WO2022080715A1 - Novel compound and organic light-emitting device comprising same - Google Patents

Novel compound and organic light-emitting device comprising same Download PDF

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WO2022080715A1
WO2022080715A1 PCT/KR2021/013360 KR2021013360W WO2022080715A1 WO 2022080715 A1 WO2022080715 A1 WO 2022080715A1 KR 2021013360 W KR2021013360 W KR 2021013360W WO 2022080715 A1 WO2022080715 A1 WO 2022080715A1
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compound
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layer
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이성재
차용범
홍성길
조우진
이용한
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주식회사 엘지화학
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    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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    • C07D209/56—Ring systems containing three or more rings
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    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a novel compound and an organic light emitting device including the same.
  • the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material.
  • the organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.
  • An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode.
  • the organic material layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, it may be made of an electron injection layer, etc.
  • a voltage when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.
  • Patent Document 0001 Korean Patent Publication No. 10-2000-0051826
  • the present invention relates to a novel compound and an organic light emitting device comprising the same.
  • the present invention provides a compound represented by the following formula (1):
  • L 1 and L 2 are each independently a direct bond; substituted or unsubstituted C 6-60 arylene; Or substituted or unsubstituted C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of N, O and S,
  • L 3 is a direct bond; Or a substituted or unsubstituted C 6-60 arylene,
  • Ar 1 and Ar 2 are each independently substituted or unsubstituted C 6-60 aryl; or unsubstituted C 2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S;
  • A is each independently substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
  • R 1 are each independently hydrogen; heavy hydrogen; halogen; nitrile; silyl; substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
  • R 2 are each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted C 6-60 aryl,
  • p is an integer from 1 to 4,
  • a is an integer of 0 to 3, provided that a+p is 1 to 4,
  • b is an integer from 0 to 4.
  • the present invention is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound represented by Formula 1 above. do.
  • the compound represented by Chemical Formula 1 described above may be used as a material for an organic layer of an organic light emitting device, and may improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light emitting device.
  • the compound represented by the above formula (1) may be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection.
  • FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a hole transport layer 3 , a light emitting layer 4 , an electron injection and transport layer 5 , and a cathode 6 .
  • FIG. 2 is a substrate (1), an anode (2), a hole injection layer (7), a hole transport layer (3), an electron blocking layer (8), a light emitting layer (4), a hole blocking layer (9), an electron injection and transport layer ( 5) and an example of an organic light-emitting device including a cathode 6 are shown.
  • substituted or unsubstituted refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; a phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; Or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocycl
  • a substituent in which two or more substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.
  • the number of carbon atoms in the carbonyl group is not particularly limited, but preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms.
  • a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms.
  • it may be a compound of the following structural formula, but is not limited thereto.
  • the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like.
  • the present invention is not limited thereto.
  • the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms.
  • alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl
  • the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms.
  • the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20.
  • the aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.
  • the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.
  • the fluorenyl group is substituted, etc. can be
  • the present invention is not limited thereto.
  • the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms.
  • heterocyclic group examples include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothioph
  • the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the example of the aryl group described above.
  • the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the above-described alkyl group.
  • the description of the heterocyclic group described above for heteroaryl among heteroarylamines may be applied.
  • the alkenyl group among the aralkenyl groups is the same as the above-described examples of the alkenyl group.
  • the description of the above-described aryl group may be applied, except that arylene is a divalent group.
  • the description of the above-described heterocyclic group may be applied, except that heteroarylene is a divalent group.
  • the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining two substituents.
  • the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.
  • the present invention provides a compound represented by Formula 1 above.
  • Formula 1 may be represented by any one selected from the group consisting of the following Formulas 1-1 to 1-3:
  • L 1 , L 2 , L 3 , Ar 1 , Ar 2 , A, R 1 , R 2 , p, a, and b are as defined in claim 1 .
  • L 1 and L 2 are each independently a direct bond, phenylene, or biphenylylene.
  • it is L 3 direct bond, or phenylene.
  • Ar 1 and Ar 2 are each independently phenyl, phenyl substituted with tert-butyl, phenyl substituted with adamantyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenylcarbazolyl.
  • each A is independently phenyl, phenyl substituted with tert-butyl, phenyl substituted with carbazol-9-yl, biphenylyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl.
  • R 1 is hydrogen or phenyl.
  • R 2 is hydrogen or phenyl.
  • p is 1 or 2.
  • a and b are each 0 or 1.
  • the present invention provides a method for preparing a compound represented by Formula 1 as shown in Scheme 1 below.
  • the reaction as an amine substitution reaction, is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art.
  • the manufacturing method may be more specific in Preparation Examples to be described later.
  • the present invention provides an organic light emitting device comprising the compound represented by Formula 1 above.
  • the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Formula 1 above. do.
  • the organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron suppression layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer.
  • the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.
  • the organic layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 It may include the indicated compound.
  • the organic material layer may include an electron blocking layer, and an electron blocking layer between the anode and the light emitting layer.
  • the electron blocking layer is included in contact with the anode side of the light emitting layer.
  • the electron suppression layer serves to improve the efficiency of the organic light emitting device by suppressing electrons injected from the cathode from being transferred to the anode without recombination in the light emitting layer.
  • the electron blocking layer may include a compound represented by Formula 1 above.
  • the organic material layer may include an emission layer, and the emission layer may include a compound represented by Formula 1 above.
  • the organic layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include the compound represented by Formula 1 above.
  • the organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention further comprises a hole injection layer and a hole transport layer between the first electrode and the light emitting layer, and an electron transport layer and an electron injection layer between the light emitting layer and the second electrode in addition to the light emitting layer as an organic layer can have a structure that
  • the structure of the organic light emitting device is not limited thereto and may include a smaller number or a larger number of organic layers.
  • the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.
  • the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.
  • FIGS. 1 and 2 the structure of the organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS. 1 and 2 .
  • FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a hole transport layer 3 , a light emitting layer 4 , an electron injection and transport layer 5 , and a cathode 6 .
  • the compound represented by Formula 1 may be included in the hole transport layer.
  • the compound represented by Formula 1 may be included in the hole injection layer, the hole transport layer, or the electron suppression layer.
  • the organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Formula 1 above. Also, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
  • the organic light emitting diode according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate.
  • a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation
  • a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode
  • it can be prepared by depositing a material that can be used as a cathode thereon.
  • an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
  • the compound represented by Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device.
  • the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.
  • an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890).
  • the manufacturing method is not limited thereto.
  • the first electrode is an anode
  • the second electrode is a cathode
  • the first electrode is a cathode and the second electrode is an anode
  • anode material a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer.
  • the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
  • the cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer.
  • the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multilayer structure material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
  • the hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer
  • a compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • HOMO highest occupied molecular orbital
  • hole injection material examples include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material.
  • organic substances anthraquinones, and conductive polymers of polyaniline and polythiophene series, but are not limited thereto.
  • the hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer.
  • the electron suppression layer is formed on the hole transport layer, preferably provided in contact with the light emitting layer, adjusts hole mobility, prevents excessive movement of electrons, and increases the hole-electron coupling probability, thereby increasing the efficiency of the organic light emitting device It means a layer that plays a role in improving
  • the electron blocking layer includes an electron blocking material, and as an example of the electron blocking material, a compound represented by Formula 1 or an arylamine-based organic material may be used, but is not limited thereto.
  • the light emitting material is a material capable of emitting light in the visible ray region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable.
  • Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.
  • the emission layer may include a host material and a dopant material.
  • the host material includes a condensed aromatic ring derivative or a heterocyclic compound containing compound.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like
  • heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • the dopant material examples include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex.
  • the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene, and the like, having an arylamino group.
  • styrylamine compound a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted.
  • substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted.
  • the metal complex include, but are not limited to, an iridium complex and a platinum complex.
  • the hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to control electron mobility and prevent excessive movement of holes to increase the hole-electron coupling probability, thereby improving the efficiency of the organic light emitting device layer that plays a role.
  • the hole blocking layer includes a hole blocking material.
  • the hole blocking material include an electron withdrawing group such as an azine derivative including triazine, a triazole derivative, an oxadiazole derivative, a phenanthroline derivative, and a phosphine oxide derivative. compounds may be used, but the present invention is not limited thereto.
  • the electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer.
  • Do Specific examples include Al complex of 8-hydroxyquinoline; complexes comprising Alq3; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto.
  • the electron transport layer may be used with any desired cathode material as used in accordance with the prior art.
  • suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.
  • the electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer.
  • a compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable.
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.
  • the metal complex compound examples include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc.
  • the present invention is not limited thereto.
  • the "electron injection and transport layer” is a layer that performs both the role of the electron injection layer and the electron transport layer, and the materials serving the respective layers may be used alone or in combination, but limited thereto. doesn't happen
  • the organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.
  • the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
  • Tetrahydrofuran (THF) (240 ml) was added to Compound 1-A (50.00 g, 115.81 mmol) and phenylboronic acid (14.83 g, 121.60 mmol) obtained in Step 1 of Synthesis Example 1, followed by heating and stirring. .
  • potassium carbonate 48.02 g, 347.43 mmol
  • aqueous solution 120 ml
  • [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.68 g, 0.93 mmol) was slowly added dropwise to the solution, followed by heating and stirring for 1 hour. After completion of the reaction and filtration, the layers were separated with chloroform and water. After removal of the solvent, it was recrystallized from ethyl acetate to obtain compound 1-B (38.0 g, 76.49 % yield).
  • Example 1 using Compound 1-A (50.00 g, 115.81 mmol) and [1,1'-biphenyl]-4-ylboronic acid (24.08 g, 121.60 mmol) obtained in Step 1 of Example 1
  • Compound 8-A (45.0 g, 76.93 % yield) was obtained in the same manner as in step 2.
  • Example 1 using compound 14-A (50.00 g, 115.81 mmol) and [1,1'-biphenyl]-4-ylboronic acid (24.08 g, 121.60 mmol) obtained in step 1 of Example 14
  • Compound 21-A (46.0 g, 78.64 % yield) was obtained in the same manner as in step 2.
  • a glass substrate coated with ITO (Indium Tin Oxide) to a thickness of 1,400 ⁇ was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves.
  • a product manufactured by Fischer Co. was used as the detergent
  • distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water.
  • ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water.
  • ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner.
  • the substrate was transported to a vacuum evaporator.
  • a hole injection layer was formed by thermal vacuum deposition of a compound represented by the following formula HAT on the prepared ITO transparent electrode to a thickness of 100 ⁇ .
  • the compound 1 prepared in Example 1 was thermally vacuum deposited to a thickness of 150 ⁇ as an electron suppression layer.
  • the compound represented by the following formula BH and the compound represented by the following formula BD were vacuum-deposited to a thickness of 200 ⁇ in a weight ratio of 25:1.
  • a compound represented by the following Chemical Formula HB1 was vacuum-deposited to a thickness of 50 ⁇ .
  • a compound represented by the following formula ET1 and a compound represented by the following LiQ were thermally vacuum deposited to a thickness of 310 ⁇ in a weight ratio of 1:1.
  • An organic light-emitting device was manufactured by sequentially depositing lithium fluoride (LiF) to a thickness of 12 ⁇ and aluminum to a thickness of 1000 ⁇ on the electron transport and electron injection layers to form a cathode.
  • LiF lithium fluoride
  • T95 means the time it takes for the luminance to decrease from the initial luminance (6000 nit) to 95%.
  • the compound of the present invention has excellent electron suppression ability, and it was confirmed that the organic light emitting device using the same as the electron suppression layer exhibited remarkable effects in terms of driving voltage, efficiency, and lifespan.
  • T95 denotes a time required for the luminance to decrease from the initial luminance (6000 nit) to 95%.
  • the compound of the present invention has excellent hole transport ability, and it was confirmed that the organic light emitting device using the compound as a hole transport layer exhibits remarkable effects in terms of driving voltage, efficiency, and lifespan.
  • Substrate 2 Anode
  • hole transport layer 4 light emitting layer
  • Electron injection and transport layer 6 Cathode

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Abstract

The present invention provides a novel compound and an organic light-emitting device comprising same.

Description

신규한 화합물 및 이를 포함한 유기 발광 소자Novel compound and organic light emitting device including same
관련 출원(들)과의 상호 인용Cross-Citation with Related Application(s)
본 출원은 2020년 10월 12일자 한국 특허 출원 제10-2020-0131023호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0131023 dated October 12, 2020, and all contents disclosed in the documents of the Korean patent applications are incorporated as a part of this specification.
본 발명은 신규한 화합물 및 이를 포함한 유기 발광 소자에 관한 것이다.The present invention relates to a novel compound and an organic light emitting device including the same.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 넓은 시야각, 우수한 콘트라스트, 빠른 응답 시간을 가지며, 휘도, 구동 전압 및 응답 속도 특성이 우수하여 많은 연구가 진행되고 있다. In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.
유기 발광 소자는 일반적으로 양극과 음극 및 상기 양극과 음극 사이에 유기물층을 포함하는 구조를 가진다. 상기 유기물층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어질 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, it may be made of an electron injection layer, etc. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.
상기와 같은 유기 발광 소자에 사용되는 유기물에 대하여 새로운 재료의 개발이 지속적으로 요구되고 있다.The development of new materials for organic materials used in organic light emitting devices as described above is continuously required.
[선행기술문헌][Prior art literature]
[특허문헌][Patent Literature]
(특허문헌 0001) 한국특허 공개번호 제10-2000-0051826호(Patent Document 0001) Korean Patent Publication No. 10-2000-0051826
본 발명은 신규한 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다. The present invention relates to a novel compound and an organic light emitting device comprising the same.
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다:The present invention provides a compound represented by the following formula (1):
[화학식 1][Formula 1]
Figure PCTKR2021013360-appb-img-000001
Figure PCTKR2021013360-appb-img-000001
상기 화학식 1에서,In Formula 1,
L1 및 L2는 각각 독립적으로 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴렌이고,L 1 and L 2 are each independently a direct bond; substituted or unsubstituted C 6-60 arylene; Or substituted or unsubstituted C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of N, O and S,
L3은 직접 결합; 또는 치환 또는 비치환된 C6-60 아릴렌이고,L 3 is a direct bond; Or a substituted or unsubstituted C 6-60 arylene,
Ar1 및 Ar2는 각각 독립적으로 치환 또는 비치환된 C6-60 아릴; 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이고,Ar 1 and Ar 2 are each independently substituted or unsubstituted C 6-60 aryl; or unsubstituted C 2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S;
A는 각각 독립적으로 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이고,A is each independently substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
R1은 각각 독립적으로 수소; 중수소; 할로겐; 니트릴; 실릴; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이고,R 1 are each independently hydrogen; heavy hydrogen; halogen; nitrile; silyl; substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
R2는 각각 독립적으로 수소; 중수소; 또는 치환 또는 비치환된 C6-60 아릴이고,R 2 are each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted C 6-60 aryl,
p는 1 내지 4의 정수이고,p is an integer from 1 to 4,
a는 0 내지 3의 정수이고, 단, a+p는 1 내지 4이고, a is an integer of 0 to 3, provided that a+p is 1 to 4,
b는 0 내지 4의 정수이다.b is an integer from 0 to 4.
또한, 본 발명은 제1전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물 층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화학식 1로 표시되는 화합물을 포함하는, 유기 발광 소자를 제공한다.In addition, the present invention is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound represented by Formula 1 above. do.
상술한 화학식 1로 표시되는 화합물은 유기 발광 소자의 유기물 층의 재료로서 사용될 수 있으며, 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다. 특히, 상술한 화학식 1로 표시되는 화합물은 정공주입, 정공수송, 정공주입 및 수송, 발광, 전자수송, 또는 전자주입 재료로 사용될 수 있다.The compound represented by Chemical Formula 1 described above may be used as a material for an organic layer of an organic light emitting device, and may improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light emitting device. In particular, the compound represented by the above formula (1) may be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection.
도 1은 기판(1), 양극(2), 정공수송층(3), 발광층(4), 전자주입 및 수송층(5) 및 음극(6)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a hole transport layer 3 , a light emitting layer 4 , an electron injection and transport layer 5 , and a cathode 6 .
도 2는 기판(1), 양극(2), 정공주입층(7), 정공수송층(3), 전자억제층(8), 발광층(4), 정공저지층(9), 전자주입 및 수송층(5) 및 음극(6)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.2 is a substrate (1), an anode (2), a hole injection layer (7), a hole transport layer (3), an electron blocking layer (8), a light emitting layer (4), a hole blocking layer (9), an electron injection and transport layer ( 5) and an example of an organic light-emitting device including a cathode 6 are shown.
이하, 본 발명의 이해를 돕기 위하여 보다 상세히 설명한다.Hereinafter, it will be described in more detail to help the understanding of the present invention.
본 명세서에서,
Figure PCTKR2021013360-appb-img-000002
또는
Figure PCTKR2021013360-appb-img-000003
는 다른 치환기에 연결되는 결합을 의미한다. In this specification,
Figure PCTKR2021013360-appb-img-000002
or
Figure PCTKR2021013360-appb-img-000003
means a bond connected to another substituent.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 할로겐기; 니트릴기; 니트로기; 히드록시기; 카보닐기; 에스테르기; 이미드기; 아미노기; 포스핀옥사이드기; 알콕시기; 아릴옥시기; 알킬티옥시기; 아릴티옥시기; 알킬술폭시기; 아릴술폭시기; 실릴기; 붕소기; 알킬기; 사이클로알킬기; 알케닐기; 아릴기; 아르알킬기; 아르알케닐기; 알킬아릴기; 알킬아민기; 아랄킬아민기; 헤테로아릴아민기; 아릴아민기; 아릴포스핀기; 또는 N, O 및 S 원자 중 1개 이상을 포함하는 헤테로고리기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환되거나, 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환 또는 비치환된 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 비페닐기일 수 있다. 즉, 비페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수 있다.As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; a phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; Or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group including one or more, or substituted or unsubstituted, two or more of the above-exemplified substituents are linked. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.
본 명세서에서 카보닐기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 40인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the number of carbon atoms in the carbonyl group is not particularly limited, but preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2021013360-appb-img-000004
Figure PCTKR2021013360-appb-img-000004
본 명세서에 있어서, 에스테르기는 에스테르기의 산소가 탄소수 1 내지 25의 직쇄, 분지쇄 또는 고리쇄 알킬기 또는 탄소수 6 내지 25의 아릴기로 치환될 수 있다. 구체적으로, 하기 구조식의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, in the ester group, oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure PCTKR2021013360-appb-img-000005
Figure PCTKR2021013360-appb-img-000005
본 명세서에 있어서, 이미드기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 25인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2021013360-appb-img-000006
Figure PCTKR2021013360-appb-img-000006
본 명세서에 있어서, 실릴기는 구체적으로 트리메틸실릴기, 트리에틸실릴기, t-부틸디메틸실릴기, 비닐디메틸실릴기, 프로필디메틸실릴기, 트리페닐실릴기, 디페닐실릴기, 페닐실릴기 등이 있으나 이에 한정되지 않는다. In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.
본 명세서에 있어서, 붕소기는 구체적으로 트리메틸붕소기, 트리에틸붕소기, t-부틸디메틸붕소기, 트리페닐붕소기, 페닐붕소기 등이 있으나 이에 한정되지 않는다.In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.
본 명세서에 있어서, 할로겐기의 예로는 불소, 염소, 브롬 또는 요오드가 있다.In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 6이다. 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 사이클로펜틸메틸,사이클로헥틸메틸, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 2-메틸펜틸, 4-메틸헥실, 5-메틸헥실 등이 있으나, 이들에 한정되지 않는다.In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.
본 명세서에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 6이다. 구체적인 예로는 비닐, 1-프로페닐, 이소프로페닐, 1-부테닐, 2-부테닐, 3-부테닐, 1-펜테닐, 2-펜테닐, 3-펜테닐, 3-메틸-1-부테닐, 1,3-부타디에닐, 알릴, 1-페닐비닐-1-일, 2-페닐비닐-1-일, 2,2-디페닐비닐-1-일, 2-페닐-2-(나프틸-1-일)비닐-1-일, 2,2-비스(디페닐-1-일)비닐-1-일, 스틸베닐기, 스티레닐기 등이 있으나 이들에 한정되지 않는다.In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.
본 명세서에 있어서, 사이클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 60인 것이 바람직하며, 일 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 30이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 20이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 6이다. 구체적으로 사이클로프로필, 사이클로부틸, 사이클로펜틸, 3-메틸사이클로펜틸, 2,3-디메틸사이클로펜틸, 사이클로헥실, 3-메틸사이클로헥실, 4-메틸사이클로헥실, 2,3-디메틸사이클로헥실, 3,4,5-트리메틸사이클로헥실, 4-tert-부틸사이클로헥실, 사이클로헵틸, 사이클로옥틸 등이 있으나, 이에 한정되지 않는다.In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나 탄소수 6 내지 60인 것이 바람직하며, 단환식 아릴기 또는 다환식 아릴기일 수 있다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 30이다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 20이다. 상기 아릴기가 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트릴기, 파이레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.
본 명세서에 있어서, 플루오레닐기는 치환될 수 있고, 치환기 2개가 서로 결합하여 스피로 구조를 형성할 수 있다. 상기 플루오레닐기가 치환되는 경우,
Figure PCTKR2021013360-appb-img-000007
등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,
Figure PCTKR2021013360-appb-img-000007
etc. can be However, the present invention is not limited thereto.
본 명세서에 있어서, 헤테로고리기는 이종 원소로 O, N, Si 및 S 중 1개 이상을 포함하는 헤테로고리기로서, 탄소수는 특별히 한정되지 않으나, 탄소수 2 내지 60인 것이 바람직하다. 헤테로고리기의 예로는 티오펜기, 퓨란기, 피롤기, 이미다졸기, 티아졸기, 옥사졸기, 옥사디아졸기, 트리아졸기, 피리딜기, 비피리딜기, 피리미딜기, 트리아진기, 아크리딜기, 피리다진기, 피라지닐기, 퀴놀리닐기, 퀴나졸린기, 퀴녹살리닐기, 프탈라지닐기, 피리도 피리미디닐기, 피리도 피라지닐기, 피라지노 피라지닐기, 이소퀴놀린기, 인돌기, 카바졸기, 벤조옥사졸기, 벤조이미다졸기, 벤조티아졸기, 벤조카바졸기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨라닐기, 페난쓰롤린기(phenanthroline), 이소옥사졸릴기, 티아디아졸릴기, 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia and a jolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.
본 명세서에 있어서, 아르알킬기, 아르알케닐기, 알킬아릴기, 아릴아민기 중의 아릴기는 전술한 아릴기의 예시와 같다. 본 명세서에 있어서, 아르알킬기, 알킬아릴기, 알킬아민기 중 알킬기는 전술한 알킬기의 예시와 같다. 본 명세서에 있어서, 헤테로아릴아민 중 헤테로아릴은 전술한 헤테로고리기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 아르알케닐기 중 알케닐기는 전술한 알케닐기의 예시와 같다. 본 명세서에 있어서, 아릴렌은 2가기인 것을 제외하고는 전술한 아릴기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 헤테로아릴렌은 2가기인 것을 제외하고는 전술한 헤테로고리기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 탄화수소 고리는 1가기가 아니고, 2개의 치환기가 결합하여 형성한 것을 제외하고는 전술한 아릴기 또는 사이클로알킬기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 헤테로고리는 1가기가 아니고, 2개의 치환기가 결합하여 형성한 것을 제외하고는 전술한 헤테로고리기에 관한 설명이 적용될 수 있다.In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the above-described alkyl group. In the present specification, the description of the heterocyclic group described above for heteroaryl among heteroarylamines may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the above-described examples of the alkenyl group. In the present specification, the description of the above-described aryl group may be applied, except that arylene is a divalent group. In the present specification, the description of the above-described heterocyclic group may be applied, except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.
(화합물)(compound)
본 발명은 상기 화학식 1로 표시되는 화합물을 제공한다.The present invention provides a compound represented by Formula 1 above.
바람직하게는 상기 화학식 1은 하기 화학식 1-1 내지 화학식 1-3으로 구성되는 군으로부터 선택되는 어느 하나로 표시될 수 있다:Preferably, Formula 1 may be represented by any one selected from the group consisting of the following Formulas 1-1 to 1-3:
[화학식 1-1][Formula 1-1]
Figure PCTKR2021013360-appb-img-000008
Figure PCTKR2021013360-appb-img-000008
[화학식 1-2][Formula 1-2]
Figure PCTKR2021013360-appb-img-000009
Figure PCTKR2021013360-appb-img-000009
[화학식 1-3][Formula 1-3]
Figure PCTKR2021013360-appb-img-000010
Figure PCTKR2021013360-appb-img-000010
상기 화학식 1-1 내지 1-3에서, In Formulas 1-1 to 1-3,
L1, L2, L3, Ar1, Ar2, A, R1, R2, p, a, 및 b는 제1항에서 정의한 바와 같다.L 1 , L 2 , L 3 , Ar 1 , Ar 2 , A, R 1 , R 2 , p, a, and b are as defined in claim 1 .
바람직하게는, L1 및 L2는 각각 독립적으로 직접 결합, 페닐렌, 또는 비페닐릴렌이다.Preferably, L 1 and L 2 are each independently a direct bond, phenylene, or biphenylylene.
바람직하게는, L3 직접 결합, 또는 페닐렌이다.Preferably, it is L 3 direct bond, or phenylene.
바람직하게는, Ar1 및 Ar2는 각각 독립적으로 페닐, 터트-부틸로 치환된 페닐, 아다만틸로 치환된 페닐, 비페닐릴, 터페닐릴, 나프틸, 페난트레닐, 트리페닐레닐, 디메틸플루오레닐, 디페닐플루오레닐, 스피로비플루오레닐, 디벤조퓨라닐, 디벤조티오페닐, 카바졸-9-일, 또는 9-페닐카바졸일이다.Preferably, Ar 1 and Ar 2 are each independently phenyl, phenyl substituted with tert-butyl, phenyl substituted with adamantyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenylcarbazolyl.
바람직하게는, A는 각각 독립적으로 페닐, 터트-부틸로 치환된 페닐, 카바졸-9-일로 치환된 페닐, 비페닐릴, 나프틸, 디벤조퓨라닐, 또는 디벤조티오페닐이다.Preferably, each A is independently phenyl, phenyl substituted with tert-butyl, phenyl substituted with carbazol-9-yl, biphenylyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl.
바람직하게는, R1은 수소, 또는 페닐이다.Preferably, R 1 is hydrogen or phenyl.
바람직하게는, R2는 수소, 또는 페닐이다.Preferably, R 2 is hydrogen or phenyl.
바람직하게는, p는 1 또는 2이다.Preferably, p is 1 or 2.
바람직하게는, a 및 b는 각각 0 또는 1이다.Preferably, a and b are each 0 or 1.
상기 화학식 1로 표시되는 화합물의 대표적인 예는 다음과 같다:Representative examples of the compound represented by Formula 1 are as follows:
Figure PCTKR2021013360-appb-img-000011
Figure PCTKR2021013360-appb-img-000011
Figure PCTKR2021013360-appb-img-000012
Figure PCTKR2021013360-appb-img-000012
Figure PCTKR2021013360-appb-img-000013
Figure PCTKR2021013360-appb-img-000013
Figure PCTKR2021013360-appb-img-000014
Figure PCTKR2021013360-appb-img-000014
Figure PCTKR2021013360-appb-img-000015
Figure PCTKR2021013360-appb-img-000015
Figure PCTKR2021013360-appb-img-000016
Figure PCTKR2021013360-appb-img-000016
Figure PCTKR2021013360-appb-img-000017
Figure PCTKR2021013360-appb-img-000017
Figure PCTKR2021013360-appb-img-000018
Figure PCTKR2021013360-appb-img-000018
Figure PCTKR2021013360-appb-img-000019
Figure PCTKR2021013360-appb-img-000019
Figure PCTKR2021013360-appb-img-000020
Figure PCTKR2021013360-appb-img-000020
Figure PCTKR2021013360-appb-img-000021
Figure PCTKR2021013360-appb-img-000021
Figure PCTKR2021013360-appb-img-000022
Figure PCTKR2021013360-appb-img-000022
Figure PCTKR2021013360-appb-img-000023
Figure PCTKR2021013360-appb-img-000023
Figure PCTKR2021013360-appb-img-000024
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Figure PCTKR2021013360-appb-img-000087
또한, 본 발명은 하기 반응식 1과 같은 상기 화학식 1로 표시되는 화합물의 제조 방법을 제공한다.In addition, the present invention provides a method for preparing a compound represented by Formula 1 as shown in Scheme 1 below.
[반응식 1][Scheme 1]
Figure PCTKR2021013360-appb-img-000088
Figure PCTKR2021013360-appb-img-000088
상기 반응식 1에서, L1 내지 L3, Ar1, Ar2, A, R1, R2, a, b, p는 앞서 정의한 바와 같으며, X는 할로겐이고, 바람직하게는 브로모, 또는 클로로이다.In Scheme 1, L 1 to L 3 , Ar 1 , Ar 2 , A, R 1 , R 2 , a, b, p are as defined above, X is halogen, preferably bromo, or chloro am.
상기 반응은, 아민 치환 반응으로서, 팔라듐 촉매와 염기 존재하에 수행하는 것이 바람직하며, 아민 치환 반응을 위한 반응기는 당업계에 알려진 바에 따라 변경이 가능하다. 상기 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.The reaction, as an amine substitution reaction, is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.
(유기 발광 소자)(organic light emitting element)
또한, 본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기 발광 소자를 제공한다. 일례로, 본 발명은 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물 층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화학식 1로 표시되는 화합물을 포함하는, 유기 발광 소자를 제공한다.In addition, the present invention provides an organic light emitting device comprising the compound represented by Formula 1 above. In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Formula 1 above. do.
본 발명의 유기 발광 소자의 유기물 층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기 발광 소자는 유기물 층으로서 정공주입층, 정공수송층, 전자억제층, 발광층, 전자수송층, 전자주입층 등을 포함하는 구조를 가질 수 있다. 그러나 유기 발광 소자의 구조는 이에 한정되지 않고 더 적은 수의 유기층을 포함할 수 있다.The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron suppression layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.
또한, 상기 유기물 층은 정공주입층, 정공수송층, 또는 정공 주입과 수송을 동시에 하는 층을 포함할 수 있고, 상기 정공주입층, 정공수송층, 또는 정공 주입과 수송을 동시에 하는 층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.In addition, the organic layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 It may include the indicated compound.
상기 유기물층은 전자억제층을 포함할 수 있고, 상기 양극과 발광층 사이에 전자억제층을 포함한다. 바람직하게는, 상기 전자억제층은 상기 발광층의 양극 쪽에 접하여 포함된다. 상기 전자억제층은, 음극에서 주입된 전자가 발광층에서 재결합하지 않고 양극 쪽으로 전달되는 것을 억제하여 유기 발광 소자의 효율을 향상시키는 역할을 한다. 상기 전자억제층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.The organic material layer may include an electron blocking layer, and an electron blocking layer between the anode and the light emitting layer. Preferably, the electron blocking layer is included in contact with the anode side of the light emitting layer. The electron suppression layer serves to improve the efficiency of the organic light emitting device by suppressing electrons injected from the cathode from being transferred to the anode without recombination in the light emitting layer. The electron blocking layer may include a compound represented by Formula 1 above.
또한, 상기 유기물층은 발광층을 포함할 수 있고, 상기 발광층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.In addition, the organic material layer may include an emission layer, and the emission layer may include a compound represented by Formula 1 above.
또한, 상기 유기물 층은 전자수송층, 또는 전자주입층을 포함할 수 있고, 상기 전자수송층, 또는 전자주입층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.In addition, the organic layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include the compound represented by Formula 1 above.
본 발명의 유기 발광 소자의 유기물 층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기 발광 소자는 유기물 층으로서 발광층 이외에, 상기 제1전극과 상기 발광층 사이의 정공주입층 및 정공수송층, 및 상기 발광층과 상기 제2전극 사이의 전자수송층 및 전자주입층을 더 포함하는 구조를 가질 수 있다. 그러나 유기 발광 소자의 구조는 이에 한정되지 않고 더 적은 수 또는 더 많은 수의 유기층을 포함할 수 있다.The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention further comprises a hole injection layer and a hole transport layer between the first electrode and the light emitting layer, and an electron transport layer and an electron injection layer between the light emitting layer and the second electrode in addition to the light emitting layer as an organic layer can have a structure that However, the structure of the organic light emitting device is not limited thereto and may include a smaller number or a larger number of organic layers.
또한, 본 발명에 따른 유기 발광 소자는, 기판 상에 양극, 1층 이상의 유기물층 및 음극이 순차적으로 적층된 구조(normal type)의 유기 발광 소자일 수 있다. 또한, 본 발명에 따른 유기 발광 소자는 기판 상에 음극, 1층 이상의 유기물층 및 양극이 순차적으로 적층된 역방향 구조(inverted type)의 유기 발광 소자일 수 있다. 예컨대, 본 발명의 일실시예에 따른 유기 발광 소자의 구조는 도 1 및 2에 예시되어 있다.Also, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Also, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of the organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS. 1 and 2 .
도 1은 기판(1), 양극(2), 정공수송층(3), 발광층(4), 전자주입 및 수송층(5) 및 음극(6)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 정공수송층에 포함될 수 있다.FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a hole transport layer 3 , a light emitting layer 4 , an electron injection and transport layer 5 , and a cathode 6 . In such a structure, the compound represented by Formula 1 may be included in the hole transport layer.
도 2는 기판(1), 양극(2), 정공주입층(7), 정공수송층(3), 전자억제층(8), 발광층(4), 정공저지층(9), 전자주입 및 수송층(5) 및 음극(6)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 정공주입층, 정공수송층, 또는 전자억제층에 포함될 수 있다.2 is a substrate (1), an anode (2), a hole injection layer (7), a hole transport layer (3), an electron blocking layer (8), a light emitting layer (4), a hole blocking layer (9), an electron injection and transport layer ( 5) and an example of an organic light-emitting device including a cathode 6 are shown. In such a structure, the compound represented by Formula 1 may be included in the hole injection layer, the hole transport layer, or the electron suppression layer.
본 발명에 따른 유기 발광 소자는, 상기 유기물 층 중 1층 이상이 상기 화학식 1로 표시되는 화합물을 포함하는 것을 제외하고는 당 기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다. 또한, 상기 유기 발광 소자가 복수개의 유기물층을 포함하는 경우, 상기 유기물층은 동일한 물질 또는 다른 물질로 형성될 수 있다. The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Formula 1 above. Also, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
예컨대, 본 발명에 따른 유기 발광 소자는 기판 상에 제1 전극, 유기물층 및 제2 전극을 순차적으로 적층시켜 제조할 수 있다. 이때, 스퍼터링법(sputtering)이나 전자빔 증발법(e-beam evaporation)과 같은 PVD(physical Vapor Deposition)방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공 주입층, 정공 수송층, 발광층 및 전자 수송층을 포함하는 유기물 층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시켜 제조할 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수 있다. For example, the organic light emitting diode according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode And, after forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
또한, 상기 화학식 1로 표시되는 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물 층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.In addition, the compound represented by Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.
이와 같은 방법 외에도, 기판 상에 음극 물질로부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 제조할 수 있다(WO 2003/012890). 다만, 제조 방법이 이에 한정되는 것은 아니다. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.
일례로, 상기 제1 전극은 양극이고, 상기 제2 전극은 음극이거나, 또는 상기 제1 전극은 음극이고, 상기 제2 전극은 양극이다.In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.
상기 양극 물질로는 통상 유기물 층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 상기 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
상기 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 상기 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multilayer structure material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
상기 정공주입층은 전극으로부터 정공을 주입하는 층으로, 정공 주입 물질로는 정공을 수송하는 능력을 가져 양극에서의 정공 주입효과, 발광층 또는 발광재료에 대하여 우수한 정공 주입 효과를 갖고, 발광층에서 생성된 여기자의 전자주입층 또는 전자주입재료에의 이동을 방지하며, 또한, 박막 형성 능력이 우수한 화합물이 바람직하다. 정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물 층의 HOMO 사이인 것이 바람직하다. 정공 주입 물질의 구체적인 예로는 금속 포피린(porphyrin), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone)계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정 되는 것은 아니다. The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, and conductive polymers of polyaniline and polythiophene series, but are not limited thereto.
상기 정공수송층은 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로, 정공 수송 물질로 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다. The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. A material capable of transporting holes from the anode or hole injection layer to the light emitting layer as a hole transport material. A material with high hole mobility. This is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.
상기 전자억제층은 상기 정공수송층 상에 형성되어, 바람직하게는 발광층에 접하여 구비되어, 정공이동도를 조절하고, 전자의 과다한 이동을 방지하여 정공-전자간 결합 확률을 높여줌으로써 유기 발광 소자의 효율을 개선하는 역할을 하는 층을 의미한다. 상기 전자억제층은 전자저지물질을 포함하고, 이러한 전자저지물질의 예로 상기 화학식 1로 표시되는 화합물을 사용하거나, 또는 아릴아민 계열의 유기물 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.The electron suppression layer is formed on the hole transport layer, preferably provided in contact with the light emitting layer, adjusts hole mobility, prevents excessive movement of electrons, and increases the hole-electron coupling probability, thereby increasing the efficiency of the organic light emitting device It means a layer that plays a role in improving The electron blocking layer includes an electron blocking material, and as an example of the electron blocking material, a compound represented by Formula 1 or an arylamine-based organic material may be used, but is not limited thereto.
상기 발광 물질로는 정공수송층과 전자수송층으로부터 정공과 전자를 각각 수송 받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다. 구체적인 예로 8-히드록시-퀴놀린 알루미늄 착물(Alq3); 카르바졸 계열 화합물; 이량체화 스티릴(dimerized styryl) 화합물; BAlq; 10-히드록시벤조 퀴놀린-금속 화합물; 벤족사졸, 벤즈티아졸 및 벤즈이미다졸 계열의 화합물; 폴리(p-페닐렌비닐렌)(PPV) 계열의 고분자; 스피로(spiro) 화합물; 폴리플루오렌, 루브렌 등이 있으나, 이들에만 한정되는 것은 아니다. The light emitting material is a material capable of emitting light in the visible ray region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.
상기 발광층은 호스트 재료 및 도펀트 재료를 포함할 수 있다. 호스트 재료는 축합 방향족환 유도체 또는 헤테로환 함유 화합물 등이 있다. 구체적으로 축합 방향족환 유도체로는 안트라센 유도체, 피렌 유도체, 나프탈렌 유도체, 펜타센 유도체, 페난트렌 화합물, 플루오란텐 화합물 등이 있고, 헤테로환 함유 화합물로는 카바졸 유도체, 디벤조퓨란 유도체, 래더형 퓨란 화합물, 피리미딘 유도체 등이 있으나, 이에 한정되지 않는다. The emission layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a heterocyclic compound containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
도펀트 재료로는 방향족 아민 유도체, 스트릴아민 화합물, 붕소 착체, 플루오란텐 화합물, 금속 착체 등이 있다. 구체적으로 방향족 아민 유도체로는 치환 또는 비치환된 아릴아미노기를 갖는 축합 방향족환 유도체로서, 아릴아미노기를 갖는 피렌, 안트라센, 크리센, 페리플란텐 등이 있으며, 스티릴아민 화합물로는 치환 또는 비치환된 아릴아민에 적어도 1개의 아릴비닐기가 치환되어 있는 화합물로, 아릴기, 실릴기, 알킬기, 사이클로알킬기 및 아릴아미노기로 이루어진 군에서 1 또는 2 이상 선택되는 치환기가 치환 또는 비치환된다. 구체적으로 스티릴아민, 스티릴디아민, 스티릴트리아민, 스티릴테트라아민 등이 있으나, 이에 한정되지 않는다. 또한, 금속 착체로는 이리듐 착체, 백금 착체 등이 있으나, 이에 한정되지 않는다.Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.
상기 정공저지층은 발광층 상에 형성되어, 바람직하게는 발광층에 접하여 구비되어, 전자이동도를 조절하고 정공의 과다한 이동을 방지하여 정공-전자간 결합 확률을 높여줌으로써 유기 발광 소자의 효율을 개선하는 역할을 하는 층을 의미한다. 상기 정공저지층은 정공저지물질을 포함하고, 이러한 정공저지물질의 예로 트리아진을 포함한 아진류유도체, 트리아졸 유도체, 옥사디아졸 유도체, 페난트롤린 유도체, 포스핀옥사이드 유도체 등의 전자흡인기가 도입된 화합물을 사용할 수 있으나, 이에 한정되는 것은 아니다.The hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to control electron mobility and prevent excessive movement of holes to increase the hole-electron coupling probability, thereby improving the efficiency of the organic light emitting device layer that plays a role. The hole blocking layer includes a hole blocking material. Examples of the hole blocking material include an electron withdrawing group such as an azine derivative including triazine, a triazole derivative, an oxadiazole derivative, a phenanthroline derivative, and a phosphine oxide derivative. compounds may be used, but the present invention is not limited thereto.
상기 전자수송층은 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하는 층으로 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자 수송층은 종래기술에 따라 사용된 바와 같이 임의의 원하는 캐소드 물질과 함께 사용할 수 있다. 특히, 적절한 캐소드 물질의 예는 낮은 일함수를 가지고 알루미늄층 또는 실버층이 뒤따르는 통상적인 물질이다. 구체적으로 세슘, 바륨, 칼슘, 이테르븀 및 사마륨이고, 각 경우 알루미늄 층 또는 실버층이 뒤따른다.The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. Do. Specific examples include Al complex of 8-hydroxyquinoline; complexes comprising Alq3; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.
상기 전자주입층은 전극으로부터 전자를 주입하는 층으로, 전자를 수송하는 능력을 갖고, 음극으로부터의 전자 주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자주입 효과를 가지며, 발광층에서 생성된 여기자의 정공주입층에의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물이 바람직하다. 구체적으로는 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 질소 함유 5원환 유도체 등이 있으나, 이에 한정되지 않는다. The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.
상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.
한편, 본 발명에 있어서 "전자 주입 및 수송층"은 상기 전자주입층과 상기 전자수송층의 역할을 모두 수행하는 층으로 상기 각 층의 역할을 하는 물질을 단독으로, 혹은 혼합하여 사용할 수 있으나, 이에 한정되지 않는다. On the other hand, in the present invention, the "electron injection and transport layer" is a layer that performs both the role of the electron injection layer and the electron transport layer, and the materials serving the respective layers may be used alone or in combination, but limited thereto. doesn't happen
본 발명에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.
또한, 본 발명에 따른 화합물은 유기 발광 소자 외에도 유기 태양 전지 또는 유기 트랜지스터에 포함될 수 있다.In addition, the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
상기 화학식 1로 표시되는 화합물 및 이를 포함하는 유기 발광 소자의 제조는 이하 실시예에서 구체적으로 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범위가 이들에 의하여 한정되는 것은 아니다.The compound represented by Formula 1 and the preparation of an organic light emitting device including the same will be described in detail in Examples below. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.
[실시예][Example]
실시예 1: 화합물 1의 합성Example 1: Synthesis of compound 1
단계 1) 화합물 1-A의 합성Step 1) Synthesis of compound 1-A
Figure PCTKR2021013360-appb-img-000089
Figure PCTKR2021013360-appb-img-000089
2,2’-디브로모-1,1’-비페닐 (50.00 g, 160.25 mmol)을 테트라하이드로퓨란(THF) (300 ml)에 용해 후 -78℃로 온도를 하강시켰다. 상기 용액에 1.6 M n-부틸리튬(n-butyllithium) (100 ml)을 천천히 투입 후 10 분 간 교반하였다. 상기 용액에 (4-클로로페닐)(페닐)메타논 (34.72 g, 160.25 mmol)을 테트라하이드로퓨란(THF) (300 ml)에 용해 후 천천히 투입하였다. 반응 종결 후 1 N 염산 (400 ml)을 투입하여 층분리 하였다. 용매 제거 후 아세트산 (800 ml)을 투입하여 환류, 교반하고 황산(cat.)을 적가하였다. 반응 종결 및 여과 후, 클로로포름과 탄산수소나트륨(NaHCO3) 수용액으로 층분리 하였다. 용매 제거 후 에틸아세테이트로 재결정하여 화합물 1-A (52.0 g, 75.16 % 수율)를 수득하였다.After dissolving 2,2'-dibromo-1,1'-biphenyl (50.00 g, 160.25 mmol) in tetrahydrofuran (THF) (300 ml), the temperature was lowered to -78°C. 1.6 M n-butyllithium (100 ml) was slowly added to the solution and stirred for 10 minutes. (4-chlorophenyl)(phenyl)methanone (34.72 g, 160.25 mmol) was dissolved in tetrahydrofuran (THF) (300 ml) in the solution, and then slowly added. After completion of the reaction, 1 N hydrochloric acid (400 ml) was added to separate the layers. After removal of the solvent, acetic acid (800 ml) was added, refluxed, stirred, and sulfuric acid (cat.) was added dropwise. After completion of the reaction and filtration, the layers were separated with chloroform and an aqueous solution of sodium hydrogen carbonate (NaHCO 3 ). After removal of the solvent, it was recrystallized from ethyl acetate to obtain compound 1-A (52.0 g, 75.16 % yield).
단계 2) 화합물 1-B의 합성Step 2) Synthesis of compound 1-B
Figure PCTKR2021013360-appb-img-000090
Figure PCTKR2021013360-appb-img-000090
상기 합성예 1의 단계 1에서 수득한 화합물 1-A (50.00 g, 115.81 mmol)와 페닐보론산 (14.83 g, 121.60 mmol)에 테트라하이드로퓨란(THF) (240 ml)을 가한 후 가열, 교반하였다. 상기 용액에 탄산칼륨 (48.02 g, 347.43 mmol) 수용액 (120 ml)을 가한 후 5분 동안 가열, 교반하였다. 상기 용액에 [1,1’-비스(디페닐포스피노)페로센]디클로로팔라듐(II) (0.68 g, 0.93 mmol)을 천천히 적가한 후 1시간 동안 가열, 교반하였다. 반응 종결 및 여과 후, 클로로포름과 물로 층분리 하였다. 용매 제거 후 에틸아세테이트로 재결정하여 화합물 1-B (38.0 g, 76.49 % 수율)를 수득하였다.Tetrahydrofuran (THF) (240 ml) was added to Compound 1-A (50.00 g, 115.81 mmol) and phenylboronic acid (14.83 g, 121.60 mmol) obtained in Step 1 of Synthesis Example 1, followed by heating and stirring. . To the solution was added potassium carbonate (48.02 g, 347.43 mmol) aqueous solution (120 ml), followed by heating and stirring for 5 minutes. [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.68 g, 0.93 mmol) was slowly added dropwise to the solution, followed by heating and stirring for 1 hour. After completion of the reaction and filtration, the layers were separated with chloroform and water. After removal of the solvent, it was recrystallized from ethyl acetate to obtain compound 1-B (38.0 g, 76.49 % yield).
단계 3) 화합물 1의 합성Step 3) Synthesis of compound 1
Figure PCTKR2021013360-appb-img-000091
Figure PCTKR2021013360-appb-img-000091
상기 합성예 1의 단계 2에서 수득한 화합물 1-B (20.00 g, 46.62 mmol), 4-(페난트렌-9-일)-N-페닐아닐린 (16.43 g, 47.56 mmol) 그리고 소듐 터트-부톡사이드(6.27 g, 65.27 mmol)에 자일렌(200 ml)을 가한 후, 10분 동안 가열 교반하였다. 상기 혼합물에 자일렌(20ml)에 용해시킨 비스(트리-터트-부틸포스핀)팔라듐 (0.12 g, 0.23 mmol)을 가한 후 1시간 동안 가열 교반하였다. 반응 종결 및 여과 후, 톨루엔과 물로 층분리 하였다. 용매 제거 후 에틸아세테이트로 재결정하여 상기 화합물 1 (27.0 g, 78.48 % 수율)을 수득하였다. Compound 1-B (20.00 g, 46.62 mmol), 4-(phenanthren-9-yl) -N -phenylaniline (16.43 g, 47.56 mmol) obtained in step 2 of Synthesis Example 1, and sodium tert-butoxide (6.27 g, 65.27 mmol) was added with xylene (200 ml), followed by heating and stirring for 10 minutes. Bis(tri-tert-butylphosphine)palladium (0.12 g, 0.23 mmol) dissolved in xylene (20ml) was added to the mixture, followed by heating and stirring for 1 hour. After completion of the reaction and filtration, the layers were separated with toluene and water. After removal of the solvent, it was recrystallized from ethyl acetate to obtain Compound 1 (27.0 g, 78.48 % yield).
MS: [M+H]+ = 738MS: [M+H] + = 738
실시예 2: 화합물 2의 합성Example 2: Synthesis of compound 2
Figure PCTKR2021013360-appb-img-000092
Figure PCTKR2021013360-appb-img-000092
상기 실시예 1의 단계 2에서 수득한 화합물 1-B (20.0 g, 46.62 mmol)와 디([1,1’-비페닐]-4-일)아민 (15.29 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 2 (26.0 g, 78.12 % 수율)를 수득하였다. Using compound 1-B (20.0 g, 46.62 mmol) and di([1,1'-biphenyl]-4-yl)amine (15.29 g, 47.56 mmol) obtained in step 2 of Example 1 above Compound 2 (26.0 g, 78.12 % yield) was obtained in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 714MS: [M+H] + = 714
실시예 3: 화합물 3의 합성Example 3: Synthesis of compound 3
Figure PCTKR2021013360-appb-img-000093
Figure PCTKR2021013360-appb-img-000093
상기 실시예 1의 단계 2에서 수득한 화합물 1-B (20.0 g, 46.62 mmol)와 N-([1,1’-비페닐]-4-일)-9,9-디메틸-9H-플루오렌-2-아민 (17.19 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 3 (27.5 g, 78.23 % 수율)을 수득하였다. Compound 1-B (20.0 g, 46.62 mmol) obtained in step 2 of Example 1 and N -([1,1'-biphenyl]-4-yl) -9,9 -dimethyl-9H-flu Compound 3 (27.5 g, 78.23 % yield) was obtained in the same manner as in step 3 of Example 1 using oren-2-amine (17.19 g, 47.56 mmol).
MS: [M+H]+ = 754MS: [M+H] + = 754
실시예 4: 화합물 4의 합성Example 4: Synthesis of compound 4
Figure PCTKR2021013360-appb-img-000094
Figure PCTKR2021013360-appb-img-000094
상기 실시예 1의 단계 2에서 수득한 화합물 1-B (20.0 g, 46.62 mmol)와 N-([1,1’-비페닐]-4-일)디벤조[b,d]퓨란-4-아민 (15.95 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 4 (27.0 g, 79.56 % 수율)를 수득하였다.Compound 1-B (20.0 g, 46.62 mmol) obtained in step 2 of Example 1 and N -([1,1'-biphenyl]-4-yl)dibenzo[ b , d ]furan-4- Compound 4 (27.0 g, 79.56 % yield) was obtained in the same manner as in step 3 of Example 1 using an amine (15.95 g, 47.56 mmol).
MS: [M+H]+ = 728MS: [M+H] + = 728
실시예 5: 화합물 5의 합성Example 5: Synthesis of compound 5
Figure PCTKR2021013360-appb-img-000095
Figure PCTKR2021013360-appb-img-000095
상기 실시예 1의 단계 2에서 수득한 화합물 1-B (20.0 g, 46.62 mmol)와 N-(4-(나프탈렌-1-일)페닐)나프탈렌-1-아민 (16.43 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 5 (27.0 g, 78.48 % 수율)를 수득하였다. Compound 1-B (20.0 g, 46.62 mmol) obtained in step 2 of Example 1 and N- (4-(naphthalen-1-yl)phenyl)naphthalen-1-amine (16.43 g, 47.56 mmol) were used. to obtain the compound 5 (27.0 g, 78.48 % yield) in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 738MS: [M+H] + = 738
실시예 6: 화합물 6의 합성Example 6: Synthesis of compound 6
Figure PCTKR2021013360-appb-img-000096
Figure PCTKR2021013360-appb-img-000096
상기 실시예 1의 단계 2에서 수득한 화합물 1-B (20.0 g, 46.62 mmol)와 비스(4-(나프탈렌-1-일)페닐)-아민 (19.65 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 6 (30.2 g, 79.58 % 수율)을 수득하였다. Using Compound 1-B (20.0 g, 46.62 mmol) obtained in Step 2 of Example 1 and bis(4-(naphthalen-1-yl)phenyl)-amine (19.65 g, 47.56 mmol) Compound 6 (30.2 g, 79.58 % yield) was obtained in the same manner as in Step 3 of 1.
MS: [M+H]+ = 814MS: [M+H] + = 814
실시예 7. 화합물 7의 합성Example 7. Synthesis of compound 7
Figure PCTKR2021013360-appb-img-000097
Figure PCTKR2021013360-appb-img-000097
상기 실시예 1의 단계 2에서 수득한 화합물 1-B (20.0 g, 46.62 mmol)와 비스(9,9-디메틸-9H-플루오렌-2-일)아민 (19.10 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 7 (28.5 g, 76.99 % 수율)을 수득하였다. Compound 1-B (20.0 g, 46.62 mmol) obtained in step 2 of Example 1 and bis(9,9-dimethyl-9H-fluoren-2-yl)amine (19.10 g, 47.56 mmol) were used. to obtain the compound 7 (28.5 g, 76.99 % yield) in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 794MS: [M+H] + = 794
실시예 8: 화합물 8의 합성Example 8: Synthesis of compound 8
단계 1) 화합물 8-A의 합성Step 1) Synthesis of compound 8-A
Figure PCTKR2021013360-appb-img-000098
Figure PCTKR2021013360-appb-img-000098
상기 실시예 1의 단계 1에서 수득한 화합물 1-A (50.00 g, 115.81 mmol)와 [1,1’-비페닐]-4-일보론산 (24.08 g, 121.60 mmol)을 이용하여 상기 실시예 1의 단계 2와 동일한 방법으로 상기 화합물 8-A (45.0 g, 76.93 % 수율)를 수득하였다.Example 1 using Compound 1-A (50.00 g, 115.81 mmol) and [1,1'-biphenyl]-4-ylboronic acid (24.08 g, 121.60 mmol) obtained in Step 1 of Example 1 Compound 8-A (45.0 g, 76.93 % yield) was obtained in the same manner as in step 2.
단계 2) 화합물 8의 합성Step 2) Synthesis of compound 8
Figure PCTKR2021013360-appb-img-000099
Figure PCTKR2021013360-appb-img-000099
상기 실시예 8의 단계 1에서 수득한 화합물 8-A (20.0 g, 39.60 mmol)와 디([1,1’-비페닐]-4-일)아민 (12.98 g, 40.39 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 8 (25.0 g, 79.91 % 수율)을 수득하였다. Using compound 8-A (20.0 g, 39.60 mmol) obtained in step 1 of Example 8 and di([1,1'-biphenyl]-4-yl)amine (12.98 g, 40.39 mmol) Compound 8 (25.0 g, 79.91 % yield) was obtained in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 790MS: [M+H] + = 790
실시예 9: 화합물 9의 합성Example 9: Synthesis of compound 9
Figure PCTKR2021013360-appb-img-000100
Figure PCTKR2021013360-appb-img-000100
상기 실시예 8의 단계 1에서 수득한 화합물 8-A (20.0 g, 39.60 mmol)와 N-([1,1’-비페닐]-4-일)-9,9-디메틸-9H-플루오렌-2-아민 (14.60 g, 40.39 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 9 (25.8 g, 78.49 % 수율)를 수득하였다. Compound 8-A (20.0 g, 39.60 mmol) obtained in step 1 of Example 8 and N -([1,1'-biphenyl]-4-yl) -9,9 -dimethyl-9H-flu Compound 9 (25.8 g, 78.49 % yield) was obtained in the same manner as in step 3 of Example 1 using oren-2-amine (14.60 g, 40.39 mmol).
MS: [M+H]+ = 830MS: [M+H] + = 830
실시예 10: 화합물 10의 합성Example 10: Synthesis of compound 10
단계 1) 화합물 10-A의 합성Step 1) Synthesis of compound 10-A
Figure PCTKR2021013360-appb-img-000101
Figure PCTKR2021013360-appb-img-000101
상기 실시예 1의 단계 1에서 수득한 화합물 1-A (50.00 g, 115.81 mmol)와 나프탈렌-1-일보론산 (20.91 g, 121.60 mmol)을 이용하여 상기 실시예 1의 단계 2와 동일한 방법으로 상기 화합물 10-A (44.0 g, 79.31 % 수율)를 수득하였다.In the same manner as in Step 2 of Example 1, using Compound 1-A (50.00 g, 115.81 mmol) and naphthalen-1-ylboronic acid (20.91 g, 121.60 mmol) obtained in Step 1 of Example 1 above Compound 10-A (44.0 g, 79.31 % yield) was obtained.
단계 2) 화합물 10의 합성Step 2) Synthesis of compound 10
Figure PCTKR2021013360-appb-img-000102
Figure PCTKR2021013360-appb-img-000102
상기 실시예 10의 단계 1에서 수득한 화합물 10-A (20.0 g, 41.75 mmol)와 디([1,1’-비페닐]-4-일)아민 (13.69 g, 42.59 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 10 (25.5 g, 79.95 % 수율)을 수득하였다. Using the compound 10-A (20.0 g, 41.75 mmol) obtained in step 1 of Example 10 and di([1,1'-biphenyl]-4-yl)amine (13.69 g, 42.59 mmol) The compound 10 (25.5 g, 79.95 % yield) was obtained in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 764MS: [M+H] + = 764
실시예 11: 화합물 11의 합성Example 11: Synthesis of compound 11
단계 1) 화합물 11-A의 합성Step 1) Synthesis of compound 11-A
Figure PCTKR2021013360-appb-img-000103
Figure PCTKR2021013360-appb-img-000103
상기 실시예 1의 단계 1에서 수득한 화합물 1-A (50.00 g, 115.81 mmol)와 나프탈렌-2-일보론산 (20.91 g, 121.60 mmol)을 이용하여 상기 실시예 1의 단계 2와 동일한 방법으로 상기 화합물 11-A (43.0 g, 77.51 % 수율)를 수득하였다.In the same manner as in Step 2 of Example 1, using Compound 1-A (50.00 g, 115.81 mmol) and naphthalen-2-ylboronic acid (20.91 g, 121.60 mmol) obtained in Step 1 of Example 1 above Compound 11-A (43.0 g, 77.51 % yield) was obtained.
단계 2) 화합물 11의 합성Step 2) Synthesis of compound 11
Figure PCTKR2021013360-appb-img-000104
Figure PCTKR2021013360-appb-img-000104
상기 실시예 11의 단계 1에서 수득한 화합물 11-A (20.0 g, 41.75 mmol)와 디([1,1’-비페닐]-4-일)아민 (13.69 g, 42.59 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 11 (26.0 g, 81.51 % 수율)을 수득하였다. Using compound 11-A (20.0 g, 41.75 mmol) obtained in step 1 of Example 11 and di([1,1'-biphenyl]-4-yl)amine (13.69 g, 42.59 mmol) Compound 11 (26.0 g, 81.51 % yield) was obtained in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 764MS: [M+H] + = 764
실시예 12: 화합물 12의 합성Example 12: Synthesis of compound 12
단계 1) 화합물 12-A의 합성Step 1) Synthesis of compound 12-A
Figure PCTKR2021013360-appb-img-000105
Figure PCTKR2021013360-appb-img-000105
상기 실시예 1의 단계 1에서 수득한 화합물 1-A (50.00 g, 115.81 mmol)와 디벤조[b,d]퓨란-4-일보론산 (25.78 g, 121.60 mmol)을 이용하여 상기 실시예 1의 단계 2와 동일한 방법으로 상기 화합물 12-A (47.0 g, 78.19 % 수율)를 수득하였다.Compound 1-A (50.00 g, 115.81 mmol) obtained in step 1 of Example 1 and dibenzo[ b , d ]furan-4-ylboronic acid (25.78 g, 121.60 mmol) of Example 1 Compound 12-A (47.0 g, 78.19 % yield) was obtained in the same manner as in step 2.
단계 2) 화합물 12의 합성Step 2) Synthesis of compound 12
Figure PCTKR2021013360-appb-img-000106
Figure PCTKR2021013360-appb-img-000106
상기 실시예 12의 단계 1에서 수득한 화합물 12-A (20.0 g, 38.52 mmol)와 디([1,1’-비페닐]-4-일)아민 (12.63 g, 39.30 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 12 (24.5 g, 79.11 % 수율)를 수득하였다. Using the compound 12-A (20.0 g, 38.52 mmol) obtained in step 1 of Example 12 and di([1,1'-biphenyl]-4-yl)amine (12.63 g, 39.30 mmol) Compound 12 (24.5 g, 79.11 % yield) was obtained in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 804MS: [M+H] + = 804
실시예 13: 화합물 13의 합성Example 13: Synthesis of compound 13
Figure PCTKR2021013360-appb-img-000107
Figure PCTKR2021013360-appb-img-000107
상기 실시예 12의 단계 1에서 수득한 화합물 12-A (20.0 g, 38.52 mmol)와 N-([1,1’-비페닐]-4-일)-9,9-디메틸-9H-플루오렌-2-아민 (14.21 g, 39.30 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 13 (25.0 g, 76.89 % 수율)을 수득하였다. Compound 12-A (20.0 g, 38.52 mmol) obtained in step 1 of Example 12 and N -([1,1'-biphenyl]-4-yl) -9,9 -dimethyl-9H-flu Compound 13 (25.0 g, 76.89 % yield) was obtained in the same manner as in step 3 of Example 1 using oren-2-amine (14.21 g, 39.30 mmol).
MS: [M+H]+ = 844MS: [M+H] + = 844
실시예 14. 화합물 14의 합성Example 14. Synthesis of compound 14
단계 1) 화합물 14-A의 합성Step 1) Synthesis of compound 14-A
Figure PCTKR2021013360-appb-img-000108
Figure PCTKR2021013360-appb-img-000108
2,2’-디브로모-1,1’-비페닐 (50.00 g, 160.25 mmol)과 (3-클로로페닐)(페닐)메타논 (34.72 g, 160.25 mmol)을 이용하여 상기 실시예 1의 단계 1과 동일한 방법으로 상기 화합물 14-A (55.0 g, 79.49 % 수율)를 수득하였다.2,2'-dibromo-1,1'-biphenyl (50.00 g, 160.25 mmol) and (3-chlorophenyl) (phenyl) methanone (34.72 g, 160.25 mmol) of Example 1 Compound 14-A (55.0 g, 79.49 % yield) was obtained in the same manner as in step 1.
단계 2) 화합물 14-B의 합성Step 2) Synthesis of compound 14-B
Figure PCTKR2021013360-appb-img-000109
Figure PCTKR2021013360-appb-img-000109
상기 실시예 14의 단계 1에서 수득한 화합물 14-A (50.00 g, 115.81 mmol)와 페닐보론산 (14.83 g, 121.60 mmol)을 이용하여 상기 실시예 1의 단계 2와 동일한 방법으로 상기 화합물 14-B (39.0 g, 78.51 % 수율)를 수득하였다.Compound 14-A (50.00 g, 115.81 mmol) and phenylboronic acid (14.83 g, 121.60 mmol) obtained in Step 1 of Example 14 were used in the same manner as in Step 2 of Example 1 above. B (39.0 g, 78.51 % yield) was obtained.
단계 3) 화합물 14의 합성Step 3) Synthesis of compound 14
Figure PCTKR2021013360-appb-img-000110
Figure PCTKR2021013360-appb-img-000110
상기 실시예 14의 단계 2에서 수득한 화합물 14-B (20.00 g, 46.62 mmol)와 4-(페난트렌-9-일)-N-페닐아닐린 (16.43 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 14 (28.0 g, 81.39 % 수율)를 수득하였다. Using the compound 14-B (20.00 g, 46.62 mmol) and 4-(phenanthren-9-yl) -N -phenylaniline (16.43 g, 47.56 mmol) obtained in step 2 of Example 14 above Compound 14 (28.0 g, 81.39 % yield) was obtained in the same manner as in Step 3 of 1.
MS: [M+H]+ = 738MS: [M+H] + = 738
실시예 15: 화합물 15의 합성Example 15: Synthesis of compound 15
Figure PCTKR2021013360-appb-img-000111
Figure PCTKR2021013360-appb-img-000111
상기 실시예 14의 단계 2에서 수득한 화합물 14-B (20.0 g, 46.62 mmol)와 디([1,1’-비페닐]-4-일)아민 (15.29 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 15 (26.5 g, 79.62 % 수율)를 수득하였다. Using compound 14-B (20.0 g, 46.62 mmol) obtained in step 2 of Example 14 and di([1,1'-biphenyl]-4-yl)amine (15.29 g, 47.56 mmol) Compound 15 (26.5 g, 79.62 % yield) was obtained in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 714MS: [M+H] + = 714
실시예 16: 화합물 16의 합성Example 16: Synthesis of compound 16
Figure PCTKR2021013360-appb-img-000112
Figure PCTKR2021013360-appb-img-000112
상기 실시예 14의 단계 2에서 수득한 화합물 14-B (20.0 g, 46.62 mmol)와 N-([1,1’-비페닐]-4-일)-9,9-디메틸-9H-플루오렌-2-아민 (17.19 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 16 (27.0 g, 76.81 % 수율)을 수득하였다. Compound 14-B (20.0 g, 46.62 mmol) obtained in step 2 of Example 14 and N -([1,1'-biphenyl]-4-yl) -9,9 -dimethyl-9H-flu Compound 16 (27.0 g, 76.81 % yield) was obtained in the same manner as in Step 3 of Example 1 using oren-2-amine (17.19 g, 47.56 mmol).
MS: [M+H]+ = 754MS: [M+H] + = 754
실시예 17: 화합물 17의 합성Example 17: Synthesis of compound 17
Figure PCTKR2021013360-appb-img-000113
Figure PCTKR2021013360-appb-img-000113
상기 실시예 14의 단계 2에서 수득한 화합물 14-B (20.0 g, 46.62 mmol)와 N-([1,1’-비페닐]-4-일)디벤조[b,d]퓨란-4-아민 (15.95 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 17 (26.8 g, 78.97 % 수율)을 수득하였다. Compound 14-B (20.0 g, 46.62 mmol) obtained in step 2 of Example 14 and N -([1,1'-biphenyl]-4-yl)dibenzo[ b , d ]furan-4- Compound 17 (26.8 g, 78.97 % yield) was obtained in the same manner as in step 3 of Example 1 using an amine (15.95 g, 47.56 mmol).
MS: [M+H]+ = 728MS: [M+H] + = 728
실시예 18. 화합물 18의 합성Example 18. Synthesis of compound 18
Figure PCTKR2021013360-appb-img-000114
Figure PCTKR2021013360-appb-img-000114
상기 실시예 14의 단계 2에서 수득한 화합물 14-B (20.0 g, 46.62 mmol)와 N-(4-(나프탈렌-1-일)페닐)나프탈렌-1-아민 (16.43 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 18 (27.5 g, 79.93 % 수율)을 수득하였다. Compound 14-B (20.0 g, 46.62 mmol) obtained in step 2 of Example 14 and N- (4-(naphthalen-1-yl)phenyl)naphthalen-1-amine (16.43 g, 47.56 mmol) were used. to obtain the compound 18 (27.5 g, 79.93 % yield) in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 738MS: [M+H] + = 738
실시예 19: 화합물 19의 합성Example 19: Synthesis of compound 19
Figure PCTKR2021013360-appb-img-000115
Figure PCTKR2021013360-appb-img-000115
상기 실시예 14의 단계 2에서 수득한 화합물 14-B (20.0 g, 46.62 mmol)와 비스(4-(나프탈렌-1-일)페닐)-아민 (19.65 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 19 (31.0 g, 81.69 % 수율)를 수득하였다. Using the compound 14-B (20.0 g, 46.62 mmol) obtained in step 2 of Example 14 and bis(4-(naphthalen-1-yl)phenyl)-amine (19.65 g, 47.56 mmol) Compound 19 (31.0 g, 81.69 % yield) was obtained in the same manner as in Step 3 of 1.
MS: [M+H]+ = 814MS: [M+H] + = 814
실시예 20: 화합물 20의 합성Example 20: Synthesis of compound 20
Figure PCTKR2021013360-appb-img-000116
Figure PCTKR2021013360-appb-img-000116
상기 실시예 14의 단계 2에서 수득한 화합물 14-B (20.0 g, 46.62 mmol)와 비스(9,9-디메틸-9H-플루오렌-2-일)아민 (19.10 g, 47.56 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 20 (29.0 g, 78.34 % 수율)을 수득하였다. Compound 14-B (20.0 g, 46.62 mmol) obtained in step 2 of Example 14 and bis(9,9-dimethyl-9H-fluoren-2-yl)amine (19.10 g, 47.56 mmol) were used. to obtain the compound 20 (29.0 g, 78.34 % yield) in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 794MS: [M+H] + = 794
실시예 21. 화합물 21의 합성Example 21. Synthesis of compound 21
단계 1) 화합물 21-A의 합성Step 1) Synthesis of compound 21-A
Figure PCTKR2021013360-appb-img-000117
Figure PCTKR2021013360-appb-img-000117
상기 실시예 14의 단계 1에서 수득한 화합물 14-A (50.00 g, 115.81 mmol)와 [1,1’-비페닐]-4-일보론산 (24.08 g, 121.60 mmol)을 이용하여 상기 실시예 1의 단계 2와 동일한 방법으로 상기 화합물 21-A (46.0 g, 78.64 % 수율)를 수득하였다.Example 1 using compound 14-A (50.00 g, 115.81 mmol) and [1,1'-biphenyl]-4-ylboronic acid (24.08 g, 121.60 mmol) obtained in step 1 of Example 14 Compound 21-A (46.0 g, 78.64 % yield) was obtained in the same manner as in step 2.
단계 2) 화합물 21의 합성Step 2) Synthesis of compound 21
Figure PCTKR2021013360-appb-img-000118
Figure PCTKR2021013360-appb-img-000118
상기 실시예 21의 단계 1에서 수득한 화합물 21-A (20.0 g, 39.60 mmol)와 디([1,1’-비페닐]-4-일)아민 (12.98 g, 40.39 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 21 (25.0 g, 79.91 % 수율)을 수득하였다. Using the compound 21-A (20.0 g, 39.60 mmol) obtained in step 1 of Example 21 and di([1,1'-biphenyl]-4-yl)amine (12.98 g, 40.39 mmol) Compound 21 (25.0 g, 79.91 % yield) was obtained in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 790MS: [M+H] + = 790
실시예 22: 화합물 22의 합성Example 22: Synthesis of compound 22
Figure PCTKR2021013360-appb-img-000119
Figure PCTKR2021013360-appb-img-000119
상기 실시예 21의 단계 1에서 수득한 화합물 21-A (20.0 g, 39.60 mmol)와 N-([1,1’-비페닐]-4-일)-9,9-디메틸-9H-플루오렌-2-아민 (14.60 g, 40.39 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 22 (26.0 g, 79.10 % 수율)를 수득하였다.Compound 21-A (20.0 g, 39.60 mmol) obtained in step 1 of Example 21 and N -([1,1'-biphenyl]-4-yl) -9,9 -dimethyl-9H-flu Compound 22 (26.0 g, 79.10 % yield) was obtained in the same manner as in step 3 of Example 1 using oren-2-amine (14.60 g, 40.39 mmol).
MS: [M+H]+ = 830MS: [M+H] + = 830
실시예 23: 화합물 23의 합성Example 23: Synthesis of compound 23
단계 1) 화합물 23-A의 합성Step 1) Synthesis of compound 23-A
Figure PCTKR2021013360-appb-img-000120
Figure PCTKR2021013360-appb-img-000120
상기 실시예 14의 단계 1에서 수득한 화합물 14-A (50.00 g, 115.81 mmol)와 나프탈렌-1-일보론산 (20.91 g, 121.60 mmol)을 이용하여 상기 실시예 1의 단계 2와 동일한 방법으로 상기 화합물 23-A (42.5 g, 76.61 % 수율)를 수득하였다.Using the compound 14-A (50.00 g, 115.81 mmol) and naphthalen-1-ylboronic acid (20.91 g, 121.60 mmol) obtained in step 1 of Example 14, in the same manner as in step 2 of Example 1, Compound 23-A (42.5 g, 76.61 % yield) was obtained.
단계 2) 화합물 23의 합성Step 2) Synthesis of compound 23
Figure PCTKR2021013360-appb-img-000121
Figure PCTKR2021013360-appb-img-000121
상기 실시예 23의 단계 1에서 수득한 화합물 23-A (20.0 g, 41.75 mmol)와 디([1,1’-비페닐]-4-일)아민 (13.69 g, 42.59 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 23 (26.0 g, 81.51 % 수율)을 수득하였다. Using the compound 23-A (20.0 g, 41.75 mmol) obtained in step 1 of Example 23 and di([1,1'-biphenyl]-4-yl)amine (13.69 g, 42.59 mmol) Compound 23 (26.0 g, 81.51 % yield) was obtained in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 764MS: [M+H] + = 764
실시예 24: 화합물 24의 합성Example 24: Synthesis of compound 24
단계 1) 화합물 24-A의 합성Step 1) Synthesis of compound 24-A
Figure PCTKR2021013360-appb-img-000122
Figure PCTKR2021013360-appb-img-000122
상기 실시예 14의 단계 1에서 수득한 화합물 14-A (50.00 g, 115.81 mmol)와 나프탈렌-2-일보론산 (20.91 g, 121.60 mmol)을 이용하여 상기 실시예 1의 단계 2와 동일한 방법으로 상기 화합물 24-A (44.0 g, 79.31 % 수율)를 수득하였다.In the same manner as in Step 2 of Example 1, using Compound 14-A (50.00 g, 115.81 mmol) and naphthalen-2-ylboronic acid (20.91 g, 121.60 mmol) obtained in Step 1 of Example 14 above Compound 24-A (44.0 g, 79.31 % yield) was obtained.
단계 2) 화합물 24의 합성Step 2) Synthesis of compound 24
Figure PCTKR2021013360-appb-img-000123
Figure PCTKR2021013360-appb-img-000123
상기 실시예 24의 단계 1에서 수득한 화합물 24-A (20.0 g, 41.75 mmol)와 디([1,1’-비페닐]-4-일)아민 (13.69 g, 42.59 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 24 (25.0 g, 78.38 % 수율)를 수득하였다.Using compound 24-A (20.0 g, 41.75 mmol) and di([1,1'-biphenyl]-4-yl)amine (13.69 g, 42.59 mmol) obtained in step 1 of Example 24 above Compound 24 (25.0 g, 78.38 % yield) was obtained in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 764MS: [M+H] + = 764
실시예 25: 화합물 25의 합성Example 25: Synthesis of compound 25
단계 1) 화합물 25-A의 합성Step 1) Synthesis of compound 25-A
Figure PCTKR2021013360-appb-img-000124
Figure PCTKR2021013360-appb-img-000124
상기 실시예 14의 단계 1에서 수득한 화합물 14-A (50.00 g, 115.81 mmol)와 디벤조[b,d]퓨란-4-일보론산 (25.78 g, 121.60 mmol)을 이용하여 상기 실시예 1의 단계 2와 동일한 방법으로 상기 화합물 25-A (48.0 g, 79.85 % 수율)를 수득하였다.Compound 14-A (50.00 g, 115.81 mmol) obtained in step 1 of Example 14 and dibenzo[ b , d ]furan-4-ylboronic acid (25.78 g, 121.60 mmol) of Example 1 Compound 25-A (48.0 g, 79.85 % yield) was obtained in the same manner as in step 2.
단계 2) 화합물 25의 합성Step 2) Synthesis of compound 25
Figure PCTKR2021013360-appb-img-000125
Figure PCTKR2021013360-appb-img-000125
상기 실시예 25의 단계 1에서 수득한 화합물 25-A (20.0 g, 38.52 mmol)와 디([1,1’-비페닐]-4-일)아민 (12.63 g, 39.30 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 25 (25.0 g, 80.72 % 수율)를 수득하였다. Using the compound 25-A (20.0 g, 38.52 mmol) obtained in step 1 of Example 25 and di([1,1'-biphenyl]-4-yl)amine (12.63 g, 39.30 mmol) Compound 25 (25.0 g, 80.72 % yield) was obtained in the same manner as in step 3 of Example 1.
MS: [M+H]+ = 804MS: [M+H] + = 804
실시예 26: 화합물 26의 합성Example 26: Synthesis of compound 26
Figure PCTKR2021013360-appb-img-000126
Figure PCTKR2021013360-appb-img-000126
상기 실시예 25의 단계 1에서 수득한 화합물 25-A (20.0 g, 38.52 mmol)와 N-([1,1’-비페닐]-4-일)-9,9-디메틸-9H-플루오렌-2-아민 (14.21 g, 39.30 mmol)을 이용하여 상기 실시예 1의 단계 3과 동일한 방법으로 상기 화합물 26 (26.0 g, 79.97 % 수율)을 수득하였다. Compound 25-A (20.0 g, 38.52 mmol) obtained in step 1 of Example 25 and N -([1,1'-biphenyl]-4-yl) -9,9 -dimethyl-9H-flu Compound 26 (26.0 g, 79.97 % yield) was obtained in the same manner as in step 3 of Example 1 using oren-2-amine (14.21 g, 39.30 mmol).
MS: [M+H]+ = 844MS: [M+H] + = 844
실시예 27: 화합물 27의 합성Example 27: Synthesis of compound 27
Figure PCTKR2021013360-appb-img-000127
Figure PCTKR2021013360-appb-img-000127
상기 실시예 1의 단계 2에서 수득한 화합물 1-B (20.00 g, 46.62 mmol)와 (4-(디페닐아미노)페닐)보론산 (14.16 g, 48.96 mmol)에 1-4-디옥산 (100 ml)을 가한 후 가열, 교반하였다. 상기 용액에 탄산칼륨 (19.33 g, 139.86 mmol) 수용액 (50 ml)을 가한 후 5분 동안 가열, 교반하였다. 상기 용액에 비스(트리-터트-부틸포스핀)팔라듐 (0.07 g, 0.14 mmol)을 천천히 적가한 후 5시간 동안 가열, 교반하였다. 반응 종결 및 여과 후, 톨루엔과 물로 층분리 하였다. 용매 제거 후 에틸아세테이트로 재결정하여 화합물 27 (22.0 g, 73.99 % 수율)을 수득하였다. Compound 1-B (20.00 g, 46.62 mmol) and (4-(diphenylamino)phenyl)boronic acid (14.16 g, 48.96 mmol) obtained in step 2 of Example 1 above 1-4-dioxane (100) ml) was added, followed by heating and stirring. To the solution was added potassium carbonate (19.33 g, 139.86 mmol) aqueous solution (50 ml), followed by heating and stirring for 5 minutes. Bis(tri-tert-butylphosphine)palladium (0.07 g, 0.14 mmol) was slowly added dropwise to the solution, followed by heating and stirring for 5 hours. After completion of the reaction and filtration, the layers were separated with toluene and water. After removal of the solvent, it was recrystallized from ethyl acetate to obtain compound 27 (22.0 g, 73.99 % yield).
MS: [M+H]+ = 638MS: [M+H] + = 638
실시예 28: 화합물 28Example 28: Compound 28 의 합성synthesis of
Figure PCTKR2021013360-appb-img-000128
Figure PCTKR2021013360-appb-img-000128
상기 실시예 1의 단계 2에서 수득한 화합물 1-B (20.00 g, 46.62 mmol)와 (4-(디([1,1’-비페닐]-4-일)아미노)페닐)보론산 (21.61 g, 48.96 mmol)을 이용하여 상기 실시예 27과 동일한 방법으로 상기 화합물 28 (28.5 g, 77.38 % 수율)을 수득하였다. Compound 1-B (20.00 g, 46.62 mmol) obtained in step 2 of Example 1 and (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid (21.61 g, 48.96 mmol) was used to obtain Compound 28 (28.5 g, 77.38 % yield) in the same manner as in Example 27.
MS: [M+H]+ = 790MS: [M+H] + = 790
실시예 29: 화합물 29Example 29: Compound 29 의 합성synthesis of
Figure PCTKR2021013360-appb-img-000129
Figure PCTKR2021013360-appb-img-000129
상기 실시예 14의 단계 2에서 수득한 화합물 14-B (20.00 g, 46.62 mmol)와 (4-(디([1,1’-비페닐]-4-일)아미노)페닐)보론산 (21.61 g, 48.96 mmol)을 이용하여 상기 실시예 27과 동일한 방법으로 상기 화합물 29 (29.0 g, 78.74 % 수율)를 수득하였다. Compound 14-B (20.00 g, 46.62 mmol) obtained in step 2 of Example 14 and (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid (21.61 g, 48.96 mmol) was used to obtain Compound 29 (29.0 g, 78.74 % yield) in the same manner as in Example 27.
MS: [M+H]+ = 790MS: [M+H] + = 790
실시예 30: 화합물 30 의 합성Example 30: Synthesis of compound 30
Figure PCTKR2021013360-appb-img-000130
Figure PCTKR2021013360-appb-img-000130
상기 실시예 14의 단계 2에서 수득한 화합물 14-B (20.00 g, 46.62 mmol)와 (4-([1,1’-비페닐]-4-일(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)보론산 (23.57 g, 48.96 mmol)을 이용하여 상기 실시예 27과 동일한 방법으로 상기 화합물 30 (30.0 g, 77.52 % 수율)을 수득하였다.Compound 14-B (20.00 g, 46.62 mmol) obtained in step 2 of Example 14 and (4-([1,1'-biphenyl]-4-yl( 9,9 -dimethyl-9H-flu) Compound 30 (30.0 g, 77.52 % yield) was obtained in the same manner as in Example 27 using oren-2-yl)amino)phenyl)boronic acid (23.57 g, 48.96 mmol).
MS: [M+H]+ = 830MS: [M+H] + = 830
실시예 31: 화합물 31의 합성Example 31: Synthesis of compound 31
단계 1) 화합물 31-A의 합성Step 1) Synthesis of compound 31-A
Figure PCTKR2021013360-appb-img-000131
Figure PCTKR2021013360-appb-img-000131
2,2’-디브로모-1,1’-비페닐 (50.00 g, 160.25 mmol)과 (2-클로로페닐)(페닐)메타논 (34.72 g, 160.25 mmol)을 이용하여 상기 실시예 1의 단계 1과 동일한 방법으로 상기 화합물 31-A (52.0 g, 75.16 % 수율)를 수득하였다.2,2'-dibromo-1,1'-biphenyl (50.00 g, 160.25 mmol) and (2-chlorophenyl) (phenyl) methanone (34.72 g, 160.25 mmol) of Example 1 Compound 31-A (52.0 g, 75.16 % yield) was obtained in the same manner as in step 1.
단계 2) 화합물 31-B의 합성Step 2) Synthesis of compound 31-B
Figure PCTKR2021013360-appb-img-000132
Figure PCTKR2021013360-appb-img-000132
상기 실시예 31의 단계 1에서 수득한 화합물 31-A (50.00 g, 115.81 mmol)와 페닐보론산 (14.83 g, 121.60 mmol)을 이용하여 상기 실시예 1의 단계 2와 동일한 방법으로 상기 화합물 31-B (38.0 g, 76.49 % 수율)를 수득하였다.Compound 31-A (50.00 g, 115.81 mmol) and phenylboronic acid (14.83 g, 121.60 mmol) obtained in Step 1 of Example 31 were used in the same manner as in Step 2 of Example 1 above. B (38.0 g, 76.49 % yield) was obtained.
단계 3) 화합물 31의 합성Step 3) Synthesis of compound 31
Figure PCTKR2021013360-appb-img-000133
Figure PCTKR2021013360-appb-img-000133
상기 실시예 31의 단계 2에서 수득한 화합물 31-B (20.00 g, 46.62 mmol)와 (4-(디([1,1’-비페닐]-4-일)아미노)페닐)보론산 (21.61 g, 48.96 mmol)을 이용하여 상기 실시예 27과 동일한 방법으로 상기 화합물 31 (28.0 g, 76.02 % 수율)을 수득하였다. Compound 31-B (20.00 g, 46.62 mmol) obtained in step 2 of Example 31 and (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid (21.61 g, 48.96 mmol) was used to obtain compound 31 (28.0 g, 76.02 % yield) in the same manner as in Example 27.
MS: [M+H]+ = 790MS: [M+H] + = 790
실시예 32: 화합물 32Example 32: Compound 32 의 합성synthesis of
Figure PCTKR2021013360-appb-img-000134
Figure PCTKR2021013360-appb-img-000134
상기 실시예 31의 단계 2에서 수득한 화합물 31-B (20.00 g, 46.62 mmol)와 (4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)보론산 (25.53 g, 48.96 mmol)을 이용하여 상기 실시예 27과 동일한 방법으로 상기 화합물 32 (31.0 g, 76.42 % 수율)를 수득하였다.Compound 31-B (20.00 g, 46.62 mmol) obtained in step 2 of Example 31 and (4-(bis(9,9-dimethyl-9H- fluoren -2-yl)amino)phenyl)boronic acid Compound 32 (31.0 g, 76.42 % yield) was obtained in the same manner as in Example 27 using (25.53 g, 48.96 mmol).
MS: [M+H]+ = 870MS: [M+H] + = 870
[실험예][Experimental example]
실험예 1-1Experimental Example 1-1
ITO(Indium Tin Oxide)가 1,400Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀러포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다.A glass substrate coated with ITO (Indium Tin Oxide) to a thickness of 1,400 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 하기 화학식 HAT로 표시되는 화합물을 100Å의 두께로 열 진공 증착하여 정공주입층을 형성하였다. 그 위에 정공수송층으로 하기 화학식 HT1로 표시되는 화합물을 1150Å 두께로 진공 증착한 후, 전자억제층으로 상기 실시예 1에서 제조된 화합물 1을 150Å의 두께로 열 진공 증착하였다. 이어서, 발광층으로 하기 화학식 BH로 표시되는 화합물 및 하기 화학식 BD로 표시되는 화합물을 25:1의 중량비로 200Å의 두께로 진공 증착하였다. 이어서, 정공저지층으로 하기 화학식 HB1으로 표시되는 화합물을 50Å의 두께로 진공 증착하였다. 이어서, 전자수송 및 전자주입을 동시에 하는 층으로 하기 화학식 ET1로 표시되는 화합물과 하기 LiQ로 표시되는 화합물을 1:1의 중량비로 310Å의 두께로 열 진공 증착하였다. 상기 전자 수송 및 전자 주입층 위에 순차적으로 12Å의 두께로 리튬플로라이드(LiF)와 1000Å 두께로 알루미늄을 증착하여 음극을 형성하여, 유기 발광 소자를 제조하였다.A hole injection layer was formed by thermal vacuum deposition of a compound represented by the following formula HAT on the prepared ITO transparent electrode to a thickness of 100 Å. After vacuum deposition of the compound represented by the following formula HT1 as a hole transport layer to a thickness of 1150 Å, the compound 1 prepared in Example 1 was thermally vacuum deposited to a thickness of 150 Å as an electron suppression layer. Then, as a light emitting layer, the compound represented by the following formula BH and the compound represented by the following formula BD were vacuum-deposited to a thickness of 200 Å in a weight ratio of 25:1. Then, as a hole blocking layer, a compound represented by the following Chemical Formula HB1 was vacuum-deposited to a thickness of 50 Å. Then, as a layer that simultaneously transports electrons and injects electrons, a compound represented by the following formula ET1 and a compound represented by the following LiQ were thermally vacuum deposited to a thickness of 310 Å in a weight ratio of 1:1. An organic light-emitting device was manufactured by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1000 Å on the electron transport and electron injection layers to form a cathode.
Figure PCTKR2021013360-appb-img-000135
Figure PCTKR2021013360-appb-img-000135
실험예 1-2 내지 1-26 Experimental Examples 1-2 to 1-26
화합물 1 대신 하기 표 1에 기재된 화합물을 사용하는 것을 제외하고는, 상기 실험예 1-1과 동일한 방법으로 실험예 1-2 내지 1-26의 유기 발광 소자를 제조하였다.Organic light emitting devices of Experimental Examples 1-2 to 1-26 were prepared in the same manner as in Experimental Example 1-1, except that the compound shown in Table 1 was used instead of Compound 1.
비교실험예 1-1 내지 1-4Comparative Experimental Examples 1-1 to 1-4
화합물 1 대신 하기 화합물 EB1, EB2, EB3, EB4를 사용한 것을 제외하고는 실험예 1-1과 동일한 방법으로 비교실험예 1-1 내지 1-4의 유기 발광 소자를 제조하였다.Organic light emitting devices of Comparative Experimental Examples 1-1 to 1-4 were prepared in the same manner as in Experimental Example 1-1 except that the following compounds EB1, EB2, EB3, and EB4 were used instead of Compound 1.
Figure PCTKR2021013360-appb-img-000136
Figure PCTKR2021013360-appb-img-000136
실험예 1-1 내지 1-26 및 비교실험예 1-1 내지 1-4에서 제조한 유기 발광 소자에 10 mA/cm2의 전류를 인가하였을 때, 전압, 효율, 색좌표 및 수명을 측정하고 그 결과를 하기 표 1에 나타내었다. 한편, T95는 휘도가 초기 휘도(6000 nit)에서 95%로 감소되는 데 소요되는 시간을 의미한다When a current of 10 mA/cm 2 was applied to the organic light emitting diodes prepared in Experimental Examples 1-1 to 1-26 and Comparative Experimental Examples 1-1 to 1-4, voltage, efficiency, color coordinates, and lifetime were measured and the The results are shown in Table 1 below. On the other hand, T95 means the time it takes for the luminance to decrease from the initial luminance (6000 nit) to 95%.
전자억제층electron suppression layer 전압
(V@10mA/cm2)Voltage
(V@10mA/cm 2 ) 		효율
(cd/A@10mA/cm2)efficiency
(cd/A@10mA/cm 2 ) 		색좌표 (x, y)color coordinates (x, y) T95
(hr@10mA/cm2)T95
(hr@10mA/cm 2 )
실험예 1-1Experimental Example 1-1 화합물 1compound 1 3.693.69 6.086.08 0.140, 0.0430.140, 0.043 210210
실험예 1-2Experimental Example 1-2 화합물 2compound 2 3.633.63 6.106.10 0.140, 0.0430.140, 0.043 220220
실험예 1-3Experimental Example 1-3 화합물 3compound 3 3.603.60 5.955.95 0.141, 0.0440.141, 0.044 195195
실험예 1-4Experimental Example 1-4 화합물 4compound 4 3.683.68 6.016.01 0.140, 0.0440.140, 0.044 215215
실험예 1-5Experimental Example 1-5 화합물 5compound 5 3.693.69 6.036.03 0.141, 0.0430.141, 0.043 215215
실험예 1-6Experimental Example 1-6 화합물 6compound 6 3.633.63 6.086.08 0.141, 0.0430.141, 0.043 215215
실험예 1-7Experimental Example 1-7 화합물 8compound 8 3.703.70 6.016.01 0.140, 0.0430.140, 0.043 210210
실험예 1-8Experimental Example 1-8 화합물 9compound 9 3.613.61 5.945.94 0.141, 0.0440.141, 0.044 195195
실험예 1-9Experimental Example 1-9 화합물 10compound 10 3.693.69 6.006.00 0.140, 0.0440.140, 0.044 210210
실험예 1-10Experimental Example 1-10 화합물 11compound 11 3.683.68 6.006.00 0.140, 0.0440.140, 0.044 205205
실험예 1-11Experimental Example 1-11 화합물 12compound 12 3.693.69 6.056.05 0.140, 0.0430.140, 0.043 210210
실험예 1-12Experimental Example 1-12 화합물 13compound 13 3.643.64 5.945.94 0.141, 0.0440.141, 0.044 190190
실험예 1-13Experimental Example 1-13 화합물 14compound 14 3.683.68 6.096.09 0.140, 0.0430.140, 0.043 210210
실험예 1-14Experimental Example 1-14 화합물 15compound 15 3.613.61 6.136.13 0.140, 0.0430.140, 0.043 225225
실험예 1-15Experimental Example 1-15 화합물 16compound 16 3.603.60 5.915.91 0.141, 0.0440.141, 0.044 205205
실험예 1-16Experimental Example 1-16 화합물 17compound 17 3.683.68 6.016.01 0.141, 0.0440.141, 0.044 205205
실험예 1-17Experimental Example 1-17 화합물 18compound 18 3.673.67 6.026.02 0.140, 0.0440.140, 0.044 210210
실험예 1-18Experimental Example 1-18 화합물 19compound 19 3.633.63 6.056.05 0.140, 0.0440.140, 0.044 215215
실험예 1-19Experimental Example 1-19 화합물 21compound 21 3.693.69 6.006.00 0.141, 0.0430.141, 0.043 215215
실험예 1-20Experimental Example 1-20 화합물 23compound 23 3.703.70 6.036.03 0.141, 0.0430.141, 0.043 210210
실험예 1-21Experimental Example 1-21 화합물 24compound 24 3.683.68 6.006.00 0.140, 0.0430.140, 0.043 200200
실험예 1-22Experimental Example 1-22 화합물 25compound 25 3.643.64 6.096.09 0.140, 0.0440.140, 0.044 215215
실험예 1-23Experimental Example 1-23 화합물 27compound 27 3.693.69 6.036.03 0.141, 0.0430.141, 0.043 205205
실험예 1-24Experimental Example 1-24 화합물 28compound 28 3.633.63 5.955.95 0.140, 0.0440.140, 0.044 205205
실험예 1-25Experimental Example 1-25 화합물 29compound 29 3.633.63 6.076.07 0.140, 0.0430.140, 0.043 210210
실험예 1-26Experimental Example 1-26 화합물 31compound 31 3.643.64 5.965.96 0.140, 0.0440.140, 0.044 195195
비교실험예 1-1Comparative Experimental Example 1-1 EB1EB1 3.933.93 5.115.11 0.144, 0.0480.144, 0.048 150150
비교실험예 1-2Comparative Experimental Example 1-2 EB2EB2 3.983.98 5.165.16 0.145, 0.0480.145, 0.048 115115
비교실험예 1-3Comparative Experimental Example 1-3 EB3EB3 3.903.90 4.954.95 0.144, 0.0480.144, 0.048 105105
비교실험예 1-4Comparative Experimental Example 1-4 EB4EB4 4.124.12 4.864.86 0.145, 0.0490.145, 0.049 7070
상기 표 1에 나타난 바와 같이, 본 발명의 화합물은 전자 억제 능력이 우수하여 이를 전자억제층으로 사용한 유기 발광 소자는 구동 전압, 효율 및 수명 면에서 현저한 효과를 나타내는 것으로 확인되었다.As shown in Table 1, the compound of the present invention has excellent electron suppression ability, and it was confirmed that the organic light emitting device using the same as the electron suppression layer exhibited remarkable effects in terms of driving voltage, efficiency, and lifespan.
실험예 2-1 내지 2-19 및 비교실험예 2-1 내지 2-4Experimental Examples 2-1 to 2-19 and Comparative Experimental Examples 2-1 to 2-4
화합물 1 대신 상기 화학식 EB1으로 표시되는 화합물을 사용하고, 정공수송층으로 상기 화학식 HT1으로 표시되는 화합물 대신 하기 표 2에 기재된 화합물을 사용하는 것을 제외하고는, 상기 실험예 1-1과 동일한 방법으로 실험예 2-1 내지 2-19 및 비교실험예 2-1 내지 2-4의 유기 발광 소자를 제조하였다.Experiment in the same manner as in Experimental Example 1-1, except that the compound represented by Formula EB1 was used instead of Compound 1, and the compound shown in Table 2 was used instead of the compound represented by Formula HT1 as the hole transport layer. Organic light emitting devices of Examples 2-1 to 2-19 and Comparative Experimental Examples 2-1 to 2-4 were prepared.
Figure PCTKR2021013360-appb-img-000137
Figure PCTKR2021013360-appb-img-000137
실험예 및 비교 실험예에서 제조한 유기 발광 소자에 10 mA/cm2의 전류를 인가하였을 때, 전압, 효율, 색좌표 및 수명을 측정하고 그 결과를 하기 표 2에 나타내었다. 한편, T95는 휘도가 초기 휘도(6000 nit)에서 95%로 감소되는 데 소요되는 시간을 의미한다.When a current of 10 mA/cm 2 was applied to the organic light emitting diodes prepared in Experimental Examples and Comparative Experimental Examples, voltage, efficiency, color coordinates and lifetime were measured, and the results are shown in Table 2 below. Meanwhile, T95 denotes a time required for the luminance to decrease from the initial luminance (6000 nit) to 95%.
정공수송층hole transport layer 전압
(V@10mA/cm2)Voltage
(V@10mA/cm 2 ) 		효율
(cd/A@10mA/cm2)efficiency
(cd/A@10mA/cm 2 ) 		색좌표 (x, y)color coordinates (x, y) T95
(hr@10mA/cm2)T95
(hr@10mA/cm 2 )
실험예 2-1Experimental Example 2-1 화합물 2compound 2 3.673.67 6.056.05 0.141, 0.0440.141, 0.044 200200
실험예 2-2Experimental Example 2-2 화합물 3compound 3 3.583.58 6.086.08 0.141, 0.0430.141, 0.043 205205
실험예 2-3Experimental Example 2-3 화합물 4compound 4 3.703.70 6.006.00 0.141, 0.0440.141, 0.044 195195
실험예 2-4Experimental Example 2-4 화합물 7compound 7 3.573.57 6.106.10 0.140, 0.0430.140, 0.043 215215
실험예 2-5Experimental Example 2-5 화합물 8compound 8 3.643.64 5.965.96 0.140, 0.0440.140, 0.044 195195
실험예 2-6Experimental Example 2-6 화합물 9compound 9 3.593.59 6.056.05 0.140, 0.0440.140, 0.044 205205
실험예 2-7Experimental Example 2-7 화합물 13compound 13 3.603.60 6.066.06 0.140, 0.0440.140, 0.044 200200
실험예 2-8Experimental Example 2-8 화합물 15compound 15 3.673.67 6.006.00 0.140, 0.0440.140, 0.044 200200
실험예 2-9Experimental Example 2-9 화합물 16compound 16 3.593.59 6.056.05 0.140, 0.0430.140, 0.043 210210
실험예 2-10Experimental Example 2-10 화합물 17compound 17 3.683.68 5.995.99 0.141, 0.0440.141, 0.044 205205
실험예 2-11Experimental Example 2-11 화합물 20compound 20 3.553.55 6.126.12 0.140, 0.0430.140, 0.043 220220
실험예 2-12Experimental Example 2-12 화합물 21compound 21 3.693.69 6.026.02 0.141, 0.0440.141, 0.044 190190
실험예 2-13Experimental Example 2-13 화합물 22compound 22 3.593.59 6.086.08 0.140, 0.0440.140, 0.044 205205
실험예 2-14Experimental Example 2-14 화합물 26compound 26 3.593.59 6.046.04 0.141, 0.0430.141, 0.043 210210
실험예 2-15Experimental Example 2-15 화합물 28compound 28 3.673.67 6.006.00 0.141, 0.0430.141, 0.043 200200
실험예 2-16Experimental Example 2-16 화합물 29compound 29 3.593.59 6.016.01 0.141, 0.0440.141, 0.044 195195
실험예 2-17Experimental Example 2-17 화합물 30compound 30 3.603.60 6.056.05 0.141, 0.0430.141, 0.043 205205
실험예 2-18Experimental Example 2-18 화합물 31compound 31 3.673.67 6.006.00 0.141, 0.0440.141, 0.044 200200
실험예 2-19Experimental Example 2-19 화합물 32compound 32 3.663.66 5.985.98 0.140, 0.0440.140, 0.044 200200
비교실험예 1-1Comparative Experimental Example 1-1 HT1HT1 3.933.93 5.115.11 0.144, 0.0480.144, 0.048 150150
비교실험예 2-1Comparative Experimental Example 2-1 HT2HT2 3.893.89 5.055.05 0.145, 0.0480.145, 0.048 160160
비교실험예 2-2Comparative Experimental Example 2-2 HT3HT3 4.054.05 4.854.85 0.145, 0.0490.145, 0.049 125125
비교실험예 2-3Comparative Experimental Example 2-3 HT4HT4 3.983.98 4.964.96 0.144, 0.0480.144, 0.048 130130
비교실험예 2-4Comparative Experimental Example 2-4 HT5HT5 4.104.10 4.754.75 0.144, 0.0490.144, 0.049 8080
상기 표 2에 나타난 바와 같이, 본 발명의 화합물은 정공 수송 능력이 우수하여 이를 정공수송층으로 사용한 유기 발광 소자는 구동 전압, 효율 및 수명 면에서 현저한 효과를 나타내는 것으로 확인되었다.As shown in Table 2, the compound of the present invention has excellent hole transport ability, and it was confirmed that the organic light emitting device using the compound as a hole transport layer exhibits remarkable effects in terms of driving voltage, efficiency, and lifespan.
[부호의 설명][Explanation of code]
1: 기판 2: 양극1: Substrate 2: Anode
3: 정공수송층 4: 발광층3: hole transport layer 4: light emitting layer
5: 전자주입 및 수송층 6: 음극5: Electron injection and transport layer 6: Cathode
7: 정공주입층 8: 전자억제층7: hole injection layer 8: electron suppression layer
9: 정공저지층 9: hole blocking layer

Claims (13)

  1. 하기 화학식 1로 표시되는 화합물:A compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2021013360-appb-img-000138
    Figure PCTKR2021013360-appb-img-000138
    상기 화학식 1에서,In Formula 1,
    L1 및 L2는 각각 독립적으로 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴렌이고,L 1 and L 2 are each independently a direct bond; substituted or unsubstituted C 6-60 arylene; Or substituted or unsubstituted C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of N, O and S,
    L3은 직접 결합; 또는 치환 또는 비치환된 C6-60 아릴렌이고,L 3 is a direct bond; Or a substituted or unsubstituted C 6-60 arylene,
    Ar1 및 Ar2는 각각 독립적으로 치환 또는 비치환된 C6-60 아릴; 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이고,Ar 1 and Ar 2 are each independently substituted or unsubstituted C 6-60 aryl; or unsubstituted C 2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S;
    A는 각각 독립적으로 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이고,A is each independently substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
    R1은 각각 독립적으로 수소; 중수소; 할로겐; 니트릴; 실릴; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이고,R 1 are each independently hydrogen; heavy hydrogen; halogen; nitrile; silyl; substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
    R2는 각각 독립적으로 수소; 중수소; 또는 치환 또는 비치환된 C6-60 아릴이고,R 2 are each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted C 6-60 aryl,
    p는 1 내지 4의 정수이고,p is an integer from 1 to 4,
    a는 0 내지 3의 정수이고, 단, a+p는 1 내지 4이고, a is an integer of 0 to 3, provided that a+p is 1 to 4,
    b는 0 내지 4의 정수이다.b is an integer from 0 to 4.
  2. 제1항에 있어서,According to claim 1,
    상기 화학식 1은 하기 화학식 1-1 내지 1-3으로 구성되는 군으로부터 선택되는 어느 하나로 표시되는,Formula 1 is represented by any one selected from the group consisting of the following Formulas 1-1 to 1-3,
    화합물:compound:
    [화학식 1-1][Formula 1-1]
    Figure PCTKR2021013360-appb-img-000139
    Figure PCTKR2021013360-appb-img-000139
    [화학식 1-2][Formula 1-2]
    Figure PCTKR2021013360-appb-img-000140
    Figure PCTKR2021013360-appb-img-000140
    [화학식 1-3][Formula 1-3]
    Figure PCTKR2021013360-appb-img-000141
    Figure PCTKR2021013360-appb-img-000141
    상기 화학식 1-1 내지 1-3에서, In Formulas 1-1 to 1-3,
    L1, L2, L3, Ar1, Ar2, A, R1, R2, p, a, 및 b는 제1항에서 정의한 바와 같다.L 1 , L 2 , L 3 , Ar 1 , Ar 2 , A, R 1 , R 2 , p, a, and b are as defined in claim 1 .
  3. 제1항에 있어서,According to claim 1,
    L1 및 L2는 각각 독립적으로 직접 결합, 페닐렌, 또는 비페닐릴렌인,L 1 and L 2 are each independently a direct bond, phenylene, or biphenylylene;
    화합물.compound.
  4. 제1항에 있어서,According to claim 1,
    L3은 직접 결합, 또는 페닐렌인,L 3 is a direct bond, or phenylene,
    화합물.compound.
  5. 제1항에 있어서,According to claim 1,
    Ar1 및 Ar2는 각각 독립적으로 페닐, 터트-부틸로 치환된 페닐, 아다만틸로 치환된 페닐, 비페닐릴, 터페닐릴, 나프틸, 페난트레닐, 트리페닐레닐, 디메틸플루오레닐, 디페닐플루오레닐, 스피로비플루오레닐, 디벤조퓨라닐, 디벤조티오페닐, 카바졸-9-일, 또는 9-페닐카바졸일이고,Ar 1 and Ar 2 are each independently phenyl, phenyl substituted with tert-butyl, phenyl substituted with adamantyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl , diphenylfluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenylcarbazolyl;
    화합물.compound.
  6. 제1항에 있어서,According to claim 1,
    A는 각각 독립적으로 페닐, 터트-부틸로 치환된 페닐, 카바졸-9-일로 치환된 페닐, 비페닐릴, 나프틸, 디벤조퓨라닐, 또는 디벤조티오페닐인,A is each independently phenyl, phenyl substituted with tert-butyl, phenyl substituted with carbazol-9-yl, biphenylyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl;
    화합물.compound.
  7. 제1항에 있어서,According to claim 1,
    R1은 수소, 또는 페닐인, R 1 is hydrogen or phenyl;
    화합물.compound.
  8. 제1항에 있어서,According to claim 1,
    R2는 수소, 또는 페닐인R 2 is hydrogen or phenyl
    화합물.compound.
  9. 제1항에 있어서,According to claim 1,
    p는 1 또는 2인,p is 1 or 2;
    화합물.compound.
  10. 제1항에 있어서,According to claim 1,
    a 및 b는 각각 0 또는 1인,a and b are each 0 or 1;
    화합물.compound.
  11. 제1항에 있어서,According to claim 1,
    상기 화학식 1로 표시되는 화합물은 하기 화합물로 구성되는 군으로부터 선택되는 어느 하나인,The compound represented by Formula 1 is any one selected from the group consisting of the following compounds,
    화합물:compound:
    Figure PCTKR2021013360-appb-img-000142
    Figure PCTKR2021013360-appb-img-000142
    Figure PCTKR2021013360-appb-img-000143
    Figure PCTKR2021013360-appb-img-000143
    Figure PCTKR2021013360-appb-img-000144
    Figure PCTKR2021013360-appb-img-000144
    Figure PCTKR2021013360-appb-img-000145
    Figure PCTKR2021013360-appb-img-000145
    Figure PCTKR2021013360-appb-img-000146
    Figure PCTKR2021013360-appb-img-000146
    Figure PCTKR2021013360-appb-img-000147
    Figure PCTKR2021013360-appb-img-000147
    Figure PCTKR2021013360-appb-img-000148
    Figure PCTKR2021013360-appb-img-000148
    Figure PCTKR2021013360-appb-img-000149
    Figure PCTKR2021013360-appb-img-000149
    Figure PCTKR2021013360-appb-img-000150
    Figure PCTKR2021013360-appb-img-000150
    Figure PCTKR2021013360-appb-img-000151
    Figure PCTKR2021013360-appb-img-000151
    Figure PCTKR2021013360-appb-img-000152
    Figure PCTKR2021013360-appb-img-000152
    Figure PCTKR2021013360-appb-img-000153
    Figure PCTKR2021013360-appb-img-000153
    Figure PCTKR2021013360-appb-img-000154
    Figure PCTKR2021013360-appb-img-000154
    Figure PCTKR2021013360-appb-img-000155
    Figure PCTKR2021013360-appb-img-000155
    Figure PCTKR2021013360-appb-img-000156
    Figure PCTKR2021013360-appb-img-000156
    Figure PCTKR2021013360-appb-img-000157
    Figure PCTKR2021013360-appb-img-000157
    Figure PCTKR2021013360-appb-img-000158
    Figure PCTKR2021013360-appb-img-000158
    Figure PCTKR2021013360-appb-img-000159
    Figure PCTKR2021013360-appb-img-000159
    Figure PCTKR2021013360-appb-img-000160
    Figure PCTKR2021013360-appb-img-000160
    Figure PCTKR2021013360-appb-img-000161
    Figure PCTKR2021013360-appb-img-000161
    Figure PCTKR2021013360-appb-img-000162
    Figure PCTKR2021013360-appb-img-000162
    Figure PCTKR2021013360-appb-img-000163
    Figure PCTKR2021013360-appb-img-000163
    Figure PCTKR2021013360-appb-img-000164
    Figure PCTKR2021013360-appb-img-000164
    Figure PCTKR2021013360-appb-img-000165
    Figure PCTKR2021013360-appb-img-000165
    Figure PCTKR2021013360-appb-img-000166
    Figure PCTKR2021013360-appb-img-000166
    Figure PCTKR2021013360-appb-img-000167
    Figure PCTKR2021013360-appb-img-000167
    Figure PCTKR2021013360-appb-img-000168
    Figure PCTKR2021013360-appb-img-000168
    Figure PCTKR2021013360-appb-img-000169
    Figure PCTKR2021013360-appb-img-000169
    Figure PCTKR2021013360-appb-img-000170
    Figure PCTKR2021013360-appb-img-000170
    Figure PCTKR2021013360-appb-img-000171
    Figure PCTKR2021013360-appb-img-000171
    Figure PCTKR2021013360-appb-img-000172
    Figure PCTKR2021013360-appb-img-000172
    Figure PCTKR2021013360-appb-img-000173
    Figure PCTKR2021013360-appb-img-000173
    Figure PCTKR2021013360-appb-img-000174
    Figure PCTKR2021013360-appb-img-000174
    Figure PCTKR2021013360-appb-img-000175
    Figure PCTKR2021013360-appb-img-000175
    Figure PCTKR2021013360-appb-img-000176
    Figure PCTKR2021013360-appb-img-000176
    Figure PCTKR2021013360-appb-img-000177
    Figure PCTKR2021013360-appb-img-000177
    Figure PCTKR2021013360-appb-img-000178
    Figure PCTKR2021013360-appb-img-000178
    Figure PCTKR2021013360-appb-img-000179
    Figure PCTKR2021013360-appb-img-000179
    Figure PCTKR2021013360-appb-img-000180
    Figure PCTKR2021013360-appb-img-000180
    Figure PCTKR2021013360-appb-img-000181
    Figure PCTKR2021013360-appb-img-000181
    Figure PCTKR2021013360-appb-img-000182
    Figure PCTKR2021013360-appb-img-000182
    Figure PCTKR2021013360-appb-img-000183
    Figure PCTKR2021013360-appb-img-000183
    Figure PCTKR2021013360-appb-img-000184
    Figure PCTKR2021013360-appb-img-000184
    Figure PCTKR2021013360-appb-img-000185
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  12. 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 제1항 내지 제11항 중 어느 하나의 항에 따른 화합물을 포함하는, 유기 발광 소자.a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one organic material layer includes the compound according to any one of claims 1 to 11 which is an organic light emitting device.
  13. 제12항에 있어서,13. The method of claim 12,
    상기 유기물층은 전자억제층, 또는 정공수송층인,The organic layer is an electron suppression layer, or a hole transport layer,
    유기 발광 소자.organic light emitting device.
PCT/KR2021/013360 2020-10-12 2021-09-29 Novel compound and organic light-emitting device comprising same WO2022080715A1 (en)

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