗪基)-8-溴二苯并呋喃4.2g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的二甲苯。升温至150℃后反应12小时。降至室温后旋干溶剂，用100ml水和200ml甲醇分别清洗3次，使用邻二甲苯100ml重结晶，得到淡黄色固体化合物[22]5.13g(纯度99.9％)。4.2g of 2-(4,6-diphenyl-1,3,5-triazinyl)-8-bromodibenzofuran, 2.2g of fluoranthene boronic acid, and 0.06g of ditriphenylphosphinepalladium dichloride , Potassium carbonate 3.6g was added in the flask, replaced with argon three times and then injected with dehydrated and deoxygenated xylene. After heating up to 150°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 200 ml of methanol, and recrystallized with 100 ml of o-xylene to obtain 5.13 g of light yellow solid compound [22] (purity 99.9%).
合成例8Synthesis Example 8
化合物[25]的合成Synthesis of compound [25]
Figure PCTCN2022143372-appb-000025
Figure PCTCN2022143372-appb-000025
将2-氯-4,6-二苯基嘧啶2.64g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶 剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-(4-氯苯基)-4,6-二苯基嘧啶3.4g。Put 2.64g of 2-chloro-4,6-diphenylpyrimidine, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphine palladium dichloride, and 3.60g of potassium carbonate into the flask, replace it with argon three times, and inject Dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain 3.4g of white solid 2-(4-chlorophenyl)-4,6-diphenylpyrimidine.
将2-(4-氯苯基)-4,6-二苯基嘧啶3.4g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-4’-(4,6-二苯基嘧啶)联苯4.0g。Add 3.4g of 2-(4-chlorophenyl)-4,6-diphenylpyrimidine, 1.56g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, and 3.60g of potassium carbonate into the flask, and use After argon replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain 4.0g of white solid 4-chloro-4'-(4,6-diphenylpyrimidine)biphenyl.
将4-氯-4’-(4,6-二苯基嘧啶)联苯4.0g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[25]5.90g(纯度99.9％)。Add 4.0 g of 4-chloro-4'-(4,6-diphenylpyrimidine) biphenyl, 2.2 g of fluoranthene boronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.6 g of potassium carbonate into the flask, and use After argon replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 5.90 g of light yellow solid compound [25] (purity 99.9%).
合成例9Synthesis Example 9
化合物[26]的合成Synthesis of compound [26]
Figure PCTCN2022143372-appb-000026
Figure PCTCN2022143372-appb-000026
将4-氯-2,6-二苯基嘧啶2.64g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体4-(4-氯苯基)-2,6-二苯基嘧啶3.4g。Put 2.64g of 4-chloro-2,6-diphenylpyrimidine, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphine palladium dichloride, and 3.60g of potassium carbonate into the flask, replace it with argon three times, and inject Dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water, and recrystallized using 50 ml of o-xylene to obtain 3.4 g of white solid 4-(4-chlorophenyl)-2,6-diphenylpyrimidine.
将4-(4-氯苯基)-2,6-二苯基嘧啶3.4g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-4’-(2,6-二苯基嘧啶)联苯4.0g。Add 3.4g of 4-(4-chlorophenyl)-2,6-diphenylpyrimidine, 1.56g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, and 3.60g of potassium carbonate into the flask, and use After argon replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain 4.0g of white solid 4-chloro-4'-(2,6-diphenylpyrimidine)biphenyl.
将4-氯-4’-(2,6-二苯基嘧啶)联苯4.0g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[26]5.90g(纯度99.9％)。Add 4.0 g of 4-chloro-4'-(2,6-diphenylpyrimidine) biphenyl, 2.2 g of fluoranthene boronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.6 g of potassium carbonate into the flask, and use After argon replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 5.90 g of light yellow solid compound [26] (purity 99.9%).
合成例10Synthesis Example 10
化合物[28]的合成Synthesis of compound [28]
Figure PCTCN2022143372-appb-000027
Figure PCTCN2022143372-appb-000027
将2，6-二苯基-4氯吡啶2.9g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗2次，得到白色固体4-(2，6-二苯基吡啶基)氯苯3.4g。Put 2.9g of 2,6-diphenyl-4-chloropyridine, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphine palladium dichloride, and 3.60g of potassium carbonate into the flask, replace it with argon three times, and inject it into the flask for dehydration Deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried and washed twice with 100 ml of water to obtain 3.4 g of white solid 4-(2,6-diphenylpyridyl)chlorobenzene.
将4-(2，6-二苯基吡啶基)氯苯3.4g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，用100ml甲醇清洗3次，得到白色固体4-氯-4’-(2，6-二苯基吡啶基)联苯4.0g。Put 3.4g of 4-(2,6-diphenylpyridyl)chlorobenzene, 1.56g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphine palladium dichloride, and 3.60g of potassium carbonate into the flask, and replace with argon Dehydrated and deoxygenated toluene was injected three times later. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and washed 3 times with 100ml of methanol to obtain 4.0g of white solid 4-chloro-4'-(2,6-diphenylpyridyl)biphenyl.
将4-氯-4’-(2，6-二苯基吡啶基)联苯4.0g，荧蒽硼酸2.1g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应4小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯 100ml重结晶，得到淡黄色固体化合物[28]5.45g(纯度99.9％)。Add 4.0 g of 4-chloro-4'-(2,6-diphenylpyridyl) biphenyl, 2.1 g of fluoranthene boronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.6 g of potassium carbonate into the flask, After replacing with argon three times, dehydrated and deoxygenated toluene was injected. After heating up to 120° C., the reaction was carried out for 4 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water and 100ml of methanol, and recrystallized using 100ml of o-xylene to obtain 5.45g of light yellow solid compound [28] (purity 99.9%).
合成例11Synthesis Example 11
化合物[30]的合成Synthesis of compound [30]
Figure PCTCN2022143372-appb-000028
Figure PCTCN2022143372-appb-000028
将2-([1,1'-联苯]-4-基)-4-氯-6-苯基嘧啶3.67g，间氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-([1,1'-联苯]-4-基)-4-(3-氯苯基)-6-苯基嘧啶4.60g。3.67g of 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenylpyrimidine, 1.22g of m-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 2-([1,1'-biphenyl]-4-yl)-4-(3-chloro Phenyl)-6-phenylpyrimidine 4.60g.
将2-([1,1'-联苯]-4-基)-4-(3-氯苯基)-6-苯基嘧啶4.6g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反 应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-3’-(2-苯基-[1,1'-联苯]-4-基-嘧啶)联苯4.8g。4.6g of 2-([1,1'-biphenyl]-4-yl)-4-(3-chlorophenyl)-6-phenylpyrimidine, 1.56g of p-chlorophenylboronic acid, ditriphenylphosphine di Add 0.06 g of palladium chloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After raising the temperature to 120°C, the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 4-chloro-3'-(2-phenyl-[1,1'-biphenyl]-4 -yl-pyrimidine)biphenyl 4.8g.
将4-氯-3’-(2-苯基-[1,1'-联苯]-4-基-嘧啶)联苯4.8g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[30]6.10g(纯度99.9％)。4.8g of 4-chloro-3'-(2-phenyl-[1,1'-biphenyl]-4-yl-pyrimidine)biphenyl, 2.2g of fluoranthene boronic acid, ditriphenylphosphine palladium dichloride 0.06g and 3.6g of potassium carbonate were added into the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 6.10 g of light yellow solid compound [30] (purity 99.9%).
合成例12Synthesis Example 12
化合物[37]的合成Synthesis of compound [37]
Figure PCTCN2022143372-appb-000029
Figure PCTCN2022143372-appb-000029
将2-苯基-4,6-二氯-1,3,5-三嗪2.55g，盐酸活性化后的镁块0.24g，放入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯，并搅 拌20分钟。加入用甲苯溶解的间溴联苯2.00g，并升温至120℃。4小时后冷却至室温后，加入冷水淬灭反应。之后用甲苯萃取反应物，再用水萃取反应物中的盐。将有机相旋干后得到固体。使用硅胶柱分离(PE：EA＝1：10)得到3.1g的白色固体2-(4-苯基)-4-氯-6-间联苯基-1,3,5三嗪。Put 2.55g of 2-phenyl-4,6-dichloro-1,3,5-triazine and 0.24g of magnesium block activated by hydrochloric acid into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene , and stirred for 20 minutes. 2.00 g of m-bromobiphenyl dissolved in toluene was added, and the temperature was raised to 120°C. After cooling to room temperature after 4 hours, cold water was added to quench the reaction. Then the reactant was extracted with toluene, and the salt in the reactant was extracted with water. The organic phase was spin-dried to give a solid. A silica gel column separation (PE:EA=1:10) was used to obtain 3.1 g of white solid 2-(4-phenyl)-4-chloro-6-m-biphenyl-1,3,5-triazine.
将2-(4-苯基)-4-氯-6-间联苯基-1,3,5三嗪3.1g，间氯苯硼酸1.21g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-(3-氯苯基)-4苯基-6-间联苯基-1,3,5-三嗪3.9g。3.1g of 2-(4-phenyl)-4-chloro-6-m-biphenyl-1,3,5-triazine, 1.21g of m-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 2-(3-chlorophenyl)-4-phenyl-6-m-biphenyl-1,3 , 3.9 g of 5-triazine.
将2-(3-氯苯基)-4苯基-6-间联苯基-1,3,5-三嗪3.9g，间氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应2小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体3-氯-3’-(4-苯基-6-间联苯基-1,3,5-三嗪基)联苯5.0g。3.9 g of 2-(3-chlorophenyl)-4-phenyl-6-m-biphenyl-1,3,5-triazine, 1.56 g of m-chlorophenylboronic acid, and 0.06 g of ditriphenylphosphine palladium dichloride g, 3.60 g of potassium carbonate was added into the flask, replaced with argon for three times, and injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 2 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 3-chloro-3'-(4-phenyl-6-m-biphenyl-1,3, 5-triazinyl)biphenyl 5.0g.
将3-氯-3’-(4苯基-6-间联苯基-1,3,5-三嗪基)联苯5.0g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应2小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯100ml重结晶，得到淡黄色固体化合物[37]6.3g(纯度 99.9％)。5.0 g of 3-chloro-3'-(4-phenyl-6-m-biphenyl-1,3,5-triazinyl)biphenyl, 2.2 g of fluoranthene boronic acid, ditriphenylphosphine palladium dichloride 0.06g and 3.6g of potassium carbonate were added into the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 2 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water and 100ml of methanol, and recrystallized with 100ml of o-xylene to obtain 6.3g of light yellow solid compound [37] (purity 99.9%).
合成例13Synthesis Example 13
化合物[38]的合成Synthesis of compound [38]
Figure PCTCN2022143372-appb-000030
Figure PCTCN2022143372-appb-000030
将4-氯-2,6-二苯基嘧啶2.64g，间氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体4-(3-氯苯基)-2,6-二苯基嘧啶3.4g。Put 2.64g of 4-chloro-2,6-diphenylpyrimidine, 1.22g of m-chlorophenylboronic acid, 0.06g of ditriphenylphosphine palladium dichloride, and 3.60g of potassium carbonate into the flask, replace it with argon three times, and inject Dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water, and recrystallized using 50 ml of o-xylene to obtain 3.4 g of white solid 4-(3-chlorophenyl)-2,6-diphenylpyrimidine.
将4-(3-氯苯基)-2,6-二苯基嘧啶3.4g，间氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体3-氯-3’-(2,6-二苯基嘧啶)联苯4.0g。Add 3.4g of 4-(3-chlorophenyl)-2,6-diphenylpyrimidine, 1.56g of m-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, and 3.60g of potassium carbonate into the flask, and use After argon replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain 4.0g of white solid 3-chloro-3'-(2,6-diphenylpyrimidine)biphenyl.
将3-氯-3’-(2,6-二苯基嘧啶)联苯4.0g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[38]5.78g(纯度99.9％)。Add 4.0 g of 3-chloro-3'-(2,6-diphenylpyrimidine) biphenyl, 2.2 g of fluoranthene boronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.6 g of potassium carbonate into the flask, and use After argon replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 5.78 g of light yellow solid compound [38] (purity 99.9%).
合成例14Synthesis Example 14
化合物[39]的合成Synthesis of compound [39]
Figure PCTCN2022143372-appb-000031
Figure PCTCN2022143372-appb-000031
将2-氯-4,6-二苯基嘧啶2.64g，间氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-(3-氯苯基)-4,6-二苯基嘧啶3.4g。Put 2.64g of 2-chloro-4,6-diphenylpyrimidine, 1.22g of m-chlorophenylboronic acid, 0.06g of ditriphenylphosphine palladium dichloride, and 3.60g of potassium carbonate into the flask, replace it with argon three times, and inject Dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water, and recrystallized using 50 ml of o-xylene to obtain 3.4 g of white solid 2-(3-chlorophenyl)-4,6-diphenylpyrimidine.
将2-(3-氯苯基)-4,6-二苯基嘧啶3.4g，间氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体3-氯-3’-(4,6-二苯基嘧啶)联苯4.0g。Add 3.4g of 2-(3-chlorophenyl)-4,6-diphenylpyrimidine, 1.56g of m-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, and 3.60g of potassium carbonate into the flask, and use After argon replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain 4.0g of white solid 3-chloro-3'-(4,6-diphenylpyrimidine)biphenyl.
将3-氯-3’-(4,6-二苯基嘧啶)联苯4.0g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[39]5.92g(纯度99.9％)。Add 4.0 g of 3-chloro-3'-(4,6-diphenylpyrimidine) biphenyl, 2.2 g of fluoranthene boronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.6 g of potassium carbonate into the flask, and use After argon replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 5.92 g of light yellow solid compound [39] (purity 99.9%).
合成例15Synthesis Example 15
化合物[43]的合成Synthesis of compound [43]
Figure PCTCN2022143372-appb-000032
Figure PCTCN2022143372-appb-000032
将2-氯-4,6-二苯基-1,3,5-三嗪2.67g，邻氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至80℃后反应24小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-(2-氯苯基)-4,6-二苯基嘧啶3.2g。Add 2.67g of 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.22g of o-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, and 3.60g of potassium carbonate into the flask , replaced with argon three times and then injected with dehydrated and deoxygenated toluene. After heating up to 80°C, the reaction was carried out for 24 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water, and recrystallized using 50 ml of o-xylene to obtain 3.2 g of white solid 2-(2-chlorophenyl)-4,6-diphenylpyrimidine.
将2-(2-氯苯基)-4,6-二苯基嘧啶3.2g，间氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体3-氯-2’-(4,6-二苯基嘧啶)联苯3.8g。Add 3.2g of 2-(2-chlorophenyl)-4,6-diphenylpyrimidine, 1.56g of m-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, and 3.60g of potassium carbonate into the flask, and use After argon replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain 3.8g of white solid 3-chloro-2'-(4,6-diphenylpyrimidine)biphenyl.
将3-氯-2’-(4,6-二苯基嘧啶)联苯3.8g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[43]5.65g(纯度99.9％)。Add 3.8 g of 3-chloro-2'-(4,6-diphenylpyrimidine) biphenyl, 2.2 g of fluoranthene boronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.6 g of potassium carbonate into the flask, and use After argon replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 5.65 g of light yellow solid compound [43] (purity 99.9%).
合成例16Synthesis Example 16
化合物[61]的合成Synthesis of compound [61]
Figure PCTCN2022143372-appb-000033
Figure PCTCN2022143372-appb-000033
将2-(4-联苯基)-4,6-二氯-1,3,5-三嗪3.00g，盐酸活性化后的镁块0.24g，放入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯，并搅拌20分钟。加入用甲苯溶解的溴苯1.22g，并升温至120℃。4小时后冷却至室温后，加入冷水淬灭反应。之后用甲苯萃取反应物，再用水萃取反应物中的盐。将有机相旋干后得到固体。使用硅胶柱分离(PE：EA＝1：10)得到3.2g的白色固体2-(4-对联苯基)-4-氯-6-苯基-1,3,5三嗪。Put 3.00 g of 2-(4-biphenyl)-4,6-dichloro-1,3,5-triazine and 0.24 g of magnesium block activated by hydrochloric acid into the flask, and replace it with argon three times Dehydrated and deoxygenated toluene was injected and stirred for 20 minutes. 1.22 g of bromobenzene dissolved in toluene was added, and the temperature was raised to 120°C. After cooling to room temperature after 4 hours, cold water was added to quench the reaction. Then the reactant was extracted with toluene, and the salt in the reactant was extracted with water. The organic phase was spin-dried to give a solid. A silica gel column separation (PE:EA=1:10) was used to obtain 3.2 g of white solid 2-(4-p-biphenyl)-4-chloro-6-phenyl-1,3,5-triazine.
将2-(4-对联苯基)-4-氯-6-苯基-1,3,5三嗪3.2g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯100ml重结晶，得到白色固体2-(4-氯苯基)-4-对联苯基-6-苯基-1,3,5-三嗪4.0g。3.2g of 2-(4-p-biphenyl)-4-chloro-6-phenyl-1,3,5 triazine, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, carbonic acid Add 3.60 g of potassium into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 100ml of o-xylene to obtain a white solid 2-(4-chlorophenyl)-4-p-biphenyl-6-phenyl-1,3 , 5-triazine 4.0g.
将2-(4-氯苯基)-4-对联苯基-6-苯基-1,3,5-三嗪4.0g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中， 用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯100ml重结晶，得到白色固体4-氯-4’-(4-对联苯基-6-苯基-1,3,5-三嗪基)联苯4.8g。2-(4-chlorophenyl)-4-p-biphenyl-6-phenyl-1,3,5-triazine 4.0g, p-chlorophenylboronic acid 1.56g, ditriphenylphosphine palladium dichloride 0.06 g, 3.60 g of potassium carbonate was added to the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 100ml of o-xylene to obtain a white solid 4-chloro-4'-(4-p-biphenyl-6-phenyl-1,3,5 - Triazinyl) biphenyl 4.8 g.
将4-氯-4’-(4-对联苯基-6-苯基-1,3,5-三嗪基)联苯4.8g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯200ml重结晶，得到淡黄色固体化合物[61]6.4g(纯度99.9％)。4-chloro-4'-(4-p-biphenyl-6-phenyl-1,3,5-triazinyl)biphenyl 4.8g, fluoranthene boronic acid 2.2g, ditriphenylphosphine palladium dichloride 0.06g and 3.6g of potassium carbonate were added into the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 200 ml of o-xylene to obtain 6.4 g of light yellow solid compound [61] (purity 99.9%).
合成例17Synthesis Example 17
化合物[62]的合成Synthesis of compound [62]
Figure PCTCN2022143372-appb-000034
Figure PCTCN2022143372-appb-000034
将2-苯基-4,6-二氯-1,3,5-三嗪2.55g，盐酸活性化后的镁块 0.24g，放入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯，并搅拌20分钟。加入用甲苯溶解的间溴联苯2.00g，并升温至120℃。4小时后冷却至室温后，加入冷水淬灭反应。之后用甲苯萃取反应物，再用水萃取反应物中的盐。将有机相旋干后得到固体。使用硅胶柱分离(PE：EA＝1：10)得到3.1g的白色固体2-(4-苯基)-4-氯-6-间联苯基-1,3,5三嗪。Put 2.55g of 2-phenyl-4,6-dichloro-1,3,5-triazine and 0.24g of magnesium block activated by hydrochloric acid into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene , and stirred for 20 minutes. 2.00 g of m-bromobiphenyl dissolved in toluene was added, and the temperature was raised to 120°C. After cooling to room temperature after 4 hours, cold water was added to quench the reaction. Then the reactant was extracted with toluene, and the salt in the reactant was extracted with water. The organic phase was spin-dried to give a solid. A silica gel column separation (PE:EA=1:10) was used to obtain 3.1 g of white solid 2-(4-phenyl)-4-chloro-6-m-biphenyl-1,3,5-triazine.
将2-(4-苯基)-4-氯-6-间联苯基-1,3,5三嗪3.1g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体2-(4-氯苯基)-4-间联苯基-6-苯基-1,3,5-三嗪3.9g。3.1g of 2-(4-phenyl)-4-chloro-6-m-biphenyl-1,3,5-triazine, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 2-(4-chlorophenyl)-4-m-biphenyl-6-phenyl-1, 3,5-triazine 3.9g.
将2-(4-氯苯基)-4-间联苯基-6-苯基-1,3,5-三嗪3.9g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-4’-(4-间联苯基-6-苯基-1,3,5-三嗪基)联苯4.8g。3.9g of 2-(4-chlorophenyl)-4-m-biphenyl-6-phenyl-1,3,5-triazine, 1.56g of p-chlorophenylboronic acid, ditriphenylphosphine palladium dichloride 0.06g and 3.60g of potassium carbonate were added to the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 4-chloro-4'-(4-m-biphenyl-6-phenyl-1,3, 5-triazinyl)biphenyl 4.8g.
将4-氯-4’-(4-间联苯基-6-苯基-1,3,5-三嗪基)联苯4.8g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次， 使用邻二甲苯100ml重结晶，得到淡黄色固体化合物[62]6.5g(纯度99.9％)。4-chloro-4'-(4-m-biphenyl-6-phenyl-1,3,5-triazinyl)biphenyl 4.8g, fluoranthene boronic acid 2.2g, ditriphenylphosphine dichloride Add 0.06 g of palladium and 3.6 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized using 100 ml of o-xylene to obtain 6.5 g of light yellow solid compound [62] (purity 99.9%).
合成例18Synthesis Example 18
化合物[63]的合成Synthesis of Compound [63]
Figure PCTCN2022143372-appb-000035
Figure PCTCN2022143372-appb-000035
将2-苯基-4,6-二氯-1,3,5-三嗪2.55g，盐酸活性化后的镁块0.24g，放入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯，并搅拌20分钟。加入用甲苯溶解的邻溴联苯2.00g，并升温至120℃。4小时后冷却至室温后，加入冷水淬灭反应。之后用甲苯萃取反应物，再用水萃取反应物中的盐。将有机相旋干后得到固体。使用硅胶柱分离(PE：EA＝1：30)得到3.0g的白色固体2-(4-苯基)-4-氯-6-邻联苯基-1,3,5三嗪。Put 2.55g of 2-phenyl-4,6-dichloro-1,3,5-triazine and 0.24g of magnesium block activated by hydrochloric acid into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene , and stirred for 20 minutes. 2.00 g of o-bromobiphenyl dissolved in toluene was added, and the temperature was raised to 120°C. After cooling to room temperature after 4 hours, cold water was added to quench the reaction. Then the reactant was extracted with toluene, and the salt in the reactant was extracted with water. The organic phase was spin-dried to give a solid. Separation on a silica gel column (PE:EA=1:30) gave 3.0 g of white solid 2-(4-phenyl)-4-chloro-6-o-biphenyl-1,3,5-triazine.
将2-(4-苯基)-4-氯-6-邻联苯基-1,3,5三嗪3.0g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用 氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯40ml重结晶，得到白色固体2-(4-氯苯基)-4-邻联苯基-6-苯基-1,3,5-三嗪3.7g。3.0g of 2-(4-phenyl)-4-chloro-6-o-biphenyl-1,3,5-triazine, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 40ml of o-xylene to obtain a white solid 2-(4-chlorophenyl)-4-o-biphenyl-6-phenyl-1, 3,5-triazine 3.7g.
将2-(4-氯苯基)-4-邻联苯基-6-苯基-1,3,5-三嗪3.7g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-4’-(4-邻联苯基-6-苯基-1,3,5-三嗪基)联苯4.5g。3.7g of 2-(4-chlorophenyl)-4-o-biphenyl-6-phenyl-1,3,5-triazine, 1.56g of p-chlorophenylboronic acid, ditriphenylphosphine palladium dichloride 0.06g and 3.60g of potassium carbonate were added to the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 4-chloro-4'-(4-o-biphenyl-6-phenyl-1,3, 5-triazinyl)biphenyl 4.5g.
将4-氯-4’-(4-邻联苯基-6-苯基-1,3,5-三嗪基)联苯4.5g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯100ml重结晶，得到淡黄色固体化合物[63]6.1g(纯度99.9％)。4-chloro-4'-(4-o-biphenyl-6-phenyl-1,3,5-triazinyl)biphenyl 4.5g, fluoranthene boronic acid 2.2g, ditriphenylphosphine dichloride Add 0.06 g of palladium and 3.6 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 100 ml of o-xylene to obtain 6.1 g of light yellow solid compound [63] (purity 99.9%).
合成例19Synthesis Example 19
化合物[106]的合成Synthesis of compound [106]
Figure PCTCN2022143372-appb-000036
Figure PCTCN2022143372-appb-000036
将1，3，5-三氯三嗪1.82g，盐酸活性化后的镁块0.48g，放入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯，并搅拌20分钟。加入用甲苯溶解的3-溴二苯并呋喃5.0g，并升温至120℃。4小时后冷却至室温后，加入冷水淬灭反应。之后用甲苯萃取反应物，再用水萃取反应物中的盐。将有机相旋干后得到固体。使用硅胶柱分离(PE：EA＝1：10)得到4.0g的白色固体双二苯并呋喃取代物。Put 1.82 g of 1,3,5-trichlorotriazine and 0.48 g of magnesium block activated by hydrochloric acid into a flask, replace with argon three times, inject dehydrated and deoxygenated toluene, and stir for 20 minutes. 5.0 g of 3-bromodibenzofuran dissolved in toluene was added, and the temperature was raised to 120°C. After cooling to room temperature after 4 hours, cold water was added to quench the reaction. Then the reactant was extracted with toluene, and the salt in the reactant was extracted with water. The organic phase was spin-dried to give a solid. A silica gel column separation (PE:EA=1:10) was used to obtain 4.0 g of a white solid bis-dibenzofuran substitute.
将双二苯并呋喃取代物4.0g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯100ml重结晶，得到白色固体2-(4-氯苯基)-4,6-双二苯并呋喃-1,3,5-三嗪5.1g。Add 4.0 g of bis-dibenzofuran substituent, 1.22 g of p-chlorophenylboronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.60 g of potassium carbonate into the flask, replace with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 100ml of o-xylene to obtain a white solid 2-(4-chlorophenyl)-4,6-dibenzofuran-1,3, 5-triazine 5.1g.
将2-(4-氯苯基)-4,6-双二苯并呋喃-1,3,5-三嗪5.1g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中， 用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯100ml重结晶，得到白色固体4-氯-4’-(4,6-双二苯并呋喃-1,3,5-三嗪基)联苯5.7g。5.1g of 2-(4-chlorophenyl)-4,6-bisdibenzofuran-1,3,5-triazine, 1.56g of p-chlorophenylboronic acid, and 0.06g of ditriphenylphosphinepalladium dichloride , Potassium carbonate 3.60g was added to the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 100ml of o-xylene to obtain a white solid 4-chloro-4'-(4,6-bisdibenzofuran-1,3,5- Triazinyl)biphenyl 5.7g.
将4-氯-4’-(4,6-双二苯并呋喃-1,3,5-三嗪基)联苯5.7g，荧蒽硼酸2.1g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯200ml重结晶，得到淡黄色固体化合物[106]6.5g(纯度99.9％)。5.7g of 4-chloro-4'-(4,6-bisdibenzofuran-1,3,5-triazinyl)biphenyl, 2.1g of fluoranthene boronic acid, 0.06 ditriphenylphosphine palladium dichloride g, 3.6 g of potassium carbonate was added to the flask, replaced with argon for three times, and injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 200 ml of o-xylene to obtain 6.5 g of light yellow solid compound [106] (purity 99.9%).
合成例20Synthesis Example 20
化合物[110]的合成Synthesis of compound [110]
Figure PCTCN2022143372-appb-000037
Figure PCTCN2022143372-appb-000037
将1，3，5-三氯三嗪1.82g，盐酸活性化后的镁块0.48g，放入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯，并搅拌20分钟。加入用甲苯溶解的3-溴二苯并呋喃5.0g，并升温至120℃。4小时后冷却至室温后，加入冷水淬灭反应。之后用甲苯萃取反应物，再用水萃取反应物中的盐。将有机相旋干后得到固体。使用硅胶柱分离(PE：EA＝1：10)得到4.0g的白色固体双二苯并呋喃取代物。Put 1.82 g of 1,3,5-trichlorotriazine and 0.48 g of magnesium block activated by hydrochloric acid into a flask, replace with argon three times, inject dehydrated and deoxygenated toluene, and stir for 20 minutes. 5.0 g of 3-bromodibenzofuran dissolved in toluene was added, and the temperature was raised to 120°C. After cooling to room temperature after 4 hours, cold water was added to quench the reaction. Then the reactant was extracted with toluene, and the salt in the reactant was extracted with water. The organic phase was spin-dried to give a solid. A silica gel column separation (PE:EA=1:10) was used to obtain 4.0 g of a white solid bis-dibenzofuran substitute.
将双二苯并呋喃取代物4.0g，间氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-(3-氯苯基)-4,6-双二苯并呋喃-1,3,5-三嗪5.2g。Add 4.0 g of bis-dibenzofuran substituent, 1.22 g of m-chlorophenylboronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.60 g of potassium carbonate into the flask, replace with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 2-(3-chlorophenyl)-4,6-dibenzofuran-1,3, 5-triazine 5.2g.
将2-(3-氯苯基)-4,6-双二苯并呋喃-1,3,5-三嗪5.2g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体3-氯-3’-(4,6-双二苯并呋喃-1,3,5-三嗪基)联苯5.8g。5.2g of 2-(3-chlorophenyl)-4,6-bisdibenzofuran-1,3,5-triazine, 1.56g of p-chlorophenylboronic acid, and 0.06g of ditriphenylphosphinepalladium dichloride , Potassium carbonate 3.60g was added in the flask, replaced with argon three times and then injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 3-chloro-3'-(4,6-dibenzofuran-1,3,5- Triazinyl)biphenyl 5.8g.
将3-氯-3’-(4,6-双二苯并呋喃-1,3,5-三嗪基)联苯5.8g，荧蒽硼酸2.1g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[110]6.5g(纯 度99.9％)。5.8g of 3-chloro-3'-(4,6-dibenzofuran-1,3,5-triazinyl)biphenyl, 2.1g of fluoranthene boronic acid, 0.06 ditriphenylphosphine palladium dichloride g, 3.6 g of potassium carbonate was added to the flask, replaced with argon for three times, and injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 6.5 g of light yellow solid compound [110] (purity 99.9%).
合成例21Synthesis Example 21
化合物[111]的合成Synthesis of compound [111]
Figure PCTCN2022143372-appb-000038
Figure PCTCN2022143372-appb-000038
将3，5-二溴氯苯2.7g，荧蒽硼酸5.0g，二三苯基膦二氯化钯0.06g，碳酸钾7.20g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应2小时。降至室温后旋干溶剂，用100ml水清洗3次，用200ml甲醇清洗3次，使用邻二甲苯100ml重结晶，得到黄色固体3，5-二荧蒽氯苯5.0g。Add 2.7 g of 3,5-dibromochlorobenzene, 5.0 g of fluoranthene boric acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 7.20 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 2 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and three times with 200 ml of methanol, and recrystallized with 100 ml of o-xylene to obtain 5.0 g of yellow solid 3,5-difluoranthene chlorobenzene.
将1，3-二荧蒽-5氯苯5.0g，1，3-二苯基-5-硼酸三嗪2.33g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应5小时。降至室温后旋干溶剂，用100ml水清洗3次，用100ml甲醇清洗2次，使用邻二甲苯70ml重结晶，得到6.5g(纯度99.9)的淡黄色的固体化合物[111]。Add 5.0g of 1,3-difluoranthene-5-chlorobenzene, 2.33g of 1,3-diphenyl-5-boronic acid triazine, 0.06g of ditriphenylphosphinepalladium dichloride, and 3.60g of potassium carbonate into the flask , replaced with argon three times and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 5 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water, washed twice with 100 ml of methanol, and recrystallized using 70 ml of o-xylene to obtain 6.5 g (purity 99.9) of light yellow solid compound [111].
合成例22Synthesis Example 22
化合物[112]的合成Synthesis of compound [112]
Figure PCTCN2022143372-appb-000039
Figure PCTCN2022143372-appb-000039
将2,4,6-三溴氯苯3.46g，荧蒽硼酸7.5g，二三苯基膦二氯化钯0.06g，碳酸钾10.0g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应2小时。降至室温后旋干溶剂，用100ml水清洗3次，用200ml甲醇清洗3次，使用邻二甲苯200ml重结晶，得到黄色固体2，4，6-三荧蒽氯苯7.1g。Add 3.46g of 2,4,6-tribromochlorobenzene, 7.5g of fluoranthene boric acid, 0.06g of ditriphenylphosphine palladium dichloride, and 10.0g of potassium carbonate into the flask, replace it with argon for three times, and then inject the dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 2 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and three times with 200 ml of methanol, and recrystallized with 200 ml of o-xylene to obtain 7.1 g of yellow solid 2,4,6-trifluoranthene chlorobenzene.
将2，4，6-三荧蒽氯苯7.1g，1，3-二苯基-5-硼酸三嗪2.33g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应5小时。降至室温后旋干溶剂，用100ml水清洗3次，用100ml甲醇清洗2次，使用邻二甲苯300ml重结晶，得到8.0g(纯度99.9)的黄色的固体化合物[112]。Add 7.1g of 2,4,6-trifluoranthene chlorobenzene, 2.33g of 1,3-diphenyl-5-boronic acid triazine, 0.06g of ditriphenylphosphinepalladium dichloride, and 3.60g of potassium carbonate into the flask , replaced with argon three times and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 5 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water, washed twice with 100 ml of methanol, and recrystallized using 300 ml of o-xylene to obtain 8.0 g (purity 99.9) of a yellow solid compound [112].
合成例23Synthesis Example 23
化合物[113]的合成Synthesis of compound [113]
Figure PCTCN2022143372-appb-000040
Figure PCTCN2022143372-appb-000040
将3，5-二溴氯苯2.7g，1，3-二苯基-5-硼酸三嗪4.66g，二三苯基膦二氯化钯0.06g，碳酸钾5.0g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应4小时。降至室温后旋干溶剂，用100ml水清洗3次，用100ml甲醇清洗3次，使用邻二甲苯100ml重结晶，得到白色固体3，5-二(3，5-二苯基三嗪基)氯苯5.5g。Add 2.7g of 3,5-dibromochlorobenzene, 4.66g of 1,3-diphenyl-5-boronic acid triazine, 0.06g of ditriphenylphosphine palladium dichloride, and 5.0g of potassium carbonate into the flask, and use argon After gas replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120° C., the reaction was carried out for 4 hours. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, washed 3 times with 100ml of methanol, and recrystallized with 100ml of o-xylene to obtain a white solid 3,5-bis(3,5-diphenyltriazinyl) Chlorobenzene 5.5g.
将3，5-二(3，5-二苯基三嗪基)氯苯5.5g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，用100ml甲醇清洗3次，使用邻 二甲苯200ml重结晶，得到白色固体1-(4-氯苯基)-3，5-双(1，3-二苯基三嗪基)苯6.2g。Add 5.5 g of 3,5-bis(3,5-diphenyltriazinyl)chlorobenzene, 1.22 g of p-chlorophenylboronic acid, 0.06 g of ditriphenylphosphinepalladium dichloride, and 3.60 g of potassium carbonate into the flask, After replacing with argon three times, dehydrated and deoxygenated toluene was injected. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, washed 3 times with 100ml of methanol, and recrystallized with 200ml of o-xylene to obtain a white solid 1-(4-chlorophenyl)-3,5-bis(1 , 3-diphenyltriazinyl)benzene 6.2g.
将1-(4-氯苯基)-3，5-双(1，3-二苯基三嗪基)苯6.2g，荧蒽硼酸2.1g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯500ml重结晶，得到白色固体化合物[113]8.0g(纯度99.9％)。6.2 g of 1-(4-chlorophenyl)-3,5-bis(1,3-diphenyltriazinyl)benzene, 2.1 g of fluoranthene boric acid, 0.06 g of ditriphenylphosphinepalladium dichloride, Add 3.6 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized using 500 ml of o-xylene to obtain 8.0 g of white solid compound [113] (purity 99.9%).
合成例24Synthesis Example 24
化合物[114]的合成Synthesis of compound [114]
Figure PCTCN2022143372-appb-000041
Figure PCTCN2022143372-appb-000041
将3，5-二苯基氯苯2.8g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，得到白色固体2-(4-氯苯基)-4,6-二苯基苯3.4g。Put 2.8g of 3,5-diphenylchlorobenzene, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphine palladium dichloride, and 3.60g of potassium carbonate into the flask, replace it with argon three times, and then inject the dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried and washed three times with 100 ml of water to obtain 3.4 g of white solid 2-(4-chlorophenyl)-4,6-diphenylbenzene.
将2-(4-氯苯基)-4,6-二苯基苯3.4g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-4’-(4,6-二苯基苯)联苯4.0g。Add 3.4g of 2-(4-chlorophenyl)-4,6-diphenylbenzene, 1.56g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, and 3.60g of potassium carbonate into the flask, and use After argon replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain 4.0g of white solid 4-chloro-4'-(4,6-diphenylbenzene)biphenyl.
将4-氯-4’-(4,6-二苯基苯)联苯4.0g，荧蒽硼酸2.1g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应4小时。降至室温后旋干溶剂，用100ml水和300ml甲醇分别清洗3次，使用邻二甲苯6000ml重结晶，得到淡黄色固体化合物[114]5.31g(纯度99.9％)。Put 4.0g of 4-chloro-4'-(4,6-diphenylphenyl)biphenyl, 2.1g of fluoranthene boronic acid, 0.06g of ditriphenylphosphine palladium dichloride, and 3.6g of potassium carbonate into the flask, and use After argon replacement three times, dehydrated and deoxygenated toluene was injected. After heating up to 120° C., the reaction was carried out for 4 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 300 ml of methanol, and recrystallized with 6000 ml of o-xylene to obtain 5.31 g of light yellow solid compound [114] (purity 99.9%).
合成例25Synthesis Example 25
化合物[115]的合成Synthesis of compound [115]
Figure PCTCN2022143372-appb-000042
Figure PCTCN2022143372-appb-000042
将1-(4-氯苯基)-3-对联苯基-2，4，5，6-四嗪3.4g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重 结晶，得到白色固体4-氯-4’-(1-3-对联苯基-2，4，5，6-四嗪基)联苯4.1g。3.4g of 1-(4-chlorophenyl)-3-p-biphenyl-2,4,5,6-tetrazine, 1.56g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, carbonic acid Add 3.60 g of potassium into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 4-chloro-4'-(1-3-p-biphenyl-2,4,5,6- Tetrazine base) biphenyl 4.1g.
将4-氯-4’-(1-3-对联苯基-2，4，5，6-四嗪基)联苯4.1g，荧蒽硼酸2.1g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗4次，使用邻二甲苯100ml重结晶，得到白色固体化合物[115]3.13g(纯度99.9％)。4-chloro-4'-(1-3-p-biphenyl-2,4,5,6-tetrazinyl)biphenyl 4.1g, fluoranthene boronic acid 2.1g, ditriphenylphosphine palladium dichloride 0.06 g, 3.6 g of potassium carbonate was added to the flask, replaced with argon for three times, and injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed four times with 100 ml of water and 100 ml of methanol, and recrystallized with 100 ml of o-xylene to obtain 3.13 g of white solid compound [115] (purity 99.9%).
合成例26Synthesis Example 26
化合物[138]的合成Synthesis of compound [138]
Figure PCTCN2022143372-appb-000043
Figure PCTCN2022143372-appb-000043
将2-([1,1'-联苯]-4-基)-4-氯-6-苯基三嗪3.67g，邻氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。 降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-([1,1'-联苯]-4-基)-4-(2-氯苯基)-6-苯基三嗪4.63g。2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyltriazine 3.67g, o-chlorophenylboronic acid 1.22g, ditriphenylphosphinepalladium dichloride 0.06g , Potassium carbonate 3.60g was added in the flask, replaced with argon three times and then injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 2-([1,1'-biphenyl]-4-yl)-4-(2-chloro 4.63 g of phenyl)-6-phenyltriazine.
将2-([1,1'-联苯]-4-基)-4-(2-氯苯基)-6-苯基三嗪4.63g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-2’-(2-苯基-[1,1'-联苯]-4-基-三嗪)联苯4.7g。4.63g of 2-([1,1'-biphenyl]-4-yl)-4-(2-chlorophenyl)-6-phenyltriazine, 1.56g of p-chlorophenylboronic acid, ditriphenylphosphine Add 0.06 g of palladium dichloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 4-chloro-2'-(2-phenyl-[1,1'-biphenyl]-4 -yl-triazine) biphenyl 4.7g.
将4-氯-2’-(2-苯基-[1,1'-联苯]-4-基-三嗪)联苯4.7g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[138]3.25g(纯度99.9％)。4.7g of 4-chloro-2'-(2-phenyl-[1,1'-biphenyl]-4-yl-triazine)biphenyl, 2.2g of fluoranthene boronic acid, dichlorinated ditriphenylphosphine Add 0.06 g of palladium and 3.6 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 3.25 g of light yellow solid compound [138] (purity 99.9%).
合成例27Synthesis Example 27
化合物[139]的合成Synthesis of compound [139]
Figure PCTCN2022143372-appb-000044
Figure PCTCN2022143372-appb-000044
将4-([1,1'-联苯]-4-基)-6-氯-2-苯基嘧啶3.67g，邻氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体4-([1,1'-联苯]-4-基)-6-(2-氯苯基)-2-苯基嘧啶4.61g。3.67g of 4-([1,1'-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine, 1.22g of o-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 4-([1,1'-biphenyl]-4-yl)-6-(2-chloro Phenyl)-2-phenylpyrimidine 4.61g.
将4-([1,1'-联苯]-4-基)-6-(2-氯苯基)-2-苯基嘧啶4.61g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-2’-(4-苯基-[1,1'-联苯]-6-基-嘧啶)联苯4.6g。4-([1,1'-biphenyl]-4-yl)-6-(2-chlorophenyl)-2-phenylpyrimidine 4.61g, p-chlorophenylboronic acid 1.56g, ditriphenylphosphine di Add 0.06 g of palladium chloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 4-chloro-2'-(4-phenyl-[1,1'-biphenyl]-6 -yl-pyrimidine)biphenyl 4.6g.
将4-氯-2’-(4-苯基-[1,1'-联苯]-6-基-嘧啶)联苯4.6g，荧蒽 硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[139]3.24g(纯度99.9％)。4.6g of 4-chloro-2'-(4-phenyl-[1,1'-biphenyl]-6-yl-pyrimidine)biphenyl, 2.2g of fluoranthene boronic acid, ditriphenylphosphine palladium dichloride 0.06g and 3.6g of potassium carbonate were added into the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 3.24 g of light yellow solid compound [139] (purity 99.9%).
合成例28Synthesis Example 28
化合物[140]的合成Synthesis of Compound [140]
Figure PCTCN2022143372-appb-000045
Figure PCTCN2022143372-appb-000045
将2-([1,1'-联苯]-4-基)-4-氯-6-苯基嘧啶3.67g，邻氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-([1,1'-联苯]-4-基)-4-(2-氯苯基)-6-苯基嘧啶4.65g。3.67g of 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenylpyrimidine, 1.22g of o-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 2-([1,1'-biphenyl]-4-yl)-4-(2-chloro Phenyl)-6-phenylpyrimidine 4.65g.
将2-([1,1'-联苯]-4-基)-4-(2-氯苯基)-6-苯基嘧啶4.65g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-2’-(2-苯基-[1,1'-联苯]-4-基-嘧啶)联苯4.7g。4.65g of 2-([1,1'-biphenyl]-4-yl)-4-(2-chlorophenyl)-6-phenylpyrimidine, 1.56g of p-chlorophenylboronic acid, ditriphenylphosphine di Add 0.06 g of palladium chloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 4-chloro-2'-(2-phenyl-[1,1'-biphenyl]-4 -yl-pyrimidine)biphenyl 4.7g.
将4-氯-2’-(2-苯基-[1,1'-联苯]-4-基-嘧啶)联苯4.7g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[140]4.56g(纯度99.9％)。4.7g of 4-chloro-2'-(2-phenyl-[1,1'-biphenyl]-4-yl-pyrimidine)biphenyl, 2.2g of fluoranthene boronic acid, ditriphenylphosphine palladium dichloride 0.06g and 3.6g of potassium carbonate were added into the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 4.56 g of light yellow solid compound [140] (purity 99.9%).
合成例29Synthesis Example 29
化合物[141]的合成Synthesis of compound [141]
Figure PCTCN2022143372-appb-000046
Figure PCTCN2022143372-appb-000046
将2-([1,1'-联苯]-4-基)-4-氯-6-苯基三嗪3.67g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-([1,1'-联苯]-4-基)-4-(4-氯苯基)-6-苯基三嗪4.50g。3.67g of 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyltriazine, 1.22g of p-chlorophenylboronic acid, and 0.06g of ditriphenylphosphinepalladium dichloride , Potassium carbonate 3.60g was added in the flask, replaced with argon three times and then injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 2-([1,1'-biphenyl]-4-yl)-4-(4-chloro Phenyl)-6-phenyltriazine 4.50g.
将2-([1,1'-联苯]-4-基)-4-(4-氯苯基)-6-苯基三嗪4.50g，邻氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体2-氯-4’-(2-苯基-[1,1'-联苯]-4-基-三嗪)联苯4.6g。4.50g of 2-([1,1'-biphenyl]-4-yl)-4-(4-chlorophenyl)-6-phenyltriazine, 1.56g of o-chlorophenylboronic acid, ditriphenylphosphine Add 0.06 g of palladium dichloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 2-chloro-4'-(2-phenyl-[1,1'-biphenyl]-4 -yl-triazine) biphenyl 4.6g.
将2-氯-4’-(2-苯基-[1,1'-联苯]-4-基-三嗪)联苯4.6g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[141]3.20g(纯度99.9％)。4.6g of 2-chloro-4'-(2-phenyl-[1,1'-biphenyl]-4-yl-triazine)biphenyl, 2.2g of fluoranthene boronic acid, ditriphenylphosphine dichloride Add 0.06 g of palladium and 3.6 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 3.20 g of light yellow solid compound [141] (purity 99.9%).
合成例30Synthesis Example 30
化合物[142]的合成Synthesis of compound [142]
Figure PCTCN2022143372-appb-000047
Figure PCTCN2022143372-appb-000047
将4-([1,1'-联苯]-4-基)-6-氯-2-苯基嘧啶3.67g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体4-([1,1'-联苯]-4-基)-6-(4-氯苯基)-2-苯基嘧啶4.41g。3.67g of 4-([1,1'-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 4-([1,1'-biphenyl]-4-yl)-6-(4-chloro Phenyl)-2-phenylpyrimidine 4.41g.
将4-([1,1'-联苯]-4-基)-6-(4-氯苯基)-2-苯基嘧啶4.41g，邻氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体2-氯-4’-(2-苯基-[1,1'-联苯]-6-基-嘧啶)联苯4.6g。4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-2-phenylpyrimidine 4.41g, o-chlorophenylboronic acid 1.56g, ditriphenylphosphine di Add 0.06 g of palladium chloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 2-chloro-4'-(2-phenyl-[1,1'-biphenyl]-6 -yl-pyrimidine)biphenyl 4.6g.
将2-氯-4’-(2-苯基-[1,1'-联苯]-6-基-嘧啶)联苯4.6g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小 时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[142]3.10g(纯度99.9％)。4.6g of 2-chloro-4'-(2-phenyl-[1,1'-biphenyl]-6-yl-pyrimidine)biphenyl, 2.2g of fluoranthene boronic acid, ditriphenylphosphine palladium dichloride 0.06g and 3.6g of potassium carbonate were added into the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 3.10 g of light yellow solid compound [142] (purity 99.9%).
合成例31Synthesis Example 31
化合物[143]的合成Synthesis of compound [143]
Figure PCTCN2022143372-appb-000048
Figure PCTCN2022143372-appb-000048
将2-([1,1'-联苯]-4-基)-4-氯-6-苯基嘧啶3.67g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-([1,1'-联苯]-4-基)-4-(4-氯苯基)-6-苯基嘧啶4.50g。3.67g of 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenylpyrimidine, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 2-([1,1'-biphenyl]-4-yl)-4-(4-chloro Phenyl)-6-phenylpyrimidine 4.50g.
将2-([1,1'-联苯]-4-基)-4-(4-氯苯基)-6-苯基嘧啶4.50g，邻氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲 苯70ml重结晶，得到白色固体2-氯-4’-(2-苯基-[1,1'-联苯]-4-基-嘧啶)联苯4.41g。4.50g of 2-([1,1'-biphenyl]-4-yl)-4-(4-chlorophenyl)-6-phenylpyrimidine, 1.56g of o-chlorophenylboronic acid, ditriphenylphosphine di Add 0.06 g of palladium chloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 2-chloro-4'-(2-phenyl-[1,1'-biphenyl]-4 -yl-pyrimidine)biphenyl 4.41g.
将2-氯-4’-(2-苯基-[1,1'-联苯]-4-基-嘧啶)联苯4.41g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[143]3.08g(纯度99.9％)。4.41g of 2-chloro-4'-(2-phenyl-[1,1'-biphenyl]-4-yl-pyrimidine)biphenyl, 2.2g of fluoranthene boronic acid, ditriphenylphosphine palladium dichloride 0.06g and 3.6g of potassium carbonate were added into the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 3.08 g of light yellow solid compound [143] (purity 99.9%).
合成例32Synthesis Example 32
化合物[183]的合成Synthesis of compound [183]
Figure PCTCN2022143372-appb-000049
Figure PCTCN2022143372-appb-000049
将2，6-二苯基-4-氯三嗪3.50g，邻氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶 剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2，6-二苯基-4-(2-氯苯基)三嗪4.53g。Add 3.50 g of 2,6-diphenyl-4-chlorotriazine, 1.22 g of o-chlorophenylboronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.60 g of potassium carbonate into the flask, and replace it with argon three times Inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain 4.53g of white solid 2,6-diphenyl-4-(2-chlorophenyl)triazine.
将2，6-二苯基-4-(2-氯苯基)三嗪4.53g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-2’-(2，6-二苯基三嗪)联苯4.61g。Add 4.53g of 2,6-diphenyl-4-(2-chlorophenyl)triazine, 1.56g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, and 3.60g of potassium carbonate into the flask, After replacing with argon three times, dehydrated and deoxygenated toluene was injected. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain 4.61g of white solid 4-chloro-2'-(2,6-diphenyltriazine)biphenyl.
将4-氯-2’-(2，6-二苯基三嗪)联苯4.61g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[183]3.46g(纯度99.9％)。Add 4.61 g of 4-chloro-2'-(2,6-diphenyltriazine) biphenyl, 2.2 g of fluoranthene boronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.6 g of potassium carbonate into the flask, After replacing with argon three times, dehydrated and deoxygenated toluene was injected. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 3.46 g of light yellow solid compound [183] (purity 99.9%).
合成例33Synthesis Example 33
化合物[186]的合成Synthesis of compound [186]
Figure PCTCN2022143372-appb-000050
Figure PCTCN2022143372-appb-000050
将2，6-二苯基-4-氯-三嗪3.50g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2，6-二苯基-4-(4-氯苯基)三嗪4.30g。Add 3.50 g of 2,6-diphenyl-4-chloro-triazine, 1.22 g of p-chlorophenylboronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.60 g of potassium carbonate into the flask, and replace with argon three times Then inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water, and recrystallized using 50 ml of o-xylene to obtain 4.30 g of white solid 2,6-diphenyl-4-(4-chlorophenyl)triazine.
将2，6-二苯基-4-(4-氯苯基)三嗪4.30g，邻氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体2-氯-4’-(2，6-二苯基-4-基-三嗪)联苯4.50g。Add 4.30 g of 2,6-diphenyl-4-(4-chlorophenyl) triazine, 1.56 g of o-chlorophenylboronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.60 g of potassium carbonate into the flask, After replacing with argon three times, dehydrated and deoxygenated toluene was injected. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 2-chloro-4'-(2,6-diphenyl-4-yl-triazine)bis Benzene 4.50g.
将2-氯-4’-(2，6-二苯基-4-基-三嗪)联苯4.50g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[186]3.10g(纯度99.9％)。4.50 g of 2-chloro-4'-(2,6-diphenyl-4-yl-triazine) biphenyl, 2.2 g of fluoranthene boronic acid, 0.06 g of ditriphenylphosphine palladium dichloride, and 3.6 g of potassium carbonate g was added to the flask, replaced with argon three times and injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 3.10 g of light yellow solid compound [186] (purity 99.9%).
合成例34Synthesis Example 34
化合物[148]的合成Synthesis of compound [148]
Figure PCTCN2022143372-appb-000051
Figure PCTCN2022143372-appb-000051
将4-([1,1'-联苯]-4-基)-6-氯-2-苯基嘧啶3.67g，邻氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体4-([1,1'-联苯]-4-基)-6-(2-氯苯基)-2-苯基嘧啶4.61g。3.67g of 4-([1,1'-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine, 1.22g of o-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 4-([1,1'-biphenyl]-4-yl)-6-(2-chloro Phenyl)-2-phenylpyrimidine 4.61g.
将4-([1,1'-联苯]-4-基)-6-(2-氯苯基)-2-苯基嘧啶4.61g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-2’-(4-苯基-[1,1'-联苯]-6-基-嘧啶)联苯4.6g。4-([1,1'-biphenyl]-4-yl)-6-(2-chlorophenyl)-2-phenylpyrimidine 4.61g, p-chlorophenylboronic acid 1.56g, ditriphenylphosphine di Add 0.06 g of palladium chloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 4-chloro-2'-(4-phenyl-[1,1'-biphenyl]-6 -yl-pyrimidine)biphenyl 4.6g.
将4-氯-2’-(4-苯基-[1,1'-联苯]-6-基-嘧啶)联苯4.60g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应 1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-(4-氯苯基)-3’-(4-苯基-[1,1'-联苯]-6-基-嘧啶)联苯3.01g。4-chloro-2'-(4-phenyl-[1,1'-biphenyl]-6-yl-pyrimidine)biphenyl 4.60g, p-chlorophenylboronic acid 1.56g, ditriphenylphosphine dichloride Add 0.06 g of palladium and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 4-(4-chlorophenyl)-3'-(4-phenyl-[1,1' -biphenyl]-6-yl-pyrimidine)biphenyl 3.01 g.
将4-(4-氯苯基)-3’-(4-苯基-[1,1'-联苯]-6-基-嘧啶)联苯3.01g，荧蒽硼酸2.0g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[148]2.11g(纯度99.9％)。3.01g of 4-(4-chlorophenyl)-3'-(4-phenyl-[1,1'-biphenyl]-6-yl-pyrimidine)biphenyl, 2.0g of fluoranthene boronic acid, ditriphenyl Add 0.06 g of phosphine palladium dichloride and 3.6 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized using 120 ml of o-xylene to obtain 2.11 g of light yellow solid compound [148] (purity 99.9%).
合成例35Synthesis Example 35
化合物[151]的合成Synthesis of compound [151]
Figure PCTCN2022143372-appb-000052
Figure PCTCN2022143372-appb-000052
将4-([1,1'-联苯]-4-基)-6-氯-2-苯基嘧啶3.67g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重 结晶，得到白色固体4-([1,1'-联苯]-4-基)-6-(4-氯苯基)-2-苯基嘧啶4.41g。3.67g of 4-([1,1'-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 4-([1,1'-biphenyl]-4-yl)-6-(4-chloro Phenyl)-2-phenylpyrimidine 4.41g.
将4-([1,1'-联苯]-4-基)-6-(4-氯苯基)-2-苯基嘧啶4.41g，邻氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体2-氯-4’-(2-苯基-[1,1'-联苯]-6-基-嘧啶)联苯4.6g。4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-2-phenylpyrimidine 4.41g, o-chlorophenylboronic acid 1.56g, ditriphenylphosphine di Add 0.06 g of palladium chloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 2-chloro-4'-(2-phenyl-[1,1'-biphenyl]-6 -yl-pyrimidine)biphenyl 4.6g.
将2-氯-4’-(2-苯基-[1,1'-联苯]-6-基-嘧啶)联苯4.60g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体2-(4-氯苯基)-4’-(2-苯基-[1,1'-联苯]-6-基-嘧啶)联苯2.54g。4.60g of 2-chloro-4'-(2-phenyl-[1,1'-biphenyl]-6-yl-pyrimidine)biphenyl, 1.56g of p-chlorophenylboronic acid, ditriphenylphosphine dichloride Add 0.06 g of palladium and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 2-(4-chlorophenyl)-4'-(2-phenyl-[1,1' -biphenyl]-6-yl-pyrimidine)biphenyl 2.54 g.
将2-(4-氯苯基)-4’-(2-苯基-[1,1'-联苯]-6-基-嘧啶)联苯2.54g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[151]1.02g(纯度99.9％)。2-(4-chlorophenyl)-4'-(2-phenyl-[1,1'-biphenyl]-6-yl-pyrimidine)biphenyl 2.54g, ditriphenylphosphinepalladium dichloride 0.06g and 3.6g of potassium carbonate were added into the flask, replaced with argon three times, and then injected with dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 1.02 g of light yellow solid compound [151] (purity 99.9%).
合成例36Synthesis Example 36
化合物[154]的合成Synthesis of compound [154]
Figure PCTCN2022143372-appb-000053
Figure PCTCN2022143372-appb-000053
将4-([1,1'-联苯]-4-基)-6-氯-2-苯基嘧啶3.67g，对氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体4-([1,1'-联苯]-4-基)-6-(4-氯苯基)-2-苯基嘧啶4.41g。3.67g of 4-([1,1'-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine, 1.22g of p-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 4-([1,1'-biphenyl]-4-yl)-6-(4-chloro Phenyl)-2-phenylpyrimidine 4.41g.
将4-([1,1'-联苯]-4-基)-6-(4-氯苯基)-2-苯基嘧啶4.41g，对氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体4-氯-4’-(2-苯基-[1,1'-联苯]-6-基-嘧啶)联苯4.6g。4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-2-phenylpyrimidine 4.41g, p-chlorophenylboronic acid 1.56g, ditriphenylphosphine di Add 0.06 g of palladium chloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 4-chloro-4'-(2-phenyl-[1,1'-biphenyl]-6 -yl-pyrimidine)biphenyl 4.6g.
将4-([1,1'-联苯]-4-基)-6-(4-氯苯基)-2-苯基嘧啶4.60g，邻氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入 烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体2”-氯-4-(2-苯基-[1,1'-联苯]-6-基-嘧啶)三联苯3.12g。4-([1,1'-biphenyl]-4-yl)-6-(4-chlorophenyl)-2-phenylpyrimidine 4.60g, o-chlorophenylboronic acid 1.56g, ditriphenylphosphine di Add 0.06 g of palladium chloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized with 70ml of o-xylene to obtain a white solid 2”-chloro-4-(2-phenyl-[1,1’-biphenyl]-6 -yl-pyrimidine) terphenyl 3.12g.
将2”-氯-4-(2-苯基-[1,1'-联苯]-6-基-嘧啶)三联苯3.12g，荧蒽硼酸2.0g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[154]1.20g(纯度99.9％)。3.12g of 2"-chloro-4-(2-phenyl-[1,1'-biphenyl]-6-yl-pyrimidine) terphenyl, 2.0g of fluoranthene boronic acid, ditriphenylphosphine palladium dichloride Add 0.06g and 3.6g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, react for 12 hours. After cooling down to room temperature, spin the solvent to dry, and wash with 100ml of water and 100ml of methanol for 3 times , recrystallized using 120 ml of o-xylene to obtain 1.20 g of light yellow solid compound [154] (purity 99.9%).
合成例37Synthesis Example 37
化合物[34]的合成Synthesis of compound [34]
Figure PCTCN2022143372-appb-000054
Figure PCTCN2022143372-appb-000054
将2-([1,1'-联苯]-4-基)-4-氯-6-苯基三嗪3.67g，间氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-([1,1'-联苯]-4-基)-4-(3-氯苯基)-6-苯基三嗪3.50g。2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyltriazine 3.67g, m-chlorophenylboronic acid 1.22g, ditriphenylphosphinepalladium dichloride 0.06g , Potassium carbonate 3.60g was added in the flask, replaced with argon three times and then injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 2-([1,1'-biphenyl]-4-yl)-4-(3-chloro Phenyl)-6-phenyltriazine 3.50g.
将2-([1,1'-联苯]-4-基)-4-(3-氯苯基)-6-苯基三嗪3.50g。，间氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体3-氯-3’-(2-([1,1'-联苯]-4-基)-6-苯基三嗪)联苯4.2g。3.50 g of 2-([1,1'-biphenyl]-4-yl)-4-(3-chlorophenyl)-6-phenyltriazine. , 1.56g of m-chlorophenylboronic acid, 0.06g of ditriphenylphosphine palladium dichloride, and 3.60g of potassium carbonate were added to the flask, replaced with argon three times, and injected with dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 3-chloro-3'-(2-([1,1'-biphenyl]-4-yl )-6-phenyltriazine)biphenyl 4.2g.
将白色固体3-氯-3’-(2-([1,1'-联苯]-4-基)-6-苯基三嗪)联苯4.2g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[34]4.73g(纯度99.9％)。White solid 3-chloro-3'-(2-([1,1'-biphenyl]-4-yl)-6-phenyltriazine)biphenyl 4.2g, fluoranthene boronic acid 2.2g, ditriphenyl Add 0.06 g of phosphine palladium dichloride and 3.6 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized using 120 ml of o-xylene to obtain 4.73 g of light yellow solid compound [34] (purity 99.9%).
合成例38Synthesis Example 38
化合物[40]的合成Synthesis of compound [40]
Figure PCTCN2022143372-appb-000055
Figure PCTCN2022143372-appb-000055
将4-([1,1'-联苯]-4-基)-6-氯-2-苯基嘧啶3.67g，间氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体4-([1,1'-联苯]-4-基)-6-(3-氯苯基)-2-苯基嘧啶3.70g。3.67g of 4-([1,1'-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine, 1.22g of m-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed 3 times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 4-([1,1'-biphenyl]-4-yl)-6-(3-chloro Phenyl)-2-phenylpyrimidine 3.70g.
将4-([1,1'-联苯]-4-基)-6-(3-氯苯基)-2-苯基嘧啶3.70g，间氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体3-氯-3’-(4-([1,1'-联苯]-4-基)-2-苯基嘧啶)联苯4.10g。3.70g of 4-([1,1'-biphenyl]-4-yl)-6-(3-chlorophenyl)-2-phenylpyrimidine, 1.56g of m-chlorophenylboronic acid, ditriphenylphosphine di Add 0.06 g of palladium chloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 3-chloro-3'-(4-([1,1'-biphenyl]-4-yl )-2-phenylpyrimidine)biphenyl 4.10g.
将白色固体3-氯-3’-(4-([1,1'-联苯]-4-基)-2-苯基嘧啶)联 苯4.10g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[40]4.31g(纯度99.9％)。White solid 3-chloro-3'-(4-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidine)biphenyl 4.10g, fluoranthene boronic acid 2.2g, ditriphenyl Add 0.06 g of phosphine palladium dichloride and 3.6 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 4.31 g of light yellow solid compound [40] (purity 99.9%).
合成例39Synthesis Example 39
化合物[41]的合成Synthesis of compound [41]
Figure PCTCN2022143372-appb-000056
Figure PCTCN2022143372-appb-000056
将2-([1,1'-联苯]-4-基)-4-氯-6-苯基嘧啶3.67g，间氯苯硼酸1.22g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯50ml重结晶，得到白色固体2-([1,1'-联苯]-4-基)-4-(3-氯苯基)-6-苯基嘧啶3.69g。3.67g of 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenylpyrimidine, 1.22g of m-chlorophenylboronic acid, 0.06g of ditriphenylphosphinepalladium dichloride, Add 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 50ml of o-xylene to obtain a white solid 2-([1,1'-biphenyl]-4-yl)-4-(3-chloro Phenyl)-6-phenylpyrimidine 3.69g.
将2-([1,1'-联苯]-4-基)-4-(3-氯苯基)-6-苯基嘧啶3.69g，间氯苯硼酸1.56g，二三苯基膦二氯化钯0.06g，碳酸钾3.60g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应1小时。降至室温后旋干溶剂，用100ml水清洗3次，使用邻二甲苯70ml重结晶，得到白色固体3-氯-3’-(2-([1,1'-联苯]-4-基)-6-苯基嘧啶)联苯4.02g。3.69g of 2-([1,1'-biphenyl]-4-yl)-4-(3-chlorophenyl)-6-phenylpyrimidine, 1.56g of m-chlorophenylboronic acid, ditriphenylphosphine di Add 0.06 g of palladium chloride and 3.60 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120° C., the reaction was carried out for 1 hour. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100ml of water, and recrystallized using 70ml of o-xylene to obtain a white solid 3-chloro-3'-(2-([1,1'-biphenyl]-4-yl )-6-phenylpyrimidine)biphenyl 4.02g.
将白色固体3-氯-3’-(2-([1,1'-联苯]-4-基)-6-苯基嘧啶)联苯4.02g，荧蒽硼酸2.2g，二三苯基膦二氯化钯0.06g，碳酸钾3.6g加入烧瓶中，用氩气置换三次后注入脱水脱氧的甲苯。升温至120℃后反应12小时。降至室温后旋干溶剂，用100ml水和100ml甲醇分别清洗3次，使用邻二甲苯120ml重结晶，得到淡黄色固体化合物[41]3.90g(纯度99.9％)。White solid 3-chloro-3'-(2-([1,1'-biphenyl]-4-yl)-6-phenylpyrimidine)biphenyl 4.02g, fluoranthene boronic acid 2.2g, ditriphenyl Add 0.06 g of phosphine palladium dichloride and 3.6 g of potassium carbonate into the flask, replace it with argon three times, and inject dehydrated and deoxygenated toluene. After heating up to 120°C, the reaction was carried out for 12 hours. After cooling down to room temperature, the solvent was spin-dried, washed three times with 100 ml of water and 100 ml of methanol, and recrystallized with 120 ml of o-xylene to obtain 3.90 g of light yellow solid compound [41] (purity 99.9%).
实施例1Example 1
将堆积有165nmITO透明导电膜的玻璃基板(吉奥马科技(Geomatec)股份有限公司制造、11Ω/□、溅镀品)切断为38mm×46mm而进行蚀刻。用“硅科库林(Semico Clean)56”(商品名、古内化学(Furuuchi Chemical)股份有限公司制造)对所得的基板进行15分钟的超声波清洗，然后用超纯水加以清洗。在制作元件之前对该基板进行1小时的紫外线(Ultraviolet，UV)-臭氧处理，设置在真空蒸镀装置内，进行排气直至装置内的真空度成为5×10 -4Pa以下。利用电阻加热法首先蒸镀75nm的HAT-CN6作为空穴注入层，并蒸镀42.5nm的 HT-1作为空穴传输层。然后，将主体材料H-1、掺杂材料D-1以掺杂浓度成为5重量％的方式蒸镀为20nm的厚度而作为发光层。然后，将化合物[6]蒸镀层叠为30nm的厚度而作为电子传输层。然后，蒸镀1nm的Yb后，蒸镀15nm的Mg/Aa(1:9)作为阴极，制作5mm×5mm见方的元件。此处所谓的膜厚是石英振荡式膜厚监视器(Conltaec的Eon LT)的显示值。该发光元件的10mA/cm 2时的特性是驱动电压为4.51V、效率为6.6cd/A。而且，将初始亮度设定为10mA/cm 2，进行恒定电流驱动时亮度降低50％的亮度减半时间为1600小时。其中，HAT-CN6、HT-1、H-1、D-1是以下所示的化合物。这种由一个发光单元组成的器件我们称为单层(single)器件，以与下述由一个以上的发光单元组成的叠层(tandem)器件进行区分。 A glass substrate (manufactured by Geomatec Co., Ltd., 11Ω/□, sputtered product) on which a 165 nm ITO transparent conductive film was deposited was cut into 38 mm×46 mm and etched. The obtained substrate was ultrasonically cleaned with "Semico Clean 56" (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 15 minutes, and then washed with ultrapure water. The substrate was subjected to ultraviolet (Ultraviolet, UV)-ozone treatment for 1 hour before the device was fabricated, placed in a vacuum evaporation device, and exhausted until the vacuum degree in the device became below 5×10 −4 Pa. Using the resistance heating method, 75nm HAT-CN6 was evaporated as the hole injection layer, and 42.5nm HT-1 was evaporated as the hole transport layer. Then, the host material H-1 and the dopant material D-1 were vapor-deposited to a thickness of 20 nm so that the doping concentration became 5% by weight to form a light-emitting layer. Then, compound [6] was vapor-deposited and laminated to a thickness of 30 nm as an electron transport layer. Then, after vapor-depositing 1 nm of Yb, 15 nm of Mg/Aa (1:9) was vapor-deposited as a cathode to fabricate a 5 mm×5 mm square element. The film thickness referred to here is a display value of a quartz oscillator type film thickness monitor (Eon LT of Conltaec). The characteristics of this light-emitting element at 10 mA/cm 2 are a driving voltage of 4.51 V and an efficiency of 6.6 cd/A. Furthermore, the initial luminance was set to 10 mA/cm 2 , and the halving time for the luminance to decrease by 50% when the constant current driving was performed was 1600 hours. Among them, HAT-CN6, HT-1, H-1, and D-1 are compounds shown below. Such a device composed of one light-emitting unit is called a single-layer (single) device to distinguish it from the following tandem device composed of more than one light-emitting unit.
Figure PCTCN2022143372-appb-000057
Figure PCTCN2022143372-appb-000057
实施例2～实施例41Embodiment 2 to Embodiment 41
在电子传输层中使用表1中所记载的化合物，除此以外与实施例1同样地进行而制成发光元件并进行评价。Except having used the compound described in Table 1 for the electron transport layer, it carried out similarly to Example 1, and produced and evaluated the light-emitting element.
比较例1～比较例8Comparative example 1 to comparative example 8
在电子传输层中使用表1中所记载的化合物，除此以外与实施例1同样地进行而制成发光元件并进行评价。C-1至C-7以及HB-1是以下所示的化合物。Except having used the compound described in Table 1 for the electron transport layer, it carried out similarly to Example 1, and produced and evaluated the light-emitting element. C-1 to C-7 and HB-1 are compounds shown below.
Figure PCTCN2022143372-appb-000058
Figure PCTCN2022143372-appb-000058
实施例42～实施例45Example 42 to Example 45
在电子传输层中使用化合物C-4，在空穴阻挡层中使用化合物 HB-1，除此以外与实施例1同样地进行而制成发光元件，该发光元件制作后蒸镀表1中所记载的化合物作为电荷产生层用化合物，然后再蒸镀同样的发光元件制作成叠层(tandem)器件并进行评价。Except that compound C-4 was used in the electron transport layer, and compound HB-1 was used in the hole blocking layer, a light-emitting element was produced in the same manner as in Example 1. The described compound was used as the compound for the charge generation layer, and then the same light-emitting element was vapor-deposited to prepare a tandem device and evaluated.
比较例9Comparative Example 9
在电子传输层中使用化合物C-4，在空穴阻挡层中使用化合物HB-1，除此以外与实施例1同样地进行而制成发光元件，该发光元件制作后蒸镀Alq3作为电荷产生层化合物，然后再蒸镀同样的发光元件制作成叠层(tandem)器件并进行评价。Except for using compound C-4 in the electron transport layer and compound HB-1 in the hole blocking layer, a light-emitting device was produced in the same manner as in Example 1. After the light-emitting device was produced, Alq3 was evaporated as a charge generator layer compound, and then vapor-deposit the same light-emitting element to make a tandem device and evaluate it.
Figure PCTCN2022143372-appb-000059
Figure PCTCN2022143372-appb-000059
Figure PCTCN2022143372-appb-000060
Figure PCTCN2022143372-appb-000060
Figure PCTCN2022143372-appb-000061
Figure PCTCN2022143372-appb-000061
比较例1和比较例2是市面上常见的荧蒽及类荧蒽系材料。比较例1的效率虽然较高，但是有电压高寿命短的问题。而比较例2的寿命虽然长，但是效率偏低。比较例3和比较例4是市面上具有领先水平的电子传输材料，比较例3的电压低，效率高，但是寿命很短。而比较例4的效率高，但电压也高，寿命也不长。器件性能有短板效应，短板会严重影响期间的实际应用。比较例5和比较例6是一些有被研究过的荧蒽系材料，比较例5的电压较低，但是寿命和效率也低。另外比较例5本身不稳定，升华过程中有时会分解。难以制作成器件，降低良率。比较例6的寿命相对较长，但是电压略高，效率很低，实施例1-31的材料在综合性能上比比较例1-6更优秀，作为器件能有更好的表现。Comparative example 1 and comparative example 2 are common fluoranthene and fluoranthene-like materials on the market. Although comparative example 1 has high efficiency, it has a problem of high voltage and short life. While Comparative Example 2 has a long life, but the efficiency is low. Comparative example 3 and comparative example 4 are the leading electron transport materials on the market, the voltage of comparative example 3 is low, the efficiency is high, but the life is very short. On the other hand, the efficiency of Comparative Example 4 is high, but the voltage is also high, and the life is not long. The performance of the device has a short board effect, and the short board will seriously affect the actual application during the period. Comparative example 5 and comparative example 6 are some fluoranthene-based materials that have been studied. The voltage of comparative example 5 is low, but the life and efficiency are also low. In addition, Comparative Example 5 itself is unstable, and sometimes decomposes during the sublimation process. Difficult to make into devices, reducing yield. Comparative Example 6 has a relatively long life, but the voltage is slightly higher and the efficiency is very low. The materials of Examples 1-31 are better than Comparative Examples 1-6 in terms of overall performance, and can perform better as devices.
通过比较实施例1，实施例21，实施例22可以发现，减少荧蒽基团后由于分子轨道能级过度变深，与电子注入层材料的匹配提升，电压有所降低，寿命也有上升的趋势。特别的，优选一个荧蒽基团时，电压及寿命都得到了大幅提升。另外，优选一个荧蒽基团时，材料的 蒸镀也更加容易。By comparing Example 1, Example 21, and Example 22, it can be found that after the fluoranthene group is reduced, the energy level of the molecular orbital becomes too deep, the matching with the material of the electron injection layer is improved, the voltage is reduced, and the life is also on the rise. . In particular, when a fluoranthene group is preferred, the voltage and lifetime are greatly improved. In addition, when one fluoranthene group is preferred, the vapor deposition of the material is also easier.
通过比较实施例6，实施例23可以发现，减少氮杂苯系基团后由于分子轨道能级过度变深，与电子注入层材料的匹配提升，电压有所降低，寿命也有上升的趋势。特别的，优选一个氮杂苯系基团时，电压及寿命都得到了大幅提升。另外，优选一个氮杂苯系基团时，材料的蒸镀也更加容易。倾向性虽然与荧蒽基团体现的倾向类似，但是程度上来说氮杂苯系基团的减少对器件效果的优化程度比荧蒽更强。By comparing Example 6 and Example 23, it can be found that after reducing the azabenzene group, the energy level of the molecular orbital becomes too deep, the matching with the material of the electron injection layer is improved, the voltage is reduced, and the life span also tends to increase. In particular, when an azabenzene group is preferred, the voltage and lifetime are greatly improved. In addition, when one azabenzene-based group is preferable, vapor deposition of the material is also easier. Although the tendency is similar to the tendency reflected by the fluoranthene group, to a certain extent, the reduction of the azabenzene group can optimize the device effect more than the fluoranthene group.
通过比较实施例6，实施例9，实施例10，实施例24，实施例25可见当氮杂苯系主体中含有氮原子时，由于电子的提供变多，整体分子中的电子数量提升，使得器件效率提升。当氮杂苯系主体的中心部分没有氮时，效率非常低，当含有一个氮时，可以得到相较于完全无氮的情况较高的效率，但是仍然处于没有显著优势的水准。而4个氮时则会能级过深，电压过高。优选当氮杂主体的中心部分含有2个氮(嘧啶)或3个氮(三嗪)时，在效率提升的同时，能够保持低电压，使两者达到很好的平衡。其中中心部分含有2个氮时，展示了更高的效率，而由3个氮时，展示了更长的寿命。这种倾向在实施例26-31中也有同样的体现。By comparing Example 6, Example 9, Example 10, Example 24, and Example 25, it can be seen that when the nitrogen atom is contained in the main body of the azobenzene system, due to the increase in the supply of electrons, the number of electrons in the overall molecule is increased, so that Device efficiency is improved. When there is no nitrogen in the central part of the azobenzene-based body, the efficiency is very low, and when one nitrogen is included, higher efficiencies can be obtained compared to the case of no nitrogen at all, but still at a level where there is no significant advantage. And when there are 4 nitrogens, the energy level will be too deep and the voltage will be too high. Preferably, when the central part of the aza body contains 2 nitrogens (pyrimidine) or 3 nitrogens (triazine), while the efficiency is improved, the voltage can be kept low, so that the two can reach a good balance. When the central part contains 2 nitrogens, it shows higher efficiency, and when it consists of 3 nitrogens, it shows a longer lifetime. This tendency also has the same reflection in embodiment 26-31.
通过比较实施例11-14与比较例7可见，二苯基三嗪与荧蒽用两个间亚苯基连接时电压、效率及寿命均不理想，但是当将氮杂苯系主体改变为嘧啶、及/或将苯基改变为联苯基后能够降低电压、提高效率和寿命。By comparing Examples 11-14 and Comparative Example 7, it can be seen that when diphenyltriazine and fluoranthene are connected with two m-phenylene groups, the voltage, efficiency and life are not ideal, but when the main body of the azobenzene system is changed to pyrimidine , and/or changing phenyl to biphenyl can reduce voltage, improve efficiency and life.
通过比较实施例6，实施例16，实施例26-31可见，在分子中导 入邻位苯可以拉近荧蒽主体和氮杂苯系主体的距离，加强电子处理能力，从而提高其电学表现，降低电压，提高效率，且效果非常显著。By comparing Example 6, Example 16, and Examples 26-31, it can be seen that the introduction of ortho-benzene in the molecule can shorten the distance between the fluoranthene main body and the azabenzene-based main body, strengthen the electronic processing ability, and thereby improve its electrical performance. Reduce voltage, improve efficiency, and the effect is very significant.
通过比较实施例6，实施例16可见氮杂苯系主体的取代基为苯与联苯时，相较于两个苯而言，可以提高效率和寿命，然而电压略有提高。另外，实施例6所用的化合物由于氮杂苯系主体更对称，其蒸镀时更容易堵孔，导致良率下降，生产节奏降低。而改善了氮杂苯系主体不对成性的实施例16则有更好的生产表现。进一步地，比较实施例26，实施例29，实施例32，实施例33可见，导入邻位取代基进一步强化电子处理能力后，苯与联苯取代的氮杂苯系主体进一步地降低电压，提高效率，提高寿命，而双苯系材料的上升幅度较小。除了与周边材料的匹配性外，联苯的空间排阻效应限制了氮杂苯系主体的旋转，从而加固了离域大Π键的稳定性，强化了电子处理性能也是很重要的原因。By comparing Example 6 and Example 16, it can be seen that when the main substituents of the azabenzene series are benzene and biphenyl, compared with two benzenes, the efficiency and life can be improved, but the voltage is slightly increased. In addition, the compound used in Example 6 is more symmetrical due to the azobenzene system, and it is easier to block holes during evaporation, resulting in a decrease in yield and a decrease in production rhythm. However, Example 16, which improved the asymmetry of the main azobenzene system, had better production performance. Further, comparing Example 26, Example 29, Example 32, and Example 33, it can be seen that after the introduction of ortho-position substituents further strengthens the electron processing ability, the azabenzene-based main body substituted by benzene and biphenyl further reduces the voltage and improves Efficiency, improve life, but the rise of biphenyl materials is small. In addition to the compatibility with surrounding materials, the steric exclusion effect of biphenyl restricts the rotation of the azobenzene-based host, thereby strengthening the stability of the delocalized large Π bond and enhancing the electronic processing performance is also an important reason.
通过比较实施例16，实施例18与比较例5可见，当使用含氮取代基取代氮杂苯系主体时，由于能级调整过度，与周边层材料不匹配，从而降低了效率。By comparing Example 16, Example 18 and Comparative Example 5, it can be seen that when nitrogen-containing substituents are used to replace the azobenzene-based host, due to excessive adjustment of the energy level, it does not match the material of the surrounding layer, thereby reducing the efficiency.
通过比较实施例16，实施例18与比较例6可见，当在氮杂苯系主体连接稠环时，稠环会扰乱荧蒽带来的规律性电子移动，降低分子的电子处理能力，从而提高电压降低效率。By comparing Example 16, Example 18 and Comparative Example 6, it can be seen that when a condensed ring is connected to the main body of the azobenzene system, the fused ring will disturb the regular electron movement brought by fluoranthene, reduce the electron processing ability of the molecule, and thereby improve voltage reduces efficiency.
通过比较实施例29-31与实施例34-36可见，增加L1和L2中的苯环长度，增加了大Π键的长度，从而让性能又有进一步提升。By comparing Examples 29-31 and Examples 34-36, it can be seen that increasing the length of the benzene rings in L1 and L2 increases the length of the large Π bond, thereby further improving the performance.
通过比较实施例37-41与比较例4，比较例8可见，本发明提供 的荧蒽类化合物由于针对电子特化，所以降低了对空穴的处理能力，作为空穴阻挡层使用时，相较于常见的空穴阻挡材料HB-1以及化合物C-7，可以有效阻止空穴通过，提高效率，延长寿命。By comparing Examples 37-41 with Comparative Example 4 and Comparative Example 8, it can be seen that the fluoranthene compound provided by the present invention is specialized for electrons, so it reduces the ability to handle holes. When used as a hole blocking layer, it is relatively Compared with the common hole blocking materials HB-1 and compound C-7, it can effectively prevent holes from passing through, improve efficiency and prolong life.
通过比较实施例42-45与比较例9可见，本发明提供的荧蒽类化合物作为电荷产生层材料使用时，也能比常见的电荷产生层材料Alq3实现更低的电压，更高的效率和更长的寿命。然而，应当指出的是，器件不是每一层材料的性能的线性叠加，而是多层材料的配合。因此当周边材料发生变化时，也会有相应的最贴合的电子传输层材料。因此本发明提供了一系列材料以便针对不同的实际器件，对分子进行调整。By comparing Examples 42-45 with Comparative Example 9, it can be seen that when the fluoranthene compound provided by the present invention is used as a charge generation layer material, it can also achieve lower voltage than the common charge generation layer material Alq3, higher efficiency and longer life. However, it should be pointed out that the device is not a linear superposition of the properties of each layer of materials, but the coordination of multiple layers of materials. Therefore, when the surrounding material changes, there will also be a corresponding most suitable electron transport layer material. The present invention therefore provides a series of materials to tune the molecules for different practical devices.

Claims (19)

  1. 一种荧蒽衍生物,其具有以下通式1所示的结构：A fluoranthene derivative, which has a structure shown in the following general formula 1:
    Figure PCTCN2022143372-appb-100001
    Figure PCTCN2022143372-appb-100001
    L1为可被取代的亚芳基；L1 is an arylene group that may be substituted;
    L2为单键、可被取代的亚苯基或可被取代的亚杂芳基；L2 is a single bond, a phenylene group that may be substituted, or a heteroarylene group that may be substituted;
    X1、X2、X3、X4、X5相同或不同，各自独立地为N或者C-R1；X1, X2, X3, X4, and X5 are the same or different, each independently being N or C-R1;
    其中R1各自独立地选自氢、氘、可被取代的烷基、可被取代的环烷基、可被取代的杂环基、可被取代的链烯基、可被取代的环烯基、可被取代的炔基、可被取代的烷氧基、可被取代的烷硫基、可被取代的芳基醚基、可被取代的芳基硫醚基、可被取代的芳基、可被取代的杂芳基、可被取代的羰基、可被取代的羧基、可被取代的氧羰基、可被取代的氨基甲酰基、可被取代的硅烷基、可被取代的烷氨基或可被取代的芳基氨基中的一种或多种；Wherein R1 is independently selected from hydrogen, deuterium, alkyl that may be substituted, cycloalkyl that may be substituted, heterocyclic group that may be substituted, alkenyl that may be substituted, cycloalkenyl that may be substituted, Alkynyl which may be substituted, alkoxy which may be substituted, alkylthio which may be substituted, aryl ether which may be substituted, arylsulfide which may be substituted, aryl which may be substituted, Substituted heteroaryl, optionally substituted carbonyl, optionally substituted carboxy, optionally substituted oxycarbonyl, optionally substituted carbamoyl, optionally substituted silyl, optionally substituted alkylamino, or optionally substituted One or more of substituted arylamino groups;
    当X1、X3、X5均为N，X2和X4均为C-R1且R1均为苯基，L1与L2均为亚苯基时，L1和L2中至少有一个选自邻亚苯基或者对亚苯基；When X1, X3, and X5 are all N, X2 and X4 are all C-R1 and R1 is both phenyl, and L1 and L2 are both phenylene, at least one of L1 and L2 is selected from o-phenylene or p- phenylene;
    n1,n4为1-3的整数；n1, n4 are integers of 1-3;
    n2,n3为0-3的整数。n2 and n3 are integers of 0-3.
  2. 根据权利要求1所述的荧蒽衍生物，其特征在于：所述通式1中，n1＝1，n4＝1。The fluoranthene derivative according to claim 1, characterized in that: in the general formula 1, n1=1, n4=1.
  3. 根据权利要求1所述的荧蒽衍生物，其特征在于：所述通式1中， 当n1＝1时，n1×n2+n3×n4的值为1-5的整数。The fluoranthene derivative according to claim 1, characterized in that: in the general formula 1, when n1=1, the value of n1×n2+n3×n4 is an integer of 1-5.
  4. 根据权利要求1所述的荧蒽衍生物，其特征在于：所述通式1中，当n1＝1时，n1×n2+n3×n4的值为2-3的整数。The fluoranthene derivative according to claim 1, characterized in that: in the general formula 1, when n1=1, the value of n1×n2+n3×n4 is an integer of 2-3.
  5. 根据权利要求1所述的荧蒽衍生物，其特征在于：X1、X2、X3、X4、X5中有2个N。The fluoranthene derivative according to claim 1, characterized in that: there are 2 N in X1, X2, X3, X4, and X5.
  6. 根据权利要求1所述的荧蒽衍生物，其特征在于：X1、X2、X3、X4、X5中有3个N。The fluoranthene derivative according to claim 1, characterized in that: there are 3 N in X1, X2, X3, X4, and X5.
  7. 根据权利要求1所述的荧蒽衍生物，其特征在于：X2和X4各自独立地为C-R1。The fluoranthene derivative according to claim 1, characterized in that X2 and X4 are each independently C-R1.
  8. 根据权利要求1所述的荧蒽衍生物，其特征在于：C-R1中的R1选自可取代的苯基、可取代的二苯并呋喃基、可取代的咔唑基、芴基、二苯并噻吩基。The fluoranthene derivative according to claim 1, wherein R1 in C-R1 is selected from substitutable phenyl, substitutable dibenzofuranyl, substitutable carbazolyl, fluorenyl, di Benzothienyl.
  9. 根据权利要求1所述的荧蒽衍生物，其特征在于：X2为C-(Ph)n5，X4为C-(Ph)n6，Ph为苯基，n5+n6>2。The fluoranthene derivative according to claim 1, characterized in that: X2 is C-(Ph)n5, X4 is C-(Ph)n6, Ph is phenyl, n5+n6>2.
  10. 根据权利要求9所述的荧蒽衍生物，其特征在于：n5不等于n6。The fluoranthene derivative according to claim 9, characterized in that: n5 is not equal to n6.
  11. 根据权利要求1所述的荧蒽衍生物，其特征在于L1与L2各自独立地选自亚苯基,但是L1和L2不同时为间亚苯基。The fluoranthene derivative according to claim 1, characterized in that L1 and L2 are each independently selected from phenylene, but L1 and L2 are not m-phenylene at the same time.
  12. 根据权利要求1所述的荧蒽衍生物，其特征在于L1与L2中至少有一个为邻亚苯基。The fluoranthene derivative according to claim 1, characterized in that at least one of L1 and L2 is o-phenylene.
  13. 根据权利要求1所述的荧蒽衍生物，其特征在于：选自如下化合物，The fluoranthene derivative according to claim 1, characterized in that: it is selected from the following compounds,
    Figure PCTCN2022143372-appb-100002
    Figure PCTCN2022143372-appb-100002
    Figure PCTCN2022143372-appb-100003
    Figure PCTCN2022143372-appb-100003
    Figure PCTCN2022143372-appb-100004
    Figure PCTCN2022143372-appb-100004
    Figure PCTCN2022143372-appb-100005
    Figure PCTCN2022143372-appb-100005
    Figure PCTCN2022143372-appb-100006
    Figure PCTCN2022143372-appb-100006
    Figure PCTCN2022143372-appb-100007
    Figure PCTCN2022143372-appb-100007
    Figure PCTCN2022143372-appb-100008
    Figure PCTCN2022143372-appb-100008
    Figure PCTCN2022143372-appb-100009
    Figure PCTCN2022143372-appb-100009
    Figure PCTCN2022143372-appb-100010
    Figure PCTCN2022143372-appb-100010
    Figure PCTCN2022143372-appb-100011
    Figure PCTCN2022143372-appb-100011
    Figure PCTCN2022143372-appb-100012
    Figure PCTCN2022143372-appb-100012
  14. 一种发光元件，其含在阳极与阴极之间存在有机层，有机层为负责发光的层和/或负责处理电子或者空穴的层，在所述有机层中含有 权利要求1-13中任一项所述的荧蒽衍生物。A light-emitting element, which contains an organic layer between the anode and the cathode, the organic layer is a layer responsible for emitting light and/or a layer responsible for handling electrons or holes, and any of the components in claims 1-13 are contained in the organic layer. A fluoranthene derivative according to one item.
  15. 如权利要求14所述的发光元件，其中，所述有机层为负责处理电子或空穴的层，在所述有机层中含有权利要求1-13中任一项所述的荧蒽衍生物。The light-emitting device according to claim 14, wherein the organic layer is a layer responsible for processing electrons or holes, and the fluoranthene derivative according to any one of claims 1-13 is contained in the organic layer.
  16. 如权利要求14所述的发光元件，其中，所述有机层具有电子传输层，在所述电子传输层中含有权利要求1-13中任一项所述的荧蒽衍生物。The light-emitting device according to claim 14, wherein the organic layer has an electron transport layer, and the fluoranthene derivative according to any one of claims 1 to 13 is contained in the electron transport layer.
  17. 如权利要求14所述的发光元件，其中，所述有机层具有电子产生层，在所述电子产生层中含有权利要求1-13中任一项所述的荧蒽衍生物。The light-emitting device according to claim 14, wherein the organic layer has an electron generation layer, and the fluoranthene derivative according to any one of claims 1 to 13 is contained in the electron generation layer.
  18. 如权利要求14所述的发光元件，其中，所述有机层具有空穴阻挡层，在所述空穴阻挡层中含有权利要求1-13中任一项所述的荧蒽衍生物。The light-emitting device according to claim 14, wherein the organic layer has a hole blocking layer, and the fluoranthene derivative according to any one of claims 1 to 13 is contained in the hole blocking layer.
  19. 一种光电转换元件，其含有权利要求1-13中任一项所述的荧蒽生物。A photoelectric conversion element containing the fluoranthene organism according to any one of claims 1-13.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070249878A1 (en) * 2006-04-25 2007-10-25 Canon Kabushiki Kaisha Compound and organic light-emitting element
CN106458899A (en) * 2014-05-28 2017-02-22 东丽株式会社 Fluoranthene derivative, electronic device containing same, light-emitting element, and photoelectric conversion element
CN106803539A (en) * 2015-11-25 2017-06-06 乐金显示有限公司 Organic light-emitting display device
CN107635978A (en) * 2016-01-26 2018-01-26 株式会社Lg化学 Heterocyclic compound and the organic luminescent device for including it
CN107778260A (en) * 2016-08-24 2018-03-09 株式会社Lg化学 Novel organic luminescent material and the organic illuminating element for including it
WO2018103749A1 (en) * 2016-12-08 2018-06-14 广州华睿光电材料有限公司 Triazine fused ring derivative and application thereof in organic electronic device
CN113646916A (en) * 2019-02-06 2021-11-12 诺瓦尔德股份有限公司 Method for preparing organic semiconductor layer, composition for the method, and organic electronic device

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070249878A1 (en) * 2006-04-25 2007-10-25 Canon Kabushiki Kaisha Compound and organic light-emitting element
CN106458899A (en) * 2014-05-28 2017-02-22 东丽株式会社 Fluoranthene derivative, electronic device containing same, light-emitting element, and photoelectric conversion element
CN106803539A (en) * 2015-11-25 2017-06-06 乐金显示有限公司 Organic light-emitting display device
CN107635978A (en) * 2016-01-26 2018-01-26 株式会社Lg化学 Heterocyclic compound and the organic luminescent device for including it
CN107778260A (en) * 2016-08-24 2018-03-09 株式会社Lg化学 Novel organic luminescent material and the organic illuminating element for including it
WO2018103749A1 (en) * 2016-12-08 2018-06-14 广州华睿光电材料有限公司 Triazine fused ring derivative and application thereof in organic electronic device
CN113646916A (en) * 2019-02-06 2021-11-12 诺瓦尔德股份有限公司 Method for preparing organic semiconductor layer, composition for the method, and organic electronic device

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