WO2021033980A1 - 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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WO2021033980A1
WO2021033980A1 PCT/KR2020/010538 KR2020010538W WO2021033980A1 WO 2021033980 A1 WO2021033980 A1 WO 2021033980A1 KR 2020010538 W KR2020010538 W KR 2020010538W WO 2021033980 A1 WO2021033980 A1 WO 2021033980A1
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group
compound
substituted
unsubstituted
formula
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PCT/KR2020/010538
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Korean (ko)
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서상덕
이동훈
김민준
김영석
김동희
오중석
김서연
이다정
최승원
심재훈
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주식회사 엘지화학
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Priority claimed from KR1020200099129A external-priority patent/KR102455462B1/en
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Priority to CN202080019642.XA priority Critical patent/CN113544133B/en
Publication of WO2021033980A1 publication Critical patent/WO2021033980A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a novel compound and an organic light emitting device comprising the same.
  • the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material.
  • An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.
  • the organic light emitting device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode.
  • the organic material layer is often made of a multi-layered structure made of different materials in order to increase the efficiency and stability of the organic light-emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
  • a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.
  • the present invention provides a material for a novel organic light-emitting device that can be used in an organic light-emitting device and at the same time in a solution process.
  • Patent Document 1 Korean Patent Publication No. 10-2000-0051826
  • the present invention relates to a novel compound and an organic light emitting device comprising the same.
  • the present invention provides a compound represented by the following formula 1:
  • X is O or S
  • L is a single bond; Substituted or unsubstituted C 6-60 arylene; C 2-60 heteroarylene containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S; and,
  • R 1 , R 2 , R 3 , and R 4 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 1-60 alkoxy; Substituted or unsubstituted C 2-60 alkenyl; Substituted or unsubstituted C 2-60 alkynyl; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 6-60 aryl; C 2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S; Substituted or unsubstituted tri(C 1-60 alkyl)silyl; Or a substituted or unsubstituted tri(C 6-60 aryl)silyl, or two adjacent substituents are bonded to form a C 6-60 aromatic
  • n1 is an integer from 0 to 2
  • n2 to n4 are each independently an integer of 0 to 3
  • Ar 1 is represented by the following formula (2),
  • Ar 2 is substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S; and,
  • V 1 to V 4 are each independently CR a or N,
  • W 1 and W 2 are each independently a single bond, CR b , O or S,
  • R a and R b are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S; Or, or two adjacent R a , or two adjacent R b are bonded to each other to C 6- 60 forms an aromatic ring,
  • p is an integer of 0 or 1.
  • the present invention the first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound represented by Formula 1, wherein the organic light-emitting device comprises: to provide.
  • the compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an organic light-emitting device, and may improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light-emitting device.
  • FIG. 1 shows an example of an organic light emitting device comprising 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 comprising 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 refers to 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; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituent
  • a substituent to which two or more substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group, or may be interpreted as a substituent to which two phenyl groups are connected.
  • the number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the ester group may be substituted with an oxygen of the ester group with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms.
  • it may be a compound of the following structural formula, but is not limited thereto.
  • the number of carbon atoms of the imide group is not particularly limited, but it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.
  • the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, but is not limited thereto.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms.
  • alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhex
  • the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.
  • the cycloalkyl group is not particularly limited, but is preferably 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms.
  • the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms.
  • the aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.
  • the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.
  • Etc When the fluorenyl group is substituted, Etc.
  • Etc it is not limited thereto.
  • heteroaryl is a heteroaryl containing at least one of O, N, Si, and S as a heterogeneous element, and the number of carbons is not particularly limited, but is preferably 2 to 60 carbon atoms.
  • heteroaryl include xanthene, thioxanthen, thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, Pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino Pyrazinyl group, isoquinoline group
  • the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the example of the aryl group described above.
  • the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group.
  • heteroaryl among heteroarylamines the above-described description of heteroaryl may be applied.
  • the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above.
  • the description of the aryl group described above may be applied except that the arylene is a divalent group.
  • the description of the above-described heteroaryl may be applied except that the heteroarylene is a divalent group.
  • the hydrocarbon ring is not a monovalent group, and the description of the aryl group or the cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents.
  • the heteroaryl is not a monovalent group, and the description of the above-described heteroaryl may be applied except that two substituents are bonded to each other.
  • the present invention provides a compound represented by Chemical Formula 1.
  • L is a single bond.
  • R 1 , R 2 , R 3 and R 4 are hydrogen. At this time, preferably, n1 to n4 are 0.
  • one of R 1 , R 2 , R 3 and R 4 is phenyl or pyridinyl and the other is hydrogen.
  • one of n1 to n4 is 1, and the others are 0.
  • two adjacent R 1 , two adjacent R 2 , two adjacent R 3 , or two adjacent R 4 are bonded to each other to form a benzene ring, and the remaining R 1 to R 4 are hydrogen.
  • Ar 1 is preferably any one selected from the group consisting of the following Formulas 2-1 to 2-3:
  • Ar 2 is as defined in Formula 1,
  • R a1 , R a2 and R a3 are each independently hydrogen or deuterium; Or two adjacent R a1 , two adjacent R a2 , or two adjacent R a3 bonded to each other to form a benzene ring, and the rest is hydrogen,
  • Each R b1 is independently hydrogen or deuterium
  • W 3 and W 4 are each independently O or S,
  • p is an integer of 0 or 1.
  • Ar 1 is any one selected from the group consisting of:
  • Ar 2 is as defined in Chemical Formula 1,
  • W 3 and W 4 are each independently O or S.
  • Ar 2 is phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, di Benzothiophenyl, carbazol-9-yl, or 9-phenyl-carbazolyl, and Ar 2 is unsubstituted or substituted with one or more deuterium.
  • the present invention provides a method for preparing a compound represented by Formula 1, such as the following Scheme 1 as an example:
  • X, L, and Ar 2 are as defined in Formula 1
  • Y 1 and Y 2 are each independently a halogen group such as chloro or boromo
  • Z is a boronic acid group, a boronic acid ester group, or It is a boron-containing organic group such as a boronic acid pinacol ester group
  • Ar 1 ′ is a substituent having the following structure
  • V 1 to V 4 , W 1 and W 2 are as defined in Formula 1.
  • compound (1) of Formula 1 is a palladium-catalyzed coupling reaction between a compound (i) having a parental structure and a compound (ii) including an electron acceptor substituent bonded to the parental structure, and compound (iii) Manufacturing a; And it can be prepared by a production method comprising the step of subjecting the compound (iii) to a Suzuki coupling reaction in the presence of a compound (iv) containing an organic group containing boron and a base and a palladium catalyst.
  • the palladium catalyzed coupling reaction and the Suzuki coupling reaction may be carried out in the presence of a base, and at this time, the base is sodium tert-butoxide, potassium tert-butoxide. -butoxide), sodium tert-pentoxide, sodium ethoxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride hydride), lithium hydride, or potassium hydride;
  • Organic bases such as tetraethylammonium hydroxide ((Et 4 NOH), bis(tetraethylammonium) carbonate, triethylamine; inorganic salts such as cesium fluoride, and any one or a mixture of two or more of them may be used.
  • I can.
  • the palladium catalyzed coupling reaction may be performed in an organic solvent, and the Suzuki coupling reaction may be performed in water as a solvent.
  • organic solvent diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol diethyl ether, dimethoxyethane, bis(2-methoxyethyl) ether, diethylene glycol diethyl ether, tetrahydro Ether solvents such as furan or anisole; Aromatic hydrocarbon-based solvents such as benzene, toluene or xylene; Halogenated aromatic solvents such as chlorobenzene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylimidazolidone or acetonitrile; Or a sulfoxide-based solvent such as dimethyl sulfoxide (DMSO), and any one or a mixture of two or more of them may be used.
  • DMSO dimethyl sulfoxide
  • reactants used in the preparation of compound (1) of Formula 1 may be prepared by using a conventional organic reaction, or may be obtained and used commercially.
  • the compound (i) having the parental structure may be prepared in the same manner as in Scheme 2 below.
  • Reaction Scheme 2 below is only an example for explaining the present invention, but the present invention is not limited thereto.
  • X is O or S
  • Y is a halogen group such as bromo
  • the present invention provides an organic light-emitting device including the compound represented by Chemical Formula 1.
  • 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 contains the compound according to the present invention.
  • 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 comprising a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
  • the compound represented by Formula 1 may be included in the emission layer.
  • the compound represented by Formula 1 may be included in the hole injection layer, the hole transport layer, or the emission layer.
  • an electron blocking layer (not shown) may be further included between the hole transport layer and the emission layer, and a hole blocking layer (not shown) may be further included between the emission layer and the electron injection and transport layer.
  • the organic light emitting device according to the present invention can be manufactured using materials and methods known in the art, except for using the compound according to the present invention.
  • the organic light-emitting device may be manufactured by sequentially laminating an anode, an organic material layer, and a cathode on a substrate.
  • the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate.
  • an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron injection and transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon.
  • an organic light-emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890).
  • the manufacturing method is not limited thereto.
  • an organic light-emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890).
  • the manufacturing method is not limited thereto.
  • the first electrode is an anode
  • the second electrode is a cathode
  • the first electrode is a cathode
  • the second electrode is an anode
  • the cathode material a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer.
  • the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide 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 a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO 2 /Al, but are not limited thereto.
  • the hole injection layer is a layer that injects holes from an electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for a light emitting layer or a light emitting material.
  • a compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable.
  • the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances.
  • the hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the emission layer
  • the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission layer, and has high mobility for holes.
  • the material is suitable. Specific examples include an arylamine-based organic material, a conductive compound, and a block copolymer having a conjugated portion and a non-conjugated portion, but are not limited thereto.
  • the organic light emitting device may further include an electron blocking layer selectively on the hole transport layer.
  • the electron blocking layer is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons, thereby increasing the probability of hole-electron coupling, thereby increasing the efficiency of the organic light-emitting device. It refers to the layer that plays a role in improving the value.
  • the electron blocking layer includes an electron blocking material, and an arylamine-based organic material may be used as an example of the electron blocking material, but is not limited thereto.
  • the emission layer may include a host material and a dopant material.
  • Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds
  • heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.
  • the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group
  • the styrylamine compound is substituted or unsubstituted
  • the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group
  • the styrylamine compound is substituted or unsubstituted
  • at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting
  • the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.
  • the organic light emitting device may further include a hole blocking layer selectively on the emission layer.
  • the hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to improve the efficiency of the organic light emitting device by increasing the probability of hole-electron coupling by controlling electron mobility and preventing excessive movement of holes. It means the layer that plays a role.
  • the hole-blocking layer includes a hole-blocking material, and examples of the hole-blocking material include: a subazine derivative including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; A compound into which an electron withdrawing group such as a phosphine oxide derivative has been introduced may be used, but is not limited thereto.
  • An electron transport layer is formed on the emission layer or on the hole blocking layer.
  • the electron transport layer is a layer that receives electrons from the cathode or an electron injection layer to be described later and transports electrons to the emission layer.
  • As an electron transport material electrons are well injected from the cathode and can be transferred to the emission layer. Larger materials are suitable. Specific examples include pyridine derivatives; Pyrimidine derivatives; Triazole derivatives; Al complex of 8-hydroxyquinoline; Complexes containing Alq 3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
  • the electron injection layer is a layer located between the electron transport layer and the cathode to inject electrons from the cathode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect for the light emitting layer or the light emitting material. It has, and prevents the movement of excitons generated in the light-emitting layer to the hole injection layer, and also, a compound excellent in the ability to form a thin film is preferable.
  • the metal complex compound examples include lithium 8-hydroxyquinolinato, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.
  • the electron transport layer and the electron injection layer may be provided in the form of an electron transport layer for transporting received electrons to the light emitting layer and an electron injection and transport layer that simultaneously functions as an electron injection layer.
  • the organic light emitting device may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.
  • the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
  • Dibenzo[b,d]furan-1-ylboronic acid (25.0g, 117.9mmol) and 1-bromo-2-nitronaphthalene (32.7g, 129.7mmol) were dissolved in Tetrahydrofuran (THF) 255ml, and in the resulting mixed solution, A solution in which potassium carbonate (65.2 g, 471.7 mmol) was dissolved in 125 ml of H 2 O was added.
  • tetrakis(triphenylphosphine)palladium(0) Pd(PPh 3 ) 4 , 6.8g, 5.9mmol
  • a glass substrate on which ITO (Indium Tin Oxide) was deposited to a thickness of 1,400 ⁇ was put in distilled water dissolved in a detergent and washed with ultrasonic waves.
  • a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured by Millipore Co. was used as distilled water.
  • ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.
  • the following HI-A and hexaazatriphenylene (HAT-CN) were sequentially thermally vacuum deposited to a thickness of 800 ⁇ and 50 ⁇ , respectively, to form a hole injection layer.
  • the following HT-A was vacuum-deposited to a thickness of 800 ⁇ as a hole transport layer
  • EB-A was thermally vacuum-deposited to a thickness of 600 ⁇ as an electron blocking layer thereon.
  • the following host RH-A and dopant RD were mixed at a weight ratio of 98:2 and then vacuum deposited to a thickness of 400 ⁇ to form a light emitting layer.
  • ET-A and Liq were mixed at a weight ratio of 1:1 and thermally vacuum deposited to a thickness of 360 ⁇ , and Liq was vacuum deposited thereon to a thickness of 5 ⁇ to form an electron injection layer.
  • magnesium and silver were sequentially mixed at a weight ratio of 10:1 and deposited to a thickness of 220 ⁇ , and aluminum was deposited thereon to a thickness of 1000 ⁇ to form a cathode, thereby manufacturing an organic light-emitting device.
  • LT97 driving voltage, current efficiency, and lifetime
  • Example 1 Compound 1 4.54 22.5 110 Example 2 Compound 2 4.53 22.3 121 Example 3 Compound 3 4.56 22.0 123 Example 4 Compound 4 4.61 22.8 111 Example 5 Compound 5 4.58 22.1 108 Example 6 Compound 6 4.53 21.3 97 Example 7 Compound 7 4.56 22.6 101 Example 8 Compound 8 4.76 23.1 106 Example 9 Compound 9 4.71 23.0 104 Example 10 Compound 10 4.73 23.3 108 Example 11 Compound 11 4.58 22.1 132 Example 12 Compound 12 4.65 22.9 95 Comparative Example 1 RH-A 5.10 18.3 65 Comparative Example 2 RH-B 5.15 20.9 83 Comparative Example 3 RH-C 5.81 12.3 46
  • Compounds RH-B and RH-C used in Comparative Examples 2 and 3 are compounds each having the following structure.
  • the compound represented by Formula 1 has a structure in which the structure of Formula 2 serves as an electron acceptor and a parental structure that serves as an electron donor are connected.
  • the parental structure serving as an electron donor exhibits high stability by condensing both benzocarbazole and benzofuran or benzothiophene to form a ring.
  • the structure in which the unit serving as an electron acceptor has two nitrogen atoms facing each other in the form of pyrazine, as in the structure of Formula 2, has a stronger electron pulling property than the quinazoline structure applied in the Comparative Example. Show.
  • substrate 2 anode

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Abstract

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

Description

신규한 화합물 및 이를 이용한 유기 발광 소자Novel compound and organic light emitting device using the same
관련 출원(들)과의 상호 인용Cross-reference with related application(s)
본 출원은 2019년 8월 20일자 한국 특허 출원 제10-2019-0101898호 및 2020년 8월 7일자 한국 특허 출원 제10-2020-0099129호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0101898 filed on August 20, 2019 and Korean Patent Application No. 10-2020-0099129 filed on August 7, 2020. All contents disclosed in the literature 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 comprising the same.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 넓은 시야각, 우수한 콘트라스트, 빠른 응답 시간을 가지며, 휘도, 구동 전압 및 응답 속도 특성이 우수하여 많은 연구가 진행되고 있다. In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.
유기 발광 소자는 일반적으로 양극과 음극 및 상기 양극과 음극 사이에 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. The organic light emitting device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure made of different materials in order to increase the efficiency and stability of the organic light-emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.
상기와 같은 유기 발광 소자에 사용되는 유기물에 대하여 새로운 재료의 개발이 지속적으로 요구되고 있다.Development of new materials for organic materials used in organic light emitting devices as described above is continuously required.
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 material for a novel organic light-emitting device that can be used in an organic light-emitting device and at the same time in a solution process.
[선행기술문헌][Prior technical literature]
[특허문헌][Patent Literature]
(특허문헌 1) 한국특허 공개번호 제10-2000-0051826호(Patent Document 1) Korean Patent Publication No. 10-2000-0051826
본 발명은 신규한 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다. The present invention relates to a novel compound and an organic light emitting device comprising the same.
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다: The present invention provides a compound represented by the following formula 1:
[화학식 1][Formula 1]
Figure PCTKR2020010538-appb-img-000001
Figure PCTKR2020010538-appb-img-000001
상기 화학식 1에서, In Formula 1,
X는 O, 또는 S이고,X is O or S,
L은 단일 결합; 치환 또는 비치환된 C 6-60 아릴렌; 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴렌;이고, L is a single bond; Substituted or unsubstituted C 6-60 arylene; C 2-60 heteroarylene containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S; and,
R 1, R 2, R 3, 및 R 4는 각각 독립적으로 수소; 중수소; 할로겐; 시아노; 치환 또는 비치환된 C 1-60 알킬; 치환 또는 비치환된 C 1-60 알콕시; 치환 또는 비치환된 C 2-60 알케닐; 치환 또는 비치환된 C 2-60 알키닐; 치환 또는 비치환된 C 3-60 사이클로알킬; 치환 또는 비치환된 C 6-60 아릴; 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴; 치환 또는 비치환된 트리(C 1-60 알킬)실릴; 또는 치환 또는 비치환된 트리(C 6-60 아릴)실릴이거나, 또는 인접한 두 개의 치환기가 결합하여 C 6-60 방향족 고리를 형성하고, R 1 , R 2 , R 3 , and R 4 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 1-60 alkoxy; Substituted or unsubstituted C 2-60 alkenyl; Substituted or unsubstituted C 2-60 alkynyl; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 6-60 aryl; C 2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S; Substituted or unsubstituted tri(C 1-60 alkyl)silyl; Or a substituted or unsubstituted tri(C 6-60 aryl)silyl, or two adjacent substituents are bonded to form a C 6-60 aromatic ring,
n1은 0 내지 2의 정수이고, n1 is an integer from 0 to 2,
n2 내지 n4는 각각 독립적으로 0 내지 3의 정수이고, n2 to n4 are each independently an integer of 0 to 3,
Ar 1은 하기 화학식 2로 표시되고,Ar 1 is represented by the following formula (2),
[화학식 2][Formula 2]
Figure PCTKR2020010538-appb-img-000002
Figure PCTKR2020010538-appb-img-000002
상기 화학식 2에서, In Formula 2,
Ar 2는 치환 또는 비치환된 C 6-60 아릴; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴;이고,Ar 2 is substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S; and,
V 1 내지 V 4는 각각 독립적으로 CR a 또는 N이고, V 1 to V 4 are each independently CR a or N,
W 1 및 W 2는 각각 독립적으로 단일 결합, CR b, O 또는 S이며,W 1 and W 2 are each independently a single bond, CR b , O or S,
R a 및 R b는 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C 1-60 알킬; 치환 또는 비치환된 C 6-60 아릴; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴;이거나, 또는 인접한 두 개의 R a, 또는 인접한 두 개의 R b가 서로 결합하여 C 6-60 방향족 고리를 형성하며,R a and R b are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S; Or, or two adjacent R a , or two adjacent R b are bonded to each other to C 6- 60 forms an aromatic ring,
p는 0 또는 1의 정수이다.p is an integer of 0 or 1.
또한, 본 발명은, 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화학식 1로 표시되는 화합물을 포함하는 것인, 유기 발광 소자를 제공한다.In addition, the present invention, the first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound represented by Formula 1, wherein the organic light-emitting device comprises: to provide.
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. The compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an organic light-emitting device, and may improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light-emitting device.
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 comprising 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 comprising 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, it will be described in more detail to aid the understanding of the present invention.
본 명세서에서,
Figure PCTKR2020010538-appb-img-000003
또는
Figure PCTKR2020010538-appb-img-000004
는 다른 치환기에 연결되는 결합을 의미한다.In this specification,
Figure PCTKR2020010538-appb-img-000003
or
Figure PCTKR2020010538-appb-img-000004
Means a bond connected to another substituent.
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 the present specification, the term "substituted or unsubstituted" refers to 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; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or may be interpreted as a substituent to which two phenyl groups are connected.
본 명세서에서 카보닐기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 40인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2020010538-appb-img-000005
Figure PCTKR2020010538-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 oxygen of the ester group with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure PCTKR2020010538-appb-img-000006
Figure PCTKR2020010538-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 it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2020010538-appb-img-000007
Figure PCTKR2020010538-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 trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.
본 명세서에 있어서, 붕소기는 구체적으로 트리메틸붕소기, 트리에틸붕소기, t-부틸디메틸붕소기, 트리페닐붕소기, 페닐붕소기 등이 있으나 이에 한정되지 않는다.In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, but is not limited thereto.
본 명세서에 있어서, 할로겐기의 예로는 불소, 염소, 브롬 또는 요오드가 있다.In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 6이다. 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 사이클로펜틸메틸, 사이클로헥틸메틸, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 2-메틸펜틸, 4-메틸헥실, 5-메틸헥실 등이 있으나, 이들에 한정되지 않는다.In the present specification, the alkyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.
본 명세서에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 6이다. 구체적인 예로는 비닐, 1-프로페닐, 이소프로페닐, 1-부테닐, 2-부테닐, 3-부테닐, 1-펜테닐, 2-펜테닐, 3-펜테닐, 3-메틸-1-부테닐, 1,3-부타디에닐, 알릴, 1-페닐비닐-1-일, 2-페닐비닐-1-일, 2,2-디페닐비닐-1-일, 2-페닐-2-(나프틸-1-일)비닐-1-일, 2,2-비스(디페닐-1-일)비닐-1-일, 스틸베닐기, 스티레닐기 등이 있으나 이들에 한정되지 않는다.In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.
본 명세서에 있어서, 사이클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 60인 것이 바람직하며, 일 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 30이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 20이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 6이다. 구체적으로 사이클로프로필, 사이클로부틸, 사이클로펜틸, 3-메틸사이클로펜틸, 2,3-디메틸사이클로펜틸, 사이클로헥실, 3-메틸사이클로헥실, 4-메틸사이클로헥실, 2,3-디메틸사이클로헥실, 3,4,5-트리메틸사이클로헥실, 4-tert-부틸사이클로헥실, 사이클로헵틸, 사이클로옥틸 등이 있으나, 이에 한정되지 않는다.In the present specification, the cycloalkyl group is not particularly limited, but is preferably 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나 탄소수 6 내지 60인 것이 바람직하며, 단환식 아릴기 또는 다환식 아릴기일 수 있다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 30이다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 20이다. 상기 아릴기가 단환식 아릴기로는 페닐기, 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 is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.
본 명세서에 있어서, 플루오레닐기는 치환될 수 있고, 치환기 2개가 서로 결합하여 스피로 구조를 형성할 수 있다. 상기 플루오레닐기가 치환되는 경우,
Figure PCTKR2020010538-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 PCTKR2020010538-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 carbons is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl include xanthene, thioxanthen, thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, Pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino Pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group ( phenanthroline), isoxazolyl group, thiadiazolyl group, phenothiazinyl group, and 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, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the above-described description of heteroaryl may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the above-described heteroaryl may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or the cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heteroaryl is not a monovalent group, and the description of the above-described heteroaryl may be applied except that two substituents are bonded to each other.
본 발명은 상기 화학식 1로 표시되는 화합물을 제공한다. The present invention provides a compound represented by Chemical Formula 1.
상기 화학식 1에서, 바람직하게는 L은 단일결합이다.In Formula 1, preferably L is a single bond.
바람직하게는, R 1, R 2, R 3 및 R 4는 수소이다. 이때 바람직하게는, n1 내지 n4가 0이다. Preferably, R 1 , R 2 , R 3 and R 4 are hydrogen. At this time, preferably, n1 to n4 are 0.
바람직하게는, R 1, R 2, R 3 및 R 4 중 하나는 페닐 또는 피리디닐이고, 나머지는 수소이다. 이때 바람직하게는, n1 내지 n4 중 하나는 1이고, 나머지는 0이다.Preferably, one of R 1 , R 2 , R 3 and R 4 is phenyl or pyridinyl and the other is hydrogen. At this time, preferably, one of n1 to n4 is 1, and the others are 0.
바람직하게는, 인접한 두 개의 R 1, 인접한 두 개의 R 2, 인접한 두 개의 R 3, 또는 인접한 두 개의 R 4가 서로 결합하여 벤젠 고리를 형성하고, 나머지 R 1 내지 R 4는 수소이다. Preferably, two adjacent R 1 , two adjacent R 2 , two adjacent R 3 , or two adjacent R 4 are bonded to each other to form a benzene ring, and the remaining R 1 to R 4 are hydrogen.
또, 상기 화학식 1에서, Ar 1은 바람직하게는 하기 화학식 2-1 내지 2-3으로 구성되는 군으로부터 선택되는 어느 하나이다:In addition, in Formula 1, Ar 1 is preferably any one selected from the group consisting of the following Formulas 2-1 to 2-3:
[화학식 2-1][Formula 2-1]
Figure PCTKR2020010538-appb-img-000009
Figure PCTKR2020010538-appb-img-000009
[화학식 2-2][Formula 2-2]
Figure PCTKR2020010538-appb-img-000010
Figure PCTKR2020010538-appb-img-000010
[화학식 2-3][Formula 2-3]
Figure PCTKR2020010538-appb-img-000011
Figure PCTKR2020010538-appb-img-000011
상기 화학식 2-1 내지 2-3에서,In Formulas 2-1 to 2-3,
Ar 2는 상기 화학식 1에서 정의한 바와 같고, Ar 2 is as defined in Formula 1,
R a1, R a2 및 R a3은 각각 독립적으로 수소 또는 중수소이거나; 또는 인접한 두 개의 R a1, 인접한 두 개의 R a2, 또는 인접한 두 개의 R a3이 서로 결합하여 벤젠 고리를 형성하고, 나머지는 수소이며,R a1 , R a2 and R a3 are each independently hydrogen or deuterium; Or two adjacent R a1 , two adjacent R a2 , or two adjacent R a3 bonded to each other to form a benzene ring, and the rest is hydrogen,
R b1은 각각 독립적으로 수소 또는 중수소이고,Each R b1 is independently hydrogen or deuterium,
W 3 및 W 4는 각각 독립적으로 O 또는 S이며,W 3 and W 4 are each independently O or S,
p는 0 또는 1의 정수이다.p is an integer of 0 or 1.
보다 바람직하게는 상기 Ar 1은 하기로 구성되는 군으로부터 선택되는 어느 하나이다:More preferably, Ar 1 is any one selected from the group consisting of:
Figure PCTKR2020010538-appb-img-000012
Figure PCTKR2020010538-appb-img-000012
상기 화학식들에서, In the above formulas,
Ar 2는 상기 화학식 1에서 정의한 바와 같으며,Ar 2 is as defined in Chemical Formula 1,
W 3 및 W 4는 각각 독립적으로 O 또는 S이다.W 3 and W 4 are each independently O or S.
바람직하게는 상기 Ar 2는 페닐, 비페닐, 터페닐, 나프틸, 안트라세닐, 페난쓰레닐, 9,9-디메틸플루오레닐, 9,9-디페닐플루오레닐, 디벤조퓨라닐, 디벤조티오페닐, 카바졸-9-일, 또는 9-페닐-카바졸릴이고, 상기 Ar 2는 비치환되거나, 또는 하나 이상의 중수소로 치환된다. Preferably, Ar 2 is phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, di Benzothiophenyl, carbazol-9-yl, or 9-phenyl-carbazolyl, and Ar 2 is unsubstituted or substituted with one or more deuterium.
상기 화학식 1로 표시되는 화합물의 대표적인 예는 하기와 같다.Representative examples of the compound represented by Formula 1 are as follows.
Figure PCTKR2020010538-appb-img-000013
Figure PCTKR2020010538-appb-img-000013
Figure PCTKR2020010538-appb-img-000014
Figure PCTKR2020010538-appb-img-000014
Figure PCTKR2020010538-appb-img-000015
Figure PCTKR2020010538-appb-img-000015
Figure PCTKR2020010538-appb-img-000016
Figure PCTKR2020010538-appb-img-000016
Figure PCTKR2020010538-appb-img-000017
Figure PCTKR2020010538-appb-img-000017
Figure PCTKR2020010538-appb-img-000018
Figure PCTKR2020010538-appb-img-000018
Figure PCTKR2020010538-appb-img-000019
Figure PCTKR2020010538-appb-img-000019
Figure PCTKR2020010538-appb-img-000020
Figure PCTKR2020010538-appb-img-000020
한편, 본 발명은 일례로 하기 반응식 1과 같은, 상기 화학식 1로 표시되는 화합물의 제조 방법을 제공한다:On the other hand, the present invention provides a method for preparing a compound represented by Formula 1, such as the following Scheme 1 as an example:
[반응식 1][Scheme 1]
Figure PCTKR2020010538-appb-img-000021
Figure PCTKR2020010538-appb-img-000021
상기 반응식 1에서, X, L, 및 Ar 2는 화학식 1에서 정의한 바와 같고, Y 1 및 Y 2는 각각 독립적으로 클로로 또는 보로모 등과 같은 할로겐기이고, Z는 보론산기, 보론산 에스터기, 또는 보론산 피나콜에스터(boronic acid pinacol ester)기 등과 같은 붕소 함유 유기기이며, Ar 1′은 하기 구조를 갖는 치환기이고,In Reaction Scheme 1, X, L, and Ar 2 are as defined in Formula 1, Y 1 and Y 2 are each independently a halogen group such as chloro or boromo, and Z is a boronic acid group, a boronic acid ester group, or It is a boron-containing organic group such as a boronic acid pinacol ester group, and Ar 1 ′ is a substituent having the following structure,
Figure PCTKR2020010538-appb-img-000022
Figure PCTKR2020010538-appb-img-000022
상기 구조에서 V 1 내지 V 4, W 1 및 W 2는 화학식 1에서 정의한 바와 같다. In the above structure, V 1 to V 4 , W 1 and W 2 are as defined in Formula 1.
구체적으로, 상기 화학식 1의 화합물(1)은 모핵 구조를 갖는 화합물(i)과, 상기 모핵 구조에 결합되는, 전자 받개 치환기 포함 화합물(ii)을 팔라듐 촉매화된 커플링 반응시켜 화합물(iii)을 제조하는 단계; 및 상기 화합물 (iii)을 상기한 붕소 함유 유기기를 포함하는 화합물(iv)과, 염기 및 팔라듐 촉매의 존재 하에, 스즈키 커플링 반응시키는 단계를 포함하는 제조방법에 의해 제조될 수 있다. Specifically, compound (1) of Formula 1 is a palladium-catalyzed coupling reaction between a compound (i) having a parental structure and a compound (ii) including an electron acceptor substituent bonded to the parental structure, and compound (iii) Manufacturing a; And it can be prepared by a production method comprising the step of subjecting the compound (iii) to a Suzuki coupling reaction in the presence of a compound (iv) containing an organic group containing boron and a base and a palladium catalyst.
상기 팔라듐 촉매화된 커플링 반응 및 스즈키 커플링 반응에 사용가능한 팔라듐계 촉매로는, 비스(트리스-tert-부틸포스핀)팔라듐(bis(tri-tert-butylphosphine)palladium(0), Pd(P-tBu 3) 2), 테트라키스-(트리페닐포스핀)팔라듐 (tetrakis(triphenylphosphine)palladium(0), Pd(PPh 3) 4), 트리스(디벤질리덴아세톤)디팔라듐(Tris(dibenzylideneacetone)dipalladium, Pd 2(dba) 3)), 비스(트리페닐포스핀)팔라듐 클로라이드(Bis(triphenylphosphine)palladium chloride, Pd(PPh 3) 2Cl 2), 비스(아세토니트릴)팔라듐 클로라이드(Bis(acetonitrile)palladium(Ⅱ) chloride, Pd(CH 3CN) 2Cl 2), 팔라듐(Ⅱ) 아세테이트(Palladium(Ⅱ) acetate, Pd(OAc) 2), 팔라듐(Ⅱ) 아세틸아세토네이트(Palladium(Ⅱ) acetylacetonate, Pd(acac) 2], 알릴팔라듐(Ⅱ) 클로라이드 다이머(Allylpalladium(Ⅱ) chloride dimer, Pd(allyl)Cl] 2), 팔라듐 카본(Palladium on carbon, Pd/C), 또는 팔라듐(Ⅱ) 클로라이드(Palladium(Ⅱ) chloride, PdCl 2) 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다.As a palladium-based catalyst usable in the palladium-catalyzed coupling reaction and Suzuki coupling reaction, bis(tri-tert-butylphosphine)palladium (bis(tri-tert-butylphosphine)palladium(0), Pd(P -tBu 3 ) 2 ), tetrakis-(triphenylphosphine) palladium (tetrakis(triphenylphosphine)palladium(0), Pd(PPh 3 ) 4 ), tris(dibenzylideneacetone)dipalladium (Tris(dibenzylideneacetone)dipalladium) , Pd 2 (dba) 3 )), bis (triphenylphosphine) palladium chloride, Pd (PPh 3 ) 2 Cl 2 ), bis (acetonitrile) palladium chloride (Bis (acetonitrile) palladium (II) chloride, Pd(CH 3 CN) 2 Cl 2 ), palladium(II) acetate, Pd(OAc) 2 ), palladium(II) acetylacetonate, Pd (acac) 2 ], Allylpalladium(II) chloride dimer (Pd(allyl)Cl) 2 ), Palladium on carbon (Pd/C), or palladium(II) chloride (Palladium (II) chloride, PdCl 2 ), and the like, and any one or a mixture of two or more of them may be used.
또, 상기 팔라듐 촉매화된 커플링 반응과 스즈키 커플링 반응은 염기 존재 하에 수행될 수 있으며, 이때 염기(base)로는 소듐 tert-부톡사이드(sodium tert-butoxide), 포타슘 tert-부톡사이드(potassium tert-butoxide), 소듐 tert―펜톡사이드(sodium tert-pentoxide), 소듐 에톡사이드(sodium ethoxide), 소듐 카보네이트(sodium carbonate), 포타슘 카보네이트(potassium carbonate), 세슘 카보네이트(cesium carbonate), 소듐 하이드리드(sodium hydride), 리튬 하이드리드(lithium hydride) 또는 포타슘 하이드리드(potassium hydride) 등과 같은 무기 염기; 테트라에틸암모늄 히드록시드((Et 4NOH), 비스(테트라에틸암모늄)탄산염, 트리에틸아민 등의 유기 염기; 불화세슘 등의 무기염을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다. In addition, the palladium catalyzed coupling reaction and the Suzuki coupling reaction may be carried out in the presence of a base, and at this time, the base is sodium tert-butoxide, potassium tert-butoxide. -butoxide), sodium tert-pentoxide, sodium ethoxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride hydride), lithium hydride, or potassium hydride; Organic bases such as tetraethylammonium hydroxide ((Et 4 NOH), bis(tetraethylammonium) carbonate, triethylamine; inorganic salts such as cesium fluoride, and any one or a mixture of two or more of them may be used. I can.
상기 팔라듐 촉매화된 커플링 반응은 유기 용매 중에서 수행될 수 있고, 상기 스즈키 커플링 반응은 용매로서 물 중에서 수행될 수 있다.The palladium catalyzed coupling reaction may be performed in an organic solvent, and the Suzuki coupling reaction may be performed in water as a solvent.
상기 유기 용매로는, 디에틸 에테르, 테트라히드로푸란, 1,4-디옥산, 에틸렌 글리콜 디에틸 에테르, 디메톡시에탄, 비스(2-메톡시에틸)에테르, 디에틸렌 글리콜 디에틸 에테르, 테트라하이드로퓨란 또는 아니솔과 같은 에테르 용매; 벤젠, 톨루엔 또는 자일렌과 같은 방향족 탄화수소계 용매; 클로로벤젠, 디메틸포름아마이드, 디메틸아세트아마이드, N-메틸피롤리돈, 디메틸이미다졸리돈 또는 아세토니트릴과 같은 할로겐화 방향족 용매; 또는 디메틸술폭사이드(DMSO)와 같은 설폭사이드계 용매 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다.As the organic solvent, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol diethyl ether, dimethoxyethane, bis(2-methoxyethyl) ether, diethylene glycol diethyl ether, tetrahydro Ether solvents such as furan or anisole; Aromatic hydrocarbon-based solvents such as benzene, toluene or xylene; Halogenated aromatic solvents such as chlorobenzene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylimidazolidone or acetonitrile; Or a sulfoxide-based solvent such as dimethyl sulfoxide (DMSO), and any one or a mixture of two or more of them may be used.
또 상기 화학식 1의 화합물(1) 제조에 사용되는 반응 물질들은 통상의 유기 반응을 이용하여 제조할 수도 있고, 또는 상업적으로 입수하여 사용할 수도 있다. In addition, the reactants used in the preparation of compound (1) of Formula 1 may be prepared by using a conventional organic reaction, or may be obtained and used commercially.
일례로, 상기 모핵 구조를 갖는 화합물(i)은, 하기 반응식 2에서와 같은 방법으로 제조될 수 있다. 하기 반응식 2는 본 발명을 설명하기 위한 일 예일뿐, 본 발명이 이에 한정되는 것은 아니다.For example, the compound (i) having the parental structure may be prepared in the same manner as in Scheme 2 below. Reaction Scheme 2 below is only an example for explaining the present invention, but the present invention is not limited thereto.
[반응식 2] [Scheme 2]
Figure PCTKR2020010538-appb-img-000023
Figure PCTKR2020010538-appb-img-000023
상기 반응식 2에서, X는 O 또는 S이고, Y는 브로모와 같은 할로겐기이다.In Reaction Scheme 2, X is O or S, and Y is a halogen group such as bromo.
상기 화학식 1의 화합물의 제조방법의 구체예는, 이하 제조예에서 보다 구체적으로 제시한다.Specific examples of the method for preparing the compound of Formula 1 are presented in more detail in the following Preparation Examples.
또한, 본 발명은 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 Chemical Formula 1.
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 본 발명에 따른 화합물을 포함하는 것인, 유기 발광 소자를 제공한다. For example, the present invention provides a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the compound according to the present invention. .
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.In addition, 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. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 발광층에 포함될 수 있다. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by Formula 1 may be included in the emission layer.
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 정공주입층, 정공수송층, 또는 발광층에 포함될 수 있다. 또 상기 구조에 있어서, 정공 수송층과 발광층 사이에 전자 저지층(미도시)이, 그리고 상기 발광층과 전자 주입 및 수송층 사이에 정공 저지층(미도시)이 더 포함될 수도 있다.2 is an example of an organic light-emitting device comprising 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 such a structure, the compound represented by Formula 1 may be included in the hole injection layer, the hole transport layer, or the emission layer. In addition, in the above structure, an electron blocking layer (not shown) may be further included between the hole transport layer and the emission layer, and a hole blocking layer (not shown) may be further included between the emission layer and the electron injection and transport layer.
본 발명에 따른 유기 발광 소자는, 본 발명에 따른 화합물을 사용하는 것을 제외하고는, 당 기술분야에 알려져 있는 재료와 방법으로 제조할 수 있다.The organic light emitting device according to the present invention can be manufactured using materials and methods known in the art, except for using the compound according to the present invention.
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 주입 및 수송층을 포함하는 유기물 층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시켜 제조할 수 있다. For example, the organic light-emitting device according to the present invention may be manufactured by sequentially laminating an anode, an organic material layer, and a cathode on a substrate. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron injection and transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon.
이와 같은 방법 외에도, 기판 상에 음극 물질로부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 제조할 수 있다(WO 2003/012890). 다만, 제조 방법이 이에 한정되는 것은 아니다. In addition to such a method, an organic light-emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.
이와 같은 방법 외에도, 기판 상에 음극 물질로부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 제조할 수 있다(WO 2003/012890). 다만, 제조 방법이 이에 한정되는 것은 아니다. In addition to such a method, an organic light-emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.
일례로, 상기 제1 전극은 양극이고, 상기 제2 전극은 음극이거나, 또는 상기 제1 전극은 음극이고, 상기 제2 전극은 양극이다.For example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode.
상기 양극 물질로는 통상 유기물층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 상기 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SNO 2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 화합물 등이 있으나, 이들에만 한정되는 것은 아니다. As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide 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 LiO 2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO 2 /Al, but are not limited thereto.
상기 정공주입층은 전극으로부터 정공을 주입하는 층으로, 정공 주입 물질로는 정공을 수송하는 능력을 가져 양극에서의 정공 주입효과, 발광층 또는 발광재료에 대하여 우수한 정공 주입 효과를 갖고, 발광층에서 생성된 여기자의 전자주입층 또는 전자주입재료에의 이동을 방지하며, 또한, 박막 형성 능력이 우수한 화합물이 바람직하다. 정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 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 that injects holes from an electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for a light emitting layer or a light emitting material. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive compounds, but are not limited thereto.
상기 정공 수송층은 정공 주입층으로부터 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 holes to the emission layer, and the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission layer, and has high mobility for holes. The material is suitable. Specific examples include an arylamine-based organic material, a conductive compound, and a block copolymer having a conjugated portion and a non-conjugated portion, but are not limited thereto.
한편, 일 구현예에 따른 유기 발광 소자는 상기 정공 수송층 상에 전자 저지층을 선택적으로 더 포함할 수 있다. 상기 전자 저지층은 상기 정공 수송층 상에 형성되어, 바람직하게는 발광층에 접하여 구비되어, 정공이동도를 조절하고, 전자의 과다한 이동을 방지하여 정공-전자간 결합 확률을 높여줌으로써 유기 발광 소자의 효율을 개선하는 역할을 하는 층을 의미한다. 상기 전자저지층은 전자저지물질을 포함하고, 이러한 전자저지물질의 예로 아릴아민 계열의 유기물 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.Meanwhile, the organic light emitting device according to an embodiment may further include an electron blocking layer selectively on the hole transport layer. The electron blocking layer is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons, thereby increasing the probability of hole-electron coupling, thereby increasing the efficiency of the organic light-emitting device. It refers to the layer that plays a role in improving the value. The electron blocking layer includes an electron blocking material, and an arylamine-based organic material may be used as an example of the electron blocking material, but is not limited thereto.
또, 상기 발광층은 호스트 재료 및 도펀트 재료를 포함할 수 있다. 호스트 재료는 축합 방향족환 유도체 또는 헤테로환 함유 화합물 등이 있다. 구체적으로 축합 방향족환 유도체로는 안트라센 유도체, 피렌 유도체, 나프탈렌 유도체, 펜타센 유도체, 페난트렌 화합물, 플루오란텐 화합물 등이 있고, 헤테로환 함유 화합물로는 카바졸 유도체, 디벤조퓨란 유도체, 래더형 퓨란 화합물, 피리미딘 유도체 등이 있으나, 이에 한정되지 않는다. In addition, the emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
도펀트 재료로는 방향족 아민 유도체, 스트릴아민 화합물, 붕소 착체, 플루오란텐 화합물, 금속 착체 등이 있다. 구체적으로 방향족 아민 유도체로는 치환 또는 비치환된 아릴아미노기를 갖는 축합 방향족환 유도체로서, 아릴아미노기를 갖는 피렌, 안트라센, 크리센, 페리플란텐 등이 있으며, 스티릴아민 화합물로는 치환 또는 비치환된 아릴아민에 적어도 1개의 아릴비닐기가 치환되어 있는 화합물로, 아릴기, 실릴기, 알킬기, 사이클로알킬기 및 아릴아미노기로 이루어진 군에서 1 또는 2 이상 선택되는 치환기가 치환 또는 비치환된다. 구체적으로 스티릴아민, 스티릴디아민, 스티릴트리아민, 스티릴테트라아민 등이 있으나, 이에 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, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of an aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.
한편, 일 구현예에 따른 유기 발광 소자는 상기 발광층 상에 정공저지층을 선택적으로 더 포함할 수 있다. 상기 정공저지층은 발광층 상에 형성되어, 바람직하게는 발광층에 접하여 구비되어, 전자이동도를 조절하고 정공의 과다한 이동을 방지하여 정공-전자간 결합 확률을 높여줌으로써 유기 발광 소자의 효율을 개선하는 역할을 하는 층을 의미한다. 상기 정공저지층은 정공저지물질을 포함하고, 이러한 정공저지물질의 예로 트리아진을 포함한 아진류유도체; 트리아졸 유도체; 옥사디아졸 유도체; 페난트롤린 유도체; 포스핀옥사이드 유도체 등의 전자흡인기가 도입된 화합물을 사용할 수 있으나, 이에 한정되는 것은 아니다.Meanwhile, the organic light emitting device according to the exemplary embodiment may further include a hole blocking layer selectively on the emission layer. The hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to improve the efficiency of the organic light emitting device by increasing the probability of hole-electron coupling by controlling electron mobility and preventing excessive movement of holes. It means the layer that plays a role. The hole-blocking layer includes a hole-blocking material, and examples of the hole-blocking material include: a subazine derivative including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; A compound into which an electron withdrawing group such as a phosphine oxide derivative has been introduced may be used, but is not limited thereto.
상기 발광층 상에, 또는 상기 정공저지층 상에 전자수송층이 형성된다. 상기 전자수송층은 음극 또는 후술하는 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 피리딘 유도체; 피리미딘 유도체; 트리아졸 유도체; 8-히드록시퀴놀린의 Al 착물; Alq 3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. An electron transport layer is formed on the emission layer or on the hole blocking layer. The electron transport layer is a layer that receives electrons from the cathode or an electron injection layer to be described later and transports electrons to the emission layer. As an electron transport material, electrons are well injected from the cathode and can be transferred to the emission layer. Larger materials are suitable. Specific examples include pyridine derivatives; Pyrimidine derivatives; Triazole derivatives; Al complex of 8-hydroxyquinoline; Complexes containing Alq 3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
한편, 상기 전자주입층은 전자수송층과 음극 사이에 위치하여 음극으로부터 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, 박막 형성 능력이 우수한 화합물이 바람직하다. 구체적으로는 LiF, NaCl, CsF, Li 2O, BaO, 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. Meanwhile, the electron injection layer is a layer located between the electron transport layer and the cathode to inject electrons from the cathode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect for the light emitting layer or the light emitting material. It has, and prevents the movement of excitons generated in the light-emitting layer to the hole injection layer, and also, a compound excellent in the ability to form a thin film is preferable. Specifically, LiF, NaCl, CsF, Li 2 O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, pre Orenylidene methane, anthrone, and the like, derivatives thereof, metal 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 lithium 8-hydroxyquinolinato, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.
한편, 상기의 전자수송층 및 전자주입층은 수취된 전자를 발광층까지 수송하는 전자수송층과 전자주입층의 역할을 동시에 수행하는 전자 주입 및 수송층의 형태로도 구비 가능하다.Meanwhile, the electron transport layer and the electron injection layer may be provided in the form of an electron transport layer for transporting received electrons to the light emitting layer and an electron injection and transport layer that simultaneously functions as an electron injection layer.
본 발명에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.
또한, 본 발명에 따른 화합물은 유기 발광 소자 외에도 유기 태양 전지 또는 유기 트랜지스터에 포함될 수 있다.In addition, the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
상기 화학식 1로 표시되는 화합물 및 이를 포함하는 유기 발광 소자의 제조는 이하 실시예에서 구체적으로 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범위가 이들에 의하여 한정되는 것은 아니다.Preparation of the compound represented by Formula 1 and an organic light emitting device including the same will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.
[합성예] [Synthesis Example]
합성예 A: 중간체 A의 합성Synthesis Example A: Synthesis of Intermediate A
단계 1) 중간체 A-1의 합성Step 1) Synthesis of Intermediate A-1
Figure PCTKR2020010538-appb-img-000024
Figure PCTKR2020010538-appb-img-000024
Dibenzo[b,d]furan-1-ylboronic acid (25.0g, 117.9mmol) 및 1-bromo-2-nitronaphthalene (32.7g, 129.7mmol)을 Tetrahydrofuran (THF) 255ml에 용해시키고, 결과의 혼합용액에, potassium carbonate (65.2g, 471.7mmol)을 H 2O 125ml에 용해시킨 용액을 첨가하였다. 여기에 tetrakis(triphenylphosphine)palladium(0) (Pd(PPh 3) 4, 6.8g, 5.9mmol)를 넣고, 아르곤 분위기 환류 조건하에서 8시간 동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, 반응액을 분액 깔대기에 옮기고, ethyl acetate로 추출하였다. 추출액을 MgSO 4로 건조 후, 여과 및 농축한 후, 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 중간체 A-1을 28.8g 수득하였다. (수율 72%, MS[M+H]+= 339) Dibenzo[b,d]furan-1-ylboronic acid (25.0g, 117.9mmol) and 1-bromo-2-nitronaphthalene (32.7g, 129.7mmol) were dissolved in Tetrahydrofuran (THF) 255ml, and in the resulting mixed solution, A solution in which potassium carbonate (65.2 g, 471.7 mmol) was dissolved in 125 ml of H 2 O was added. Here, tetrakis(triphenylphosphine)palladium(0) (Pd(PPh 3 ) 4 , 6.8g, 5.9mmol) was added and stirred for 8 hours under reflux conditions in an argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO 4 , filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 28.8 g of Intermediate A-1. (Yield 72%, MS[M+H]+= 339)
단계 2) 중간체 A-2의 합성Step 2) Synthesis of Intermediate A-2
Figure PCTKR2020010538-appb-img-000025
Figure PCTKR2020010538-appb-img-000025
상기 단계 1에서 제조한 중간체 A-1 (25.0g, 73.7mmol), triphenylphosphine (PPh 3, 15.3g, 110.5mmol), 및 o-dichlorobenzene(o-DCB) 250ml를 반응기에 넣고 환류 조건하에서 24시간 동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, 감압 증류하여 용매를 제거하고 CH 2Cl 2로 추출하였다. 추출액을 MgSO 4로 건조, 여과 및 농축한 후, 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 중간체 A-2를 15.4g 수득하였다. (수율 68%, MS[M+H]+= 307)Intermediate A-1 (25.0g, 73.7mmol) prepared in step 1, triphenylphosphine (PPh 3 , 15.3g, 110.5mmol), and 250 ml of o-dichlorobenzene (o-DCB) were added to a reactor and under reflux conditions for 24 hours. Stirred. When the reaction was completed, the mixture was cooled to room temperature, distilled under reduced pressure to remove the solvent, and extracted with CH 2 Cl 2. The extract was dried over MgSO 4 , filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 15.4 g of Intermediate A-2. (Yield 68%, MS[M+H]+= 307)
단계 3) 중간체 A의 합성Step 3) Synthesis of Intermediate A
Figure PCTKR2020010538-appb-img-000026
Figure PCTKR2020010538-appb-img-000026
상기 단계 2에서 제조한 중간체 A-2 (15.0g, 48.8mmol), sodium chloride (48.5g, 829.7mmol), aluminum chloride (AlCl 3, 247.3g, 1854.6mmol) 및 benzene 450ml를 넣고 0℃에서 16시간 동안 교반하였다. 반응이 종료되면 물과 NaHCO 3 수용액으로 씻어주고, MgSO 4로 건조, 여과 및 농축한 후, 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 중간체 A를 5.4g 수득하였다. (수율 36%, MS[M+H]+= 305)Intermediate A-2 (15.0g, 48.8mmol), sodium chloride (48.5g, 829.7mmol), aluminum chloride (AlCl 3 , 247.3g, 1854.6mmol) and 450ml of benzene prepared in step 2 were added and then at 0℃ for 16 hours. While stirring. When the reaction was completed, the mixture was washed with water and an aqueous NaHCO 3 solution, dried over MgSO 4 , filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 5.4 g of intermediate A. (Yield 36%, MS[M+H]+= 305)
합성예 B: 중간체 B의 합성Synthesis Example B: Synthesis of Intermediate B
Figure PCTKR2020010538-appb-img-000027
Figure PCTKR2020010538-appb-img-000027
합성예 A에서, dibenzo[b,d]furan-1-ylboronic acid을 dibenzo[b,d]thiophen-1-ylboronic acid로 변경하여 사용한 것을 제외하고는, 중간체 A의 제조 방법과 동일한 제조 방법으로 중간체 B를 제조하였다. (MS[M+H] += 382)In Synthesis Example A, an intermediate in the same manner as in the preparation method of Intermediate A, except that dibenzo[b,d]furan-1-ylboronic acid was changed to dibenzo[b,d]thiophen-1-ylboronic acid. Prepared B. (MS[M+H] + = 382)
합성예 C: 중간체 C의 합성Synthesis Example C: Synthesis of Intermediate C
Figure PCTKR2020010538-appb-img-000028
Figure PCTKR2020010538-appb-img-000028
합성예 A에서, 1-bromo-2-nitronaphthalene을 1-bromo-2-nitro-6-phenylnaphthalene으로 변경하여 사용한 것을 제외하고는, 중간체 A의 제조 방법과 동일한 제조 방법으로 중간체 C를 제조하였다. (MS[M+H] += 381)In Synthesis Example A, Intermediate C was prepared in the same manner as in Intermediate A, except that 1-bromo-2-nitronaphthalene was changed to 1-bromo-2-nitro-6-phenylnaphthalene. (MS[M+H] + = 381)
합성예 D: 중간체 D의 합성Synthesis Example D: Synthesis of Intermediate D
Figure PCTKR2020010538-appb-img-000029
Figure PCTKR2020010538-appb-img-000029
합성예 A에서, dibenzo[b,d]furan-1-ylboronic acid을 naphtho[1,2-b]benzofuran-7-ylboronic acid로 변경하여 사용한 것을 제외하고는, 중간체 A의 제조 방법과 동일한 제조 방법으로 중간체 D를 제조하였다. (MS[M+H] += 355)In Synthesis Example A, the same production method as that of the intermediate A, except that dibenzo[b,d]furan-1-ylboronic acid was changed to naphtho[1,2-b]benzofuran-7-ylboronic acid. To prepare Intermediate D. (MS[M+H] + = 355)
합성예 1: 화합물 1의 합성Synthesis Example 1: Synthesis of Compound 1
단계 1) 화합물 1-1의 합성Step 1) Synthesis of Compound 1-1
Figure PCTKR2020010538-appb-img-000030
Figure PCTKR2020010538-appb-img-000030
중간체 A (10.0g, 32.8mmol), 2,3-dichloroquinoxaline (7.2g, 36.0mmol)을 toluene 300ml에 녹이고 sodium tert-butoxide (NaOtBu, 4.7g, 49.1mmol), bis(tri-tert-butylphosphine)palladium(0) (Pd(P-tBu 3) 2, 0.3g, 0.7mmol)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간 동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H 2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO 4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-1 11.5g을 수득하였다. (수율 75%, MS[M+H]+= 467)Intermediate A (10.0g, 32.8mmol), 2,3-dichloroquinoxaline (7.2g, 36.0mmol) is dissolved in 300ml of toluene, sodium tert-butoxide (NaOtBu, 4.7g, 49.1mmol), bis(tri-tert-butylphosphine)palladium (0) (Pd(P-tBu 3 ) 2 , 0.3g, 0.7mmol) was added, followed by stirring for 6 hours under reflux conditions in an argon atmosphere. When the reaction was completed, after cooling to room temperature, H 2 O was added and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 11.5 g of compound 1-1. (Yield 75%, MS[M+H]+= 467)
단계 2) 화합물 1의 합성Step 2) Synthesis of Compound 1
Figure PCTKR2020010538-appb-img-000031
Figure PCTKR2020010538-appb-img-000031
화합물 1-1 (10.0g, 21.4mmol), phenylboronic acid (2.9g, 23.5mmol)을 THF 150ml에 녹이고 potassium carbonate (11.8g, 85.5mmol)을 H 2O 50ml에 녹여 넣었다. 여기에 tetrakis(triphenylphosphine)palladium(0) (1.2g, 1.1mmol)를 넣고, 아르곤 분위기 환류 조건하에서 8시간 동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, 반응액을 분액 깔대기에 옮기고, ethyl acetate로 추출하였다. 추출액을 MgSO 4로 건조 후, 여과 및 농축한 후, 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후, 승화정제를 통해 화합물 1을 3.5g 수득하였다. (수율 32%, MS[M+H]+= 509)Compound 1-1 (10.0g, 21.4mmol) and phenylboronic acid (2.9g, 23.5mmol) were dissolved in 150ml of THF, and potassium carbonate (11.8g, 85.5mmol) was dissolved in 50ml of H 2 O. Here, tetrakis(triphenylphosphine)palladium(0) (1.2g, 1.1mmol) was added and stirred for 8 hours under reflux conditions in an argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO 4 , filtered and concentrated, and the sample was purified by silica gel column chromatography, and then 3.5 g of Compound 1 was obtained through sublimation purification. (Yield 32%, MS[M+H]+=509)
합성예 2: 화합물 2의 합성Synthesis Example 2: Synthesis of Compound 2
Figure PCTKR2020010538-appb-img-000032
Figure PCTKR2020010538-appb-img-000032
합성예 1에서, phenylboronic acid를 naphthalen-2-ylboronic acid로 변경하여 사용한 것을 제외하고는, 화합물 1의 제조 방법과 동일한 제조 방법으로 화합물 2를 제조하였다. (MS[M+H] += 559)In Synthesis Example 1, except that phenylboronic acid was changed to naphthalen-2-ylboronic acid and used, compound 2 was prepared in the same manner as in the preparation method of compound 1. (MS[M+H] + = 559)
합성예 3: 화합물 3의 합성Synthesis Example 3: Synthesis of Compound 3
Figure PCTKR2020010538-appb-img-000033
Figure PCTKR2020010538-appb-img-000033
합성예 1에서, 2,3-dichloroquinoxaline을 2,3-dichlorobenzo[f]quinoxaline으로 변경하여 사용한 것을 제외하고는, 화합물 1의 제조 방법과 동일한 제조 방법으로 화합물 3을 제조하였다. (MS[M+H] += 559)In Synthesis Example 1, 2,3-dichloroquinoxaline was changed to 2,3-dichlorobenzo[f]quinoxaline, except that the compound 3 was prepared in the same manner as the preparation method of Compound 1. (MS[M+H] + = 559)
합성예 4: 화합물 4의 합성Synthesis Example 4: Synthesis of Compound 4
Figure PCTKR2020010538-appb-img-000034
Figure PCTKR2020010538-appb-img-000034
합성예 1에서, 2,3-dichloroquinoxaline을 2,3-dichlorobenzo[f]quinoxaline으로, phenylboronic acid를 2-(dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane으로 변경하여 사용한 것을 제외하고는, 화합물 1의 제조 방법과 동일한 제조 방법으로 화합물 4를 제조하였다. (MS[M+H] += 649)In Synthesis Example 1, 2,3-dichloroquinoxaline was used as 2,3-dichlorobenzo[f]quinoxaline, and phenylboronic acid was used as 2-(dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl Except for changing to -1,3,2-dioxaborolane and used, compound 4 was prepared by the same production method as the production method of compound 1. (MS[M+H] + = 649)
합성예 5: 화합물 5의 합성Synthesis Example 5: Synthesis of Compound 5
Figure PCTKR2020010538-appb-img-000035
Figure PCTKR2020010538-appb-img-000035
합성예 1에서, 2,3-dichloroquinoxaline을 2,3-dichlorobenzo[4,5]thieno[2,3-b]pyrazine로, phenylboronic acid를 naphthalen-1-ylboronic acid로 변경하여 사용한 것을 제외하고는, 화합물 1의 제조 방법과 동일한 제조 방법으로 화합물 5를 제조하였다. (MS[M+H] += 615)In Synthesis Example 1, 2,3-dichloroquinoxaline was changed to 2,3-dichlorobenzo[4,5]thieno[2,3-b]pyrazine, and phenylboronic acid was changed to naphthalen-1-ylboronic acid, except that Compound 5 was prepared by the same method as the method for preparing compound 1. (MS[M+H] + = 615)
합성예 6: 화합물 6의 합성Synthesis Example 6: Synthesis of Compound 6
Figure PCTKR2020010538-appb-img-000036
Figure PCTKR2020010538-appb-img-000036
합성예 1에서, 2,3-dichloroquinoxaline을 2,3-dichlorobenzo[4,5]thieno[2,3-b]pyrazine으로, phenylboronic acid를 2-(9,9-dimethyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane으로 변경하여 사용한 것을 제외하고는, 화합물 1의 제조 방법과 동일한 제조 방법으로 화합물 6을 제조하였다. (MS[M+H] += 681)In Synthesis Example 1, 2,3-dichloroquinoxaline was used as 2,3-dichlorobenzo[4,5]thieno[2,3-b]pyrazine, and phenylboronic acid was used as 2-(9,9-dimethyl-9H-fluoren-2- Compound 6 was prepared in the same manner as in the preparation method of Compound 1, except that yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used. (MS[M+H] + = 681)
합성예 7: 화합물 7의 합성Synthesis Example 7: Synthesis of Compound 7
Figure PCTKR2020010538-appb-img-000037
Figure PCTKR2020010538-appb-img-000037
합성예 1에서, 2,3-dichloroquinoxaline을 2,3-dichlorobenzofuro[2,3-b]pyrazine으로, phenylboronic acid를 (phenyl-d5)boronic acid로 변경하여 사용한 것을 제외하고는, 화합물 1의 제조 방법과 동일한 제조 방법으로 화합물 7을 제조하였다. (MS[M+H] += 554)In Synthesis Example 1, except that 2,3-dichloroquinoxaline was changed to 2,3-dichlorobenzofuro[2,3-b]pyrazine, and phenylboronic acid to (phenyl-d5)boronic acid was used. Compound 7 was prepared by the same method as described above. (MS[M+H] + = 554)
합성예 8: 화합물 8의 합성Synthesis Example 8: Synthesis of Compound 8
Figure PCTKR2020010538-appb-img-000038
Figure PCTKR2020010538-appb-img-000038
합성예 1에서, 중간체 A를 중간체 B로 변경하여 사용한 것을 제외하고는, 화합물 1의 제조 방법과 동일한 제조 방법으로 화합물 8을 제조하였다. (MS[M+H] += 525)In Synthesis Example 1, compound 8 was prepared in the same manner as in the preparation method of compound 1, except that intermediate A was changed to intermediate B and used. (MS[M+H] + = 525)
합성예 9: 화합물 9의 합성Synthesis Example 9: Synthesis of Compound 9
Figure PCTKR2020010538-appb-img-000039
Figure PCTKR2020010538-appb-img-000039
합성예 1에서, 중간체 A를 중간체 B로, phenylboronic acid를 [1,1'-biphenyl]-3-ylboronic acid로 변경하여 사용한 것을 제외하고는, 화합물 1의 제조 방법과 동일한 제조 방법으로 화합물 9를 제조하였다. (MS[M+H] += 601)In Synthesis Example 1, compound 9 was prepared in the same manner as in the preparation method of Compound 1, except that intermediate A was changed to intermediate B and phenylboronic acid was changed to [1,1'-biphenyl]-3-ylboronic acid. Was prepared. (MS[M+H] + = 601)
합성예 10: 화합물 10의 합성Synthesis Example 10: Synthesis of Compound 10
Figure PCTKR2020010538-appb-img-000040
Figure PCTKR2020010538-appb-img-000040
합성예 1에서, 중간체 A를 중간체 B로, 2,3-dichloroquinoxaline을 2,3-dichlorodibenzo[f,h]quinoxaline으로, phenylboronic acid를 9-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole로 변경하여 사용한 것을 제외하고는, 화합물 1의 제조 방법과 동일한 제조 방법으로 화합물 10을 제조하였다. (MS[M+H] += 790)In Synthesis Example 1, intermediate A was used as intermediate B, 2,3-dichloroquinoxaline was used as 2,3-dichlorodibenzo[f,h]quinoxaline, and phenylboronic acid was used as 9-phenyl-2-(4,4,5,5-tetramethyl). -1,3,2-dioxaborolan-2-yl)-9H-carbazole was used to prepare compound 10 in the same manner as in the preparation method of compound 1. (MS[M+H] + = 790)
합성예 11: 화합물 11의 합성Synthesis Example 11: Synthesis of Compound 11
Figure PCTKR2020010538-appb-img-000041
Figure PCTKR2020010538-appb-img-000041
합성예 1에서, 중간체 A를 중간체 C로, phenylboronic acid를 (phenyl-d5)boronic acid로 변경하여 사용한 것을 제외하고는, 화합물 1의 제조 방법과 동일한 제조 방법으로 화합물 11을 제조하였다. (MS[M+H] += 591)In Synthesis Example 1, compound 11 was prepared in the same manner as in the preparation method of compound 1, except that intermediate A was changed to intermediate C and phenylboronic acid was changed to (phenyl-d5) boronic acid. (MS[M+H] + = 591)
합성예 12: 화합물 12의 합성Synthesis Example 12: Synthesis of Compound 12
Figure PCTKR2020010538-appb-img-000042
Figure PCTKR2020010538-appb-img-000042
합성예 1에서, 중간체 A를 중간체 D로, phenylboronic acid를 dibenzo[b,d]furan-4-ylboronic acid로 변경하여 사용한 것을 제외하고는, 화합물 1의 제조 방법과 동일한 제조 방법으로 화합물 12를 제조하였다. (MS[M+H] += 650)In Synthesis Example 1, compound 12 was prepared in the same manner as in the preparation method of compound 1, except that intermediate A was changed to intermediate D and phenylboronic acid was changed to dibenzo[b,d]furan-4-ylboronic acid. I did. (MS[M+H] + = 650)
[소자예][Device example]
비교예 1Comparative Example 1
ITO(Indium Tin Oxide)가 1,400Å의 두께로 박막 증착된 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 on which ITO (Indium Tin Oxide) was deposited to a thickness of 1,400Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 하기 HI-A과 헥사니트릴 헥사아자트리페닐렌 (hexaazatriphenylene; HAT-CN)를 각각 800Å 및 50Å의 두께로 순차적으로 열 진공 증착하여 정공 주입층을 형성하였다. 그 위에 정공 수송층으로 하기 HT-A를 800Å 두께로 진공 증착하고, 그 위에 전자 저지층으로 하기 EB-A를 600Å의 두께로 열 진공 증착하였다. 이어서 상기 전자 저지층 위에, 하기 호스트 RH-A와 도판트 RD를 98:2의 중량비로 혼합한 후 400Å의 두께로 진공 증착하여 발광층을 형성하였다. 이어서, 전자 수송층으로 하기 ET-A와 Liq를 1:1의 중량비로 혼합하여 360Å의 두께로 열 진공 증착하고, 그 위에 다시 Liq를 5Å의 두께로 진공 증착하여 전자 주입층을 형성하였다.On the prepared ITO transparent electrode, the following HI-A and hexaazatriphenylene (HAT-CN) were sequentially thermally vacuum deposited to a thickness of 800 Å and 50 Å, respectively, to form a hole injection layer. The following HT-A was vacuum-deposited to a thickness of 800 Å as a hole transport layer, and EB-A was thermally vacuum-deposited to a thickness of 600 Å as an electron blocking layer thereon. Subsequently, on the electron blocking layer, the following host RH-A and dopant RD were mixed at a weight ratio of 98:2 and then vacuum deposited to a thickness of 400 Å to form a light emitting layer. Subsequently, as an electron transport layer, ET-A and Liq were mixed at a weight ratio of 1:1 and thermally vacuum deposited to a thickness of 360 Å, and Liq was vacuum deposited thereon to a thickness of 5 Å to form an electron injection layer.
상기 전자 주입층 위에, 순차적으로 마그네슘과 은을 10:1의 중량비로 혼합하여 220Å의 두께로 증착하고, 그 위에 알루미늄을 1000Å 두께로 증착하여 음극을 형성하여, 유기 발광 소자를 제조하였다.On the electron injection layer, magnesium and silver were sequentially mixed at a weight ratio of 10:1 and deposited to a thickness of 220 Å, and aluminum was deposited thereon to a thickness of 1000 Å to form a cathode, thereby manufacturing an organic light-emitting device.
Figure PCTKR2020010538-appb-img-000043
Figure PCTKR2020010538-appb-img-000043
비교예 2 및 3, 및 실시예 1 내지 12Comparative Examples 2 and 3, and Examples 1 to 12
상기 비교예 1에서 RH-A 대신에 하기 표 1에 기재된 화합물을 사용하는 것을 제외하고는, 상기 비교예 1과 동일한 방법을 이용하여, 비교예 2 및 3, 그리고 실시예 1 내지 12의 유기 발광 소자를 각각 제작하였다. Organic light emission of Comparative Examples 2 and 3, and Examples 1 to 12 using the same method as in Comparative Example 1, except that the compound shown in Table 1 below was used instead of RH-A in Comparative Example 1 Each device was fabricated.
상기 실시예 및 비교예에서 제작한 유기 발광 소자에 전류를 인가하여, 구동 전압, 전류 효율, 및 수명(LT97)을 측정하고, 그 결과를 하기 표 1에 나타내었다. 이때, 전압 및 효율은 10mA/cm 2의 전류 밀도를 인가하여 측정하였다. 또 LT97은 전류 밀도 20mA/cm 2에서 초기 휘도가 97%로 저하할 때까지의 시간을 의미한다.By applying a current to the organic light emitting device fabricated in the above Examples and Comparative Examples, driving voltage, current efficiency, and lifetime (LT97) were measured, and the results are shown in Table 1 below. At this time, voltage and efficiency were measured by applying a current density of 10mA/cm 2. In addition, LT97 refers to the time until the initial luminance decreases to 97% at the current density of 20mA/cm 2.
호스트Host @10mA/cm 2 @ 10mA / cm 2 @20mA/cm 2 @20mA/cm 2
구동전압(V)Driving voltage (V) 전류 효율(cd/A)Current efficiency (cd/A) LT97 (hr)LT97 (hr)
실시예 1Example 1 화합물 1 Compound 1 4.544.54 22.522.5 110110
실시예 2Example 2 화합물 2 Compound 2 4.534.53 22.322.3 121121
실시예 3Example 3 화합물 3 Compound 3 4.564.56 22.022.0 123123
실시예 4Example 4 화합물 4 Compound 4 4.614.61 22.822.8 111111
실시예 5Example 5 화합물 5 Compound 5 4.584.58 22.122.1 108108
실시예 6Example 6 화합물 6 Compound 6 4.534.53 21.321.3 9797
실시예 7Example 7 화합물 7 Compound 7 4.564.56 22.622.6 101101
실시예 8Example 8 화합물 8 Compound 8 4.764.76 23.123.1 106106
실시예 9Example 9 화합물 9Compound 9 4.714.71 23.023.0 104104
실시예 10Example 10 화합물 10Compound 10 4.734.73 23.323.3 108108
실시예 11Example 11 화합물 11Compound 11 4.584.58 22.122.1 132132
실시예 12Example 12 화합물 12Compound 12 4.654.65 22.922.9 9595
비교예 1Comparative Example 1 RH-ARH-A 5.105.10 18.318.3 6565
비교예 2Comparative Example 2 RH-BRH-B 5.155.15 20.920.9 8383
비교예 3Comparative Example 3 RH-CRH-C 5.815.81 12.312.3 4646
비교예 2 및 3에서 사용한 화합물 RH-B 및 RH-C는 각각 하기 구조를 갖는 화합물이다. Compounds RH-B and RH-C used in Comparative Examples 2 and 3 are compounds each having the following structure.
Figure PCTKR2020010538-appb-img-000044
Figure PCTKR2020010538-appb-img-000044
화학식 1로 표시되는 화합물은, 전자 받개 역할을 하는 화학식 2의 구조와 전자 주개 역할을 하는 모핵 구조가 연결된 형태로 구성되어 있다. 또한 성질이 전혀 다른 두 유닛이 직접 결합되어 있기 때문에 분자 내부에서 전하를 주고 받아 작은 밴드갭을 갖고 있고 이는, 적색 도펀트로의 에너지 전달에 유리하여 적색 발광층의 호스트로 활용하기 적절하다. 또한, 전자 주개 역할을 하는 모핵 구조는 벤조카바졸과 벤조퓨란 혹은 벤조씨오펜이 모두 축합되어 고리를 형성함으로써 높은 안정성을 나타낸다. 특히, 전자 받개 역할을 하는 유닛이 화학식 2의 구조와 같이 피라진 형태로 두 질소 원자가 마주보고 있는 구조는 비교예에 적용된 퀴나졸린 구조에 비해 전자를 당기는 성질이 더 강해, 호스트로 적용 시 저전압 특성을 나타낸다.The compound represented by Formula 1 has a structure in which the structure of Formula 2 serves as an electron acceptor and a parental structure that serves as an electron donor are connected. In addition, since two units of completely different properties are directly bonded, they have a small bandgap by exchanging electric charges inside the molecule, which is advantageous for energy transfer to the red dopant and is suitable for use as a host of the red light emitting layer. In addition, the parental structure serving as an electron donor exhibits high stability by condensing both benzocarbazole and benzofuran or benzothiophene to form a ring. In particular, the structure in which the unit serving as an electron acceptor has two nitrogen atoms facing each other in the form of pyrazine, as in the structure of Formula 2, has a stronger electron pulling property than the quinazoline structure applied in the Comparative Example. Show.
결과적으로, 화학식 1의 구조를 갖는 화합물들을 유기 전계 발광 소자의 적색 발광층 호스트로 적용하였을 경우, 저전압, 고효율, 장수명의 특성을 나타내 최적의 소자를 얻을 수 있다. As a result, when the compounds having the structure of Formula 1 are applied as the host of the red emission layer of the organic electroluminescent device, the characteristics of low voltage, high efficiency, and long life can be obtained, thereby obtaining an optimal device.
[부호의 설명][Explanation 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: 전자 주입 및 수송층7: light emitting layer 8: electron injection and transport layer

Claims (10)

  1. 하기 화학식 1로 표시되는 화합물:Compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2020010538-appb-img-000045
    Figure PCTKR2020010538-appb-img-000045
    상기 화학식 1에서, In Formula 1,
    X는 O, 또는 S이고,X is O or S,
    L은 단일 결합; 치환 또는 비치환된 C 6-60 아릴렌; 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴렌;이고, L is a single bond; Substituted or unsubstituted C 6-60 arylene; C 2-60 heteroarylene containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S; and,
    R 1, R 2, R 3, 및 R 4는 각각 독립적으로 수소; 중수소; 할로겐; 시아노; 치환 또는 비치환된 C 1-60 알킬; 치환 또는 비치환된 C 1-60 알콕시; 치환 또는 비치환된 C 2-60 알케닐; 치환 또는 비치환된 C 2-60 알키닐; 치환 또는 비치환된 C 3-60 사이클로알킬; 치환 또는 비치환된 C 6-60 아릴; 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴; 치환 또는 비치환된 트리(C 1-60 알킬)실릴; 또는 치환 또는 비치환된 트리(C 6-60 아릴)실릴이거나, 또는 인접한 두 개의 치환기가 결합하여 C 6-60 방향족 고리를 형성하고, R 1 , R 2 , R 3 , and R 4 are each independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 1-60 alkoxy; Substituted or unsubstituted C 2-60 alkenyl; Substituted or unsubstituted C 2-60 alkynyl; Substituted or unsubstituted C 3-60 cycloalkyl; Substituted or unsubstituted C 6-60 aryl; C 2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S; Substituted or unsubstituted tri(C 1-60 alkyl)silyl; Or a substituted or unsubstituted tri(C 6-60 aryl)silyl, or two adjacent substituents are bonded to form a C 6-60 aromatic ring,
    n1은 0 내지 2의 정수이고, n1 is an integer from 0 to 2,
    n2 내지 n4는 각각 독립적으로 0 내지 3의 정수이고, n2 to n4 are each independently an integer of 0 to 3,
    Ar 1은 하기 화학식 2로 표시되고,Ar 1 is represented by the following formula (2),
    [화학식 2][Formula 2]
    Figure PCTKR2020010538-appb-img-000046
    Figure PCTKR2020010538-appb-img-000046
    상기 화학식 2에서, In Formula 2,
    Ar 2는 치환 또는 비치환된 C 6-60 아릴; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴;이고,Ar 2 is substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S; and,
    V 1 내지 V 4는 각각 독립적으로 CR a 또는 N이고, V 1 to V 4 are each independently CR a or N,
    W 1 및 W 2는 각각 독립적으로 단일 결합, CR b, O 또는 S이며,W 1 and W 2 are each independently a single bond, CR b , O or S,
    R a 및 R b는 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C 1-60 알킬; 치환 또는 비치환된 C 6-60 아릴; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴;이거나, 또는 인접한 두 개의 R a, 또는 인접한 두 개의 R b가 서로 결합하여 C 6-60 방향족 고리를 형성하며,R a and R b are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-60 alkyl; Substituted or unsubstituted C 6-60 aryl; Or C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S; Or, or two adjacent R a , or two adjacent R b are bonded to each other to C 6- 60 forms an aromatic ring,
    p는 0 또는 1의 정수이다.p is an integer of 0 or 1.
  2. 제1항에 있어서, The method of claim 1,
    상기 L은 단일 결합인,L is a single bond,
    화합물.compound.
  3. 제1항에 있어서, The method of claim 1,
    R 1, R 2, R 3 및 R 4는 모두 수소인, R 1 , R 2 , R 3 and R 4 are all hydrogen,
    화합물.compound.
  4. 제1항에 있어서, The method of claim 1,
    R 1, R 2, R 3 및 R 4 중 하나는 페닐 또는 피리디닐이고, 나머지는 수소인,One of R 1 , R 2 , R 3 and R 4 is phenyl or pyridinyl, and the other is hydrogen,
    화합물. compound.
  5. 제1항에 있어서, The method of claim 1,
    인접한 두 개의 R 1, 인접한 두 개의 R 2, 인접한 두 개의 R 3, 또는 인접한 두 개의 R 4가 서로 결합하여 벤젠 고리를 형성하고, 나머지는 수소인,Two adjacent R 1 , two adjacent R 2 , two adjacent R 3 , or two adjacent R 4 bonded to each other to form a benzene ring, the rest being hydrogen,
    화합물. compound.
  6. 제1항에 있어서, The method of claim 1,
    상기 Ar 1은 하기 화학식 2-1 내지 2-3으로 구성되는 군으로부터 선택되는 어느 하나인,The Ar 1 is any one selected from the group consisting of the following Formulas 2-1 to 2-3,
    화합물:compound:
    [화학식 2-1][Formula 2-1]
    Figure PCTKR2020010538-appb-img-000047
    Figure PCTKR2020010538-appb-img-000047
    [화학식 2-2][Formula 2-2]
    Figure PCTKR2020010538-appb-img-000048
    Figure PCTKR2020010538-appb-img-000048
    [화학식 2-3][Formula 2-3]
    Figure PCTKR2020010538-appb-img-000049
    Figure PCTKR2020010538-appb-img-000049
    상기 화학식 2-1 내지 2-3에서,In Formulas 2-1 to 2-3,
    Ar 2는 제1항에서 정의한 바와 같고, Ar 2 is as defined in claim 1,
    R a1, R a2 및 R a3은 각각 독립적으로 수소 또는 중수소이거나; 또는 인접한 두 개의 R a1, 인접한 두 개의 R a2, 또는 인접한 두 개의 R a3이 서로 결합하여 벤젠 고리를 형성하고, 나머지는 수소이며,R a1 , R a2 and R a3 are each independently hydrogen or deuterium; Or two adjacent R a1 , two adjacent R a2 , or two adjacent R a3 bonded to each other to form a benzene ring, and the rest is hydrogen,
    R b1은 각각 독립적으로 수소 또는 중수소이고,Each R b1 is independently hydrogen or deuterium,
    W 3 및 W 4는 각각 독립적으로 O 또는 S이며,W 3 and W 4 are each independently O or S,
    p는 0 또는 1의 정수이다.p is an integer of 0 or 1.
  7. 제1항에 있어서, The method of claim 1,
    상기 Ar 1은 하기로 구성되는 군으로부터 선택되는 어느 하나인,The Ar 1 is any one selected from the group consisting of,
    화합물:compound:
    Figure PCTKR2020010538-appb-img-000050
    Figure PCTKR2020010538-appb-img-000050
    상기 화학식들에서, In the above formulas,
    Ar 2는 제1항에서 정의한 바와 같으며,Ar 2 is as defined in claim 1,
    W 3 및 W 4는 각각 독립적으로 O 또는 S이다.W 3 and W 4 are each independently O or S.
  8. 제1항에 있어서, The method of claim 1,
    상기 Ar 2는 페닐, 비페닐, 터페닐, 나프틸, 안트라세닐, 페난쓰레닐, 9,9-디메틸플루오레닐, 9,9-디페닐플루오레닐, 디벤조퓨라닐, 디벤조티오페닐, 카바졸-9-일, 또는 9-페닐-카바졸릴이고,Ar 2 is phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl , Carbazol-9-yl, or 9-phenyl-carbazolyl,
    상기 Ar 2는 비치환되거나, 또는 하나 이상의 중수소로 치환된, Ar 2 is unsubstituted or substituted with one or more deuterium,
    화합물.compound.
  9. 제1항에 있어서, The method of claim 1,
    상기 화학식 1로 표시되는 화합물은, 하기로 구성되는 군으로부터 선택되는 어느 하나인,The compound represented by Formula 1 is any one selected from the group consisting of,
    화합물:compound:
    Figure PCTKR2020010538-appb-img-000051
    Figure PCTKR2020010538-appb-img-000051
    Figure PCTKR2020010538-appb-img-000052
    Figure PCTKR2020010538-appb-img-000052
    Figure PCTKR2020010538-appb-img-000053
    Figure PCTKR2020010538-appb-img-000053
    Figure PCTKR2020010538-appb-img-000054
    Figure PCTKR2020010538-appb-img-000054
    Figure PCTKR2020010538-appb-img-000055
    Figure PCTKR2020010538-appb-img-000055
    Figure PCTKR2020010538-appb-img-000056
    Figure PCTKR2020010538-appb-img-000056
    Figure PCTKR2020010538-appb-img-000057
    Figure PCTKR2020010538-appb-img-000057
    Figure PCTKR2020010538-appb-img-000058
    Figure PCTKR2020010538-appb-img-000058
  10. 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 제1항 내지 제9항 중 어느 하나의 항에 따른 화합물을 포함하는 것인, 유기 발광 소자.A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound according to any one of claims 1 to 9 That is, an organic light emitting device.
PCT/KR2020/010538 2019-08-20 2020-08-10 Novel compound and organic light-emitting device using same WO2021033980A1 (en)

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