WO2023096459A1 - 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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WO2023096459A1
WO2023096459A1 PCT/KR2022/019072 KR2022019072W WO2023096459A1 WO 2023096459 A1 WO2023096459 A1 WO 2023096459A1 KR 2022019072 W KR2022019072 W KR 2022019072W WO 2023096459 A1 WO2023096459 A1 WO 2023096459A1
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compound
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김영석
김민준
이동훈
서상덕
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주식회사 엘지화학
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Priority to CN202280038769.5A priority Critical patent/CN117396484A/en
Publication of WO2023096459A1 publication Critical patent/WO2023096459A1/en

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    • 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
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • H—ELECTRICITY
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    • H10K99/00—Subject matter not provided for in other groups of this subclass

Definitions

  • the present invention relates to a novel compound and an organic light emitting device including the same.
  • the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material.
  • An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.
  • An organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer between the anode and the cathode.
  • the organic material layer is often composed of a multi-layered structure composed of different materials, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
  • 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 when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.
  • the present invention provides a novel organic light emitting device material that can be used in an organic light emitting device and can be used in a solution process at the same time.
  • Patent Document 0001 Korean Patent Publication No. 10-2000-0051826
  • the present invention relates to a novel compound and an organic light emitting device including the same.
  • the present invention provides a compound represented by Formula 1 below:
  • One of X 1 to X 4 is CR, and the others are each independently N or CR';
  • R is a substituent represented by Formula 2 below,
  • X 5 to X 10 are each independently N or CR';
  • one of X 1 to X 10 is N,
  • R' are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • L 1 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • L 2 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • L 3 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • Ar 1 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
  • Ar 2 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
  • the present invention is a first electrode; a second electrode provided to face the first electrode; and an organic material layer provided between the first electrode and the second electrode, wherein the organic material layer includes the compound represented by Chemical Formula 1.
  • the organic material layer including the compound may be a light emitting layer.
  • 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 of an organic light emitting device.
  • the compound represented by Chemical Formula 1 may be used as a material for hole injection, hole transport, hole injection and transport, electron suppression, light emission, electron transport, or electron injection.
  • FIG. 1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
  • FIG. 2 is an example of an organic light emitting device composed of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (7), an electron injection and transport layer (8) and a cathode (4). is shown.
  • substituted or unsubstituted means deuterium; halogen group; cyano 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; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl containing at least one of N, O, and S atoms, or substituted or unsubstituted
  • a substituent in which two or more substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.
  • the number of carbon atoms of the carbonyl group is not particularly limited, but 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 aryl group having 6 to 25 carbon atoms or a straight-chain, branched-chain or cyclic chain alkyl group having 1 to 25 carbon atoms in the ester group.
  • 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 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 a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to
  • the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, 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 straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms.
  • alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl
  • the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one 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, etc., but is not limited thereto.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6.
  • the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20.
  • the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.
  • the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.
  • the fluorenyl group is substituted, etc.
  • it is not limited thereto.
  • heteroaryl is a heteroaryl containing at least one of O, N, Si, and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms.
  • the heteroaryl include xanthene, thioxanthen, thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, Pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazino Pyrazinyl group, isoquinoline group, indole group, carbazo
  • an aralkyl group, an aralkenyl group, an alkylaryl group, an arylamine group, and an aryl group among arylsilyl groups are the same as the examples 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 examples of the above-mentioned alkyl group.
  • the description of the above-described heteroaryl may be applied to the heteroaryl among heteroarylamines.
  • the alkenyl group among the aralkenyl groups is the same as the examples 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 heteroaryl described above 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 cycloalkyl group described above may be applied, except that the hydrocarbon ring is formed by combining two substituents.
  • the heterocyclic group is not a monovalent group, and the description of the above-described heteroaryl may be applied, except that it is formed by combining two substituents.
  • the present invention provides a compound represented by Formula 1 above.
  • One of X 1 to X 4 is CR, and the others are each independently N or CR', wherein R is a substituent represented by Formula 2 below, X 5 to X 10 are each independently N or CR', and , provided that one of X 1 to X 10 is N.
  • one of X 1 to X 4 is CR, the other is N, the others are each independently CR', and X 5 to X 10 are each independently CR';
  • one of X 1 to X 4 is CR, the others are each independently CR', one of X 5 to X 10 is N, and the others are each independently CR'.
  • R' are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S.
  • R' are all hydrogen; All may be deuterium.
  • L 1 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S.
  • L 1 is a direct bond; or phenylene.
  • L 1 is phenylene, it may be unsubstituted or substituted with one or more deuterium atoms.
  • L 2 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S.
  • L 2 is a direct bond; phenylene; naphthylene; biphenylylene; 9,9-dimethyl-fluorenylene; or 9,9-diphenyl-fluorenylene.
  • L 2 is phenylene; naphthylene; biphenylylene; 9,9-dimethyl-fluorenylene; or 9,9-diphenyl-fluorenylene, they may be unsubstituted or substituted with one or more deuterium atoms.
  • L 3 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S.
  • L 3 is a direct bond; phenylene; naphthylene; biphenylylene; 9,9-dimethyl-fluorenylene; or 9,9-diphenyl-fluorenylene.
  • L 3 is phenylene; naphthylene; biphenylylene; 9,9-dimethyl-fluorenylene; or 9,9-diphenyl-fluorenylene, they may be unsubstituted or substituted with one or more deuterium atoms.
  • Ar 1 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
  • Ar 1 is phenyl; biphenylyl; terphenylyl; naphthyl; phenanthrenyl; 9,9-dimethyl-fluorenyl; 9,9-diphenyl-fluorenyl; dibenzofuranyl; dibenzothiophenyl; 9-phenyl-carbazolyl; or 9,9'-spirobi[9H-fluorene]yl.
  • Ar 1 may be unsubstituted or substituted with one or more deuterium atoms.
  • Ar 2 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
  • Ar 2 is phenyl; biphenylyl; terphenylyl; naphthyl; phenanthrenyl; 9,9-dimethyl-fluorenyl; 9,9-diphenyl-fluorenyl; dibenzofuranyl; dibenzothiophenyl; 9-phenyl-carbazolyl; or 9,9'-spirobi[9H-fluorene]yl.
  • Ar 2 may be unsubstituted or substituted with one or more deuterium.
  • the compound is represented by any one of Formulas 1-1 to 1-4,
  • One of X 2 to X 10 is N and the other is CR';
  • L 1 to L 3 , Ar 1 , Ar 2 and R' are as defined in Formula 1 above;
  • One of X 1 and X 3 to X 10 is N and the other is CR';
  • L 1 to L 3 , Ar 1 and Ar 2 and R' are as defined in Formula 1 above;
  • One of X 1 , X 2 and X 4 to X 10 is N and the other is CR';
  • L 1 to L 3 , Ar 1 and Ar 2 and R' are as defined in Formula 1 above;
  • One of X 1 to X 3 and X 5 to X 10 is N and the other is CR';
  • L 1 to L 3 , Ar 1 and Ar 2 , and R' are as defined in Formula 1 above.
  • the compound may contain no deuterium or one or more deuterium atoms.
  • the present invention provides a method for producing a compound represented by Formula 1, such as the following Reaction Schemes 1 and 2, for example:
  • X 1 to X 10 , L 1 to L 3 , and Ar 1 and Ar 2 are defined as in Chemical Formulas 1 and 2, respectively.
  • Z is halogen, preferably chloro.
  • Reaction Scheme 1 is a reaction for preparing the core structure of Chemical Formula 1 through a Suzuki coupling reaction.
  • Scheme 2 is also a Suzuki coupling reaction, and it is preferable to carry out in the presence of a palladium catalyst, and the reactor for the Suzuki coupling reaction can be changed as known in the art.
  • the preparation method may be more specific in Preparation Examples and Synthesis 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 the compound represented by Chemical Formula 1. .
  • the organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like as organic layers.
  • the structure of the organic light emitting device is not limited thereto and may include fewer 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, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. may contain the indicated compounds.
  • the organic material layer may include a light emitting layer, and the light emitting layer may include the compound represented by Chemical Formula 1.
  • the organic material layer may include a hole blocking layer, an electron transport layer, an electron injection layer, or a layer that simultaneously transports and injects electrons, and the hole blocking layer, the electron transport layer, the electron injection layer, or the electron transport and electron injection layer.
  • the layer to be simultaneously injected may include the compound represented by Chemical Formula 1 above.
  • the organic material layer may include a light emitting layer and an electron injection and transport layer
  • the electron injection and transport layer may include the compound represented by Chemical Formula 1.
  • the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.
  • the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.
  • FIGS. 1 and 2 the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2 .
  • FIG. 1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
  • FIG. 2 is an example of an organic light emitting device composed of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (7), an electron injection and transport layer (8) and a cathode (4). is shown.
  • the compound represented by Chemical Formula 1 may be included in the light emitting layer.
  • the organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one of the organic layers includes the compound represented by Chemical Formula 1. Also, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
  • the organic light emitting device may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate.
  • a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode
  • PVD physical vapor deposition
  • depositing a metal or a metal oxide having conductivity or an alloy thereof depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode
  • an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and depositing a material that can be used as a cathode thereon, it can be prepared.
  • 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 Chemical 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 means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.
  • an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material on a substrate from a cathode material (WO 2003/012890).
  • the manufacturing method is not limited thereto.
  • the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.
  • the cathode material a material having a high work function is generally preferred 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; conductive compounds such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline; and the like, but are not limited thereto.
  • the cathode material is preferably a material having a small work function so as to easily inject electrons into the organic material layer.
  • Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; 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 for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer
  • a compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer.
  • HOMO highest occupied molecular orbital
  • the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic matter, anthraquinone, and polyaniline and polythiophene-based conductive compounds, but are not limited thereto.
  • the hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer.
  • the hole transport material is a material that can receive holes from the anode or the hole injection layer and transfer them to the light emitting layer, and has high hole mobility. material is suitable. Specific examples include, but are not limited to, arylamine-based organic materials, conductive compounds, and block copolymers having both conjugated and non-conjugated parts.
  • the light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable.
  • Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; Polyfluorene, rubrene, etc., but are not limited thereto.
  • the electron blocking layer is a layer placed between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from passing to the hole transport layer without recombination in the light emitting layer, and is also called an electron blocking layer.
  • a material having a smaller electron affinity than the electron transport layer is preferable for the electron blocking layer.
  • the compound represented by Chemical Formula 1 may be included as a material of the electron blocking layer.
  • the light emitting layer may include a host material and a dopant material.
  • the host material the compound represented by Chemical Formula 1 may be used.
  • a condensed aromatic ring derivative or a compound containing a heterocyclic ring can be used as a host material that can be further used.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc.
  • heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.
  • Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like.
  • aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc.
  • styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted.
  • substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted.
  • metal complexes include, but are not limited to, iridium complexes and platinum complexes.
  • the electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer.
  • the electron transport material a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. do. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes containing Alq 3 ; organic radical compounds; hydroxyflavone-metal complexes and the like, but are not limited thereto.
  • the electron transport layer can be used with any desired cathode material as used according to the prior art.
  • suitable cathode materials are conventional materials having a low work function followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by a layer of aluminum or silver.
  • the electron injection layer is a layer for injecting electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes of excitons generated in the light emitting layer.
  • a compound that prevents migration to a layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preonylidene methane, anthrone, etc. and their derivatives, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.
  • Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.
  • the "electron injection and transport layer” is a layer that performs both the roles of the electron injection layer and the electron transport layer, and materials that play the role of each layer may be used alone or in combination, but are limited thereto. It doesn't work.
  • the compound represented by Formula 1 may be included as a material for the electron injection and transport layer.
  • the organic light emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom emission device requiring relatively high light emitting efficiency.
  • the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.
  • 3-Bromo-2-chloropyridine (15g, 77.9 mmol) and (2-(methylthio)naphthalen-1-yl)boronic acid (17.8g, 81.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (32.3g, 233.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.8 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate compound A-2-3 (15 g, 55.6 mmol), amine1 (19.6 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • intermediate compound A-3-4 15 g, 55.6 mmol
  • amine2 24 g, 58.4 mmol
  • sodium tert-butoxide 8 g, 83.4 mmol
  • bis(tri-tert-butylphosphine)palladium(0) 0.3 g, 0.6 mmol
  • intermediate compound A-4-8 15 g, 55.6 mmol
  • amine3 (20.5 g, 58.4 mmol)
  • sodium tert-butoxide 8 g, 83.4 mmol
  • bis(tri-tert-butylphosphine)palladium(0) 0.3 g, 0.6 mmol
  • intermediate compound A-3-7 (15 g, 55.6 mmol), amine4 (18.8 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • intermediate compound A-3-3 (15 g, 55.6 mmol), amine5 (18.8 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • intermediate compound A-4-3 15 g, 55.6 mmol
  • amine6 (23.2 g, 58.4 mmol)
  • sodium tert-butoxide 8 g, 83.4 mmol
  • bis(tri-tert-butylphosphine)palladium(0) 0.3 g, 0.6 mmol
  • intermediate compound A-4-1 (15 g, 55.6 mmol), amine7 (21.7 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • intermediate compound A-2-2 15 g, 55.6 mmol
  • amine8 (21.1 g, 58.4 mmol)
  • sodium tert-butoxide 8 g, 83.4 mmol
  • bis(tri-tert-butylphosphine)palladium(0) 0.3 g, 0.6 mmol
  • intermediate compound A-3-2 (15 g, 55.6 mmol), amine9 (28.2 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • intermediate compound A-3-5 15 g, 55.6 mmol
  • amine10 (20.4 g, 58.4 mmol)
  • sodium tert-butoxide 8 g, 83.4 mmol
  • bis(tri-tert-butylphosphine)palladium(0) 0.3 g, 0.6 mmol
  • intermediate compound A-4-8 15 g, 55.6 mmol
  • amine11 (21.3 g, 58.4 mmol)
  • sodium tert-butoxide 8 g, 83.4 mmol
  • bis(tri-tert-butylphosphine)palladium(0) 0.3 g, 0.6 mmol
  • intermediate compound A-3-7 (15 g, 55.6 mmol), amine12 (21.3 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • intermediate compound A-3-5 15 g, 55.6 mmol
  • amine13 28.4 g, 58.4 mmol
  • sodium tert-butoxide 8 g, 83.4 mmol
  • bis(tri-tert-butylphosphine)palladium(0) 0.3 g, 0.6 mmol
  • intermediate compound A-3-1 (15 g, 55.6 mmol), amine14 (28.4 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • intermediate compound A-3-8 (15 g, 55.6 mmol), amine15 (25.5 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • intermediate compound A-4-5 (15 g, 55.6 mmol), amine16 (17.2 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • intermediate compound A-2-3 (15 g, 55.6 mmol), amine17 (23.2 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • intermediate compound A-4-2 (15 g, 55.6 mmol), amine18 (23.2 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • compound A-3-3 (15 g, 55.6 mmol), amine19 (19.6 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere, stirred and Refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • intermediate compound A-2-2 15 g, 55.6 mmol
  • amine20 24 g, 58.4 mmol
  • sodium tert-butoxide 8 g, 83.4 mmol
  • bis(tri-tert-butylphosphine)palladium(0) 0.3 g, 0.6 mmol
  • the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure.
  • intermediate compound A-4-1 (15 g, 55.6 mmol), amine21 (20.5 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure.
  • intermediate compound A-2-2 15 g, 55.6 mmol
  • amine22 (19.6 g, 58.4 mmol)
  • sodium tert-butoxide 8 g, 83.4 mmol
  • bis(tri-tert-butylphosphine)palladium(0) 0.3 g, 0.6 mmol
  • intermediate compound A-2-7 15 g, 55.6 mmol
  • amine23 (24.6 g, 58.4 mmol)
  • sodium tert-butoxide 8 g, 83.4 mmol
  • bis(tri-tert-butylphosphine)palladium(0) 0.3 g, 0.6 mmol
  • intermediate compound A-3-9 15 g, 55.6 mmol
  • amine24 (18.8 g, 58.4 mmol)
  • sodium tert-butoxide 8 g, 83.4 mmol
  • bis(tri-tert-butylphosphine)palladium(0) 0.3 g, 0.6 mmol
  • intermediate compound A-4-4 (15g, 55.6 mmol) and amine25 (21.3g, 58.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (23.1 g, 166.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate compound A-2-8 (15g, 55.6 mmol) and amine26 (23.1g, 58.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (23.1 g, 166.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer.
  • intermediate compound A-2-3 (15g, 55.6 mmol) and amine27 (22.1g, 58.4 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (23.1 g, 166.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate compound A-4-2 (15g, 55.6 mmol) and amine28 (23.1g, 58.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (23.1g, 166.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer.
  • a glass substrate coated with ITO (indium tin oxide) to a thickness of 1,000 ⁇ was put in distilled water in which detergent was dissolved and washed with ultrasonic waves.
  • a Fischer Co. product was used as the detergent, and distilled water filtered through a second filter of a Millipore Co. product was used as the distilled water.
  • ultrasonic cleaning was performed twice with distilled water for 10 minutes.
  • ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner.
  • solvents such as isopropyl alcohol, acetone, and methanol
  • the following compound HI-1 was formed to a thickness of 1150 ⁇ as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5%.
  • a hole transport layer having a thickness of 800 ⁇ was formed by vacuum depositing the following HT-1 compound on the hole injection layer.
  • an electron blocking layer was formed by vacuum depositing the following EB-1 compound to a film thickness of 150 ⁇ on the hole transport layer.
  • the following RH-1 compound and the following Dp-39 compound were vacuum-deposited on the EB-1 deposited film in a weight ratio of 98:2 to form a red light emitting layer having a thickness of 400 ⁇ .
  • a hole blocking layer was formed on the light emitting layer by vacuum depositing the HB-1 compound to a film thickness of 30 ⁇ . 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 ⁇ .
  • a negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 ⁇ and aluminum to a thickness of 1,000 ⁇ on the electron injection and transport layer.
  • the deposition rate of the organic material was maintained at 0.4 to 0.7 ⁇ /sec
  • the deposition rate of lithium fluoride on the cathode was 0.3 ⁇ /sec
  • the deposition rate of aluminum was 2 ⁇ /sec
  • the vacuum level during deposition was 2 ⁇ 10 - Maintaining 7 to 5 ⁇ 10 ⁇ 6 torr, an organic light emitting device was fabricated.
  • the organic light emitting device of the embodiment using the compound represented by Formula 1 as a red host material has a reduced driving voltage and improved efficiency and It can be seen that the lifetime characteristics are indicated.
  • substrate 2 anode

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Abstract

The present invention provides a novel compound and an organic light-emitting device including 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-citation with related application(s)
본 출원은 2021년 11월 29일자 한국 특허 출원 제10-2021-0166511호에 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. 10-2021-0166511 dated November 29, 2021, and all contents disclosed in the literature of the Korean patent applications are included as part of this specification.
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 including the same.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 넓은 시야각, 우수한 콘트라스트, 빠른 응답 시간을 가지며, 휘도, 구동 전압 및 응답 속도 특성이 우수하여 많은 연구가 진행되고 있다. In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a 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 유기물층을 포함하는 구조를 가진다. 상기 유기물층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어질 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. An organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. In the structure of this 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 when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.
상기와 같은 유기 발광 소자에 사용되는 유기물에 대하여 새로운 재료의 개발이 지속적으로 요구되고 있다.The development of new materials for organic materials used in the organic light emitting device as described above is continuously required.
한편, 최근에는 공정 비용 절감을 위하여 기존의 증착 공정 대신 용액 공정, 특히 잉크젯 공정을 이용한 유기 발광 소자가 개발되고 있다. 초창기에는 모든 유기 발광 소자 층을 용액 공정으로 코팅하여 유기 발광 소자를 개발하려 하였으나 현재 기술로는 한계가 있어, 정구조 형태에서 HIL, HTL, EML만을 용액 공정으로 진행하고 추후 공정은 기존의 증착 공정을 활용하는 하이브리드(hybrid) 공정이 연구 중이다. Meanwhile, in recent years, an organic light emitting device using a solution process, particularly an inkjet process, instead of a conventional deposition process has been developed to reduce process costs. In the early days, an attempt was made to develop an organic light emitting device by coating all organic light emitting device layers with a solution process, but the current technology has limitations, so only HIL, HTL, and EML in the form of a regular structure are carried out as a solution process, and the subsequent process is the existing deposition process A hybrid process that utilizes is being studied.
이에 본 발명에서는 유기 발광 소자에 사용될 수 있으면서 동시에 용액 공정에 사용 가능한 신규한 유기 발광 소자의 소재를 제공한다.Accordingly, the present invention provides a novel organic light emitting device material that can be used in an organic light emitting device and can be used in a solution process at the same time.
[선행기술문헌][Prior art literature]
[특허문헌][Patent Literature]
(특허문헌 0001) 한국특허 공개번호 제10-2000-0051826호(Patent Document 0001) Korean Patent Publication No. 10-2000-0051826
본 발명은 신규한 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다. The present invention relates to a novel compound and an organic light emitting device including the same.
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다: The present invention provides a compound represented by Formula 1 below:
[화학식 1][Formula 1]
Figure PCTKR2022019072-appb-img-000001
Figure PCTKR2022019072-appb-img-000001
상기 화학식 1에서,In Formula 1,
X1 내지 X4 중 하나는 CR이고, 나머지는 각각 독립적으로 N, 또는 CR’이고, One of X 1 to X 4 is CR, and the others are each independently N or CR';
여기서 R은 하기 화학식 2로 표시되는 치환기이고, Here, R is a substituent represented by Formula 2 below,
X5 내지 X10은 각각 독립적으로 N, 또는 CR’이고,X 5 to X 10 are each independently N or CR';
단, X1 내지 X10 중 하나는 N이고, However, one of X 1 to X 10 is N,
R’은 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이고,R' are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
[화학식 2][Formula 2]
Figure PCTKR2022019072-appb-img-000002
Figure PCTKR2022019072-appb-img-000002
상기 화학식 2에서, In Formula 2,
L1는 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴렌이고,L 1 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
L2는 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴렌이고,L 2 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
L3는 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴렌이고,L 3 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
Ar1은 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이고,Ar 1 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
Ar2는 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이다.Ar 2 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
또한, 본 발명은 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층은 상기 화학식 1로 표시되는 화합물을 포함하는, 유기 발광 소자를 제공한다. 구체적으로 상기 화합물을 포함하는 유기물층은 발광층일 수 있다.In addition, the present invention is a first electrode; a second electrode provided to face the first electrode; and an organic material layer provided between the first electrode and the second electrode, wherein the organic material layer includes the compound represented by Chemical Formula 1. Specifically, the organic material layer including the compound may be a light emitting layer.
상술한 화학식 1로 표시되는 화합물은 유기 발광 소자의 유기물층의 재료로서 사용될 수 있으며, 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다. 특히, 상술한 화학식 1로 표시되는 화합물은 정공주입, 정공수송, 정공주입 및 수송, 전자억제, 발광, 전자수송, 또는 전자주입 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 of an organic light emitting device. In particular, the compound represented by Chemical Formula 1 may be used as a material for hole injection, hole transport, hole injection and transport, electron suppression, light emission, electron transport, or electron injection.
도 1은 기판(1), 양극(2), 발광층(3), 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
도 2는 기판 (1), 양극(2), 정공주입층(5), 정공수송층(6), 발광층(7), 전자주입 및 수송층(8) 및 음극(4)로 이루어진 유기 발광 소자의 예를 도시한 것이다. 2 is an example of an organic light emitting device composed of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (7), an electron injection and transport layer (8) and a cathode (4). is shown.
이하, 본 발명의 이해를 돕기 위하여 보다 상세히 설명한다.Hereinafter, in order to aid understanding of the present invention, it will be described in more detail.
(용어의 정의)(Definition of Terms)
본 명세서에서,
Figure PCTKR2022019072-appb-img-000003
또는
Figure PCTKR2022019072-appb-img-000004
는 다른 치환기에 연결되는 결합을 의미하고, "D"는 중수소를 의미한다.In this specification,
Figure PCTKR2022019072-appb-img-000003
or
Figure PCTKR2022019072-appb-img-000004
means a bond connected to another substituent, and "D" means deuterium.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 할로겐기; 시아노기; 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 헤테로아릴로 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, 비페닐이기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수도 있다.In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; cyano 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; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.
본 명세서에서 카보닐기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 40인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2022019072-appb-img-000005
Figure PCTKR2022019072-appb-img-000005
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 aryl group having 6 to 25 carbon atoms or a straight-chain, branched-chain or cyclic chain alkyl group having 1 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure PCTKR2022019072-appb-img-000006
Figure PCTKR2022019072-appb-img-000006
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 is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2022019072-appb-img-000007
Figure PCTKR2022019072-appb-img-000007
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 a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to
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, a phenyl boron group, but is not limited thereto.
본 명세서에 있어서, 할로겐기의 예로는 불소, 염소, 브롬 또는 요오드가 있다.In this 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 straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.
본 명세서에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 6이다. 구체적인 예로는 비닐, 1-프로페닐, 이소프로페닐, 1-부테닐, 2-부테닐, 3-부테닐, 1-펜테닐, 2-펜테닐, 3-펜테닐, 3-메틸-1-부테닐, 1,3-부타디에닐, 알릴, 1-페닐비닐-1-일, 2-페닐비닐-1-일, 2,2-디페닐비닐-1-일, 2-페닐-2-(나프틸-1-일)비닐-1-일, 2,2-비스(디페닐-1-일)비닐-1-일, 스틸베닐기, 스티레닐기 등이 있으나 이들에 한정되지 않는다.In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one 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, etc., but is not limited thereto.
본 명세서에 있어서, 사이클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 60인 것이 바람직하며, 일 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 30이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 20이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 6이다. 구체적으로 사이클로프로필, 사이클로부틸, 사이클로펜틸, 3-메틸사이클로펜틸, 2,3-디메틸사이클로펜틸, 사이클로헥실, 3-메틸사이클로헥실, 4-메틸사이클로헥실, 2,3-디메틸사이클로헥실, 3,4,5-트리메틸사이클로헥실, 4-tert-부틸사이클로헥실, 사이클로헵틸, 사이클로옥틸 등이 있으나, 이에 한정되지 않는다.In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. 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, 비페닐이기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난쓰레닐기, 파이레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., 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 PCTKR2022019072-appb-img-000008
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 PCTKR2022019072-appb-img-000008
etc. However, it is not limited thereto.
본 명세서에 있어서, 헤테로아릴은 이종 원소로 O, N, Si 및 S 중 1개 이상을 포함하는 헤테로아릴로서, 탄소수는 특별히 한정되지 않으나, 탄소수 2 내지 60인 것이 바람직하다. 헤테로아릴의 예로는 잔텐(xanthene), 티오잔텐(thioxanthen), 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, 벤즈옥사졸기, 벤조이미다졸기, 벤조티아졸기, 벤조카바졸기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨라닐기, 페난쓰롤린기(phenanthroline), 이소옥사졸릴기, 티아디아졸릴기, 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, heteroaryl is a heteroaryl containing at least one of O, N, Si, and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. Examples of the heteroaryl include xanthene, thioxanthen, thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, Pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl 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 ( phenanthroline), an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.
본 명세서에 있어서, 아르알킬기, 아르알케닐기, 알킬아릴기, 아릴아민기, 아릴실릴기 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 헤테로아릴에 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 헤테로아릴에 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 헤테로아릴에 관한 설명이 적용될 수 있다.In the present specification, an aralkyl group, an aralkenyl group, an alkylaryl group, an arylamine group, and an aryl group among arylsilyl groups are the same as the examples 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 examples of the above-mentioned alkyl group. In the present specification, the description of the above-described heteroaryl may be applied to the heteroaryl among heteroarylamines. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples 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 heteroaryl described above 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 cycloalkyl group described above may be applied, except that the hydrocarbon ring is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heteroaryl may be applied, except that it is formed by combining two substituents.
(화합물)(compound)
본 발명은 상기 화학식 1로 표시되는 화합물을 제공한다. The present invention provides a compound represented by Formula 1 above.
X1 내지 X4 중 하나는 CR이고, 나머지는 각각 독립적으로 N, 또는 CR’이고, 여기서 R은 하기 화학식 2로 표시되는 치환기이고, X5 내지 X10은 각각 독립적으로 N, 또는 CR’이고, 단, X1 내지 X10 중 하나는 N이다.One of X 1 to X 4 is CR, and the others are each independently N or CR', wherein R is a substituent represented by Formula 2 below, X 5 to X 10 are each independently N or CR', and , provided that one of X 1 to X 10 is N.
보다 구체적으로, X1 내지 X4 중 하나는 CR이고, 다른 하나는 N이고, 나머지는 각각 독립적으로 CR’이고, X5 내지 X10은 각각 독립적으로 CR’이거나; 또는 X1 내지 X4 중 하나는 CR이고, 나머지는 각각 독립적으로 CR’이고, X5 내지 X10 중 하나는 N이고, 나머지는 각각 독립적으로 CR’일 수 있다. More specifically, one of X 1 to X 4 is CR, the other is N, the others are each independently CR', and X 5 to X 10 are each independently CR'; Alternatively, one of X 1 to X 4 is CR, the others are each independently CR', one of X 5 to X 10 is N, and the others are each independently CR'.
R’은 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴일 수 있다. 바람직하게 R’는 모두 수소이거나; 모두 중수소일 수 있다. R' are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S. Preferably R' are all hydrogen; All may be deuterium.
L1은 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴렌이다. 바람직하게는, L1은 직접 결합; 또는 페닐렌일 수 있다. L1이 페닐렌인 경우, 비치환되거나 또는 1개 이상의 중수소로 치환될 수 있다. L 1 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S. Preferably, L 1 is a direct bond; or phenylene. When L 1 is phenylene, it may be unsubstituted or substituted with one or more deuterium atoms.
L2는 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴렌이다. 바람직하게는, L2은 직접 결합; 페닐렌; 나프틸렌; 비페닐릴렌; 9,9-디메틸-플루오레닐렌; 또는 9,9-디페닐-플루오레닐렌일 수 있다. L2가 페닐렌; 나프틸렌; 비페닐릴렌; 9,9-디메틸-플루오레닐렌; 또는 9,9-디페닐-플루오레닐렌인 경우, 이들은 비치환되거나 또는 1개 이상의 중수소로 치환될 수 있다. L 2 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S. Preferably, L 2 is a direct bond; phenylene; naphthylene; biphenylylene; 9,9-dimethyl-fluorenylene; or 9,9-diphenyl-fluorenylene. L 2 is phenylene; naphthylene; biphenylylene; 9,9-dimethyl-fluorenylene; or 9,9-diphenyl-fluorenylene, they may be unsubstituted or substituted with one or more deuterium atoms.
L3는 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴렌이다. 바람직하게는, L3은 직접 결합; 페닐렌; 나프틸렌; 비페닐릴렌; 9,9-디메틸-플루오레닐렌; 또는 9,9-디페닐-플루오레닐렌일 수 있다. L3가 페닐렌; 나프틸렌; 비페닐릴렌; 9,9-디메틸-플루오레닐렌; 또는 9,9-디페닐-플루오레닐렌인 경우, 이들은 비치환되거나 또는 1개 이상의 중수소로 치환될 수 있다.L 3 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S. Preferably, L 3 is a direct bond; phenylene; naphthylene; biphenylylene; 9,9-dimethyl-fluorenylene; or 9,9-diphenyl-fluorenylene. L 3 is phenylene; naphthylene; biphenylylene; 9,9-dimethyl-fluorenylene; or 9,9-diphenyl-fluorenylene, they may be unsubstituted or substituted with one or more deuterium atoms.
Ar1은 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이다. Ar1은 페닐; 비페닐릴; 터페닐릴; 나프틸; 페난쓰레닐; 9,9-디메틸-플루오레닐; 9,9-디페닐-플루오레닐; 디벤조퓨라닐; 디벤조티오페닐; 9-페닐-카바졸일; 또는 9,9’-스피로비[9H-플루오렌]일일 수 있다. Ar1은 비치환되거나 1개 이상의 중수소로 치환될 수 있다.Ar 1 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S. Ar 1 is phenyl; biphenylyl; terphenylyl; naphthyl; phenanthrenyl; 9,9-dimethyl-fluorenyl; 9,9-diphenyl-fluorenyl; dibenzofuranyl; dibenzothiophenyl; 9-phenyl-carbazolyl; or 9,9'-spirobi[9H-fluorene]yl. Ar 1 may be unsubstituted or substituted with one or more deuterium atoms.
Ar2는 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이다. Ar2은 페닐; 비페닐릴; 터페닐릴; 나프틸; 페난쓰레닐; 9,9-디메틸-플루오레닐; 9,9-디페닐-플루오레닐; 디벤조퓨라닐; 디벤조티오페닐; 9-페닐-카바졸일; 또는 9,9’-스피로비[9H-플루오렌]일일 수 있다. Ar2은 비치환되거나 1개 이상의 중수소로 치환될 수 있다.Ar 2 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S. Ar 2 is phenyl; biphenylyl; terphenylyl; naphthyl; phenanthrenyl; 9,9-dimethyl-fluorenyl; 9,9-diphenyl-fluorenyl; dibenzofuranyl; dibenzothiophenyl; 9-phenyl-carbazolyl; or 9,9'-spirobi[9H-fluorene]yl. Ar 2 may be unsubstituted or substituted with one or more deuterium.
상기 화합물은 하기 화학식 1-1 내지 1-4 중 어느 하나로 표시되는, The compound is represented by any one of Formulas 1-1 to 1-4,
화합물:compound:
[화학식 1-1][Formula 1-1]
Figure PCTKR2022019072-appb-img-000009
Figure PCTKR2022019072-appb-img-000009
상기 화학식 1-1에서,In Formula 1-1,
X2 내지 X10 중 하나는 N이고, 나머지는 CR’이고,One of X 2 to X 10 is N and the other is CR';
L1 내지 L3, Ar1, Ar2 및 R’는 상기 화학식 1에서 정의한 바와 같고,L 1 to L 3 , Ar 1 , Ar 2 and R' are as defined in Formula 1 above;
[화학식 1-2][Formula 1-2]
Figure PCTKR2022019072-appb-img-000010
Figure PCTKR2022019072-appb-img-000010
상기 화학식 1-2에서,In Formula 1-2,
X1 및 X3 내지 X10 중 하나는 N이고, 나머지는 CR’이고,One of X 1 and X 3 to X 10 is N and the other is CR';
L1 내지 L3, Ar1 및 Ar2 및 R’는 상기 화학식 1에서 정의한 바와 같고,L 1 to L 3 , Ar 1 and Ar 2 and R' are as defined in Formula 1 above;
[화학식 1-3][Formula 1-3]
Figure PCTKR2022019072-appb-img-000011
Figure PCTKR2022019072-appb-img-000011
상기 화학식 1-3에서.In Formula 1-3 above.
X1, X2 및 X4 내지 X10 중 하나는 N이고, 나머지는 CR’이고,One of X 1 , X 2 and X 4 to X 10 is N and the other is CR';
L1 내지 L3, Ar1 및 Ar2 및 R’는 상기 화학식 1에서 정의한 바와 같고,L 1 to L 3 , Ar 1 and Ar 2 and R' are as defined in Formula 1 above;
[화학식 1-4][Formula 1-4]
Figure PCTKR2022019072-appb-img-000012
Figure PCTKR2022019072-appb-img-000012
상기 화학식 1-4에서,In Chemical Formulas 1-4,
X1 내지 X3 및 X5 내지 X10 중 하나는 N이고, 나머지는 CR’이고,One of X 1 to X 3 and X 5 to X 10 is N and the other is CR';
L1 내지 L3, Ar1 및 Ar2 및 R’는 상기 화학식 1에서 정의한 바와 같다.L 1 to L 3 , Ar 1 and Ar 2 , and R' are as defined in Formula 1 above.
상기 화학식 1로 표시되는 화합물의 대표적인 예는 하기와 같다:Representative examples of the compound represented by Formula 1 are as follows:
Figure PCTKR2022019072-appb-img-000013
Figure PCTKR2022019072-appb-img-000013
Figure PCTKR2022019072-appb-img-000014
Figure PCTKR2022019072-appb-img-000014
Figure PCTKR2022019072-appb-img-000015
Figure PCTKR2022019072-appb-img-000015
Figure PCTKR2022019072-appb-img-000016
Figure PCTKR2022019072-appb-img-000016
Figure PCTKR2022019072-appb-img-000017
Figure PCTKR2022019072-appb-img-000017
Figure PCTKR2022019072-appb-img-000018
Figure PCTKR2022019072-appb-img-000018
Figure PCTKR2022019072-appb-img-000019
Figure PCTKR2022019072-appb-img-000019
Figure PCTKR2022019072-appb-img-000020
Figure PCTKR2022019072-appb-img-000020
Figure PCTKR2022019072-appb-img-000021
Figure PCTKR2022019072-appb-img-000021
Figure PCTKR2022019072-appb-img-000022
Figure PCTKR2022019072-appb-img-000022
Figure PCTKR2022019072-appb-img-000023
Figure PCTKR2022019072-appb-img-000023
Figure PCTKR2022019072-appb-img-000024
Figure PCTKR2022019072-appb-img-000024
Figure PCTKR2022019072-appb-img-000025
Figure PCTKR2022019072-appb-img-000025
Figure PCTKR2022019072-appb-img-000026
Figure PCTKR2022019072-appb-img-000026
Figure PCTKR2022019072-appb-img-000027
Figure PCTKR2022019072-appb-img-000027
Figure PCTKR2022019072-appb-img-000028
Figure PCTKR2022019072-appb-img-000028
Figure PCTKR2022019072-appb-img-000029
Figure PCTKR2022019072-appb-img-000029
또한, 상기 화합물은 중수소를 포함하지 않거나, 또는 1개 이상의 중수소를 포함할 수 있다.In addition, the compound may contain no deuterium or one or more deuterium atoms.
한편, 본 발명은 일례로 하기 반응식 1 및 2와 같은 상기 화학식 1로 표시되는 화합물의 제조방법을 제공한다:On the other hand, the present invention provides a method for producing a compound represented by Formula 1, such as the following Reaction Schemes 1 and 2, for example:
[반응식 1][Scheme 1]
Figure PCTKR2022019072-appb-img-000030
Figure PCTKR2022019072-appb-img-000030
[반응식 2][Scheme 2]
Figure PCTKR2022019072-appb-img-000031
Figure PCTKR2022019072-appb-img-000031
상기 반응식 1 및 2에서, X1 내지 X10, L1 내지 L3, 및 Ar1 및 Ar2의 정의는 각각 화학식 1 및 2와 같다. 또한 반응식 1 및 2에서 Z는 할로겐이고, 바람직하게는 클로로이다. In Reaction Schemes 1 and 2, X 1 to X 10 , L 1 to L 3 , and Ar 1 and Ar 2 are defined as in Chemical Formulas 1 and 2, respectively. In Schemes 1 and 2, Z is halogen, preferably chloro.
상기 반응식 1은 스즈키 커플링 반응을 통해 코어 구조인 화학식 1을 제조하는 반응이다. 또한 반응식 2 역시 스즈키 커플링 반응으로서, 팔라듐 촉매 존재 하에 수행하는 것이 바람직하며, 스즈키 커플링 반응을 위한 반응기는 당업계에 알려진 바에 따라 변경이 가능하다. 상기 제조방법은 후술할 제조예 및 합성예에서 보다 구체화될 수 있다. Reaction Scheme 1 is a reaction for preparing the core structure of Chemical Formula 1 through a Suzuki coupling reaction. In addition, Scheme 2 is also a Suzuki coupling reaction, and it is preferable to carry out in the presence of a palladium catalyst, and the reactor for the Suzuki coupling reaction can be changed as known in the art. The preparation method may be more specific in Preparation Examples and Synthesis Examples to be described later.
(유기 발광 소자)(organic light emitting device)
또한, 본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기 발광 소자를 제공한다. 일례로, 본 발명은 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화학식 1로 표시되는 화합물을 포함하는, 유기 발광 소자를 제공한다.In addition, the present invention provides an organic light emitting device including the compound represented by Formula 1 above. In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and 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 the compound represented by Chemical Formula 1. .
본 발명의 유기 발광 소자의 유기물 층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기 발광 소자는 유기물 층으로서 정공주입층, 정공수송층, 발광층, 정공저지층, 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, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like as organic layers. However, the structure of the organic light emitting device is not limited thereto and may include fewer organic layers.
또한, 상기 유기물 층은 정공주입층, 정공수송층, 또는 정공 주입과 수송을 동시에 하는 층을 포함할 수 있고, 상기 정공주입층, 정공수송층, 또는 정공 주입과 수송을 동시에 하는 층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.In addition, the organic 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, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. may contain the indicated compounds.
또한, 상기 유기물 층은 발광층을 포함할 수 있고, 상기 발광층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. Also, the organic material layer may include a light emitting layer, and the light emitting layer may include the compound represented by Chemical Formula 1.
또한, 상기 유기물 층은 정공저지층, 전자수송층, 전자주입층, 또는 전자수송 및 전자주입을 동시에 하는 층을 포함할 수 있고, 상기 정공저지층, 전자수송층, 전자주입층, 또는 전자수송 및 전자주입을 동시에 하는 층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. In addition, the organic material layer may include a hole blocking layer, an electron transport layer, an electron injection layer, or a layer that simultaneously transports and injects electrons, and the hole blocking layer, the electron transport layer, the electron injection layer, or the electron transport and electron injection layer. The layer to be simultaneously injected may include the compound represented by Chemical Formula 1 above.
또한, 상기 유기물 층은 발광층 및 전자 주입 및 수송층을 포함할 수 있고, 상기 전자 주입 및 수송층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.Also, the organic material layer may include a light emitting layer and an electron injection and transport layer, and the electron injection and transport layer may include the compound represented by Chemical Formula 1.
또한, 본 발명에 따른 유기 발광 소자는, 기판 상에 양극, 1층 이상의 유기물층 및 음극이 순차적으로 적층된 구조(normal type)의 유기 발광 소자일 수 있다. 또한, 본 발명에 따른 유기 발광 소자는 기판 상에 음극, 1층 이상의 유기물층 및 양극이 순차적으로 적층된 역방향 구조(inverted type)의 유기 발광 소자일 수 있다. 예컨대, 본 발명의 일실시예에 따른 유기 발광 소자의 구조는 도 1 및 2에 예시되어 있다.Also, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. 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), 발광층(3), 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
도 2는 기판 (1), 양극(2), 정공주입층(5), 정공수송층(6), 발광층(7), 전자 주입 및 수송층(8) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 발광층에 포함될 수 있다.2 is an example of an organic light emitting device composed of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (7), an electron injection and transport layer (8) and a cathode (4). is shown. In this structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.
본 발명에 따른 유기 발광 소자는, 상기 유기물 층 중 1층 이상이 상기 화학식 1로 표시되는 화합물을 포함하는 것을 제외하고는 당 기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다. 또한, 상기 유기 발광 소자가 복수개의 유기물층을 포함하는 경우, 상기 유기물층은 동일한 물질 또는 다른 물질로 형성될 수 있다.The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one of the organic layers includes the compound represented by Chemical Formula 1. Also, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
예컨대, 본 발명에 따른 유기 발광 소자는 기판 상에 양극, 유기물층 및 음극을 순차적으로 적층시켜 제조할 수 있다. 이때, 스퍼터링법(sputtering)이나 전자빔 증발법(e-beam evaporation)과 같은 PVD(physical Vapor Deposition) 방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공 주입층, 정공 수송층, 발광층 및 전자 수송층을 포함하는 유기물 층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시켜 제조할 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수 있다.For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode After forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and depositing a material that can be used as a cathode thereon, it can be prepared. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
또한, 상기 화학식 1로 표시되는 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물 층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.In addition, the compound represented by Chemical 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 means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.
이와 같은 방법 외에도, 기판 상에 음극 물질로부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 제조할 수 있다(WO 2003/012890). 다만, 제조 방법이 이에 한정되는 것은 아니다. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material on a substrate from a cathode material (WO 2003/012890). However, the manufacturing method is not limited thereto.
일례로, 상기 제1 전극은 양극이고, 상기 제2 전극은 음극이거나, 또는 상기 제1 전극은 음극이고, 상기 제2 전극은 양극이다.In one example, the first electrode is an anode and 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 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 화합물 등이 있으나, 이들에만 한정되는 것은 아니다. As the anode material, a material having a high work function is generally preferred 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; conductive compounds such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), 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 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. The cathode material is preferably a material having a small work function so as to easily inject electrons into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; 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 유기물 층의 HOMO 사이인 것이 바람직하다. 정공 주입 물질의 구체적인 예로는 금속 포피린(porphyrin), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone)계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 화합물 등이 있으나, 이들에만 한정 되는 것은 아니다. The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic matter, anthraquinone, and polyaniline and polythiophene-based conductive compounds, 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. 구체적인 예로는 아릴아민 계열의 유기물, 전도성 화합물, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다. The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. The hole transport material is a material that can receive holes from the anode or the hole injection layer and transfer them to the light emitting layer, and has high hole mobility. material is suitable. Specific examples include, but are not limited to, arylamine-based organic materials, conductive compounds, and block copolymers having both conjugated and non-conjugated parts.
상기 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(Alq3); 카르바졸 계열 화합물; 이량체화 스티릴(dimerized styryl) 화합물; BAlq; 10-히드록시벤조 퀴놀린-금속 화합물; 벤족사졸, 벤즈티아졸 및 벤즈이미다졸 계열의 화합물; 폴리(p-페닐렌비닐렌)(PPV) 계열의 고분자; 스피로(spiro) 화합물; 폴리플루오렌, 루브렌 등이 있으나, 이들에만 한정되는 것은 아니다.The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; Polyfluorene, rubrene, etc., but are not limited thereto.
상기 전자억제층은 음극에서 주입된 전자가 발광층에서 재결합되지 않고 정공수송층으로 넘어가는 것을 방지하기 위해 정공수송층과 발광층의 사이에 두는 층으로, 전자저지층으로 불리기도 한다. 전자억제층에는 전자수송층보다 전자 친화력이 작은 물질이 바람직하다. 바람직하게는, 상기 화학식 1로 표시되는 화합물을 전자억제층의 물질로 포함할 수 있다.The electron blocking layer is a layer placed between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from passing to the hole transport layer without recombination in the light emitting layer, and is also called an electron blocking layer. A material having a smaller electron affinity than the electron transport layer is preferable for the electron blocking layer. Preferably, the compound represented by Chemical Formula 1 may be included as a material of the electron blocking layer.
상기 발광층은 호스트 재료 및 도펀트 재료를 포함할 수 있다. 호스트 재료로는 상술한 화학식 1로 표시되는 화합물이 사용될 수 있다. 또한, 추가로 사용할 수 있는 호스트 재료로는 축합 방향족환 유도체 또는 헤테로환 함유 화합물 등을 사용할 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 한정되지 않는다. The light emitting layer may include a host material and a dopant material. As the host material, the compound represented by Chemical Formula 1 may be used. In addition, as a host material that can be further used, a condensed aromatic ring derivative or a compound containing a heterocyclic ring can be used. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.
도펀트 재료로는 방향족 아민 유도체, 스트릴아민 화합물, 붕소 착체, 플루오란텐 화합물, 금속 착체 등이 있다. 구체적으로 방향족 아민 유도체로는 치환 또는 비치환된 아릴아미노기를 갖는 축합 방향족환 유도체로서, 아릴아미노기를 갖는 피렌, 안트라센, 크리센, 페리플란텐 등이 있으며, 스티릴아민 화합물로는 치환 또는 비치환된 아릴아민에 적어도 1개의 아릴비닐기가 치환되어 있는 화합물로, 아릴기, 실릴기, 알킬기, 사이클로알킬기 및 아릴아미노기로 이루어진 군에서 1 또는 2 이상 선택되는 치환기가 치환 또는 비치환된다. 구체적으로 스티릴아민, 스티릴디아민, 스티릴트리아민, 스티릴테트라아민 등이 있으나, 이에 한정되지 않는다. 또한, 금속 착체로는 이리듐 착체, 백금 착체 등이 있으나, 이에 한정되지 않는다.Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc. having an arylamino group, and styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but is not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes and platinum complexes.
상기 전자수송층은 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하는 층으로 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자 수송층은 종래기술에 따라 사용된 바와 같이 임의의 원하는 캐소드 물질과 함께 사용할 수 있다. 특히, 적절한 캐소드 물질의 예는 낮은 일함수를 가지고 알루미늄층 또는 실버층이 뒤따르는 통상적인 물질이다. 구체적으로 세슘, 바륨, 칼슘, 이테르븀 및 사마륨이고, 각 경우 알루미늄 층 또는 실버층이 뒤따른다.The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. do. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes containing Alq 3 ; organic radical compounds; hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by a layer of aluminum or silver.
상기 전자주입층은 전극으로부터 전자를 주입하는 층으로, 전자를 수송하는 능력을 갖고, 음극으로부터의 전자 주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자주입 효과를 가지며, 발광층에서 생성된 여기자의 정공주입층에의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물이 바람직하다. 구체적으로는 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 질소 함유 5원환 유도체 등이 있으나, 이에 한정되지 않는다.The electron injection layer is a layer for injecting electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes of excitons generated in the light emitting layer. A compound that prevents migration to a layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preonylidene methane, anthrone, etc. and their derivatives, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.
상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.
한편, 본 발명에 있어서 "전자 주입 및 수송층"은 상기 전자주입층과 상기 전자수송층의 역할을 모두 수행하는 층으로 상기 각 층의 역할을 하는 물질을 단독으로, 혹은 혼합하여 사용할 수 있으나, 이에 한정되지 않는다. 바람직하게는, 상기 화학식 1로 표시되는 화합물을 전자 주입 및 수송층의 물질로 포함할 수 있다.On the other hand, in the present invention, the "electron injection and transport layer" is a layer that performs both the roles of the electron injection layer and the electron transport layer, and materials that play the role of each layer may be used alone or in combination, but are limited thereto. It doesn't work. Preferably, the compound represented by Formula 1 may be included as a material for the electron injection and transport layer.
본 발명에 따른 유기 발광 소자는 배면 발광(Bottom emission) 소자, 전면 발광(Top emission) 소자, 또는 양면 발광 소자일 수 있으며, 특히 상대적으로 높은 발광 효율이 요구되는 배면 발광 소자일 수 있다.The organic light emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom emission device requiring relatively high light emitting efficiency.
또한, 본 발명에 따른 화합물은 유기 발광 소자 외에도 유기 태양 전지 또는 유기 트랜지스터에 포함될 수 있다.In addition, the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.
상기 화학식 1로 표시되는 화합물 및 이를 포함하는 유기 발광 소자의 제조는 이하 실시예에서 구체적으로 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범위가 이들에 의하여 한정되는 것은 아니다.Preparation of the compound represented by Chemical Formula 1 and the organic light emitting device including the same will be described in detail in the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.
합성예 A-1-1 : 중간제 화합물 A-1-1의 제조Synthesis Example A-1-1: Preparation of Intermediate Compound A-1-1
Figure PCTKR2022019072-appb-img-000032
Figure PCTKR2022019072-appb-img-000032
3-브로모-2-클로로피리딘 (15g, 77.9 mmol)와 (2-(메틸티오)나프탈렌-1-일)보론산 (17.8g, 81.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(32.3g, 233.8 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.4g, 0.8 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-1-1_P1를 13.8g 제조하였다. (수율 62%, MS:[M+H]+=286)3-Bromo-2-chloropyridine (15g, 77.9 mmol) and (2-(methylthio)naphthalen-1-yl)boronic acid (17.8g, 81.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (32.3g, 233.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.8 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound A-1-1_P1. (Yield 62%, MS:[M+H] + =286)
화합물 A-1-1_P1 (15g, 52.5 mmol)와 과산화수소 (2.7g, 78.7 mmol)를 아세트산 300 ml에 넣고 교반 및 환류하였다. 3 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-1-1_P2를 8.1g 제조하였다. (수율 51%, MS:[M+H]+=302)Compound A-1-1_P1 (15g, 52.5 mmol) and hydrogen peroxide (2.7g, 78.7 mmol) were added to 300 ml of acetic acid, stirred and refluxed. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.1 g of compound A-1-1_P2. (Yield 51%, MS:[M+H] + =302)
화합물 A-1-1_P2 (15g, 49.7 mmol)를 황산 300 ml에 넣고 교반 및 환류하였다. 2 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-1-1를 6.2g 제조하였다. (수율 49%, MS:[M+H]+=254)Compound A-1-1_P2 (15g, 49.7 mmol) was added to 300 ml of sulfuric acid, stirred and refluxed. After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.2 g of Compound A-1-1. (Yield 49%, MS:[M+H] + =254)
합성예 A-1-6 : 중간제 화합물 A-1-6의 제조Synthesis Example A-1-6: Preparation of Intermediate Compound A-1-6
Figure PCTKR2022019072-appb-img-000033
Figure PCTKR2022019072-appb-img-000033
1-브로모-2-클로로벤젠 (15g, 78.3 mmol)와 (6-(메틸티오)퀴놀린-5-일)보론산 (18g, 82.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(32.5g, 235 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.4g, 0.8 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-1-6_P1를 15.4g 제조하였다. (수율 69%, MS:[M+H]+=286)1-Bromo-2-chlorobenzene (15g, 78.3 mmol) and (6-(methylthio)quinolin-5-yl)boronic acid (18g, 82.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (32.5g, 235 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.8 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of compound A-1-6_P1. (Yield 69%, MS:[M+H] + =286)
화합물 A-1-6_P1 (15g, 52.5 mmol)와 과산화수소 (2.7g, 78.7 mmol)를 아세트산 300 ml에 넣고 교반 및 환류하였다. 3 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-1-6_P2를 8.2g 제조하였다. (수율 52%, MS:[M+H]+=302)Compound A-1-6_P1 (15g, 52.5 mmol) and hydrogen peroxide (2.7g, 78.7 mmol) were added to 300 ml of acetic acid, stirred and refluxed. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.2 g of compound A-1-6_P2. (Yield 52%, MS:[M+H] + =302)
화합물 A-1-6_P2 (15g, 49.7 mmol)를 황산 300 ml에 넣고 교반 및 환류하였다. 5 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-1-6를 5.9g 제조하였다. (수율 47%, MS:[M+H]+=254)Compound A-1-6_P2 (15g, 49.7 mmol) was added to 300 ml of sulfuric acid and stirred and refluxed. After reacting for 5 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.9 g of Compound A-1-6. (Yield 47%, MS:[M+H] + =254)
합성예 A-2-2 : 중간제 화합물 A-2-2의 제조Synthesis Example A-2-2: Preparation of Intermediate Compound A-2-2
Figure PCTKR2022019072-appb-img-000034
Figure PCTKR2022019072-appb-img-000034
4-브로모-2-클로로피리딘 (15g, 77.9 mmol)와 (2-(메틸티오)나프탈렌-1-일)보론산 (17.8g, 81.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(32.3g, 233.8 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.4g, 0.8 mmol)을 투입하였다. 2 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-2-2_P1를 13.8g 제조하였다. (수율 62%, MS:[M+H]+=286)4-Bromo-2-chloropyridine (15g, 77.9 mmol) and (2-(methylthio)naphthalen-1-yl)boronic acid (17.8g, 81.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (32.3g, 233.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.8 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound A-2-2_P1. (Yield 62%, MS:[M+H] + =286)
화합물 A-2-2_P1 (15g, 52.5 mmol)와 과산화수소 (2.7g, 78.7 mmol)를 아세트산 300 ml에 넣고 교반 및 환류하였다. 4 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-2-2_P2를 8.7g 제조하였다. (수율 55%, MS:[M+H]+=302)Compound A-2-2_P1 (15g, 52.5 mmol) and hydrogen peroxide (2.7g, 78.7 mmol) were added to 300 ml of acetic acid, stirred and refluxed. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.7 g of compound A-2-2_P2. (Yield 55%, MS:[M+H] + =302)
화합물 A-2-2_P2 (15g, 49.7 mmol)를 황산 300 ml에 넣고 교반 및 환류하였다. 2 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-2-2를 6.8g 제조하였다. (수율 54%, MS:[M+H]+=254)Compound A-2-2_P2 (15g, 49.7 mmol) was added to 300 ml of sulfuric acid and stirred and refluxed. After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.8 g of compound A-2-2. (Yield 54%, MS:[M+H] + =254)
합성예 A-2-4 : 중간제 화합물 A-2-4의 제조Synthesis Example A-2-4: Preparation of Intermediate Compound A-2-4
Figure PCTKR2022019072-appb-img-000035
Figure PCTKR2022019072-appb-img-000035
1-브로모-3-클로로벤젠 (15g, 78.3 mmol)와 (3-(메틸티오)이소퀴놀린-4-일)보론산 (18g, 82.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(32.5g, 235 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.4g, 0.8 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-2-4_P1를 13.8g 제조하였다. (수율 62%, MS:[M+H]+=286)1-Bromo-3-chlorobenzene (15g, 78.3 mmol) and (3-(methylthio)isoquinolin-4-yl)boronic acid (18g, 82.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (32.5g, 235 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.8 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound A-2-4_P1. (Yield 62%, MS:[M+H] + =286)
화합물 A-2-4_P1 (15g, 52.5 mmol)와 과산화수소 (2.7g, 78.7 mmol)를 아세트산 300 ml에 넣고 교반 및 환류하였다. 5 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-2-4_P2를 9.3g 제조하였다. (수율 59%, MS:[M+H]+=302)Compound A-2-4_P1 (15g, 52.5 mmol) and hydrogen peroxide (2.7g, 78.7 mmol) were added to 300 ml of acetic acid, stirred and refluxed. After reacting for 5 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.3 g of compound A-2-4_P2. (Yield 59%, MS:[M+H] + =302)
화합물 A-2-4_P2 (15g, 49.7 mmol)를 황산 300 ml에 넣고 교반 및 환류하였다. 2 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-2-4를 7.2g 제조하였다. (수율 57%, MS:[M+H]+=254)Compound A-2-4_P2 (15g, 49.7 mmol) was added to 300 ml of sulfuric acid and stirred and refluxed. After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.2 g of compound A-2-4. (Yield 57%, MS:[M+H] + =254)
합성예 A-2-7 : 중간제 화합물 A-2-7의 제조Synthesis Example A-2-7: Preparation of Intermediate Compound A-2-7
Figure PCTKR2022019072-appb-img-000036
Figure PCTKR2022019072-appb-img-000036
1-브로모-3-클로로벤젠 (15g, 78.3 mmol)와 (6-(메틸티오)이소퀴놀린-5-일)보론산 (18g, 82.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(32.5g, 235 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.4g, 0.8 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-2-7_P1를 14.3g 제조하였다. (수율 64%, MS:[M+H]+=286)1-Bromo-3-chlorobenzene (15g, 78.3 mmol) and (6-(methylthio)isoquinolin-5-yl)boronic acid (18g, 82.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (32.5g, 235 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.8 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound A-2-7_P1. (Yield 64%, MS:[M+H] + =286)
화합물 A-2-7_P1 (15g, 52.5 mmol)와 과산화수소 (2.7g, 78.7 mmol)를 아세트산 300 ml에 넣고 교반 및 환류하였다. 5 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-2-7_P2를 9.2g 제조하였다. (수율 58%, MS:[M+H]+=302)Compound A-2-7_P1 (15g, 52.5 mmol) and hydrogen peroxide (2.7g, 78.7 mmol) were added to 300 ml of acetic acid, stirred and refluxed. After reacting for 5 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.2 g of compound A-2-7_P2. (Yield 58%, MS:[M+H] + =302)
화합물 A-2-7_P2 (15g, 49.7 mmol)를 황산 300 ml에 넣고 교반 및 환류하였다. 4 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-2-7를 5.4g 제조하였다. (수율 43%, MS:[M+H]+=254)Compound A-2-7_P2 (15g, 49.7 mmol) was added to 300 ml of sulfuric acid, stirred and refluxed. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.4 g of compound A-2-7. (Yield 43%, MS:[M+H] + =254)
합성예 A-3-5 : 중간제 화합물 A-3-5의 제조Synthesis Example A-3-5: Preparation of Intermediate Compound A-3-5
Figure PCTKR2022019072-appb-img-000037
Figure PCTKR2022019072-appb-img-000037
1-브로모-4-클로로벤젠 (15g, 78.3 mmol)와 (3-(메틸티오)퀴놀린-4-일)보론산 (18g, 82.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(32.5g, 235 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.4g, 0.8 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-3-5_P1를 15.4g 제조하였다. (수율 69%, MS:[M+H]+=286)1-Bromo-4-chlorobenzene (15g, 78.3 mmol) and (3-(methylthio)quinolin-4-yl)boronic acid (18g, 82.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (32.5g, 235 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.8 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of compound A-3-5_P1. (Yield 69%, MS:[M+H] + =286)
화합물 A-3-5_P1 (15g, 52.5 mmol)와 과산화수소 (2.7g, 78.7 mmol)를 아세트산 300 ml에 넣고 교반 및 환류하였다. 4 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-3-5_P2를 9g 제조하였다. (수율 57%, MS:[M+H]+=302)Compound A-3-5_P1 (15g, 52.5 mmol) and hydrogen peroxide (2.7g, 78.7 mmol) were added to 300 ml of acetic acid, stirred and refluxed. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were removed and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound A-3-5_P2. (Yield 57%, MS:[M+H] + =302)
화합물 A-3-5_P2 (15g, 49.7 mmol)를 황산 300 ml에 넣고 교반 및 환류하였다. 2 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-3-5를 5.9g 제조하였다. (수율 47%, MS:[M+H]+=254)Compound A-3-5_P2 (15g, 49.7 mmol) was added to 300 ml of sulfuric acid and stirred and refluxed. After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.9 g of compound A-3-5. (Yield 47%, MS:[M+H] + =254)
합성예 A-3-9 : 중간제 화합물 A-3-9의 제조Synthesis Example A-3-9: Preparation of Intermediate Compound A-3-9
Figure PCTKR2022019072-appb-img-000038
Figure PCTKR2022019072-appb-img-000038
1-브로모-4-클로로벤젠 (15g, 78.3 mmol)와 (7-(메틸티오)퀴놀린-8-일)보론산 (18g, 82.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(32.5g, 235 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.4g, 0.8 mmol)을 투입하였다. 5 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-3-9_P1를 13.4g 제조하였다. (수율 60%, MS:[M+H]+=286)1-Bromo-4-chlorobenzene (15g, 78.3 mmol) and (7-(methylthio)quinolin-8-yl)boronic acid (18g, 82.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (32.5g, 235 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.8 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound A-3-9_P1. (Yield 60%, MS:[M+H] + =286)
화합물 A-3-9_P1 (15g, 52.5 mmol)와 과산화수소 (2.7g, 78.7 mmol)를 아세트산 300 ml에 넣고 교반 및 환류하였다. 3 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-3-9_P2를 8.1g 제조하였다. (수율 51%, MS:[M+H]+=302)Compound A-3-9_P1 (15g, 52.5 mmol) and hydrogen peroxide (2.7g, 78.7 mmol) were added to 300 ml of acetic acid, stirred and refluxed. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.1 g of compound A-3-9_P2. (Yield 51%, MS:[M+H] + =302)
화합물 A-3-9_P2 (15g, 49.7 mmol)를 황산 300 ml에 넣고 교반 및 환류하였다. 5 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-3-9를 5g 제조하였다. (수율 40%, MS:[M+H]+=254)Compound A-3-9_P2 (15g, 49.7 mmol) was added to 300 ml of sulfuric acid and stirred and refluxed. After reacting for 5 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5 g of compound A-3-9. (Yield 40%, MS:[M+H] + =254)
합성예 A-4-3 : 중간제 화합물 A-4-3의 제조Synthesis Example A-4-3: Preparation of Intermediate Compound A-4-3
Figure PCTKR2022019072-appb-img-000039
Figure PCTKR2022019072-appb-img-000039
4-브로모-2-클로로피리딘 (15g, 77.9 mmol)와 (2-(메틸티오)나프탈렌-1-일)보론산 (17.8g, 81.8 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(32.3g, 233.8 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.4g, 0.8 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-4-3_P1를 15.6g 제조하였다. (수율 70%, MS:[M+H]+=286)4-Bromo-2-chloropyridine (15g, 77.9 mmol) and (2-(methylthio)naphthalen-1-yl)boronic acid (17.8g, 81.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (32.3g, 233.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.8 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6 g of compound A-4-3_P1. (Yield 70%, MS:[M+H] + =286)
화합물 A-4-3_P1 (15g, 52.5 mmol)와 과산화수소 (2.7g, 78.7 mmol)를 아세트산 300 ml에 넣고 교반 및 환류하였다. 4 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-4-3_P2를 9g 제조하였다. (수율 57%, MS:[M+H]+=302)Compound A-4-3_P1 (15g, 52.5 mmol) and hydrogen peroxide (2.7g, 78.7 mmol) were added to 300 ml of acetic acid, stirred and refluxed. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were removed and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound A-4-3_P2. (Yield 57%, MS:[M+H] + =302)
화합물 A-4-3_P2 (15g, 49.7 mmol)를 황산 300 ml에 넣고 교반 및 환류하였다. 5 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-4-3를 5.7g 제조하였다. (수율 45%, MS:[M+H]+=254)Compound A-4-3_P2 (15g, 49.7 mmol) was added to 300 ml of sulfuric acid, stirred and refluxed. After reacting for 5 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred 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 5.7 g of compound A-4-3. (Yield 45%, MS:[M+H] + =254)
합성예 A-4-8 : 중간제 화합물 A-4-8의 제조Synthesis Example A-4-8: Preparation of Intermediate Compound A-4-8
Figure PCTKR2022019072-appb-img-000040
Figure PCTKR2022019072-appb-img-000040
1-브로모-3-클로로벤젠 (15g, 78.3 mmol)와 (7-(메틸티오)이소퀴놀린-8-일)보론산 (18g, 82.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(32.5g, 235 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.4g, 0.8 mmol)을 투입하였다. 2 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-4-8_P1를 13.8g 제조하였다. (수율 62%, MS:[M+H]+=286)1-Bromo-3-chlorobenzene (15g, 78.3 mmol) and (7-(methylthio)isoquinolin-8-yl)boronic acid (18g, 82.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (32.5g, 235 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.8 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound A-4-8_P1. (Yield 62%, MS:[M+H] + =286)
화합물 A-4-8_P1 (15g, 52.5 mmol)와 과산화수소 (2.7g, 78.7 mmol)를 아세트산 300 ml에 넣고 교반 및 환류하였다. 5 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-4-8_P2를 8.2g 제조하였다. (수율 52%, MS:[M+H]+=302)Compound A-4-8_P1 (15g, 52.5 mmol) and hydrogen peroxide (2.7g, 78.7 mmol) were added to 300 ml of acetic acid, stirred and refluxed. After reacting for 5 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.2 g of compound A-4-8_P2. (Yield 52%, MS:[M+H] + =302)
화합물 A-4-8_2 (15g, 49.7 mmol)를 황산 300 ml에 넣고 교반 및 환류하였다. 5 시간 반응 후 상온으로 식히고 반응물을 물 600 ml에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 A-4-8를 7g 제조하였다. (수율 56%, MS:[M+H]+=254)Compound A-4-8_2 (15 g, 49.7 mmol) was added to 300 ml of sulfuric acid and stirred and refluxed. After reacting for 5 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 600 ml of water, and crystals were dropped and filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7 g of Compound A-4-8. (Yield 56%, MS:[M+H] + =254)
합성예 1 : 화합물 1의 제조Synthesis Example 1: Preparation of Compound 1
Figure PCTKR2022019072-appb-img-000041
Figure PCTKR2022019072-appb-img-000041
먼저, 합성예 A-2-2에서 출발물질로 4-브로모-2-클로로피리딘 대신 3-브로모-5-클로로피리딘을 사용한 것을 제외하고는, 합성예 A-2-2과 동일한 방법을 사용하여 중간체 화합물 A-2-3을 제조하였다.First, the same method as in Synthesis Example A-2-2 was carried out, except that 3-bromo-5-chloropyridine was used instead of 4-bromo-2-chloropyridine as a starting material in Synthesis Example A-2-2. Intermediate compound A-2-3 was prepared using
다음으로, 질소 분위기에서 중간체 화합물 A-2-3 (15 g, 55.6 mmol), amine1 (19.6g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1 17.4g을 얻었다. (수율 55%, MS:[M+H]+=569)Next, intermediate compound A-2-3 (15 g, 55.6 mmol), amine1 (19.6 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 17.4 g of Compound 1. (Yield 55%, MS:[M+H] + =569)
합성예 2 : 화합물 2의 제조Synthesis Example 2: Preparation of Compound 2
Figure PCTKR2022019072-appb-img-000042
Figure PCTKR2022019072-appb-img-000042
먼저, 합성예 A-3-5에서 출발물질로 (3-(메틸티오)퀴놀린-4-일)보론산 대신 (3-(메틸티오)이소퀴놀린-4-일)보론산을 사용한 것을 제외하고는, 합성예 A-3-5과 동일한 방법을 사용하여 중간체 화합물 A-3-4을 제조하였다.First, except that (3-(methylthio)isoquinolin-4-yl)boronic acid was used instead of (3-(methylthio)quinolin-4-yl)boronic acid as a starting material in Synthesis Example A-3-5. was prepared intermediate compound A-3-4 using the same method as Synthesis Example A-3-5.
다음으로, 질소 분위기에서 중간체 화합물 A-3-4 (15 g, 55.6 mmol), amine2 (24g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2 17.9g을 얻었다. (수율 50%, MS:[M+H]+=645)Next, in a nitrogen atmosphere, intermediate compound A-3-4 (15 g, 55.6 mmol), amine2 (24 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene, stirred, and Refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 17.9 g of Compound 2. (Yield 50%, MS:[M+H] + =645)
합성예 3 : 화합물 3의 제조Synthesis Example 3: Preparation of Compound 3
Figure PCTKR2022019072-appb-img-000043
Figure PCTKR2022019072-appb-img-000043
질소 분위기에서 중간체 화합물 A-4-8 (15 g, 55.6 mmol), amine3 (20.5g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 3 21.8g을 얻었다. (수율 67%, MS:[M+H]+=585)In a nitrogen atmosphere, intermediate compound A-4-8 (15 g, 55.6 mmol), amine3 (20.5 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene, stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 21.8 g of Compound 3. (Yield 67%, MS:[M+H] + =585)
합성예 4 : 화합물 4의 제조Synthesis Example 4: Preparation of Compound 4
Figure PCTKR2022019072-appb-img-000044
Figure PCTKR2022019072-appb-img-000044
먼저, 합성예 A-3-5에서 출발물질로 (3-(메틸티오)퀴놀린-4-일)보론산 대신 (6-(메틸티오)이소퀴놀린-5-일)보론산을 사용한 것을 제외하고는, 합성예 A-3-5과 동일한 방법을 사용하여 중간체 화합물 A-3-7을 제조하였다.First, except that (6-(methylthio)isoquinolin-5-yl)boronic acid was used instead of (3-(methylthio)quinolin-4-yl)boronic acid as a starting material in Synthesis Example A-3-5. prepared intermediate compound A-3-7 using the same method as Synthesis Example A-3-5.
다음으로, 질소 분위기에서 중간체 화합물 A-3-7 (15 g, 55.6 mmol), amine4 (18.8g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 4 20.3g을 얻었다. (수율 66%, MS:[M+H]+=555)Next, intermediate compound A-3-7 (15 g, 55.6 mmol), amine4 (18.8 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 20.3 g of Compound 4. (Yield 66%, MS:[M+H] + =555)
합성예 5 : 화합물 5의 제조Synthesis Example 5: Preparation of Compound 5
Figure PCTKR2022019072-appb-img-000045
Figure PCTKR2022019072-appb-img-000045
먼저, 합성예 A-1-1에서 출발물질로 3-브로모-2-클로로피리딘 대신 2-브로모-6-클로로피리딘을 사용한 것을 제외하고는, 합성예 A-1-1과 동일한 방법을 사용하여 중간체 화합물 A-3-3을 제조하였다.First, the same method as in Synthesis Example A-1-1 was performed except that 2-bromo-6-chloropyridine was used instead of 3-bromo-2-chloropyridine as a starting material in Synthesis Example A-1-1. Intermediate compound A-3-3 was prepared using
다음으로, 질소 분위기에서 중간체 화합물 A-3-3 (15 g, 55.6 mmol), amine5 (18.8g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 5 16g을 얻었다. (수율 52%, MS:[M+H]+=555)Next, intermediate compound A-3-3 (15 g, 55.6 mmol), amine5 (18.8 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 16 g of Compound 5. (Yield 52%, MS:[M+H] + =555)
합성예 6 :화합물 6의 제조Synthesis Example 6: Preparation of Compound 6
Figure PCTKR2022019072-appb-img-000046
Figure PCTKR2022019072-appb-img-000046
질소 분위기에서 중간체 화합물 A-4-3 (15 g, 55.6 mmol), amine6 (23.2g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 6 23.8g을 얻었다. (수율 68%, MS:[M+H]+=631)In a nitrogen atmosphere, intermediate compound A-4-3 (15 g, 55.6 mmol), amine6 (23.2 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene, stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 23.8 g of Compound 6. (Yield 68%, MS:[M+H] + =631)
합성예 7 : 화합물 7의 제조Synthesis Example 7: Preparation of Compound 7
Figure PCTKR2022019072-appb-img-000047
Figure PCTKR2022019072-appb-img-000047
먼저, 합성예 A-4-3에서 출발물질로 4-브로모-2-클로로피리딘 대신 2-브로모-4-클로로피리딘을 사용한 것을 제외하고는, 합성예 A-4-3과 동일한 방법을 사용하여 중간체 화합물 A-4-1을 제조하였다.First, the same method as in Synthesis Example A-4-3 was performed, except that 2-bromo-4-chloropyridine was used instead of 4-bromo-2-chloropyridine as a starting material in Synthesis Example A-4-3. Intermediate compound A-4-1 was prepared using
다음으로, 질소 분위기에서 중간체 화합물 A-4-1 (15 g, 55.6 mmol), amine7 (21.7g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 7 23.2g을 얻었다. (수율 69%, MS:[M+H]+=605)Next, intermediate compound A-4-1 (15 g, 55.6 mmol), amine7 (21.7 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 23.2 g of Compound 7. (Yield 69%, MS:[M+H] + =605)
합성예 8 : 화합물 8의 제조Synthesis Example 8: Preparation of Compound 8
Figure PCTKR2022019072-appb-img-000048
Figure PCTKR2022019072-appb-img-000048
질소 분위기에서 중간체 화합물 A-2-2 (15 g, 55.6 mmol), amine8 (21.1g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 8 19.5g을 얻었다. (수율 59%, MS:[M+H]+=595)In a nitrogen atmosphere, intermediate compound A-2-2 (15 g, 55.6 mmol), amine8 (21.1 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene, stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 19.5 g of Compound 8. (Yield 59%, MS:[M+H] + =595)
합성예 9 : 화합물 9의 제조Synthesis Example 9: Preparation of Compound 9
Figure PCTKR2022019072-appb-img-000049
Figure PCTKR2022019072-appb-img-000049
먼저, 합성예 A-1-1에서 출발물질로 3-브로모-2-클로로피리딘 대신 5-브로모-2-클로로피리딘을 사용한 것을 제외하고는, 합성예 A-1-1과 동일한 방법을 사용하여 중간체 화합물 A-3-2을 제조하였다.First, the same method as in Synthesis Example A-1-1 was performed except that 5-bromo-2-chloropyridine was used instead of 3-bromo-2-chloropyridine as a starting material in Synthesis Example A-1-1. Intermediate compound A-3-2 was prepared using
다음으로, 질소 분위기에서 중간체 화합물 A-3-2 (15 g, 55.6 mmol), amine9 (28.2g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 9 21.9g을 얻었다. (수율 55%, MS:[M+H]+=717)Next, intermediate compound A-3-2 (15 g, 55.6 mmol), amine9 (28.2 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 21.9 g of Compound 9. (Yield 55%, MS:[M+H] + =717)
합성예 10 : 화합물 10의 제조Synthesis Example 10: Preparation of Compound 10
Figure PCTKR2022019072-appb-img-000050
Figure PCTKR2022019072-appb-img-000050
질소 분위기에서 중간체 화합물 A-3-5 (15 g, 55.6 mmol), amine10 (20.4g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 10 21.4g을 얻었다. (수율 66%, MS:[M+H]+=583)In a nitrogen atmosphere, intermediate compound A-3-5 (15 g, 55.6 mmol), amine10 (20.4 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene, stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 21.4 g of Compound 10. (Yield 66%, MS:[M+H] + =583)
합성예 11 : 화합물 11의 제조Synthesis Example 11: Preparation of Compound 11
Figure PCTKR2022019072-appb-img-000051
Figure PCTKR2022019072-appb-img-000051
질소 분위기에서 중간체 화합물 A-4-8 (15 g, 55.6 mmol), amine11 (21.3g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 11 19.3g을 얻었다. (수율 58%, MS:[M+H]+=599)In a nitrogen atmosphere, intermediate compound A-4-8 (15 g, 55.6 mmol), amine11 (21.3 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene, stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 19.3 g of Compound 11. (Yield 58%, MS:[M+H] + =599)
합성예 12 : 화합물 12의 제조Synthesis Example 12: Preparation of Compound 12
Figure PCTKR2022019072-appb-img-000052
Figure PCTKR2022019072-appb-img-000052
먼저, 합성예 A-3-5에서 출발물질로 (3-(메틸티오)퀴놀린-4-일)보론산 대신 (6-(메틸티오)이소퀴놀린-5-일)보론산을 사용한 것을 제외하고는, 합성예 A-3-5과 동일한 방법을 사용하여 중간체 화합물 A-3-7을 제조하였다.First, except that (6-(methylthio)isoquinolin-5-yl)boronic acid was used instead of (3-(methylthio)quinolin-4-yl)boronic acid as a starting material in Synthesis Example A-3-5. prepared intermediate compound A-3-7 using the same method as Synthesis Example A-3-5.
다음으로, 질소 분위기에서 중간체 화합물 A-3-7 (15 g, 55.6 mmol), amine12 (21.3g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 12 18.6g을 얻었다. (수율 56%, MS:[M+H]+=599)Next, intermediate compound A-3-7 (15 g, 55.6 mmol), amine12 (21.3 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 18.6 g of Compound 12. (Yield 56%, MS:[M+H] + =599)
합성예 13 : 화합물 13의 제조Synthesis Example 13: Preparation of Compound 13
Figure PCTKR2022019072-appb-img-000053
Figure PCTKR2022019072-appb-img-000053
질소 분위기에서 중간체 화합물 A-3-5 (15 g, 55.6 mmol), amine13 (28.4g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 13 24.4g을 얻었다. (수율 61%, MS:[M+H]+=719)In a nitrogen atmosphere, intermediate compound A-3-5 (15 g, 55.6 mmol), amine13 (28.4 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene, stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 24.4 g of Compound 13. (Yield 61%, MS:[M+H] + =719)
합성예 14 : 화합물 14의 제조Synthesis Example 14: Preparation of Compound 14
Figure PCTKR2022019072-appb-img-000054
Figure PCTKR2022019072-appb-img-000054
먼저, 합성예 A-1-1에서 출발물질로 3-브로모-2-클로로피리딘 대신 2-브로모-5-클로로피리딘을 사용한 것을 제외하고는, 합성예 A-1-1과 동일한 방법을 사용하여 중간체 화합물 A-3-1을 제조하였다.First, the same method as in Synthesis Example A-1-1 was performed, except that 2-bromo-5-chloropyridine was used instead of 3-bromo-2-chloropyridine as a starting material in Synthesis Example A-1-1. Intermediate compound A-3-1 was prepared using
다음으로, 질소 분위기에서 중간체 화합물 A-3-1 (15 g, 55.6 mmol), amine14 (28.4g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 14 20g을 얻었다. (수율 50%, MS:[M+H]+=719)Next, intermediate compound A-3-1 (15 g, 55.6 mmol), amine14 (28.4 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 20 g of Compound 14. (Yield 50%, MS:[M+H] + =719)
합성예 15 : 화합물 15의 제조Synthesis Example 15: Preparation of Compound 15
Figure PCTKR2022019072-appb-img-000055
Figure PCTKR2022019072-appb-img-000055
먼저, 합성예 A-3-5에서 출발물질로 (3-(메틸티오)퀴놀린-4-일)보론산 대신 (7-(메틸티오)이소퀴놀린-8-일)보론산을 사용한 것을 제외하고는, 합성예 A-3-5과 동일한 방법을 사용하여 중간체 화합물 A-3-8을 제조하였다.First, except that (7-(methylthio)isoquinolin-8-yl)boronic acid was used instead of (3-(methylthio)quinolin-4-yl)boronic acid as a starting material in Synthesis Example A-3-5. prepared intermediate compound A-3-8 using the same method as Synthesis Example A-3-5.
다음으로, 질소 분위기에서 중간체 화합물 A-3-8 (15 g, 55.6 mmol), amine15 (25.5g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 15 25.3g을 얻었다. (수율 68%, MS:[M+H]+=671)Next, intermediate compound A-3-8 (15 g, 55.6 mmol), amine15 (25.5 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 25.3 g of Compound 15. (Yield 68%, MS:[M+H] + =671)
합성예 16 : 화합물 16의 제조Synthesis Example 16: Preparation of Compound 16
Figure PCTKR2022019072-appb-img-000056
Figure PCTKR2022019072-appb-img-000056
먼저, 합성예 A-4-8에서 출발물질로 (7-(메틸티오)이소퀴놀린-8-일)보론산 대신 (3-(메틸티오)퀴놀린-4-일)보론산을 사용한 것을 제외하고는, 합성예 A-4-8과 동일한 방법을 사용하여 중간체 화합물 A-4-5을 제조하였다.First, except that (3-(methylthio)quinolin-4-yl)boronic acid was used instead of (7-(methylthio)isoquinolin-8-yl)boronic acid as a starting material in Synthesis Example A-4-8. prepared intermediate compound A-4-5 using the same method as Synthesis Example A-4-8.
다음으로, 질소 분위기에서 중간체 화합물 A-4-5 (15 g, 55.6 mmol), amine16 (17.2g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 16 15.3g을 얻었다. (수율 52%, MS:[M+H]+=529)Next, intermediate compound A-4-5 (15 g, 55.6 mmol), amine16 (17.2 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 15.3 g of Compound 16. (Yield 52%, MS:[M+H] + =529)
합성예 17 : 화합물 17의 제조Synthesis Example 17: Preparation of Compound 17
Figure PCTKR2022019072-appb-img-000057
Figure PCTKR2022019072-appb-img-000057
먼저, 합성예 A-2-2에서 출발물질로 4-브로모-2-클로로피리딘 대신 3-브로모-5-클로로피리딘을 사용한 것을 제외하고는, 합성예 A-2-2과 동일한 방법을 사용하여 중간체 화합물 A-2-3을 제조하였다.First, the same method as in Synthesis Example A-2-2 was carried out, except that 3-bromo-5-chloropyridine was used instead of 4-bromo-2-chloropyridine as a starting material in Synthesis Example A-2-2. Intermediate compound A-2-3 was prepared using
다음으로, 질소 분위기에서 중간체 화합물 A-2-3 (15 g, 55.6 mmol), amine17 (23.2g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 17 23.5g을 얻었다. (수율 67%, MS:[M+H]+=631)Next, intermediate compound A-2-3 (15 g, 55.6 mmol), amine17 (23.2 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 23.5 g of Compound 17. (Yield 67%, MS:[M+H] + =631)
합성예 18 : 화합물 18의 제조Synthesis Example 18: Preparation of Compound 18
Figure PCTKR2022019072-appb-img-000058
Figure PCTKR2022019072-appb-img-000058
먼저, 합성예 A-4-3에서 출발물질로 4-브로모-2-클로로피리딘 대신 3-브로모-5-클로로피리딘을 사용한 것을 제외하고는, 합성예 A-4-3과 동일한 방법을 사용하여 중간체 화합물 A-4-2을 제조하였다.First, the same method as in Synthesis Example A-4-3 was performed, except that 3-bromo-5-chloropyridine was used instead of 4-bromo-2-chloropyridine as a starting material in Synthesis Example A-4-3. Intermediate compound A-4-2 was prepared using
다음으로, 질소 분위기에서 중간체 화합물 A-4-2 (15 g, 55.6 mmol), amine18 (23.2g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 18 21.7g을 얻었다. (수율 62%, MS:[M+H]+=631)Next, intermediate compound A-4-2 (15 g, 55.6 mmol), amine18 (23.2 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 21.7 g of Compound 18. (Yield 62%, MS:[M+H] + =631)
합성예 19 : 화합물 19의 제조Synthesis Example 19: Preparation of Compound 19
Figure PCTKR2022019072-appb-img-000059
Figure PCTKR2022019072-appb-img-000059
먼저, 합성예 A-1-1에서 출발물질로 3-브로모-2-클로로피리딘 대신 2-브로모-6-클로로피리딘을 사용한 것을 제외하고는, 합성예 A-1-1과 동일한 방법을 사용하여 중간체 화합물 A-3-3을 제조하였다. First, the same method as in Synthesis Example A-1-1 was performed except that 2-bromo-6-chloropyridine was used instead of 3-bromo-2-chloropyridine as a starting material in Synthesis Example A-1-1. Intermediate compound A-3-3 was prepared using
다음으로, 질소 분위기에서 화합물 A-3-3 (15 g, 55.6 mmol), amine19 (19.6g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 19 19.9g을 얻었다. (수율 63%, MS:[M+H]+=569)Next, compound A-3-3 (15 g, 55.6 mmol), amine19 (19.6 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere, stirred and Refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 19.9 g of Compound 19. (Yield 63%, MS:[M+H] + =569)
합성예 20 : 화합물 20의 제조Synthesis Example 20: Preparation of Compound 20
Figure PCTKR2022019072-appb-img-000060
Figure PCTKR2022019072-appb-img-000060
질소 분위기에서 중간체 화합물 A-2-2 (15 g, 55.6 mmol), amine20 (24g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 20 20.7g을 얻었다. (수율 58%, MS:[M+H]+=644)In a nitrogen atmosphere, intermediate compound A-2-2 (15 g, 55.6 mmol), amine20 (24 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene, stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 20.7 g of Compound 20. (Yield 58%, MS:[M+H] + =644)
합성예 21 : 화합물 21의 제조Synthesis Example 21: Preparation of Compound 21
Figure PCTKR2022019072-appb-img-000061
Figure PCTKR2022019072-appb-img-000061
먼저, 합성예 A-4-3에서 출발물질로 4-브로모-2-클로로피리딘 대신 2-브로모-4-클로로피리딘을 사용한 것을 제외하고는, 합성예 A-4-3과 동일한 방법을 사용하여 중간체 화합물 A-4-1을 제조하였다.First, the same method as in Synthesis Example A-4-3 was performed, except that 2-bromo-4-chloropyridine was used instead of 4-bromo-2-chloropyridine as a starting material in Synthesis Example A-4-3. Intermediate compound A-4-1 was prepared using
다음으로, 질소 분위기에서 중간체 화합물 A-4-1 (15 g, 55.6 mmol), amine21 (20.5g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 21 17.9g을 얻었다. (수율 55%, MS:[M+H]+=585)Next, intermediate compound A-4-1 (15 g, 55.6 mmol), amine21 (20.5 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene in a nitrogen atmosphere and stirred. and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 17.9 g of Compound 21. (Yield 55%, MS:[M+H] + =585)
합성예 22 : 화합물 22의 제조Synthesis Example 22: Preparation of Compound 22
Figure PCTKR2022019072-appb-img-000062
Figure PCTKR2022019072-appb-img-000062
질소 분위기에서 중간체 화합물 A-2-2 (15 g, 55.6 mmol), amine22 (19.6g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 22 21.8g을 얻었다. (수율 69%, MS:[M+H]+=569)In a nitrogen atmosphere, intermediate compound A-2-2 (15 g, 55.6 mmol), amine22 (19.6 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene, stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 21.8 g of Compound 22. (Yield 69%, MS:[M+H] + =569)
합성예 23 : 화합물 23의 제조Synthesis Example 23: Preparation of Compound 23
Figure PCTKR2022019072-appb-img-000063
Figure PCTKR2022019072-appb-img-000063
질소 분위기에서 중간체 화합물 A-2-7 (15 g, 55.6 mmol), amine23 (24.6g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 23 24.7g을 얻었다. (수율 68%, MS:[M+H]+=655)In a nitrogen atmosphere, intermediate compound A-2-7 (15 g, 55.6 mmol), amine23 (24.6 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene, stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 24.7 g of Compound 23. (Yield 68%, MS:[M+H] + =655)
합성예 24 : 화합물 24의 제조Synthesis Example 24: Preparation of compound 24
Figure PCTKR2022019072-appb-img-000064
Figure PCTKR2022019072-appb-img-000064
질소 분위기에서 중간체 화합물 A-3-9 (15 g, 55.6 mmol), amine24 (18.8g, 58.4 mmol), 소듐 tert-부톡사이드 (8 g, 83.4 mmol)을 자일렌 150 ml에 넣고 교반 및 환류했다. 이 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3 g, 0.6 mmol)을 투입했다. 5 시간 후 반응이 종결되어서 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 24 17.6g을 얻었다. (수율 57%, MS:[M+H]+=555)In a nitrogen atmosphere, intermediate compound A-3-9 (15 g, 55.6 mmol), amine24 (18.8 g, 58.4 mmol), and sodium tert-butoxide (8 g, 83.4 mmol) were added to 150 ml of xylene, stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, 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 17.6 g of Compound 24. (Yield 57%, MS:[M+H] + =555)
합성예 25 : 화합물 25의 제조Synthesis Example 25: Preparation of Compound 25
Figure PCTKR2022019072-appb-img-000065
Figure PCTKR2022019072-appb-img-000065
먼저, 합성예 A-4-8에서 출발물질로 (7-(메틸티오)이소퀴놀린-8-일)보론산 대신 (3-(메틸티오)이소퀴놀린-4-일)보론산을 사용한 것을 제외하고는, 합성예 A-4-8과 동일한 방법을 사용하여 중간체 화합물 A-4-4을 제조하였다.First, except that (3-(methylthio)isoquinolin-4-yl)boronic acid was used instead of (7-(methylthio)isoquinolin-8-yl)boronic acid as a starting material in Synthesis Example A-4-8. Then, the intermediate compound A-4-4 was prepared using the same method as Synthesis Example A-4-8.
다음으로, 중간체 화합물 A-4-4 (15g, 55.6 mmol)와 amine25 (21.3g, 58.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(23.1g, 166.8 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3g, 0.6 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 25를 22.8g 제조하였다. (수율 74%, MS:[M+H]+=555)Next, intermediate compound A-4-4 (15g, 55.6 mmol) and amine25 (21.3g, 58.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (23.1 g, 166.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.8 g of Compound 25. (Yield 74%, MS:[M+H] + =555)
합성예 26 : 화합물 26의 제조Synthesis Example 26: Preparation of Compound 26
Figure PCTKR2022019072-appb-img-000066
Figure PCTKR2022019072-appb-img-000066
먼저, 합성예 A-2-4에서 출발물질로 (3-(메틸티오)이소퀴놀린-4-일)보론산 대신 (7-(메틸티오)이소퀴놀린-8-일)보론산을 사용한 것을 제외하고는, 합성예 A-2-4과 동일한 방법을 사용하여 중간체 화합물 A-2-8을 제조하였다.First, in Synthesis Example A-2-4, except that (7-(methylthio)isoquinolin-8-yl)boronic acid was used instead of (3-(methylthio)isoquinolin-4-yl)boronic acid as a starting material. Then, the intermediate compound A-2-8 was prepared using the same method as Synthesis Example A-2-4.
다음으로, 중간체 화합물 A-2-8 (15g, 55.6 mmol)와 amine26 (23.1g, 58.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(23.1g, 166.8 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3g, 0.6 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 26를 22.4g 제조하였다. (수율 69%, MS:[M+H]+=585)Next, intermediate compound A-2-8 (15g, 55.6 mmol) and amine26 (23.1g, 58.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (23.1 g, 166.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.4 g of compound 26. (Yield 69%, MS:[M+H] + =585)
합성예 27 : 화합물 27의 제조Synthesis Example 27: Preparation of Compound 27
Figure PCTKR2022019072-appb-img-000067
Figure PCTKR2022019072-appb-img-000067
먼저, 합성예 A-2-2에서 출발물질로 4-브로모-2-클로로피리딘 대신 3-브로모-5-클로로피리딘을 사용한 것을 제외하고는, 합성예 A-2-2과 동일한 방법을 사용하여 중간체 화합물 A-2-3을 제조하였다.First, the same method as in Synthesis Example A-2-2 was carried out, except that 3-bromo-5-chloropyridine was used instead of 4-bromo-2-chloropyridine as a starting material in Synthesis Example A-2-2. Intermediate compound A-2-3 was prepared using
다음으로, 중간체 화합물 A-2-3 (15g, 55.6 mmol)와 amine27 (22.1g, 58.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(23.1g, 166.8 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3g, 0.6 mmol)을 투입하였다. 4 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 27를 19.9g 제조하였다. (수율 63%, MS:[M+H]+=569)Next, intermediate compound A-2-3 (15g, 55.6 mmol) and amine27 (22.1g, 58.4 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (23.1 g, 166.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.9 g of Compound 27. (Yield 63%, MS:[M+H] + =569)
합성예 28 : 화합물 28의 제조Synthesis Example 28: Preparation of Compound 28
Figure PCTKR2022019072-appb-img-000068
Figure PCTKR2022019072-appb-img-000068
먼저, 합성예 A-4-3에서 출발물질로 4-브로모-2-클로로피리딘 대신 3-브로모-5-클로로피리딘을 사용한 것을 제외하고는, 합성예 A-4-3과 동일한 방법을 사용하여 중간체 화합물 A-4-2을 제조하였다.First, the same method as in Synthesis Example A-4-3 was performed, except that 3-bromo-5-chloropyridine was used instead of 4-bromo-2-chloropyridine as a starting material in Synthesis Example A-4-3. Intermediate compound A-4-2 was prepared using
다음으로, 중간체 화합물 A-4-2 (15g, 55.6 mmol)와 amine28 (23.1g, 58.4 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트 (23.1g, 166.8 mmol)를 물 100 ml에 녹여 투입하고 충분히 교반한 후 비스(트리-tert-부틸포스핀)팔라듐(0) (0.3g, 0.6 mmol)을 투입하였다. 3 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 28를 21.8g 제조하였다. (수율 67%, MS:[M+H]+=585)Next, intermediate compound A-4-2 (15g, 55.6 mmol) and amine28 (23.1g, 58.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (23.1g, 166.8 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8 g of compound 28. (Yield 67%, MS:[M+H] + =585)
비교예 1Comparative Example 1
ITO(indium tin oxide)가 1,000Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀러포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다.A glass substrate coated with ITO (indium tin oxide) to a thickness of 1,000 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a Fischer Co. product was used as the detergent, and distilled water filtered through a second filter of a Millipore Co. product was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.
이렇게 준비된 ITO 투명 전극 위에 정공주입층으로 하기 HI-1 화합물을 1150Å의 두께로 형성하되 하기 A-1 화합물을 1.5% 농도로 p-도핑 하였다. 상기 정공주입층 위에 하기 HT-1 화합물을 진공 증착하여 막 두께 800Å의 정공수송층을 형성하였다. 이어서, 상기 정공수송층 위에 막 두께 150Å으로 하기 EB-1 화합물을 진공 증착하여 전자저지층을 형성하였다. 이어서, 상기 EB-1 증착막 위에 하기 RH-1 화합물과 하기 Dp-39 화합물을 98:2의 중량비로 진공 증착하여 400Å 두께의 적색 발광층을 형성하였다. 상기 발광층 위에 막 두께 30Å으로 하기 HB-1 화합물을 진공 증착하여 정공저지층을 형성하였다. 이어서, 상기 정공저지층 위에 하기 ET-1 화합물과 하기 LiQ 화합물을 2:1의 중량비로 진공 증착하여 300Å의 두께로 전자 주입 및 수송층을 형성하였다. 상기 전자 주입 및 수송층 위에 순차적으로 12Å 두께로 리튬플로라이드(LiF)와 1,000Å 두께로 알루미늄을 증착하여 음극을 형성하였다. The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5%. A hole transport layer having a thickness of 800 Å was formed by vacuum depositing the following HT-1 compound on the hole injection layer. Subsequently, an electron blocking layer was formed by vacuum depositing the following EB-1 compound to a film thickness of 150 Å on the hole transport layer. Subsequently, the following RH-1 compound and the following Dp-39 compound were vacuum-deposited on the EB-1 deposited film in a weight ratio of 98:2 to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed on the light emitting layer by vacuum depositing the HB-1 compound to a film thickness of 30 Å. 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. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.
상기의 과정에서 유기물의 증착속도는 0.4~0.7Å/sec를 유지하였고, 음극의 리튬플로라이드는 0.3Å/sec, 알루미늄은 2Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 2×10-7 ~ 5×10-6 torr를 유지하여, 유기 발광 소자를 제작하였다.In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å/sec, the deposition rate of lithium fluoride on the cathode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum level during deposition was 2×10 - Maintaining 7 to 5×10 −6 torr, an organic light emitting device was fabricated.
Figure PCTKR2022019072-appb-img-000069
Figure PCTKR2022019072-appb-img-000069
비교예 2 내지 6Comparative Examples 2 to 6
적색 발광층 호스트 재료로서 RH-1 대신, 하기 화합물 RH-2 내지 RH-6을 각각 사용한 것을 제외하고는 비교예 1과 동일하게 실시하고 소자 성능을 측정하였다.Device performance was measured in the same manner as in Comparative Example 1, except that the following compounds RH-2 to RH-6 were used instead of RH-1 as a host material for the red light emitting layer.
Figure PCTKR2022019072-appb-img-000070
Figure PCTKR2022019072-appb-img-000070
<실시예 1 내지 28><Examples 1 to 28>
적색 발광층 호스트 재료로서 비교예 1 대신 합성예에 의해 제조된 화합물 1 내지 28를 각각 사용한 것을 제외하고는 비교예 1과 동일하게 실시하고 소자 성능을 측정하였다.Device performance was measured in the same manner as in Comparative Example 1, except that Compounds 1 to 28 prepared by Synthesis Example were used instead of Comparative Example 1 as the host material for the red light emitting layer.
상기 비교예 1 내지 6 및 실시예 1 내지 28와 같이 각각의 화합물을 적색 호스트 물질로 사용하여 제조한 유기 발광 소자에 대하여 구동전압, 전류효율 및 수명을 측정하였고, 그 결과를 하기 표 1에 나타내었다.As in Comparative Examples 1 to 6 and Examples 1 to 28, the driving voltage, current efficiency and lifespan of the organic light emitting device prepared using each compound as a red host material were measured, and the results are shown in Table 1 below. was
실험예Experimental example 호스트 물질host substance 구동전압
(V)drive voltage
(V) 		전류효율
(cd/A)current efficiency
(cd/A) 		수명
(T95%@10mA, hr)life span
(T95%@10mA, hr)
비교예 1Comparative Example 1 RH-1RH-1 5.625.62 14.0014.00 5050
비교예 2Comparative Example 2 RH-2RH-2 5.635.63 13.4513.45 6565
비교예 3Comparative Example 3 RH-3RH-3 5.815.81 13.7113.71 6666
비교예 4Comparative Example 4 RH-4RH-4 5.715.71 13.5113.51 5757
비교예 5Comparative Example 5 RH-5RH-5 5.895.89 12.6212.62 6868
비교예 6Comparative Example 6 RH-6RH-6 5.715.71 12.5512.55 6060
실시예 1Example 1 화합물 1compound 1 4.124.12 23.9923.99 180180
실시예 2Example 2 화합물 2compound 2 4.234.23 24.8724.87 196196
실시예 3Example 3 화합물 3compound 3 4.054.05 24.5624.56 176176
실시예 4Example 4 화합물 4compound 4 4.014.01 23.2923.29 198198
실시예 5Example 5 화합물 5compound 5 4.104.10 23.1423.14 198198
실시예 6Example 6 화합물 6compound 6 4.134.13 23.2323.23 174174
실시예 7Example 7 화합물 7compound 7 4.324.32 24.3624.36 182182
실시예 8Example 8 화합물 8compound 8 4.214.21 25.6625.66 188188
실시예 9Example 9 화합물 9compound 9 4.124.12 25.5925.59 181181
실시예 10Example 10 화합물 10compound 10 4.174.17 23.8423.84 189189
실시예 11Example 11 화합물 11compound 11 4.204.20 25.7725.77 190190
실시예 12Example 12 화합물 12compound 12 4.314.31 25.8425.84 195195
실시예 13Example 13 화합물 13compound 13 4.264.26 25.9125.91 182182
실시예 14Example 14 화합물 14compound 14 4.294.29 26.2626.26 180180
실시예 15Example 15 화합물 15compound 15 4.314.31 25.9025.90 191191
실시예 16Example 16 화합물 16compound 16 4.154.15 24.9924.99 199199
실시예 17Example 17 화합물 17compound 17 4.064.06 23.9623.96 188188
실시예 18Example 18 화합물 18compound 18 4.114.11 23.8823.88 200200
실시예 19Example 19 화합물 19compound 19 4.324.32 24.9624.96 189189
실시예 20Example 20 화합물 20compound 20 4.164.16 25.0825.08 180180
실시예 21Example 21 화합물 21compound 21 4.064.06 23.7723.77 185185
실시예 22Example 22 화합물 22compound 22 4.014.01 25.6225.62 186186
실시예 23Example 23 화합물 23compound 23 4.194.19 24.3924.39 191191
실시예 24Example 24 화합물 24compound 24 4.104.10 24.6524.65 195195
실시예 25Example 25 화합물 25compound 25 4.154.15 25.0125.01 199199
실시예 26Example 26 화합물 26compound 26 4.314.31 25.6825.68 203203
실시예 27Example 27 화합물 27compound 27 4.224.22 24.1724.17 192192
실시예 28Example 28 화합물 28compound 28 4.284.28 26.3326.33 195195
상기 표 1을 참조하면, 적색 호스트 물질로 상기 화학식 1로 표시되는 화합물을 사용한 실시예의 유기 발광 소자는, 이와는 상이한 구조를 가지는 화합물을 사용한 비교예의 유기 발광 소자에 비하여 감소된 구동전압 및 향상된 효율 및 수명 특성을 나타냄을 알 수 있다.Referring to Table 1, the organic light emitting device of the embodiment using the compound represented by Formula 1 as a red host material has a reduced driving voltage and improved efficiency and It can be seen that the lifetime characteristics are indicated.
[부호의 설명][Description of code]
1: 기판 2: 양극1: substrate 2: anode
3: 발광층 4: 음극3: light emitting layer 4: cathode
5: 정공주입층 6: 정공수송층5: hole injection layer 6: hole transport layer
7: 발광층 8: 전자주입 및 수송층7: light emitting layer 8: electron injection and transport layer

Claims (12)

  1. 하기 화학식 1로 표시되는 화합물:A compound represented by Formula 1 below:
    [화학식 1][Formula 1]
    Figure PCTKR2022019072-appb-img-000071
    Figure PCTKR2022019072-appb-img-000071
    상기 화학식 1에서,In Formula 1,
    X1 내지 X4 중 하나는 CR이고, 나머지는 각각 독립적으로 N, 또는 CR’이고, One of X 1 to X 4 is CR, and the others are each independently N or CR';
    여기서 R은 하기 화학식 2로 표시되는 치환기이고, Here, R is a substituent represented by Formula 2 below,
    X5 내지 X10은 각각 독립적으로 N, 또는 CR’이고,X 5 to X 10 are each independently N or CR';
    단, X1 내지 X10 중 하나는 N이고, However, one of X 1 to X 10 is N,
    R’은 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이고,R' are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
    [화학식 2][Formula 2]
    Figure PCTKR2022019072-appb-img-000072
    Figure PCTKR2022019072-appb-img-000072
    상기 화학식 2에서, In Formula 2,
    L1는 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴렌이고,L 1 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
    L2는 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴렌이고,L 2 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
    L3는 직접 결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴렌이고,L 3 is a direct bond; Substituted or unsubstituted C 6-60 arylene; Or a C 2-60 heteroarylene containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
    Ar1은 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이고,Ar 1 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
    Ar2는 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이다.Ar 2 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
  2. 제1항에 있어서, According to claim 1,
    X1 내지 X4 중 하나는 CR이고, 다른 하나는 N이고, 나머지는 각각 독립적으로 CR’이고, X5 내지 X10은 각각 독립적으로 CR’이거나; 또는One of X 1 to X 4 is CR, the other is N, the others are each independently CR', and X 5 to X 10 are each independently CR'; or
    X1 내지 X4 중 하나는 CR이고, 나머지는 각각 독립적으로 CR’이고, X5 내지 X10 중 하나는 N이고, 나머지는 각각 독립적으로 CR’인,One of X 1 to X 4 is CR, the others are each independently CR', one of X 5 to X 10 is N, and the others are each independently CR',
    화합물.compound.
  3. 제1항에 있어서, According to claim 1,
    R’는 모두 수소이거나; 또는 모두 중수소인,R' are all hydrogen; or all deuterium;
    화합물.compound.
  4. 제1항에 있어서, According to claim 1,
    L1은 직접 결합; 또는 페닐렌이고,L 1 is a direct bond; or phenylene;
    L1이 페닐렌인 경우, 비치환되거나 또는 1개 이상의 중수소로 치환되는,when L 1 is phenylene, unsubstituted or substituted with one or more deuterium;
    화합물.compound.
  5. 제1항에 있어서, According to claim 1,
    L2는 직접 결합; 페닐렌; 나프틸렌; 비페닐릴렌; 9,9-디메틸-플루오레닐렌; 또는 9,9-디페닐-플루오레닐렌이고,L 2 is a direct bond; phenylene; naphthylene; biphenylylene; 9,9-dimethyl-fluorenylene; or 9,9-diphenyl-fluorenylene;
    L2가 페닐렌; 나프틸렌; 비페닐릴렌; 9,9-디메틸-플루오레닐렌; 또는 9,9-디페닐-플루오레닐렌인 경우, 이들은 비치환되거나 또는 1개 이상의 중수소로 치환되는,L 2 is phenylene; naphthylene; biphenylylene; 9,9-dimethyl-fluorenylene; or 9,9-diphenyl-fluorenylene, which are unsubstituted or substituted with one or more deuterium,
    화합물.compound.
  6. 제1항에 있어서, According to claim 1,
    L3는 직접 결합; 페닐렌; 나프틸렌; 비페닐릴렌; 9,9-디메틸-플루오레닐렌; 또는 9,9-디페닐-플루오레닐렌이고,L 3 is a direct bond; phenylene; naphthylene; biphenylylene; 9,9-dimethyl-fluorenylene; or 9,9-diphenyl-fluorenylene;
    L3가 페닐렌; 나프틸렌; 비페닐릴렌; 9,9-디메틸-플루오레닐렌; 또는 9,9-디페닐-플루오레닐렌인 경우, 이들은 비치환되거나 또는 1개 이상의 중수소로 치환되는,L 3 is phenylene; naphthylene; biphenylylene; 9,9-dimethyl-fluorenylene; or 9,9-diphenyl-fluorenylene, which are unsubstituted or substituted with one or more deuterium,
    화합물.compound.
  7. 제1항에 있어서, According to claim 1,
    Ar1은 페닐; 비페닐릴; 터페닐릴; 나프틸; 페난쓰레닐; 9,9-디메틸-플루오레닐; 9,9-디페닐-플루오레닐; 디벤조퓨라닐; 디벤조티오페닐; 9-페닐-카바졸일; 또는 9,9’-스피로비[9H-플루오렌]일이고,Ar 1 is phenyl; biphenylyl; terphenylyl; naphthyl; phenanthrenyl; 9,9-dimethyl-fluorenyl; 9,9-diphenyl-fluorenyl; dibenzofuranyl; dibenzothiophenyl; 9-phenyl-carbazolyl; or 9,9'-spirobi[9H-fluorene]yl;
    Ar1은 비치환되거나 1개 이상의 중수소로 치환되는,Ar 1 is unsubstituted or substituted with one or more deuterium;
    화합물.compound.
  8. 제1항에 있어서, According to claim 1,
    Ar2은 페닐; 비페닐릴; 터페닐릴; 나프틸; 페난쓰레닐; 9,9-디메틸-플루오레닐; 9,9-디페닐-플루오레닐; 디벤조퓨라닐; 디벤조티오페닐; 9-페닐-카바졸일; 또는 9,9’-스피로비[9H-플루오렌]일인,Ar 2 is phenyl; biphenylyl; terphenylyl; naphthyl; phenanthrenyl; 9,9-dimethyl-fluorenyl; 9,9-diphenyl-fluorenyl; dibenzofuranyl; dibenzothiophenyl; 9-phenyl-carbazolyl; or 9,9'-spirobi[9H-fluorene]yl;
    Ar2은 비치환되거나 1개 이상의 중수소로 치환되는,Ar 2 is unsubstituted or substituted with one or more deuterium;
    화합물.compound.
  9. 제1항에 있어서, According to claim 1,
    상기 화합물은 하기 화학식 1-1 내지 1-4 중 어느 하나로 표시되는, The compound is represented by any one of Formulas 1-1 to 1-4,
    화합물:compound:
    [화학식 1-1][Formula 1-1]
    Figure PCTKR2022019072-appb-img-000073
    Figure PCTKR2022019072-appb-img-000073
    상기 화학식 1-1에서,In Formula 1-1,
    X2 내지 X10 중 하나는 N이고, 나머지는 CR’이고,One of X 2 to X 10 is N and the other is CR';
    L1 내지 L3, Ar1, Ar2 및 R’는 제1항에서 정의한 바와 같고,L 1 to L 3 , Ar 1 , Ar 2 and R' are as defined in claim 1,
    [화학식 1-2][Formula 1-2]
    Figure PCTKR2022019072-appb-img-000074
    Figure PCTKR2022019072-appb-img-000074
    상기 화학식 1-2에서,In Formula 1-2,
    X1 및 X3 내지 X10 중 하나는 N이고, 나머지는 CR’이고,One of X 1 and X 3 to X 10 is N and the other is CR';
    L1 내지 L3, Ar1 및 Ar2 및 R’는 제1항에서 정의한 바와 같고,L 1 to L 3 , Ar 1 and Ar 2 and R' are as defined in claim 1,
    [화학식 1-3][Formula 1-3]
    Figure PCTKR2022019072-appb-img-000075
    Figure PCTKR2022019072-appb-img-000075
    상기 화학식 1-3에서.In Formula 1-3 above.
    X1, X2 및 X4 내지 X10 중 하나는 N이고, 나머지는 CR’이고,One of X 1 , X 2 and X 4 to X 10 is N and the other is CR';
    L1 내지 L3, Ar1 및 Ar2 및 R’는 제1항에서 정의한 바와 같고,L 1 to L 3 , Ar 1 and Ar 2 and R' are as defined in claim 1,
    [화학식 1-4][Formula 1-4]
    Figure PCTKR2022019072-appb-img-000076
    Figure PCTKR2022019072-appb-img-000076
    상기 화학식 1-4에서,In Chemical Formulas 1-4,
    X1 내지 X3 및 X5 내지 X10 중 하나는 N이고, 나머지는 CR’이고,One of X 1 to X 3 and X 5 to X 10 is N and the other is CR';
    L1 내지 L3, Ar1 및 Ar2 및 R’는 제1항에서 정의한 바와 같다.L 1 to L 3 , Ar 1 and Ar 2 and R' are as defined in claim 1.
  10. 제1항에 있어서, According to 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 PCTKR2022019072-appb-img-000077
    Figure PCTKR2022019072-appb-img-000077
    Figure PCTKR2022019072-appb-img-000078
    Figure PCTKR2022019072-appb-img-000078
    Figure PCTKR2022019072-appb-img-000079
    Figure PCTKR2022019072-appb-img-000079
    Figure PCTKR2022019072-appb-img-000080
    Figure PCTKR2022019072-appb-img-000080
    Figure PCTKR2022019072-appb-img-000081
    Figure PCTKR2022019072-appb-img-000081
    Figure PCTKR2022019072-appb-img-000082
    Figure PCTKR2022019072-appb-img-000082
    Figure PCTKR2022019072-appb-img-000083
    Figure PCTKR2022019072-appb-img-000083
    Figure PCTKR2022019072-appb-img-000084
    Figure PCTKR2022019072-appb-img-000084
    Figure PCTKR2022019072-appb-img-000085
    Figure PCTKR2022019072-appb-img-000085
    Figure PCTKR2022019072-appb-img-000086
    Figure PCTKR2022019072-appb-img-000086
    Figure PCTKR2022019072-appb-img-000087
    Figure PCTKR2022019072-appb-img-000087
    Figure PCTKR2022019072-appb-img-000088
    Figure PCTKR2022019072-appb-img-000088
    Figure PCTKR2022019072-appb-img-000089
    Figure PCTKR2022019072-appb-img-000089
    Figure PCTKR2022019072-appb-img-000090
    Figure PCTKR2022019072-appb-img-000090
    Figure PCTKR2022019072-appb-img-000091
    Figure PCTKR2022019072-appb-img-000091
    Figure PCTKR2022019072-appb-img-000092
    Figure PCTKR2022019072-appb-img-000092
    Figure PCTKR2022019072-appb-img-000093
    Figure PCTKR2022019072-appb-img-000093
  11. 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층은 제1항 내지 제10항 중 어느 하나의 항에 따른 화합물을 포함하는 것인, 유기 발광 소자.a first electrode; a second electrode provided to face the first electrode; and an organic material layer provided between the first electrode and the second electrode, wherein the organic material layer includes the compound according to any one of claims 1 to 10. .
  12. 제11항에 있어서, According to claim 11,
    상기 화합물을 포함하는 유기물층은 발광층인,The organic material layer containing the compound is a light emitting layer,
    유기 발광 소자.organic light emitting device.
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KR20160001702A (en) * 2014-06-27 2016-01-06 희성소재 (주) Hetero-cyclic compound and organic light emitting device using the same
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