WO2021034017A1 - Novel compound and organic light emitting device using same - Google Patents

Novel compound and organic light emitting device using same Download PDF

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WO2021034017A1
WO2021034017A1 PCT/KR2020/010789 KR2020010789W WO2021034017A1 WO 2021034017 A1 WO2021034017 A1 WO 2021034017A1 KR 2020010789 W KR2020010789 W KR 2020010789W WO 2021034017 A1 WO2021034017 A1 WO 2021034017A1
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compound
group
mmol
layer
added
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김민준
전상영
이동훈
최민우
서상덕
오중석
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주식회사 엘지화학
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Priority claimed from KR1020200101330A external-priority patent/KR102430077B1/en
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Priority to CN202080007631.XA priority Critical patent/CN113272307B/en
Publication of WO2021034017A1 publication Critical patent/WO2021034017A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/16—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Definitions

  • the present invention relates to a novel compound and an organic light emitting device using the same.
  • the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material.
  • An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.
  • the 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-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
  • a voltage is applied between the two electrodes
  • holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.
  • Patent Document 0001 Korean Patent Publication No. 10-2013-073537
  • 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:
  • R is linked at position 1 or 2 to form a single bond
  • L is a single bond, or a substituted or unsubstituted C 6-60 arylene
  • Het is a substituted or unsubstituted C 5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of N, O and S,
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, deuterium, or substituted or unsubstituted C 1-60 alkyl,
  • n1, n3, n4 and n5 are each independently an integer of 0 to 4,
  • n2 is an integer from 0 to 2.
  • the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the compound of the present invention.
  • the compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an organic light-emitting device, and may improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light-emitting device.
  • the compound represented by Formula 1 described above may be used as a host material for the emission layer.
  • FIG. 1 shows an example of an organic light-emitting device comprising 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 shows a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 3, an electron suppression layer 8, a light emitting layer 4, a hole suppression layer 9, an electron injection and transport layer ( 5) and a cathode 6 is shown as an example of an organic light-emitting device.
  • substituted or unsubstituted refers to deuterium (D); Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means a substituted or unsubstituted substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O and S atoms,
  • a substituent to which two or more substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
  • the number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the ester group may be substituted with an oxygen of the ester group with a straight chain, 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 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.
  • the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, but is not limited thereto.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. 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, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhex
  • the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. 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 is preferably 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 cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms.
  • the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms.
  • the aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group 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.
  • Etc When the fluorenyl group is substituted, Etc.
  • Etc it 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 carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms.
  • the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, 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 , Car
  • the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and 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 aforementioned alkyl group.
  • the description of the aforementioned heterocyclic group may be applied.
  • the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above.
  • the description of the aryl group described above may be applied except that the arylene is a divalent group.
  • the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group.
  • the hydrocarbon ring is not a monovalent group, and the description of the aryl group or the cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents.
  • the heterocycle is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that two substituents are bonded to each other.
  • the present invention provides a compound represented by Chemical Formula 1.
  • the compound represented by Formula 1 has an indolocarbazole core structure, forms a seven-membered ring in which two benzene rings are further condensed around one nitrogen atom of the core structure, and is added to the other nitrogen atom. Characterized in that it contains a heteroaryl group.
  • the condensed ring structure has high stability against electrons and holes, and when applied as a host compound, energy transfer to the dopant is easy. Accordingly, when employed as an emission layer compound in an organic light emitting device, characteristics of a low driving voltage, high efficiency, and long life can all be improved.
  • the compound represented by Formula 1 is specifically as follows:
  • R is connected at the 1st or 2nd position to form a single bond, thereby forming a 7-membered ring around the N atom,
  • L is a single bond or a substituted or unsubstituted C 6-60 arylene
  • Het is a substituted or unsubstituted C 5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of N, O and S,
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, deuterium, or substituted or unsubstituted C 1-60 alkyl,
  • n1, n3, n4 and n5 are each independently an integer of 0 to 4,
  • n2 is an integer from 0 to 2.
  • R is connected at the 1st or 2nd position to form a seven-membered ring, in which case the compound represented by Formula 1 is represented by the following Formula 1-1 or 1-2:
  • n'2 is 0 or 1
  • n'3 is an integer from 0 to 3
  • L is a single bond, phenylene, or naphthylene.
  • Het is any one selected from the group consisting of:
  • Each R′ is independently a substituted or unsubstituted C 6-60 aryl, or a C 5-60 heteroaryl comprising at least one hetero atom selected from the group consisting of substituted or unsubstituted N, O and S. .
  • R' is each independently, phenyl, biphenylyl, naphthyl, terphenylyl, phenylnaphthyl, naphthylphenyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, dibenzofuranyl, Dibenzothiophenyl, carbazol-9-yl or 9-phenyl-9H-carbazolyl.
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen or deuterium, more preferably all of them are hydrogen.
  • the compound represented by Formula 1 may be any one selected from the group consisting of:
  • each of X is independently halogen, preferably bromo or chloro, and the definition of other substituents is as described above.
  • the compound represented by Formula 1 may be prepared through a reaction of introducing an additional hetero substituent to the core structures of Core 1-1 and Core 1-2, and a specific example may be prepared through Reaction Scheme 1-3.
  • the reactor for the reaction may be appropriately changed, and the method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.
  • the present invention provides an organic light-emitting device including the compound represented by Formula 1 above.
  • the present invention provides a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes a compound represented by Formula 1 .
  • the organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer 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, a hole suppression layer, an electron transport layer, an electron injection layer, and the like 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 material 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, a hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. Including the indicated compound.
  • the organic material layer may include an emission layer, and the emission layer includes the compound represented by Chemical Formula 1.
  • the compound represented by Formula 1 is used as a host compound of the emission layer.
  • the organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention further includes a hole injection layer and a hole transport layer between the first electrode and the emission layer, and an electron transport layer and an electron injection layer between the emission layer and the second electrode in addition to the emission layer as an organic material layer. It can have a structure to 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.
  • the first electrode is an anode and the second electrode is a cathode, and an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate (normal type). It can be a device.
  • the first electrode is a cathode and the second electrode is an anode, and a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. It may be a light emitting device.
  • FIGS. 1 and 2 the structure of an organic light-emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.
  • the compound represented by Formula 1 may be included in the emission layer.
  • the compound represented by Formula 1 may be included in the emission layer.
  • the organic light-emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1.
  • the organic material layers may be formed of the same material or different materials.
  • the organic light emitting device 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
  • the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate.
  • an organic material layer including a hole injection layer, a hole transport layer, an electron suppression layer, an emission layer, a hole suppression layer and an electron transport layer is formed thereon, and then a material that can be used as a cathode may be deposited 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 as 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
  • the second electrode is an anode
  • the cathode material a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer.
  • the cathode material include metals such as vanadium, chromium, copper, zinc, and 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; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the cathode material is a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO 2 /Al, but are not limited thereto.
  • the hole injection layer is a layer that injects holes from an electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for a light emitting layer or a light emitting material.
  • a compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable.
  • the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances.
  • the hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the emission layer
  • the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission layer, and has high mobility for holes.
  • the material is suitable.
  • the hole transport material the compound represented by Formula 1 may be used, or an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion may be used, but the present invention is not limited thereto. .
  • the electron inhibiting layer (or electron blocking layer, electron blocking layer) is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons, thereby preventing the hole-electron It refers to a layer that serves to improve the efficiency of an organic light emitting device by increasing the probability of coupling.
  • the electron inhibiting layer includes an electron blocking material, and an arylamine-based organic material may be used as an example of the electron blocking material, but is not limited thereto.
  • the light-emitting material of the light-emitting layer a material capable of emitting light in the visible 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.
  • 8-hydroxy-quinoline aluminum complex Alq 3
  • Carbazole-based compounds Dimerized styryl compounds
  • BAlq 10-hydroxybenzo quinoline-metal compound
  • Benzoxazole, benzthiazole, and benzimidazole-based compounds Poly(p-phenylenevinylene) (PPV)-based polymer
  • Spiro compounds Polyfluorene, rubrene, and the like, but are not limited thereto.
  • the light emitting layer includes a host material and a dopant material, and a compound represented by Formula 1 herein is used as a host material.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds
  • heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.
  • the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group
  • the styrylamine compound is substituted or unsubstituted
  • the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group
  • the styrylamine compound is substituted or unsubstituted
  • at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting
  • the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.
  • the light emitting layer may include the following iridium complex compound as a dopant material, but is not limited thereto.
  • the hole inhibiting layer (or hole blocking layer, hole blocking layer) is formed on the light emitting layer, and is preferably provided in contact with the light emitting layer, to control electron mobility and prevent excessive movement of holes, thereby increasing the probability of hole-electron bonding. It refers to a layer that serves to improve the efficiency of an organic light-emitting device by increasing it.
  • the hole-suppressing layer includes a hole-suppressing material, and examples of such a hole-blocking material include a subazine derivative including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; A compound into which an electron withdrawing group such as a phosphine oxide derivative has been introduced may be used, but is not limited thereto.
  • the electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting received electrons to the emission layer, and is formed on the emission layer or the hole suppression layer.
  • an electron injection and transport material a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high mobility for electrons is suitable.
  • specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complexes containing Alq 3; Organic radical compounds; Hydroxyflavone-metal complex; Triazine derivatives and the like, but are not limited thereto.
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and their derivatives, metal complex compounds , Or a nitrogen-containing 5-membered cyclic derivative, but may be used, but is not limited thereto.
  • the electron injection and transport layer may be formed as separate layers such as an electron injection layer and an electron transport layer.
  • the electron transport layer is formed on the emission layer or the hole suppression layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer.
  • the electron injection layer is formed on the electron transport layer, and electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li 2 O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and the like, their derivatives, metal complex compounds, and nitrogen-containing 5-membered ring derivatives may be used.
  • electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li 2 O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone
  • the metal complex compound examples include lithium 8-hydroxyquinolinato, 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-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited thereto.
  • the organic light emitting device may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.
  • the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
  • intermediate compound 1a (10 g, 37.4 mmol), compound 1-1 (15.2 g, 37.4 mmol), and NaOtBu (7.2 g, 74.7 mmol) were added to xylene (200 mL), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.7 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 1 (7.4 g).
  • intermediate compound 2a (10 g, 23.8 mmol), compound 1-1 (9.7 g, 23.8 mmol), and NaOtBu (4.6 g, 47.6 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2 (11.3 g).
  • intermediate compound 3a (10 g, 24.6 mmol), compound 1-1 (10 g, 24.6 mmol), and NaOtBu (4.7 g, 49.3 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 3 (8 g).
  • intermediate compound 4a (10 g, 28.8 mmol), compound 1-1 (11.7 g, 28.8 mmol), and NaOtBu (5.5 g, 57.7 mmol) were added to xylene (200 mL), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 4 (9.5 g).
  • intermediate compound 5a (10 g, 25.6 mmol), compound 1-1 (10.4 g, 25.6 mmol), and NaOtBu (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 5 (8 g).
  • intermediate compound 6a (10 g, 26.3 mmol), compound 1-1 (10.7 g, 26.3 mmol), and NaOtBu (5.1 g, 52.7 mmol) were added to xylene (200 mL), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 6 (8.5 g).
  • intermediate compound 7a (10 g, 26.3 mmol), compound 1-1 (10.7 g, 26.3 mmol), and NaOtBu (5 g, 52.5 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 7 (5.9 g).
  • intermediate compound 8a (10 g, 23.6 mmol), compound 1-1 (9.6 g, 23.6 mmol), and NaOtBu (4.5 g, 47.3 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 8 (6.6 g).
  • intermediate compound 9a (10 g, 26.8 mmol), compound 1-1 (10.9 g, 26.8 mmol), and NaOtBu (5.2 g, 53.6 mmol) were added to xylene (200 mL), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 9 (10.4 g).
  • intermediate compound 10a (10 g, 25.8 mmol), compound 1-1 (10.5 g, 25.8 mmol), and NaOtBu (5 g, 51.7 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 10 (8.8 g).
  • intermediate compound 11a (10 g, 24.8 mmol), compound 1-1 (10.1 g, 24.8 mmol), and NaOtBu (4.8 g, 49.6 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 11 (6.1 g).
  • intermediate compound 12a (10 g, 30.2 mmol), compound 1-1 (12.3 g, 30.2 mmol), and NaOtBu (5.8 g, 60.5 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 12 (8.7 g).
  • intermediate compound 13a (10 g, 27 mmol), compound 1-1 (11 g, 27 mmol), and NaOtBu (5.2 g, 53.9 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 13 (8 g).
  • intermediate compound 14a (10 g, 28 mmol), compound 1-1 (11.4 g, 28 mmol), and NaOtBu (5.4 g, 56.1 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 14 (7.7 g).
  • intermediate compound 15a (10 g, 22.4 mmol), compound 1-1 (9.1 g, 22.4 mmol), and NaOtBu (4.3 g, 44.9 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 15 (9.3 g).
  • intermediate compound 16a (10 g, 31.5 mmol), compound 1-2 (12.8 g, 31.5 mmol), and NaOtBu (6 g, 62.9 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 16 (9.7 g).
  • intermediate compound 17a (10 g, 25.4 mmol), compound 1-2 (10.3 g, 25.4 mmol), and NaOtBu (4.9 g, 50.8 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 17 (9.7 g).
  • intermediate compound 18a (10 g, 27.9 mmol), compound 1-2 (11.4 g, 27.9 mmol), and NaOtBu (5.4 g, 55.9 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 18 (9.6 g).
  • intermediate compound 19a (10 g, 41.5 mmol), compound 1-2 (16.9 g, 41.5 mmol), and NaOtBu (8 g, 83.1 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.8 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 19 (8.4 g).
  • intermediate compound 20a (10 g, 29.3 mmol), compound 1-2 (11.9 g, 29.3 mmol), and NaOtBu (5.6 g, 58.7 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 20 (8.8 g).
  • intermediate compound 21a (10 g, 24.6 mmol), compound 1-2 (10 g, 24.6 mmol), and NaOtBu (4.7 g, 49.3 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 21 (7.8 g).
  • intermediate compound 22a (10 g, 25.6 mmol), compound 1-2 (10.4 g, 25.6 mmol), and NaOtBu (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 22 (5.8 g).
  • intermediate compound 23a (10 g, 22.6 mmol), compound 1-2 (9.2 g, 22.6 mmol), and NaOtBu (4.3 g, 45.2 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 23 (11 g).
  • intermediate compound 24a (10 g, 33.7 mmol), compound 1-2 (13.7 g, 33.7 mmol), and NaOtBu (6.5 g, 67.4 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.7 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 24 (12.6 g).
  • intermediate compound 25a (10 g, 22.3 mmol), compound 1-2 (9.1 g, 22.3 mmol), and NaOtBu (4.3 g, 44.5 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 25 (8.9 g).
  • intermediate compound 26a (10 g, 25.8 mmol), compound 1-2 (10.5 g, 25.8 mmol), and NaOtBu (5 g, 51.7 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 26 (7.4 g).
  • intermediate compound 27a (10 g, 21.6 mmol), compound 1-2 (8.8 g, 21.6 mmol), and NaOtBu (4.2 g, 43.3 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 27 (8.5 g).
  • intermediate compound 28a (10 g, 35.6 mmol), compound 1-2 (14.5 g, 35.6 mmol), and NaOtBu (6.8 g, 71.2 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 28 (10.9 g).
  • intermediate compound 29a (10 g, 28 mmol), compound 1-2 (11.4 g, 28 mmol), and NaOtBu (5.4 g, 56.1 mmol) were added to xylene (200 mL), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 29 (7.5 g).
  • intermediate compound 30a (10 g, 25.8 mmol), compound 1-2 (10.5 g, 25.8 mmol), and NaOtBu (5 g, 51.7 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 30 (6.3 g).
  • a glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000 ⁇ was put in distilled water dissolved in a detergent and washed with ultrasonic waves.
  • ITO indium tin oxide
  • a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured by Millipore Co. was used as distilled water.
  • ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.
  • the HI-1 compound was formed as a hole injection layer on the prepared ITO transparent electrode to a thickness of 1150 ⁇ , but the following compound A-1 was p-doping at a concentration of 1.5%.
  • the following HT-1 compound was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800 ⁇ .
  • the following EB-1 compound was vacuum deposited on the hole transport layer with a film thickness of 150 ⁇ to form an electron suppressing layer.
  • the following RH-1 compound and the following Dp-7 compound were vacuum-deposited at a weight ratio of 98:2 on the EB-1 deposition film to form a red light emitting layer having a thickness of 400 ⁇ .
  • a hole blocking layer was formed by vacuum depositing the following HB-1 compound with a thickness of 30 ⁇ on the emission layer. Subsequently, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300 ⁇ . Lithium fluoride (LiF) at a thickness of 12 ⁇ and aluminum at a thickness of 1,000 ⁇ were sequentially deposited on the electron injection and transport layer to form a negative electrode.
  • LiF lithium fluoride
  • the deposition rate of organic material was maintained at 0.4 to 0.7 ⁇ /sec
  • the deposition rate of lithium fluoride at the cathode was 0.3 ⁇ /sec
  • the deposition rate of aluminum was 2 ⁇ /sec
  • the vacuum degree during deposition was 2X10 -7
  • an organic light emitting device was manufactured.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the compounds of Compounds 1 to 30 synthesized above were used instead of RH-1 in the organic light-emitting device of Comparative Example 1.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the following compounds C-1 to C-8 were used instead of RH-1 in the organic light-emitting device of Comparative Example 1.
  • the lifetime T95 refers to the time it takes for the luminance to decrease from initial luminance (6000 nit) to 95%.
  • the red organic light-emitting device of Comparative Example 1 uses a material that has been widely used in the past, and has a structure using compound EB-1 as an electron blocking layer and compounds RH-1/Dp-7 as a red light emitting layer.
  • an organic light-emitting device was manufactured using C-1 to C-8 instead of RH-1.
  • substrate 2 anode
  • hole transport layer 4 light emitting layer

Abstract

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

Description

신규한 화합물 및 이를 이용한 유기 발광 소자Novel compound and organic light emitting device using the same
관련 출원(들)과의 상호 인용Cross-reference with related application(s)
본 출원은 2019년 8월 16일자 한국 특허 출원 제10-2019-0100472호에 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. 10-2019-0100472 filed on August 16, 2019, and all contents disclosed in the literature of the Korean patent applications are incorporated as part of this specification.
본 발명은 신규한 화합물 및 이를 이용한 유기 발광 소자에 관한 것이다. The present invention relates to a novel compound and an organic light emitting device using 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 emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has 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 유기물 층을 포함하는 구조를 가진다. 상기 유기물 층은 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. The 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-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.
상기와 같은 유기 발광 소자에 사용되는 유기물에 대하여 새로운 재료의 개발이 지속적으로 요구되고 있다.Development of new materials for organic materials used in organic light emitting devices as described above is continuously required.
[선행기술문헌][Prior technical literature]
[특허문헌][Patent Literature]
(특허문헌 0001) 한국특허 공개번호 제10-2013-073537호(Patent Document 0001) Korean Patent Publication No. 10-2013-073537
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 PCTKR2020010789-appb-img-000001
Figure PCTKR2020010789-appb-img-000001
상기 화학식 1에서,In Formula 1,
R은 1번 또는 2번 위치에서 연결되어 단일 결합을 형성하고,R is linked at position 1 or 2 to form a single bond,
L은 단일 결합, 또는 치환 또는 비치환된 C 6-60 아릴렌이고, L is a single bond, or a substituted or unsubstituted C 6-60 arylene,
Het은 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로 원자를 포함하는 C 5-60 헤테로아릴이고, Het is a substituted or unsubstituted C 5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of N, O and S,
R 1, R 2, R 3, R 4 및 R 5는 각각 독립적으로, 수소, 중수소, 또는 치환 또는 비치환된 C 1-60 알킬이고, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, deuterium, or substituted or unsubstituted C 1-60 alkyl,
n1, n3, n4 및 n5는 각각 독립적으로 0 내지 4의 정수이고,n1, n3, n4 and n5 are each independently an integer of 0 to 4,
n2는 0 내지 2의 정수이다.n2 is an integer from 0 to 2.
또한, 본 발명은 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 전술한 본 발명의 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 one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the compound of the present invention.
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 발광층의 호스트 재료로 사용될 수 있다.The compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an organic light-emitting device, and may improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light-emitting device. In particular, the compound represented by Formula 1 described above may be used as a host material for the emission layer.
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. 1 shows an example of an organic light-emitting device comprising 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), 정공억제층(9), 전자주입 및 수송층(5) 및 음극(6)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 2 shows a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 3, an electron suppression layer 8, a light emitting layer 4, a hole suppression layer 9, an electron injection and transport layer ( 5) and a cathode 6 is shown as an example of an organic light-emitting device.
이하, 본 발명의 이해를 돕기 위하여 보다 상세히 설명한다.Hereinafter, it will be described in more detail to aid the understanding of the present invention.
(용어의 설명)(Explanation of terms)
본 명세서에서,
Figure PCTKR2020010789-appb-img-000002
및
Figure PCTKR2020010789-appb-img-000003
는 다른 치환기에 연결되는 결합을 의미한다. In this specification,
Figure PCTKR2020010789-appb-img-000002
And
Figure PCTKR2020010789-appb-img-000003
Means a bond connected to another substituent.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소(D); 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.In the present specification, the term "substituted or unsubstituted" refers to deuterium (D); Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means a substituted or unsubstituted substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O and S atoms, or linked with two or more substituents among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to 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 of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2020010789-appb-img-000004
Figure PCTKR2020010789-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, the ester group may be substituted with an oxygen of the ester group with a straight chain, 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 PCTKR2020010789-appb-img-000005
Figure PCTKR2020010789-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 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2020010789-appb-img-000006
Figure PCTKR2020010789-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 is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it 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 a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, but is not limited thereto.
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 a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. 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, cycloheptylmethyl, 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 a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. 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 is preferably 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 cycloalkyl group has 3 to 20 carbon atoms. 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 are 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 is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group 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 PCTKR2020010789-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 PCTKR2020010789-appb-img-000007
Etc. However, it 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), 티아졸릴기, 이소옥사졸릴기, 옥사디아졸릴기, 티아디아졸릴기, 벤조티아졸릴기, 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 carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, 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, thiazolyl group, isoxazolyl Group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but are 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 among the aralkyl group, aralkenyl group, alkylaryl group, and 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 aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the description of the aforementioned heterocyclic group may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or the cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that two substituents are bonded to each other.
(화합물)(compound)
본 발명은 상기 화학식 1로 표시되는 화합물을 제공한다. 화학식 1로 표시되는 화합물은 인돌로카바졸 코어 구조를 가지며, 상기 코어 구조의 하나의 질소 원자를 중심으로 두개의 벤젠 고리가 추가로 축합된 7각 고리를 형성하며, 다른 하나의 질소 원자에는 추가 헤테로 아릴기를 포함하는 것을 특징으로 한다. 상기 축합 고리 구조에 의해 전자와 정공에 대한 안정도가 높으며, 호스트 화합물로 적용 시 도판트로의 에너지 전달이 용이하다. 이에 따라, 유기 발광 소자에 발광층 화합물로 채용 시 저구동 전압, 고효율 및 장수명의 특성을 모두 향상시킬 수 있다. 화학식 1로 표시되는 화합물은 구체적으로 하기와 같다:The present invention provides a compound represented by Chemical Formula 1. The compound represented by Formula 1 has an indolocarbazole core structure, forms a seven-membered ring in which two benzene rings are further condensed around one nitrogen atom of the core structure, and is added to the other nitrogen atom. Characterized in that it contains a heteroaryl group. The condensed ring structure has high stability against electrons and holes, and when applied as a host compound, energy transfer to the dopant is easy. Accordingly, when employed as an emission layer compound in an organic light emitting device, characteristics of a low driving voltage, high efficiency, and long life can all be improved. The compound represented by Formula 1 is specifically as follows:
[화학식 1][Formula 1]
Figure PCTKR2020010789-appb-img-000008
Figure PCTKR2020010789-appb-img-000008
상기 화학식 1에서,In Formula 1,
R은 1번 또는 2번 위치에서 연결되어 단일 결합을 형성하고, 이에 따라, N 원자를 중심으로 7각 고리가 형성되고,R is connected at the 1st or 2nd position to form a single bond, thereby forming a 7-membered ring around the N atom,
L은 단일 결합 또는 치환 또는 비치환된 C 6-60 아릴렌이고, L is a single bond or a substituted or unsubstituted C 6-60 arylene,
Het은 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로 원자를 포함하는 C 5-60 헤테로아릴이고, Het is a substituted or unsubstituted C 5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of N, O and S,
R 1, R 2, R 3, R 4 및 R 5는 각각 독립적으로, 수소, 중수소 또는 치환 또는 비치환된 C 1-60 알킬이고, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, deuterium, or substituted or unsubstituted C 1-60 alkyl,
n1, n3, n4 및 n5는 각각 독립적으로 0 내지 4의 정수이고,n1, n3, n4 and n5 are each independently an integer of 0 to 4,
n2는 0 내지 2의 정수이다.n2 is an integer from 0 to 2.
상기 화학식 1로 표시되는 화합물에서, R은 1번 또는 2번 위치에서 연결되어 7각 고리를 형성하며, 이 경우 화학식 1로 표시되는 화합물은 하기 화학식 1-1 또는 1-2로 표시된다:In the compound represented by Formula 1, R is connected at the 1st or 2nd position to form a seven-membered ring, in which case the compound represented by Formula 1 is represented by the following Formula 1-1 or 1-2:
[화학식 1-1][Formula 1-1]
Figure PCTKR2020010789-appb-img-000009
Figure PCTKR2020010789-appb-img-000009
[화학식 1-2][Formula 1-2]
Figure PCTKR2020010789-appb-img-000010
Figure PCTKR2020010789-appb-img-000010
상기 화학식 1-1 내지 1-2에서, In Formulas 1-1 to 1-2,
n'2는 0 또는 1이고,n'2 is 0 or 1,
n'3는 0 내지 3의 정수이고,n'3 is an integer from 0 to 3,
L, Het, R 1, R 2, R 3, R 4, R 5, n1, n2, n3, n4, 및 n5는 앞서 정의한 바와 같다.L, Het, R 1 , R 2 , R 3 , R 4 , R 5 , n1, n2, n3, n4, and n5 are as previously defined.
바람직하게는, L은 단일 결합, 페닐렌, 또는 나프틸렌이다.Preferably, L is a single bond, phenylene, or naphthylene.
바람직하게는, Het은 하기로 이루어진 군에서 선택되는 어느 하나이다:Preferably, Het is any one selected from the group consisting of:
Figure PCTKR2020010789-appb-img-000011
Figure PCTKR2020010789-appb-img-000011
상기 군에서,In the above group,
R'은 각각 독립적으로, 치환 또는 비치환된 C 6-60 아릴, 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 하나 이상의 헤테로 원자를 포함하는 C 5-60 헤테로아릴이다.Each R′ is independently a substituted or unsubstituted C 6-60 aryl, or a C 5-60 heteroaryl comprising at least one hetero atom selected from the group consisting of substituted or unsubstituted N, O and S. .
바람직하게는, R'은 각각 독립적으로, 페닐, 비페닐릴, 나프틸, 터페닐릴, 페닐나프틸, 나프틸페닐, 페난쓰레닐, 트리페닐레닐, 디메틸플루오레닐, 디벤조퓨라닐, 디벤조티오페닐, 카바졸-9-일 또는 9-페닐-9H-카바졸릴이다.Preferably, R'is each independently, phenyl, biphenylyl, naphthyl, terphenylyl, phenylnaphthyl, naphthylphenyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, dibenzofuranyl, Dibenzothiophenyl, carbazol-9-yl or 9-phenyl-9H-carbazolyl.
바람직하게는, R 1, R 2, R 3, R 4 및 R 5는 각각 독립적으로 수소 또는 중수소이고, 더욱 바람직하게는 이들 모두가 수소이다.Preferably, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen or deuterium, more preferably all of them are hydrogen.
바람직하게는, 상기 화학식 1로 표시되는 화합물은, 하기로 구성되는 군으로부터 선택되는 어느 하나일 수 있다:Preferably, the compound represented by Formula 1 may be any one selected from the group consisting of:
Figure PCTKR2020010789-appb-img-000012
Figure PCTKR2020010789-appb-img-000012
Figure PCTKR2020010789-appb-img-000013
Figure PCTKR2020010789-appb-img-000013
Figure PCTKR2020010789-appb-img-000014
Figure PCTKR2020010789-appb-img-000014
Figure PCTKR2020010789-appb-img-000015
Figure PCTKR2020010789-appb-img-000015
Figure PCTKR2020010789-appb-img-000016
Figure PCTKR2020010789-appb-img-000016
Figure PCTKR2020010789-appb-img-000017
Figure PCTKR2020010789-appb-img-000017
Figure PCTKR2020010789-appb-img-000018
Figure PCTKR2020010789-appb-img-000018
Figure PCTKR2020010789-appb-img-000019
Figure PCTKR2020010789-appb-img-000019
Figure PCTKR2020010789-appb-img-000020
Figure PCTKR2020010789-appb-img-000020
Figure PCTKR2020010789-appb-img-000021
Figure PCTKR2020010789-appb-img-000021
Figure PCTKR2020010789-appb-img-000022
Figure PCTKR2020010789-appb-img-000022
Figure PCTKR2020010789-appb-img-000023
Figure PCTKR2020010789-appb-img-000023
Figure PCTKR2020010789-appb-img-000024
Figure PCTKR2020010789-appb-img-000024
Figure PCTKR2020010789-appb-img-000025
Figure PCTKR2020010789-appb-img-000025
Figure PCTKR2020010789-appb-img-000026
Figure PCTKR2020010789-appb-img-000026
Figure PCTKR2020010789-appb-img-000027
.
Figure PCTKR2020010789-appb-img-000027
.
Figure PCTKR2020010789-appb-img-000028
Figure PCTKR2020010789-appb-img-000028
Figure PCTKR2020010789-appb-img-000029
Figure PCTKR2020010789-appb-img-000029
Figure PCTKR2020010789-appb-img-000030
Figure PCTKR2020010789-appb-img-000030
Figure PCTKR2020010789-appb-img-000031
Figure PCTKR2020010789-appb-img-000031
Figure PCTKR2020010789-appb-img-000032
Figure PCTKR2020010789-appb-img-000032
Figure PCTKR2020010789-appb-img-000033
Figure PCTKR2020010789-appb-img-000033
Figure PCTKR2020010789-appb-img-000034
Figure PCTKR2020010789-appb-img-000034
Figure PCTKR2020010789-appb-img-000035
Figure PCTKR2020010789-appb-img-000035
Figure PCTKR2020010789-appb-img-000036
Figure PCTKR2020010789-appb-img-000036
Figure PCTKR2020010789-appb-img-000037
Figure PCTKR2020010789-appb-img-000037
Figure PCTKR2020010789-appb-img-000038
Figure PCTKR2020010789-appb-img-000038
Figure PCTKR2020010789-appb-img-000039
Figure PCTKR2020010789-appb-img-000039
Figure PCTKR2020010789-appb-img-000040
Figure PCTKR2020010789-appb-img-000040
Figure PCTKR2020010789-appb-img-000041
Figure PCTKR2020010789-appb-img-000041
Figure PCTKR2020010789-appb-img-000042
Figure PCTKR2020010789-appb-img-000042
Figure PCTKR2020010789-appb-img-000043
Figure PCTKR2020010789-appb-img-000043
Figure PCTKR2020010789-appb-img-000044
Figure PCTKR2020010789-appb-img-000044
Figure PCTKR2020010789-appb-img-000045
Figure PCTKR2020010789-appb-img-000045
Figure PCTKR2020010789-appb-img-000046
Figure PCTKR2020010789-appb-img-000046
Figure PCTKR2020010789-appb-img-000047
Figure PCTKR2020010789-appb-img-000047
Figure PCTKR2020010789-appb-img-000048
Figure PCTKR2020010789-appb-img-000048
Figure PCTKR2020010789-appb-img-000049
Figure PCTKR2020010789-appb-img-000049
Figure PCTKR2020010789-appb-img-000050
Figure PCTKR2020010789-appb-img-000050
Figure PCTKR2020010789-appb-img-000051
Figure PCTKR2020010789-appb-img-000051
Figure PCTKR2020010789-appb-img-000052
Figure PCTKR2020010789-appb-img-000052
Figure PCTKR2020010789-appb-img-000053
Figure PCTKR2020010789-appb-img-000053
Figure PCTKR2020010789-appb-img-000054
Figure PCTKR2020010789-appb-img-000054
Figure PCTKR2020010789-appb-img-000055
Figure PCTKR2020010789-appb-img-000055
Figure PCTKR2020010789-appb-img-000056
Figure PCTKR2020010789-appb-img-000056
Figure PCTKR2020010789-appb-img-000057
Figure PCTKR2020010789-appb-img-000057
Figure PCTKR2020010789-appb-img-000058
Figure PCTKR2020010789-appb-img-000058
Figure PCTKR2020010789-appb-img-000059
Figure PCTKR2020010789-appb-img-000059
Figure PCTKR2020010789-appb-img-000060
Figure PCTKR2020010789-appb-img-000060
Figure PCTKR2020010789-appb-img-000061
Figure PCTKR2020010789-appb-img-000061
Figure PCTKR2020010789-appb-img-000062
Figure PCTKR2020010789-appb-img-000062
Figure PCTKR2020010789-appb-img-000063
Figure PCTKR2020010789-appb-img-000063
Figure PCTKR2020010789-appb-img-000064
Figure PCTKR2020010789-appb-img-000064
Figure PCTKR2020010789-appb-img-000065
Figure PCTKR2020010789-appb-img-000065
Figure PCTKR2020010789-appb-img-000066
Figure PCTKR2020010789-appb-img-000066
Figure PCTKR2020010789-appb-img-000067
Figure PCTKR2020010789-appb-img-000067
Figure PCTKR2020010789-appb-img-000068
Figure PCTKR2020010789-appb-img-000068
Figure PCTKR2020010789-appb-img-000069
Figure PCTKR2020010789-appb-img-000069
Figure PCTKR2020010789-appb-img-000070
Figure PCTKR2020010789-appb-img-000070
Figure PCTKR2020010789-appb-img-000071
Figure PCTKR2020010789-appb-img-000071
Figure PCTKR2020010789-appb-img-000072
Figure PCTKR2020010789-appb-img-000072
Figure PCTKR2020010789-appb-img-000073
Figure PCTKR2020010789-appb-img-000073
Figure PCTKR2020010789-appb-img-000074
Figure PCTKR2020010789-appb-img-000074
Figure PCTKR2020010789-appb-img-000075
Figure PCTKR2020010789-appb-img-000075
Figure PCTKR2020010789-appb-img-000076
Figure PCTKR2020010789-appb-img-000076
Figure PCTKR2020010789-appb-img-000077
Figure PCTKR2020010789-appb-img-000077
Figure PCTKR2020010789-appb-img-000078
Figure PCTKR2020010789-appb-img-000078
Figure PCTKR2020010789-appb-img-000079
Figure PCTKR2020010789-appb-img-000079
Figure PCTKR2020010789-appb-img-000080
Figure PCTKR2020010789-appb-img-000080
Figure PCTKR2020010789-appb-img-000081
Figure PCTKR2020010789-appb-img-000081
Figure PCTKR2020010789-appb-img-000082
Figure PCTKR2020010789-appb-img-000082
Figure PCTKR2020010789-appb-img-000083
Figure PCTKR2020010789-appb-img-000083
Figure PCTKR2020010789-appb-img-000084
Figure PCTKR2020010789-appb-img-000084
Figure PCTKR2020010789-appb-img-000085
Figure PCTKR2020010789-appb-img-000085
Figure PCTKR2020010789-appb-img-000086
Figure PCTKR2020010789-appb-img-000086
Figure PCTKR2020010789-appb-img-000087
Figure PCTKR2020010789-appb-img-000087
Figure PCTKR2020010789-appb-img-000088
Figure PCTKR2020010789-appb-img-000088
Figure PCTKR2020010789-appb-img-000089
Figure PCTKR2020010789-appb-img-000089
Figure PCTKR2020010789-appb-img-000090
Figure PCTKR2020010789-appb-img-000090
Figure PCTKR2020010789-appb-img-000091
Figure PCTKR2020010789-appb-img-000091
Figure PCTKR2020010789-appb-img-000092
Figure PCTKR2020010789-appb-img-000092
Figure PCTKR2020010789-appb-img-000093
Figure PCTKR2020010789-appb-img-000093
Figure PCTKR2020010789-appb-img-000094
Figure PCTKR2020010789-appb-img-000094
Figure PCTKR2020010789-appb-img-000095
Figure PCTKR2020010789-appb-img-000095
Figure PCTKR2020010789-appb-img-000096
Figure PCTKR2020010789-appb-img-000096
Figure PCTKR2020010789-appb-img-000097
Figure PCTKR2020010789-appb-img-000097
..
상기 화학식 1로 표시되는 화합물은 하기 반응식 1에 따라 제조할 수 있다:The compound represented by Formula 1 can be prepared according to the following Scheme 1:
[반응식 1][Scheme 1]
Figure PCTKR2020010789-appb-img-000098
Figure PCTKR2020010789-appb-img-000098
상기 반응식에서, X는 각각 독립적으로, 할로겐이고, 바람직하게는 브로모, 또는 클로로이고, 다른 치환기에 대한 정의는 앞서 설명한 바와 같다. In the above reaction formula, each of X is independently halogen, preferably bromo or chloro, and the definition of other substituents is as described above.
상기 화학식 1로 표시되는 화합물은 Core 1-1 및 Core 1-2의 코어 구조에 추가 헤테로 치환기를 도입하는 반응을 통해 제조될 수 있고, 구체적인 예로 상기 반응식 1-3을 통해 제조될 수 있다. 상기 반응을 위한 반응기는 적절히 변경될 수 있고, 화학식 1로 표시되는 화합물의 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.The compound represented by Formula 1 may be prepared through a reaction of introducing an additional hetero substituent to the core structures of Core 1-1 and Core 1-2, and a specific example may be prepared through Reaction Scheme 1-3. The reactor for the reaction may be appropriately changed, and the method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.
(유기 발광 소자)(Organic light emitting device)
한편, 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 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화학식 1로 표시되는 화합물을 포함하는, 유기 발광 소자를 제공한다. Meanwhile, the present invention provides an organic light-emitting device including the compound represented by Formula 1 above. For example, the present invention provides a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes a compound represented by Formula 1 .
본 발명의 유기 발광 소자의 유기물층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기 발광 소자는 유기물층으로서 정공주입층, 정공수송층, 전자억제층, 발광층, 정공억제층, 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 multilayer 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, a hole suppression layer, an electron transport layer, an electron injection layer, and the like 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 포함한다. In addition, the organic material 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, a hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. Including the indicated compound.
또한, 상기 유기물층은 발광층을 포함할 수 있고, 상기 발광층은 상기 화학식 1로 표시되는 화합물을 포함한다. 바람직하게는, 상기 화학식 1로 표시되는 화합물은 발광층의 호스트 화합물로 사용된다. In addition, the organic material layer may include an emission layer, and the emission layer includes the compound represented by Chemical Formula 1. Preferably, the compound represented by Formula 1 is used as a host compound of the emission layer.
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 multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention further includes a hole injection layer and a hole transport layer between the first electrode and the emission layer, and an electron transport layer and an electron injection layer between the emission layer and the second electrode in addition to the emission layer as an organic material layer. It can have a structure to 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, 상기 제1 전극이 양극이고 상기 제2 전극은 음극인, 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, 상기 제1 전극이 음극이고 상기 제2 전극은 양극인, 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.In addition, in the organic light emitting device according to the present invention, the first electrode is an anode and the second electrode is a cathode, and an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate (normal type). It can be a device. In addition, in the organic light emitting device according to the present invention, the first electrode is a cathode and the second electrode is an anode, and a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. It may be a light emitting device. For example, the structure of an organic light-emitting device 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 발광층에 포함될 수 있다. 1 shows an example of an organic light-emitting device comprising 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 emission layer.
도 2는 기판(1), 양극(2), 정공주입층(7), 정공수송층(3), 전자억제층(8), 발광층(4), 정공억제층(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 발광층에 포함될 수 있다.2 shows a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 3, an electron suppression layer 8, a light emitting layer 4, a hole suppression layer 9, an electron injection and transport layer ( 5) and a cathode 6 is shown as an example of an organic light-emitting device. In such a structure, the compound represented by Formula 1 may be included in the emission layer.
본 발명에 따른 유기 발광 소자는, 상기 유기물층 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 by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1. In addition, 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, 전자억제층, 발광층, 정공억제층 및 전자수송층을 포함하는 유기물층을 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 device 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, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, an organic material layer including a hole injection layer, a hole transport layer, an electron suppression layer, an emission layer, a hole suppression layer and an electron transport layer is formed thereon, and then a material that can be used as a cathode may be deposited 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 유기물층으로 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 as 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 such a 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.For 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 유기물층으로 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 SnO 2: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 preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and 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; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, 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 LiO 2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO 2 /Al, but are 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 유기물층의 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 that injects holes from an electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for a light emitting layer or a light emitting material. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) 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 hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, etc., but are not limited thereto.
상기 정공수송층은 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로, 정공 수송 물질로는 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 상기 정공 수송 물질로 상기 화학식 1로 표시되는 화합물을 사용하거나, 또는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the emission layer, and the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission layer, and has high mobility for holes. The material is suitable. As the hole transport material, the compound represented by Formula 1 may be used, or an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion may be used, but the present invention is not limited thereto. .
상기 전자억제층(또는 전자저지층, 전자차단층)은 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 아릴아민 계열의 유기물 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.The electron inhibiting layer (or electron blocking layer, electron blocking layer) is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons, thereby preventing the hole-electron It refers to a layer that serves to improve the efficiency of an organic light emitting device by increasing the probability of coupling. The electron inhibiting layer includes an electron blocking material, and an arylamine-based organic material may be used as an example of the electron blocking material, but is not limited thereto.
상기 발광층의 발광 물질로는 정공 수송층과 전자 수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다. 구체적인 예로 8-히드록시-퀴놀린 알루미늄 착물(Alq 3); 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, 이에 한정되는 것은 아니다. As the light-emitting material of the light-emitting layer, a material capable of emitting light in the visible 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 of 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.
상기 발광층은 호스트 재료 및 도펀트 재료를 포함하며, 본원의 화학식 1로 표시되는 화합물을 호스트 재료로 사용한다.The light emitting layer includes a host material and a dopant material, and a compound represented by Formula 1 herein is used as a host material.
이외에 호스트 재료로 축합 방향족환 유도체 또는 헤테로환 함유 화합물 등을 더 포함할 수 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 한정되는 것은 아니다. In addition, as a host material, a condensed aromatic ring derivative or a heterocyclic compound may be further included. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type 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 한정되는 것은 아니다. 또한, 금속 착체로는 이리듐 착체, 백금 착체 등이 있으나, 이에 한정되는 것은 아니다.Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of an aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.
바람직하게는, 상기 발광층은 하기와 같은 이리듐 착체 화합물을 도펀트 재료로 포함할 수 있으나, 이에 한정되는 것은 아니다.Preferably, the light emitting layer may include the following iridium complex compound as a dopant material, but is not limited thereto.
Figure PCTKR2020010789-appb-img-000099
Figure PCTKR2020010789-appb-img-000099
Figure PCTKR2020010789-appb-img-000100
Figure PCTKR2020010789-appb-img-000100
Figure PCTKR2020010789-appb-img-000101
Figure PCTKR2020010789-appb-img-000101
Figure PCTKR2020010789-appb-img-000102
Figure PCTKR2020010789-appb-img-000102
..
상기 정공억제층(또는 정공저지층, 정공차단층)은 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 정공억제층은 정공억제물질을 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 inhibiting layer (or hole blocking layer, hole blocking layer) is formed on the light emitting layer, and is preferably provided in contact with the light emitting layer, to control electron mobility and prevent excessive movement of holes, thereby increasing the probability of hole-electron bonding. It refers to a layer that serves to improve the efficiency of an organic light-emitting device by increasing it. The hole-suppressing layer includes a hole-suppressing material, and examples of such a hole-blocking material include a subazine derivative including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; A compound into which an electron withdrawing group such as a phosphine oxide derivative has been introduced may be used, but is not limited thereto.
상기 전자 주입 및 수송층은 전극으로부터 전자를 주입하고, 수취된 전자를 발광층까지 수송하는 전자수송층 및 전자주입층의 역할을 동시에 수행하는 층으로, 상기 발광층 또는 상기 정공억제층 상에 형성된다. 이러한 전자 주입 및 수송물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 전자 주입 및 수송물질의 예로는 8-히드록시퀴놀린의 Al 착물; Alq 3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물; 트리아진 유도체 등이 있으나, 이들에만 한정되는 것은 아니다. 또는 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 플루오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물, 또는 질소 함유 5원환 유도체 등과 함께 사용할 수도 있으나, 이에 한정되는 것은 아니다. The electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting received electrons to the emission layer, and is formed on the emission layer or the hole suppression layer. As such an electron injection and transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high mobility for electrons is suitable. Examples of specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complexes containing Alq 3; Organic radical compounds; Hydroxyflavone-metal complex; Triazine derivatives and the like, but are not limited thereto. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and their derivatives, metal complex compounds , Or a nitrogen-containing 5-membered cyclic derivative, but may be used, but is not limited thereto.
상기 전자 주입 및 수송층은 전자주입층 및 전자수송층과 같은 별개의 층으로도 형성될 수 있다. 이와 같은 경우, 전자 수송층은 상기 발광층 또는 상기 정공억제층 상에 형성되고, 상기 전자 수송층에 포함되는 전자 수송 물질로는 상술한 전자 주입 및 수송 물질이 사용될 수 있다. 또한, 전자 주입층은 상기 전자 수송층 상에 형성되고, 상기 전자 주입층에 포함되는 전자 주입 물질로는 LiF, NaCl, CsF, Li 2O, BaO, 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 플루오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 질소 함유 5원환 유도체 등이 사용될 수 있다.The electron injection and transport layer may be formed as separate layers such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the emission layer or the hole suppression layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer. In addition, the electron injection layer is formed on the electron transport layer, and electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li 2 O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and the like, their derivatives, metal complex compounds, and nitrogen-containing 5-membered ring derivatives may be used.
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 한정되는 것은 아니다.Examples of the metal complex compound include lithium 8-hydroxyquinolinato, 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-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited thereto.
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 bottom emission type, or a double-sided emission type depending on the material used.
또한, 상기 화학식 1로 표시되는 화합물은 유기 발광 소자 외에도 유기 태양 전지 또는 유기 트랜지스터에 포함될 수 있다.In addition, the compound represented by Formula 1 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 제조를 이하 실시예에서 구체적으로 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범위가 이들에 의하여 한정되는 것은 아니다.Preparation of the compound represented by Formula 1 and an organic light emitting device including the same will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.
(제조예)(Production example)
제조예 1: 화합물 1-1의 합성 (코어 구조의 합성)Preparation Example 1: Synthesis of Compound 1-1 (Synthesis of Core Structure)
Figure PCTKR2020010789-appb-img-000103
Figure PCTKR2020010789-appb-img-000103
1) 화합물 1-1-5의 제조1) Preparation of compound 1-1-5
2-브로모-5-클로로아닐린(300.0 g, 1.0 eq), 2-플루오로-2'-아이오도-1,1'-비페닐(375.5 g, 1.0 eq), KOtBu(217.4 g, 1.3 eq)을 NMP(3 L)에 녹여 환류하여 교반하였다. 3시간 후 반응이 종료되면 물에 부어서 결정화를 시킨 후 여과 하였다. 이 후 에틸아세테이트에 완전히 녹여서 물로 씻어주고 다시 감압하여 용매를 70% 정도 제거하였다. 다시 환류 상태에서 헥산을 넣어주며 결정을 떨어트려 식힌 후 여과하였다. 이를 컬럼크로마토그래피하여 화합물 1-1-5(342.7 g)를 얻었다. 2-Bromo-5-chloroaniline (300.0 g, 1.0 eq), 2-fluoro-2'-iodo-1,1'-biphenyl (375.5 g, 1.0 eq), KOtBu (217.4 g, 1.3 eq ) Was dissolved in NMP (3 L) and stirred under reflux. When the reaction was completed after 3 hours, it was poured into water to crystallize and then filtered. Thereafter, it was completely dissolved in ethyl acetate, washed with water, and reduced pressure to remove about 70% of the solvent. Hexane was added under reflux again, the crystals were dropped, cooled, and filtered. This was subjected to column chromatography to obtain compound 1-1-5 (342.7 g).
(수율 73 %, MS:[M+H] +=486)(Yield 73%, MS:[M+H] + =486)
2) 화합물 1-1-4의 제조2) Preparation of compound 1-1-4
화합물 1-1-5(342.7 g, 1.0 eq)에 Pd(t-Bu 3P) 2(8.48 g, 0.01 eq), K 2CO 3(372.6 g, 2.00 eq)을 다이메틸아세트아마이드(Dimethylacetamide, 2 L)에 넣고 환류하여 교반하였다. 2시간 후 반응물을 물에 부어서 결정화를 시킨 후여과하였다. 여과한 고체를 톨루엔에 완전히 녹인 후 물로 씻어주고 생성물이 녹아있는 용액을 감압 농축하여 결정을 떨어트려 식힌 후 여과하였다. 이를 컬럼크로마토그래피로 정제하여 화합물 1-1-4(361.25 g)을 얻었다. To compound 1-1-5 (342.7 g, 1.0 eq), Pd(t-Bu 3 P) 2 (8.48 g, 0.01 eq), K 2 CO 3 (372.6 g, 2.00 eq) was added to dimethylacetamide. 2 L) and refluxed to stir. After 2 hours, the reactant was poured into water to crystallize and then filtered. The filtered solid was completely dissolved in toluene, washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure to drop crystals, cooled, and filtered. This was purified by column chromatography to obtain compound 1-1-4 (361.25 g).
(수율 61 %, MS:[M+H] +=358)(Yield 61%, MS:[M+H] + =358)
3) 화합물 1-1-3의 제조3) Preparation of compound 1-1-3
화합물 1-1-4(361.3 g, 1012.9 mmol)와 (2-플루오로페닐)보론산(304.8 g, 1012.9 mmol)를 THF(4 L)에 넣고 교반하고 포타슘 카보네이트(560 g, 4051.6 mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류했을 때 테트라키스트리페닐-포스피노팔라듐(5.2 g, 10.1 mmol)을 투입하였다. 4시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수 황산 마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-1-3(233.5 g)을 얻었다.Compound 1-1-4 (361.3 g, 1012.9 mmol) and (2-fluorophenyl) boronic acid (304.8 g, 1012.9 mmol) were added to THF (4 L), stirred, and potassium carbonate (560 g, 4051.6 mmol) was added. After dissolving in water and stirring sufficiently, when refluxed, tetrakistriphenyl-phosphinopalladium (5.2 g, 10.1 mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 1-1-3 (233.5 g).
(수율 62%, MS: [M+H] += 373)(Yield 62%, MS: [M+H] + = 373)
4) 화합물 1-1-2의 제조4) Preparation of compound 1-1-2
화합물 1-1-3(233.5 g, 1.0 eq), KOtBu(120.1 g, 1.3 eq)을 NMP(1.5 L)에 녹여 환류하여 교반하였다. 3시간 후 반응이 종료되면 물에 부어서 결정화를 시킨 후 여과하였다. 이 후 에틸아세테이트에 완전히 녹여서 물로 씻어주고 다시 감압하여 용매를 70% 정도 제거하였다. 다시 환류 상태에서 헥산을 넣어주며 결정을 떨어트려 식힌 후 여과하였다. 이를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-1-2(102.2 g)를 얻었다. Compound 1-1-3 (233.5 g, 1.0 eq) and KOtBu (120.1 g, 1.3 eq) were dissolved in NMP (1.5 L) and stirred under reflux. When the reaction was completed after 3 hours, it was poured into water to crystallize and then filtered. Thereafter, it was completely dissolved in ethyl acetate, washed with water, and reduced pressure to remove about 70% of the solvent. Hexane was added under reflux again, the crystals were dropped, cooled, and filtered. This was purified by silica gel column chromatography to obtain compound 1-1-2 (102.2 g).
(수율 54 %, MS: [M+H] +=353)(Yield 54%, MS: [M+H] + =353)
5) 화합물 1-1-1의 제조5) Preparation of compound 1-1-1
화합물 1-1-2(102.18 g, 1.0 eq), (2-니트로페닐)보론산(53.32 g, 1.1 eq)를 THF(1 L)에 넣고 교반하고 포타슘 카보네이트(97.77 g, 3.0 eq)를 물에 녹여 투입하고 충분히 교반한 후 환류했을 때 Pd(t-Bu 3P) 2(1.48 g, 0.01 eq)을 투입하였다. 2시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수 황산 마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-1-1(95.51 g)을 얻었다. Compound 1-1-2 (102.18 g, 1.0 eq), (2-nitrophenyl) boronic acid (53.32 g, 1.1 eq) was added to THF (1 L), stirred, and potassium carbonate (97.77 g, 3.0 eq) was added to water. After dissolving in and stirring sufficiently, Pd(t-Bu 3 P) 2 (1.48 g, 0.01 eq) was added when refluxed. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 1-1-1 (95.51 g).
(수율 75%, MS: [M+H] += 439)(Yield 75%, MS: [M+H] + = 439)
6) 화합물 1-1의 제조6) Preparation of compound 1-1
화합물 1-1-1(95.51 g, 1.0 eq)을 P(OEt) 3(700 mL)에 넣고 환류하여 교반하였다. 2시간 반응 후 상온으로 식히고 생성된 결정을 여과하였다. 이를 다시 에틸 아세테이트에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수 황산 마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-1(54.89 g)을 얻었다. Compound 1-1-1 (95.51 g, 1.0 eq) was added to P(OEt) 3 (700 mL), followed by reflux and stirred. After the reaction for 2 hours, it was cooled to room temperature and the resulting crystals were filtered. This was again dissolved in ethyl acetate, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 1-1 (54.89 g).
(수율 62%, MS: [M+H] += 407)(Yield 62%, MS: [M+H] + = 407)
제조예 2: 화합물 1-2의 합성(코어 구조의 합성)Preparation Example 2: Synthesis of Compound 1-2 (Synthesis of Core Structure)
Figure PCTKR2020010789-appb-img-000104
Figure PCTKR2020010789-appb-img-000104
1) 화합물 1-2-3의 제조1) Preparation of compound 1-2-3
9H-트리벤조[b,d,f]아제핀(200.0 g, 1.0 eq), 1-브로모-4-클로로-2-플루오로벤젠(223.8 g, 1.3 eq), KOtBu(184.47 g, 2.0 eq)을 NMP(2 L)에 녹여 환류하여 교반하였다. 3시간 후 반응이 종료되면 물에 부어서 결정화를 시킨 후 여과하였다. 이후 에틸아세테이트에 완전히 녹여서 물로 씻어주고 다시 감압하여 용매를 70% 정도 제거하였다. 다시 환류 상태에서 헥산을 넣어주며 결정을 떨어트려 식힌 후 여과하였다. 이를 컬럼크로마토그래피하여 화합물 1-2-3(252.5 g)를 얻었다. 9H-tribenzo[b,d,f]azepine (200.0 g, 1.0 eq), 1-bromo-4-chloro-2-fluorobenzene (223.8 g, 1.3 eq), KOtBu (184.47 g, 2.0 eq) ) Was dissolved in NMP (2 L) and stirred under reflux. When the reaction was completed after 3 hours, it was poured into water to crystallize and then filtered. Then, it was completely dissolved in ethyl acetate, washed with water, and reduced pressure to remove about 70% of the solvent. Hexane was added under reflux again, the crystals were dropped, cooled, and filtered. This was subjected to column chromatography to obtain compound 1-2-3 (252.5 g).
(수율 71 %, MS: [M+H] +=434)(Yield 71%, MS: [M+H] + =434)
2) 화합물 1-2-2의 제조2) Preparation of compound 1-2-2
화합물 1-2-3(252.56 g, 1.0 eq)에 Pd(t-Bu 3P) 2(2.98 g, 0.01 eq), K 2CO 3(130.97 g, 2.00 eq)을 다이메틸아세트아마이드(Dimethylacetamide, 2 L)에 넣고 환류하여 교반하였다. 2시간 후 반응물을 물에 부어서 결정화를 시킨 후 여과하였다. 여과한 고체를 톨루엔에 완전히 녹인 후 물로 씻어주고 생성물이 녹아있는 용액을 감압 농축하여 결정을 떨어트려 식힌 후 여과하였다. 이를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1―2-2(135.52 g)을 얻었다. To compound 1-2-3 (252.56 g, 1.0 eq), Pd(t-Bu 3 P) 2 (2.98 g, 0.01 eq), K 2 CO 3 (130.97 g, 2.00 eq) was added to dimethylacetamide. 2 L) and refluxed to stir. After 2 hours, the reactant was poured into water to crystallize and then filtered. The filtered solid was completely dissolved in toluene, washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure to drop crystals, cooled, and filtered. This was purified by silica gel column chromatography to obtain compound 1-2-2 (135.52 g).
(수율 66 %, MS: [M+H] +=353)(Yield 66%, MS: [M+H] + =353)
3) 화합물 1-2-1의 제조3) Preparation of compound 1-2-1
화합물 1-2-2(135.52 g, 1.0 eq), (2-니트로페닐)보론산(70.73 g, 1.1 eq)를 THF(1 L)에 넣고 교반 하고 포타슘 카보네이트(129.66 g, 3.0 eq)를 물에 녹여 투입하고 충분히 교반한 후 환류했을 때 Pd(t-Bu 3P) 2(1.96 g, 0.01 eq)을 투입하였다. 2시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수 황산 마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-2-1(131.74 g)을 얻었다. Compound 1-2-2 (135.52 g, 1.0 eq), (2-nitrophenyl) boronic acid (70.73 g, 1.1 eq) was added to THF (1 L), stirred, and potassium carbonate (129.66 g, 3.0 eq) was added to water. After dissolving in and stirring sufficiently, Pd(t-Bu 3 P) 2 (1.96 g, 0.01 eq) was added when refluxed. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 1-2-1 (131.74 g).
(수율 78 %, MS: [M+H] += 439)(Yield 78%, MS: [M+H] + = 439)
4) 화합물 1-2의 제조4) Preparation of compound 1-2
화합물 1-2-1(131.74 g, 1.0 eq)을 P(OEt) 3(500 mL)에 넣고 환류하여 교반하였다. 2시간 반응 후 상온으로 식히고 생성된 결정을 여과하였다. 이를 다시 에틸아세테이트에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수 황산 마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-2(50.46 g)을 얻었다. Compound 1-2-1 (131.74 g, 1.0 eq) was added to P(OEt) 3 (500 mL), followed by reflux and stirred. After the reaction for 2 hours, it was cooled to room temperature and the resulting crystals were filtered. This was again dissolved in ethyl acetate, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 1-2 (50.46 g).
(수율 57%, MS: [M+H] += 407)(Yield 57%, MS: [M+H] + = 407)
합성예 1: 화합물 1의 제조Synthesis Example 1: Preparation of Compound 1
Figure PCTKR2020010789-appb-img-000105
Figure PCTKR2020010789-appb-img-000105
질소 분위기에서 중간체 화합물 1a(10 g, 37.4 mmol), 화합물 1-1(15.2 g, 37.4 mmol), NaOtBu(7.2 g, 74.7 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.4 g, 0.7 mmol)을 투입하였다. 4시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1(7.4 g)을 얻었다.In a nitrogen atmosphere, intermediate compound 1a (10 g, 37.4 mmol), compound 1-1 (15.2 g, 37.4 mmol), and NaOtBu (7.2 g, 74.7 mmol) were added to xylene (200 mL), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.7 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 1 (7.4 g).
(수율 31%, MS: [M+H] += 639)(Yield 31%, MS: [M+H] + = 639)
합성예 2: 화합물 2의 제조Synthesis Example 2: Preparation of Compound 2
Figure PCTKR2020010789-appb-img-000106
Figure PCTKR2020010789-appb-img-000106
질소 분위기에서 중간체 화합물 2a(10 g, 23.8 mmol), 화합물 1-1(9.7 g, 23.8 mmol), NaOtBu(4.6 g, 47.6 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.2 g, 0.5 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2(11.3 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 2a (10 g, 23.8 mmol), compound 1-1 (9.7 g, 23.8 mmol), and NaOtBu (4.6 g, 47.6 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2 (11.3 g).
(수율 60%, MS: [M+H] += 790)(Yield 60%, MS: [M+H] + = 790)
합성예 3: 화합물 3의 합성Synthesis Example 3: Synthesis of Compound 3
Figure PCTKR2020010789-appb-img-000107
Figure PCTKR2020010789-appb-img-000107
질소 분위기에서 중간체 화합물 3a(10 g, 24.6 mmol), 화합물 1-1(10 g, 24.6 mmol), NaOtBu(4.7 g, 49.3 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 3(8 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 3a (10 g, 24.6 mmol), compound 1-1 (10 g, 24.6 mmol), and NaOtBu (4.7 g, 49.3 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 3 (8 g).
(수율 42%, MS: [M+H] += 777)(Yield 42%, MS: [M+H] + = 777)
합성예 4: 화합물 4의 합성Synthesis Example 4: Synthesis of Compound 4
Figure PCTKR2020010789-appb-img-000108
Figure PCTKR2020010789-appb-img-000108
질소 분위기에서 중간체 화합물 4a(10 g, 28.8 mmol), 화합물 1-1(11.7 g, 28.8 mmol), NaOtBu(5.5 g, 57.7 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.6 mmol)을 투입하였다. 2시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 4(9.5 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 4a (10 g, 28.8 mmol), compound 1-1 (11.7 g, 28.8 mmol), and NaOtBu (5.5 g, 57.7 mmol) were added to xylene (200 mL), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 4 (9.5 g).
(수율 46%, MS: [M+H] += 718)(Yield 46%, MS: [M+H] + = 718)
합성예 5: 화합물 5의 합성Synthesis Example 5: Synthesis of Compound 5
Figure PCTKR2020010789-appb-img-000109
Figure PCTKR2020010789-appb-img-000109
질소 분위기에서 중간체 화합물 5a(10 g, 25.6 mmol), 화합물 1-1(10.4 g, 25.6 mmol), NaOtBu(4.9 g, 51.2 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 5(8 g)을 얻었다.In a nitrogen atmosphere, intermediate compound 5a (10 g, 25.6 mmol), compound 1-1 (10.4 g, 25.6 mmol), and NaOtBu (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 5 (8 g).
(수율 41%, MS: [M+H] += 762)(Yield 41%, MS: [M+H] + = 762)
합성예 6: 화합물 6의 합성Synthesis Example 6: Synthesis of Compound 6
Figure PCTKR2020010789-appb-img-000110
Figure PCTKR2020010789-appb-img-000110
질소 분위기에서 중간체 화합물 6a(10 g, 26.3 mmol), 화합물 1-1(10.7 g, 26.3 mmol), NaOtBu(5.1 g, 52.7 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 6(8.5 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 6a (10 g, 26.3 mmol), compound 1-1 (10.7 g, 26.3 mmol), and NaOtBu (5.1 g, 52.7 mmol) were added to xylene (200 mL), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 6 (8.5 g).
(수율 43%, MS: [M+H] += 751)(Yield 43%, MS: [M+H] + = 751)
합성예 7: 화합물 7의 합성Synthesis Example 7: Synthesis of Compound 7
Figure PCTKR2020010789-appb-img-000111
Figure PCTKR2020010789-appb-img-000111
질소 분위기에서 중간체 화합물 7a(10 g, 26.3 mmol), 화합물 1-1(10.7 g, 26.3 mmol), NaOtBu(5 g, 52.5 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 4시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 7(5.9 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 7a (10 g, 26.3 mmol), compound 1-1 (10.7 g, 26.3 mmol), and NaOtBu (5 g, 52.5 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 7 (5.9 g).
(수율 30%, MS: [M+H] += 752)(Yield 30%, MS: [M+H] + = 752)
합성예 8: 화합물 8의 합성Synthesis Example 8: Synthesis of Compound 8
Figure PCTKR2020010789-appb-img-000112
Figure PCTKR2020010789-appb-img-000112
질소 분위기에서 중간체 화합물 8a(10 g, 23.6 mmol), 화합물 1-1(9.6 g, 23.6 mmol), NaOtBu(4.5 g, 47.3 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.2 g, 0.5 mmol)을 투입하였다. 2시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 8(6.6 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 8a (10 g, 23.6 mmol), compound 1-1 (9.6 g, 23.6 mmol), and NaOtBu (4.5 g, 47.3 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 8 (6.6 g).
(수율 35%, MS: [M+H] += 794)(Yield 35%, MS: [M+H] + = 794)
합성예 9: 화합물 9의 합성Synthesis Example 9: Synthesis of Compound 9
Figure PCTKR2020010789-appb-img-000113
Figure PCTKR2020010789-appb-img-000113
질소 분위기에서 중간체 화합물 9a(10 g, 26.8 mmol), 화합물 1-1(10.9 g, 26.8 mmol), NaOtBu(5.2 g, 53.6 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 2시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 9(10.4 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 9a (10 g, 26.8 mmol), compound 1-1 (10.9 g, 26.8 mmol), and NaOtBu (5.2 g, 53.6 mmol) were added to xylene (200 mL), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 9 (10.4 g).
(수율 52%, MS: [M+H] += 744)(Yield 52%, MS: [M+H] + = 744)
합성예 10: 화합물 10의 합성Synthesis Example 10: Synthesis of Compound 10
Figure PCTKR2020010789-appb-img-000114
Figure PCTKR2020010789-appb-img-000114
질소 분위기에서 중간체 화합물 10a(10 g, 25.8 mmol), 화합물 1-1(10.5 g, 25.8 mmol), NaOtBu(5 g, 51.7 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 10(8.8 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 10a (10 g, 25.8 mmol), compound 1-1 (10.5 g, 25.8 mmol), and NaOtBu (5 g, 51.7 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 10 (8.8 g).
(수율 45%, MS: [M+H] += 758)(Yield 45%, MS: [M+H] + = 758)
합성예 11: 화합물 11의 합성Synthesis Example 11: Synthesis of Compound 11
Figure PCTKR2020010789-appb-img-000115
Figure PCTKR2020010789-appb-img-000115
질소 분위기에서 중간체 화합물 11a(10 g, 24.8 mmol), 화합물 1-1(10.1 g, 24.8 mmol), NaOtBu(4.8 g, 49.6 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 4시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 11(6.1 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 11a (10 g, 24.8 mmol), compound 1-1 (10.1 g, 24.8 mmol), and NaOtBu (4.8 g, 49.6 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 11 (6.1 g).
(수율 32%, MS: [M+H] += 774)(Yield 32%, MS: [M+H] + = 774)
합성예 12: 화합물 12의 합성Synthesis Example 12: Synthesis of Compound 12
Figure PCTKR2020010789-appb-img-000116
Figure PCTKR2020010789-appb-img-000116
질소 분위기에서 중간체 화합물 12a(10 g, 30.2 mmol), 화합물 1-1(12.3 g, 30.2 mmol), NaOtBu(5.8 g, 60.5 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.6 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 12(8.7 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 12a (10 g, 30.2 mmol), compound 1-1 (12.3 g, 30.2 mmol), and NaOtBu (5.8 g, 60.5 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 12 (8.7 g).
(수율 41%, MS: [M+H] += 702)(Yield 41%, MS: [M+H] + = 702)
합성예 13: 화합물 13의 합성Synthesis Example 13: Synthesis of Compound 13
Figure PCTKR2020010789-appb-img-000117
Figure PCTKR2020010789-appb-img-000117
질소 분위기에서 중간체 화합물 13a(10 g, 27 mmol), 화합물 1-1(11 g, 27 mmol), NaOtBu(5.2 g, 53.9 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 13(8 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 13a (10 g, 27 mmol), compound 1-1 (11 g, 27 mmol), and NaOtBu (5.2 g, 53.9 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 13 (8 g).
(수율 40%, MS: [M+H] += 742)(Yield 40%, MS: [M+H] + = 742)
합성예 14: 화합물 14의 합성Synthesis Example 14: Synthesis of Compound 14
Figure PCTKR2020010789-appb-img-000118
Figure PCTKR2020010789-appb-img-000118
질소 분위기에서 중간체 화합물 14a(10 g, 28 mmol), 화합물 1-1(11.4 g, 28 mmol), NaOtBu(5.4 g, 56.1 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.6 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 14(7.7 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 14a (10 g, 28 mmol), compound 1-1 (11.4 g, 28 mmol), and NaOtBu (5.4 g, 56.1 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 14 (7.7 g).
(수율 38%, MS: [M+H] += 728)(Yield 38%, MS: [M+H] + = 728)
합성예 15: 화합물 15의 합성Synthesis Example 15: Synthesis of Compound 15
Figure PCTKR2020010789-appb-img-000119
Figure PCTKR2020010789-appb-img-000119
질소 분위기에서 중간체 화합물 15a(10 g, 22.4 mmol), 화합물 1-1(9.1 g, 22.4 mmol), NaOtBu(4.3 g, 44.9 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.2 g, 0.4 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 15(9.3 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 15a (10 g, 22.4 mmol), compound 1-1 (9.1 g, 22.4 mmol), and NaOtBu (4.3 g, 44.9 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 15 (9.3 g).
(수율 51%, MS: [M+H] += 817)(Yield 51%, MS: [M+H] + = 817)
합성예 16: 화합물 16의 합성Synthesis Example 16: Synthesis of Compound 16
Figure PCTKR2020010789-appb-img-000120
Figure PCTKR2020010789-appb-img-000120
질소 분위기에서 중간체 화합물 16a(10 g, 31.5 mmol), 화합물 1-2(12.8 g, 31.5 mmol), NaOtBu(6 g, 62.9 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.6 mmol)을 투입하였다. 4시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 16(9.7 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 16a (10 g, 31.5 mmol), compound 1-2 (12.8 g, 31.5 mmol), and NaOtBu (6 g, 62.9 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 16 (9.7 g).
(수율 45%, MS: [M+H] += 689)(Yield 45%, MS: [M+H] + = 689)
합성예 17: 화합물 17의 합성Synthesis Example 17: Synthesis of Compound 17
Figure PCTKR2020010789-appb-img-000121
Figure PCTKR2020010789-appb-img-000121
질소 분위기에서 중간체 화합물 17a(10 g, 25.4 mmol), 화합물 1-2(10.3 g, 25.4 mmol), NaOtBu(4.9 g, 50.8 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 17(9.7 g)을 얻었다.In a nitrogen atmosphere, intermediate compound 17a (10 g, 25.4 mmol), compound 1-2 (10.3 g, 25.4 mmol), and NaOtBu (4.9 g, 50.8 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 17 (9.7 g).
(수율 50%, MS: [M+H] += 765)(Yield 50%, MS: [M+H] + = 765)
합성예 18: 화합물 18의 합성Synthesis Example 18: Synthesis of Compound 18
Figure PCTKR2020010789-appb-img-000122
Figure PCTKR2020010789-appb-img-000122
질소 분위기에서 중간체 화합물 18a(10 g, 27.9 mmol), 화합물 1-2(11.4 g, 27.9 mmol), NaOtBu(5.4 g, 55.9 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.6 mmol)을 투입하였다. 4시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 18(9.6 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 18a (10 g, 27.9 mmol), compound 1-2 (11.4 g, 27.9 mmol), and NaOtBu (5.4 g, 55.9 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 18 (9.6 g).
(수율 47%, MS: [M+H] += 729)(Yield 47%, MS: [M+H] + = 729)
합성예 19: 화합물 19의 합성Synthesis Example 19: Synthesis of Compound 19
Figure PCTKR2020010789-appb-img-000123
Figure PCTKR2020010789-appb-img-000123
질소 분위기에서 중간체 화합물 19a(10 g, 41.5 mmol), 화합물 1-2(16.9 g, 41.5 mmol), NaOtBu(8 g, 83.1 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.4 g, 0.8 mmol)을 투입하였다. 4시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 19(8.4 g)을 얻었다.In a nitrogen atmosphere, intermediate compound 19a (10 g, 41.5 mmol), compound 1-2 (16.9 g, 41.5 mmol), and NaOtBu (8 g, 83.1 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.8 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 19 (8.4 g).
(수율 33%, MS: [M+H] += 612)(Yield 33%, MS: [M+H] + = 612)
합성예 20: 화합물 20의 합성Synthesis Example 20: Synthesis of Compound 20
Figure PCTKR2020010789-appb-img-000124
Figure PCTKR2020010789-appb-img-000124
질소 분위기에서 중간체 화합물 20a(10 g, 29.3 mmol), 화합물 1-2(11.9 g, 29.3 mmol), NaOtBu(5.6 g, 58.7 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.6 mmol)을 투입하였다. 2시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 20(8.8 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 20a (10 g, 29.3 mmol), compound 1-2 (11.9 g, 29.3 mmol), and NaOtBu (5.6 g, 58.7 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 20 (8.8 g).
(수율 42%, MS: [M+H] += 712)(Yield 42%, MS: [M+H] + = 712)
합성예 21: 화합물 21의 합성Synthesis Example 21: Synthesis of Compound 21
Figure PCTKR2020010789-appb-img-000125
Figure PCTKR2020010789-appb-img-000125
질소 분위기에서 중간체 화합물 21a(10 g, 24.6 mmol), 화합물 1-2(10 g, 24.6 mmol), NaOtBu(4.7 g, 49.3 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 2시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 21(7.8 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 21a (10 g, 24.6 mmol), compound 1-2 (10 g, 24.6 mmol), and NaOtBu (4.7 g, 49.3 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 21 (7.8 g).
(수율 41%, MS: [M+H] += 777)(Yield 41%, MS: [M+H] + = 777)
합성예 22: 화합물 22의 합성Synthesis Example 22: Synthesis of Compound 22
Figure PCTKR2020010789-appb-img-000126
Figure PCTKR2020010789-appb-img-000126
질소 분위기에서 중간체 화합물 22a(10 g, 25.6 mmol), 화합물 1-2(10.4 g, 25.6 mmol), NaOtBu(4.9 g, 51.2 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 22(5.8 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 22a (10 g, 25.6 mmol), compound 1-2 (10.4 g, 25.6 mmol), and NaOtBu (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 22 (5.8 g).
(수율 30%, MS: [M+H] += 762)(Yield 30%, MS: [M+H] + = 762)
합성예 23: 화합물 23의 합성Synthesis Example 23: Synthesis of Compound 23
Figure PCTKR2020010789-appb-img-000127
Figure PCTKR2020010789-appb-img-000127
질소 분위기에서 중간체 화합물 23a(10 g, 22.6 mmol), 화합물 1-2(9.2 g, 22.6 mmol), NaOtBu(4.3 g, 45.2 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.2 g, 0.5 mmol)을 투입하였다. 4시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 23(11 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 23a (10 g, 22.6 mmol), compound 1-2 (9.2 g, 22.6 mmol), and NaOtBu (4.3 g, 45.2 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 23 (11 g).
(수율 60%, MS: [M+H] += 814)(Yield 60%, MS: [M+H] + = 814)
합성예 24: 화합물 24의 합성Synthesis Example 24: Synthesis of Compound 24
Figure PCTKR2020010789-appb-img-000128
Figure PCTKR2020010789-appb-img-000128
질소 분위기에서 중간체 화합물 24a(10 g, 33.7 mmol), 화합물 1-2(13.7 g, 33.7 mmol), NaOtBu(6.5 g, 67.4 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.7 mmol)을 투입하였다. 2시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 24(12.6 g)을 얻었다.In a nitrogen atmosphere, intermediate compound 24a (10 g, 33.7 mmol), compound 1-2 (13.7 g, 33.7 mmol), and NaOtBu (6.5 g, 67.4 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.7 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 24 (12.6 g).
(수율 56%, MS: [M+H] += 668)(Yield 56%, MS: [M+H] + = 668)
합성예 25: 화합물 25의 합성Synthesis Example 25: Synthesis of Compound 25
Figure PCTKR2020010789-appb-img-000129
Figure PCTKR2020010789-appb-img-000129
질소 분위기에서 중간체 화합물 25a(10 g, 22.3 mmol), 화합물 1-2(9.1 g, 22.3 mmol), NaOtBu(4.3 g, 44.5 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.2 g, 0.4 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 25(8.9 g)을 얻었다.In a nitrogen atmosphere, intermediate compound 25a (10 g, 22.3 mmol), compound 1-2 (9.1 g, 22.3 mmol), and NaOtBu (4.3 g, 44.5 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 25 (8.9 g).
(수율 49%, MS: [M+H] += 820)(Yield 49%, MS: [M+H] + = 820)
합성예 26: 화합물 26의 합성Synthesis Example 26: Synthesis of Compound 26
Figure PCTKR2020010789-appb-img-000130
Figure PCTKR2020010789-appb-img-000130
질소 분위기에서 중간체 화합물 26a(10 g, 25.8 mmol), 화합물 1-2(10.5 g, 25.8 mmol), NaOtBu(5 g, 51.7 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 2시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 26(7.4 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 26a (10 g, 25.8 mmol), compound 1-2 (10.5 g, 25.8 mmol), and NaOtBu (5 g, 51.7 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 26 (7.4 g).
(수율 38%, MS: [M+H] += 758)(Yield 38%, MS: [M+H] + = 758)
합성예 27: 화합물 27의 합성Synthesis Example 27: Synthesis of Compound 27
Figure PCTKR2020010789-appb-img-000131
Figure PCTKR2020010789-appb-img-000131
질소 분위기에서 중간체 화합물 27a(10 g, 21.6 mmol), 화합물 1-2(8.8 g, 21.6 mmol), NaOtBu(4.2 g, 43.3 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.2 g, 0.4 mmol)을 투입하였다. 2시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 27(8.5 g)을 얻었다.In a nitrogen atmosphere, intermediate compound 27a (10 g, 21.6 mmol), compound 1-2 (8.8 g, 21.6 mmol), and NaOtBu (4.2 g, 43.3 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 27 (8.5 g).
(수율 47%, MS: [M+H] += 833)(Yield 47%, MS: [M+H] + = 833)
합성예 28: 화합물 28의 합성Synthesis Example 28: Synthesis of Compound 28
Figure PCTKR2020010789-appb-img-000132
Figure PCTKR2020010789-appb-img-000132
질소 분위기에서 중간체 화합물 28a(10 g, 35.6 mmol), 화합물 1-2(14.5 g, 35.6 mmol), NaOtBu(6.8 g, 71.2 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.4 g, 0.7 mmol)을 투입하였다. 3시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 28(10.9 g)을 얻었다. In a nitrogen atmosphere, intermediate compound 28a (10 g, 35.6 mmol), compound 1-2 (14.5 g, 35.6 mmol), and NaOtBu (6.8 g, 71.2 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 28 (10.9 g).
(수율 47%, MS: [M+H] += 652)(Yield 47%, MS: [M+H] + = 652)
합성예 29: 화합물 29의 합성Synthesis Example 29: Synthesis of Compound 29
Figure PCTKR2020010789-appb-img-000133
Figure PCTKR2020010789-appb-img-000133
질소 분위기에서 중간체 화합물 29a(10 g, 28 mmol), 화합물 1-2(11.4 g, 28 mmol), NaOtBu(5.4 g, 56.1 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.6 mmol)을 투입하였다. 4시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 29(7.5 g)을 얻었다.In a nitrogen atmosphere, intermediate compound 29a (10 g, 28 mmol), compound 1-2 (11.4 g, 28 mmol), and NaOtBu (5.4 g, 56.1 mmol) were added to xylene (200 mL), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 29 (7.5 g).
(수율 37%, MS: [M+H] += 728)(Yield 37%, MS: [M+H] + = 728)
합성예 30: 화합물 30의 합성Synthesis Example 30: Synthesis of Compound 30
Figure PCTKR2020010789-appb-img-000134
Figure PCTKR2020010789-appb-img-000134
질소 분위기에서 중간체 화합물 30a(10 g, 25.8 mmol), 화합물 1-2(10.5 g, 25.8 mmol), NaOtBu(5 g, 51.7 mmol)을 자일렌(200 mL)에 넣고 교반 및 환류하였다. 이 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.3 g, 0.5 mmol)을 투입하였다. 4시간 후 반응이 종결 되어서 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수 황산 마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 30(6.3 g)을 얻었다.In a nitrogen atmosphere, intermediate compound 30a (10 g, 25.8 mmol), compound 1-2 (10.5 g, 25.8 mmol), and NaOtBu (5 g, 51.7 mmol) were added to xylene (200 mL) and stirred and refluxed. After this, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After 4 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 30 (6.3 g).
(수율 32%, MS: [M+H] += 758)(Yield 32%, MS: [M+H] + = 758)
(실시예 및 비교예) (Examples and Comparative Examples)
비교예 1Comparative Example 1
ITO(indium tin oxide)가 1,000 Å의 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 a thin film of ITO (indium tin oxide) to a thickness of 1,000 Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 정공주입층으로 하기 HI-1 화합물을 1150 Å의 두께로 형성하되 하기 A-1 화합물을 1.5% 농도로 p-doping 하였다. 상기 정공주입층 위에 하기 HT-1 화합물을 진공 증착하여 막 두께 800 Å의 정공수송층을 형성하였다. 이어서, 상기 정공수송층 위에 막 두께 150 Å으로 하기 EB-1 화합물을 진공 증착하여 전자억제층을 형성하였다. 이어서, 상기 EB-1 증착막 위에 하기 RH-1 화합물과 하기 Dp-7 화합물을 98:2의 중량비로 진공 증착하여 400 Å 두께의 적색 발광층을 형성하였다. 상기 발광층 위에 막 두께 30 Å으로 하기 HB-1 화합물을 진공 증착하여 정공저지층을 형성하였다. 이어서, 상기 정공저지층 위에 하기 ET-1 화합물과 하기 LiQ 화합물을 2:1의 중량비로 진공 증착하여 300 Å의 두께로 전자 주입 및 수송층을 형성하였다. 상기 전자 주입 및 수송층 위에 순차적으로 12 Å 두께로 리튬플로라이드(LiF)와 1,000 Å 두께로 알루미늄을 증착하여 음극을 형성하였다. The HI-1 compound was formed as a hole injection layer on the prepared ITO transparent electrode to a thickness of 1150 Å, but the following compound A-1 was p-doping at a concentration of 1.5%. The following HT-1 compound was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Subsequently, the following EB-1 compound was vacuum deposited on the hole transport layer with a film thickness of 150 Å to form an electron suppressing layer. Subsequently, the following RH-1 compound and the following Dp-7 compound were vacuum-deposited at a weight ratio of 98:2 on the EB-1 deposition film to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed by vacuum depositing the following HB-1 compound with a thickness of 30 Å on the emission layer. Subsequently, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300 Å. Lithium fluoride (LiF) at a thickness of 12 Å and aluminum at a thickness of 1,000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.
상기의 과정에서 유기물의 증착속도는 0.4~0.7 Å/sec를 유지하였고, 음극의 리튬플로라이드는 0.3 Å/sec, 알루미늄은 2 Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 2X10 -7 ~ 5X10 -6 torr를 유지하여, 유기 발광 소자를 제작하였다.In the above process, the deposition rate of organic material was maintained at 0.4 to 0.7 Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum degree during deposition was 2X10 -7 By maintaining ~ 5X10 -6 torr, an organic light emitting device was manufactured.
Figure PCTKR2020010789-appb-img-000135
Figure PCTKR2020010789-appb-img-000135
실시예 1 내지 30의 제조Preparation of Examples 1 to 30
비교예 1의 유기 발광 소자에서 RH-1 대신 앞서 합성한 화합물 1 내지 30의 화합물을 사용한 것을 제외하고는, 상기 비교예 1과 동일한 방법으로 유기 발광 소자를 제조하였다.An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the compounds of Compounds 1 to 30 synthesized above were used instead of RH-1 in the organic light-emitting device of Comparative Example 1.
비교예 2 내지 9의 제조Preparation of Comparative Examples 2 to 9
비교예 1의 유기 발광 소자에서 RH-1 대신 하기 C-1 내지 C-8의 화합물을 사용하는 것을 제외하고는, 상기 비교예 1과 동일한 방법으로 유기 발광 소자를 제조하였다.An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the following compounds C-1 to C-8 were used instead of RH-1 in the organic light-emitting device of Comparative Example 1.
Figure PCTKR2020010789-appb-img-000136
Figure PCTKR2020010789-appb-img-000136
(실험예)(Experimental example)
상기 제조된 실시예 1 내지 30 및 비교예 1 내지 9의 유기 발광 소자에 전류(10 mA/cm 2)를 인가하였을 때, 전압, 효율을 측정하고 그 결과를 하기 표 1에 나타내었다. 수명 T95는 휘도가 초기 휘도(6000 nit)에서 95%로 감소되는데 소요되는 시간을 의미한다. When a current (10 mA/cm 2 ) was applied to the organic light emitting devices of Examples 1 to 30 and Comparative Examples 1 to 9, voltage and efficiency were measured, and the results are shown in Table 1 below. The lifetime T95 refers to the time it takes for the luminance to decrease from initial luminance (6000 nit) to 95%.
구분division 물질matter 구동전압(V)Driving voltage (V) 효율(cd/A)Efficiency (cd/A) 수명 T95(hr)Life T95(hr) 발광색Luminous color
실시예 1Example 1 화합물 1Compound 1 3.633.63 28.528.5 154154 적색Red
실시예 2Example 2 화합물 2Compound 2 3.513.51 28.328.3 217217 적색Red
실시예 3Example 3 화합물 3Compound 3 3.523.52 24.524.5 193193 적색Red
실시예 4Example 4 화합물 4Compound 4 3.883.88 25.725.7 160160 적색Red
실시예 5Example 5 화합물 5Compound 5 3.633.63 26.226.2 175175 적색Red
실시예 6Example 6 화합물 6Compound 6 3.653.65 26.826.8 170170 적색Red
실시예 7Example 7 화합물 7Compound 7 3.633.63 26.326.3 178178 적색Red
실시예 8Example 8 화합물 8Compound 8 3.613.61 26.426.4 191191 적색Red
실시예 9Example 9 화합물 9Compound 9 3.643.64 26.526.5 164164 적색Red
실시예 10Example 10 화합물 10Compound 10 3.583.58 26.626.6 168168 적색Red
실시예 11Example 11 화합물 11Compound 11 3.633.63 25.125.1 170170 적색Red
실시예 12Example 12 화합물 12Compound 12 3.613.61 26.826.8 173173 적색Red
실시예 13Example 13 화합물 13Compound 13 3.733.73 27.027.0 195195 적색Red
실시예 14Example 14 화합물 14Compound 14 3.613.61 26.926.9 169169 적색Red
실시예 15Example 15 화합물 15Compound 15 3.653.65 26.726.7 181181 적색Red
실시예 16Example 16 화합물 16Compound 16 3.503.50 28.128.1 192192 적색Red
실시예 17Example 17 화합물 17Compound 17 3.513.51 28.028.0 221221 적색Red
실시예 18Example 18 화합물 18Compound 18 3.483.48 28.728.7 210210 적색Red
실시예 19Example 19 화합물 19Compound 19 3.813.81 27.027.0 224224 적색Red
실시예 20Example 20 화합물 20Compound 20 3.733.73 27.527.5 163163 적색Red
실시예 21Example 21 화합물 21Compound 21 3.803.80 26.126.1 160160 적색Red
실시예 22Example 22 화합물 22Compound 22 3.743.74 26.826.8 163163 적색Red
실시예 23Example 23 화합물 23Compound 23 3.753.75 26.026.0 165165 적색Red
실시예 24Example 24 화합물 24Compound 24 3.693.69 25.925.9 205205 적색Red
실시예 25Example 25 화합물 25Compound 25 3.653.65 26.726.7 197197 적색Red
실시예 26Example 26 화합물 26Compound 26 3.633.63 26.226.2 192192 적색Red
실시예 27Example 27 화합물 27Compound 27 3.703.70 27.427.4 164164 적색Red
실시예 28Example 28 화합물 28Compound 28 3.653.65 26.326.3 201201 적색Red
실시예 29Example 29 화합물 29Compound 29 3.613.61 27.027.0 184184 적색Red
실시예 30Example 30 화합물 30Compound 30 3.673.67 27.527.5 177177 적색Red
비교예 1Comparative Example 1 RH-1RH-1 4.044.04 21.321.3 120120 적색Red
비교예 2Comparative Example 2 C-1C-1 3.953.95 13.313.3 3737 적색Red
비교예 3Comparative Example 3 C-2C-2 3.983.98 15.915.9 7777 적색Red
비교예 4Comparative Example 4 C-3C-3 3.933.93 20.720.7 103103 적색Red
비교예 5Comparative Example 5 C-4C-4 4.254.25 20.220.2 127127 적색Red
비교예 6Comparative Example 6 C-5C-5 4.034.03 18.518.5 8585 적색Red
비교예 7Comparative Example 7 C-6C-6 4.024.02 19.319.3 9191 적색Red
비교예 8Comparative Example 8 C-7C-7 4.094.09 20.520.5 105105 적색Red
비교예 9Comparative Example 9 C-8C-8 4.114.11 20.320.3 9898 적색Red
상기 비교예 1의 적색 유기 발광 소자는 종래 널리 사용되고 있는 물질을 사용하였으며, 전자 차단층으로 화합물 EB-1, 적색 발광층으로 화합물 RH-1/Dp-7을 사용하는 구조이다. 비교예 2 내지 9은 RH-1 대신 C-1 내지 C-8를 사용하여 유기 발광 소자를 제조하였다. The red organic light-emitting device of Comparative Example 1 uses a material that has been widely used in the past, and has a structure using compound EB-1 as an electron blocking layer and compounds RH-1/Dp-7 as a red light emitting layer. In Comparative Examples 2 to 9, an organic light-emitting device was manufactured using C-1 to C-8 instead of RH-1.
상기 실험 데이터에서 확인할 수 있듯이, 본 발명의 화합물이 적색 발광층의 호스트로 사용한 경우, 비교예 물질에 비해서 호스트에서 적색 도판트로의 에너지 전달이 잘 이루어져 구동 전압이 현저히 낮아졌으며, 효율 측면에도 크게 상승하였다. 또한, 본원 화합물을 채용한 유기 발광 소자는 높은 효율을 유지하면서도 수명 특성을 2배 이상 크게 개선되는 것을 확인할 수 있었다.As can be seen from the above experimental data, when the compound of the present invention was used as a host of the red light emitting layer, energy transfer from the host to the red dopant was well performed compared to the material of the comparative example, so that the driving voltage was significantly lowered and the efficiency was greatly increased. . In addition, it was confirmed that the organic light-emitting device employing the present compound significantly improved lifespan characteristics by more than two times while maintaining high efficiency.
[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: 정공억제층 9: hole suppression layer

Claims (8)

  1. 하기 화학식 1로 표시되는 화합물:Compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2020010789-appb-img-000137
    Figure PCTKR2020010789-appb-img-000137
    상기 화학식 1에서,In Formula 1,
    R은 1번 또는 2번 위치에서 연결되어 단일 결합을 형성하고,R is linked at position 1 or 2 to form a single bond,
    L은 단일 결합, 또는 치환 또는 비치환된 C 6-60 아릴렌이고, L is a single bond, or a substituted or unsubstituted C 6-60 arylene,
    Het은 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로 원자를 포함하는 C 5-60 헤테로아릴이고, Het is a substituted or unsubstituted C 5-60 heteroaryl containing any one or more hetero atoms selected from the group consisting of N, O and S,
    R 1, R 2, R 3, R 4 및 R 5는 각각 독립적으로, 수소, 중수소, 또는 치환 또는 비치환된 C 1-60 알킬이고, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, deuterium, or substituted or unsubstituted C 1-60 alkyl,
    n1, n3, n4 및 n5는 각각 독립적으로 0 내지 4의 정수이고,n1, n3, n4 and n5 are each independently an integer of 0 to 4,
    n2는 0 내지 2의 정수이다.n2 is an integer from 0 to 2.
  2. 제1항에 있어서, The method of claim 1,
    상기 화학식 1은 하기 화학식 1-1 또는 1-2로 표시되는, Formula 1 is represented by the following Formula 1-1 or 1-2,
    화합물:compound:
    [화학식 1-1][Formula 1-1]
    Figure PCTKR2020010789-appb-img-000138
    Figure PCTKR2020010789-appb-img-000138
    [화학식 1-2][Formula 1-2]
    Figure PCTKR2020010789-appb-img-000139
    Figure PCTKR2020010789-appb-img-000139
    상기 화학식 1-1 내지 1-2에서, In Formulas 1-1 to 1-2,
    n'2는 0 또는 1이고,n'2 is 0 or 1,
    n'3는 0 내지 3의 정수이고,n'3 is an integer from 0 to 3,
    L, Het, R 1, R 2, R 3, R 4, R 5, n1, n2, n3, n4 및 n5는 제1항에서 정의한 바와 같다. L, Het, R 1 , R 2 , R 3 , R 4 , R 5 , n1, n2, n3, n4 and n5 are as defined in claim 1.
  3. 제1항에 있어서, The method of claim 1,
    L은 단일 결합, 페닐렌, 또는 나프틸렌인, L is a single bond, phenylene, or naphthylene,
    화합물.compound.
  4. 제1항에 있어서, The method of claim 1,
    Het은 하기로 이루어진 군에서 선택되는 어느 하나인, Het is any one selected from the group consisting of,
    화합물:compound:
    Figure PCTKR2020010789-appb-img-000140
    Figure PCTKR2020010789-appb-img-000140
    상기 군에서,In the above group,
    R'은 각각 독립적으로, 치환 또는 비치환된 C 6-60 아릴, 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 하나 이상의 헤테로 원자를 포함하는 C 5-60 헤테로아릴이다. Each R′ is independently a substituted or unsubstituted C 6-60 aryl, or a C 5-60 heteroaryl comprising at least one hetero atom selected from the group consisting of substituted or unsubstituted N, O and S. .
  5. 제4항에 있어서, The method of claim 4,
    R'은 각각 독립적으로, 페닐, 비페닐릴, 나프틸, 터페닐릴, 페닐나프틸, 나프틸페닐, 페난쓰레닐, 트리페닐레닐, 디메틸플루오레닐, 디벤조퓨라닐, 디벤조티오페닐, 카바졸-9-일 또는 9-페닐-9H-카바졸릴인, R'is each independently phenyl, biphenylyl, naphthyl, terphenylyl, phenylnaphthyl, naphthylphenyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl , Carbazol-9-yl or 9-phenyl-9H-carbazolyl,
    화합물.compound.
  6. 제1항에 있어서, The method of claim 1,
    R 1, R 2, R 3, R 4 및 R 5는 각각 독립적으로 수소 또는 중수소인, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen or deuterium,
    화합물.compound.
  7. 제1항에 있어서, The method of claim 1,
    상기 화학식 1로 표시되는 화합물은, 하기로 구성되는 군으로부터 선택되는 어느 하나인, The compound represented by Formula 1 is any one selected from the group consisting of,
    화합물:compound:
    Figure PCTKR2020010789-appb-img-000141
    Figure PCTKR2020010789-appb-img-000141
    Figure PCTKR2020010789-appb-img-000142
    Figure PCTKR2020010789-appb-img-000142
    Figure PCTKR2020010789-appb-img-000143
    Figure PCTKR2020010789-appb-img-000143
    Figure PCTKR2020010789-appb-img-000144
    Figure PCTKR2020010789-appb-img-000144
    Figure PCTKR2020010789-appb-img-000145
    Figure PCTKR2020010789-appb-img-000145
    Figure PCTKR2020010789-appb-img-000146
    Figure PCTKR2020010789-appb-img-000146
    Figure PCTKR2020010789-appb-img-000147
    Figure PCTKR2020010789-appb-img-000147
    Figure PCTKR2020010789-appb-img-000148
    Figure PCTKR2020010789-appb-img-000148
    Figure PCTKR2020010789-appb-img-000149
    Figure PCTKR2020010789-appb-img-000149
    Figure PCTKR2020010789-appb-img-000150
    Figure PCTKR2020010789-appb-img-000150
    Figure PCTKR2020010789-appb-img-000151
    Figure PCTKR2020010789-appb-img-000151
    Figure PCTKR2020010789-appb-img-000152
    Figure PCTKR2020010789-appb-img-000152
    Figure PCTKR2020010789-appb-img-000153
    Figure PCTKR2020010789-appb-img-000153
    Figure PCTKR2020010789-appb-img-000154
    Figure PCTKR2020010789-appb-img-000154
    Figure PCTKR2020010789-appb-img-000155
    Figure PCTKR2020010789-appb-img-000155
    Figure PCTKR2020010789-appb-img-000156
    .
    Figure PCTKR2020010789-appb-img-000156
    .
    Figure PCTKR2020010789-appb-img-000157
    Figure PCTKR2020010789-appb-img-000157
    Figure PCTKR2020010789-appb-img-000158
    Figure PCTKR2020010789-appb-img-000158
    Figure PCTKR2020010789-appb-img-000159
    Figure PCTKR2020010789-appb-img-000159
    Figure PCTKR2020010789-appb-img-000160
    Figure PCTKR2020010789-appb-img-000160
    Figure PCTKR2020010789-appb-img-000161
    Figure PCTKR2020010789-appb-img-000161
    Figure PCTKR2020010789-appb-img-000162
    Figure PCTKR2020010789-appb-img-000162
    Figure PCTKR2020010789-appb-img-000163
    Figure PCTKR2020010789-appb-img-000163
    Figure PCTKR2020010789-appb-img-000164
    Figure PCTKR2020010789-appb-img-000164
    Figure PCTKR2020010789-appb-img-000165
    Figure PCTKR2020010789-appb-img-000165
    Figure PCTKR2020010789-appb-img-000166
    Figure PCTKR2020010789-appb-img-000166
    Figure PCTKR2020010789-appb-img-000167
    Figure PCTKR2020010789-appb-img-000167
    Figure PCTKR2020010789-appb-img-000168
    Figure PCTKR2020010789-appb-img-000168
    Figure PCTKR2020010789-appb-img-000169
    Figure PCTKR2020010789-appb-img-000169
    Figure PCTKR2020010789-appb-img-000170
    Figure PCTKR2020010789-appb-img-000170
    Figure PCTKR2020010789-appb-img-000171
    Figure PCTKR2020010789-appb-img-000171
    Figure PCTKR2020010789-appb-img-000172
    Figure PCTKR2020010789-appb-img-000172
    Figure PCTKR2020010789-appb-img-000173
    Figure PCTKR2020010789-appb-img-000173
    Figure PCTKR2020010789-appb-img-000174
    Figure PCTKR2020010789-appb-img-000174
    Figure PCTKR2020010789-appb-img-000175
    Figure PCTKR2020010789-appb-img-000175
    Figure PCTKR2020010789-appb-img-000176
    Figure PCTKR2020010789-appb-img-000176
    Figure PCTKR2020010789-appb-img-000177
    Figure PCTKR2020010789-appb-img-000177
    Figure PCTKR2020010789-appb-img-000178
    Figure PCTKR2020010789-appb-img-000178
    Figure PCTKR2020010789-appb-img-000179
    Figure PCTKR2020010789-appb-img-000179
    Figure PCTKR2020010789-appb-img-000180
    Figure PCTKR2020010789-appb-img-000180
    Figure PCTKR2020010789-appb-img-000181
    Figure PCTKR2020010789-appb-img-000181
    Figure PCTKR2020010789-appb-img-000182
    Figure PCTKR2020010789-appb-img-000182
    Figure PCTKR2020010789-appb-img-000183
    Figure PCTKR2020010789-appb-img-000183
    Figure PCTKR2020010789-appb-img-000184
    Figure PCTKR2020010789-appb-img-000184
    Figure PCTKR2020010789-appb-img-000185
    Figure PCTKR2020010789-appb-img-000185
    Figure PCTKR2020010789-appb-img-000186
    Figure PCTKR2020010789-appb-img-000186
    Figure PCTKR2020010789-appb-img-000187
    Figure PCTKR2020010789-appb-img-000187
    Figure PCTKR2020010789-appb-img-000188
    Figure PCTKR2020010789-appb-img-000188
    Figure PCTKR2020010789-appb-img-000189
    Figure PCTKR2020010789-appb-img-000189
    Figure PCTKR2020010789-appb-img-000190
    Figure PCTKR2020010789-appb-img-000190
    Figure PCTKR2020010789-appb-img-000191
    Figure PCTKR2020010789-appb-img-000191
    Figure PCTKR2020010789-appb-img-000192
    Figure PCTKR2020010789-appb-img-000192
    Figure PCTKR2020010789-appb-img-000193
    Figure PCTKR2020010789-appb-img-000193
    Figure PCTKR2020010789-appb-img-000194
    Figure PCTKR2020010789-appb-img-000194
    Figure PCTKR2020010789-appb-img-000195
    Figure PCTKR2020010789-appb-img-000195
    Figure PCTKR2020010789-appb-img-000196
    Figure PCTKR2020010789-appb-img-000196
    Figure PCTKR2020010789-appb-img-000197
    Figure PCTKR2020010789-appb-img-000197
    Figure PCTKR2020010789-appb-img-000198
    Figure PCTKR2020010789-appb-img-000198
    Figure PCTKR2020010789-appb-img-000199
    Figure PCTKR2020010789-appb-img-000199
    Figure PCTKR2020010789-appb-img-000200
    Figure PCTKR2020010789-appb-img-000200
    Figure PCTKR2020010789-appb-img-000201
    Figure PCTKR2020010789-appb-img-000201
    Figure PCTKR2020010789-appb-img-000202
    Figure PCTKR2020010789-appb-img-000202
    Figure PCTKR2020010789-appb-img-000203
    Figure PCTKR2020010789-appb-img-000203
    Figure PCTKR2020010789-appb-img-000204
    Figure PCTKR2020010789-appb-img-000204
    Figure PCTKR2020010789-appb-img-000205
    Figure PCTKR2020010789-appb-img-000205
    Figure PCTKR2020010789-appb-img-000206
    Figure PCTKR2020010789-appb-img-000206
    Figure PCTKR2020010789-appb-img-000207
    Figure PCTKR2020010789-appb-img-000207
    Figure PCTKR2020010789-appb-img-000208
    Figure PCTKR2020010789-appb-img-000208
    Figure PCTKR2020010789-appb-img-000209
    Figure PCTKR2020010789-appb-img-000209
    Figure PCTKR2020010789-appb-img-000210
    Figure PCTKR2020010789-appb-img-000210
    Figure PCTKR2020010789-appb-img-000211
    Figure PCTKR2020010789-appb-img-000211
    Figure PCTKR2020010789-appb-img-000212
    Figure PCTKR2020010789-appb-img-000212
    Figure PCTKR2020010789-appb-img-000213
    Figure PCTKR2020010789-appb-img-000213
    Figure PCTKR2020010789-appb-img-000214
    Figure PCTKR2020010789-appb-img-000214
    Figure PCTKR2020010789-appb-img-000215
    Figure PCTKR2020010789-appb-img-000215
    Figure PCTKR2020010789-appb-img-000216
    Figure PCTKR2020010789-appb-img-000216
    Figure PCTKR2020010789-appb-img-000217
    Figure PCTKR2020010789-appb-img-000217
    Figure PCTKR2020010789-appb-img-000218
    Figure PCTKR2020010789-appb-img-000218
    Figure PCTKR2020010789-appb-img-000219
    Figure PCTKR2020010789-appb-img-000219
    Figure PCTKR2020010789-appb-img-000220
    Figure PCTKR2020010789-appb-img-000220
    Figure PCTKR2020010789-appb-img-000221
    Figure PCTKR2020010789-appb-img-000221
    Figure PCTKR2020010789-appb-img-000222
    Figure PCTKR2020010789-appb-img-000222
    Figure PCTKR2020010789-appb-img-000223
    Figure PCTKR2020010789-appb-img-000223
    Figure PCTKR2020010789-appb-img-000224
    Figure PCTKR2020010789-appb-img-000224
    Figure PCTKR2020010789-appb-img-000225
    Figure PCTKR2020010789-appb-img-000225
    Figure PCTKR2020010789-appb-img-000226
    Figure PCTKR2020010789-appb-img-000226
    ..
  8. 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 제7항 중 어느 하나의 항에 따른 화합물을 포함하는 것인, 유기 발광 소자. A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the compound according to any one of claims 1 to 7 That is, an organic light-emitting device.
PCT/KR2020/010789 2019-08-16 2020-08-13 Novel compound and organic light emitting device using same WO2021034017A1 (en)

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KR20170086277A (en) * 2016-01-18 2017-07-26 에스에프씨 주식회사 Organic light-emitting compounds and Organic light-emitting device comprising the same
CN107686484A (en) * 2016-08-05 2018-02-13 南京高光半导体材料有限公司 Organic electroluminescent compounds and the organic electroluminescence device using the compound
KR20180032471A (en) * 2016-09-22 2018-03-30 삼성에스디아이 주식회사 Organic compound and organic optoelectronic device and display device
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KR20170086277A (en) * 2016-01-18 2017-07-26 에스에프씨 주식회사 Organic light-emitting compounds and Organic light-emitting device comprising the same
CN107686484A (en) * 2016-08-05 2018-02-13 南京高光半导体材料有限公司 Organic electroluminescent compounds and the organic electroluminescence device using the compound
KR20180032471A (en) * 2016-09-22 2018-03-30 삼성에스디아이 주식회사 Organic compound and organic optoelectronic device and display device
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