WO2020190116A1 - Organic light emitting diode - Google Patents

Organic light emitting diode Download PDF

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WO2020190116A1
WO2020190116A1 PCT/KR2020/095039 KR2020095039W WO2020190116A1 WO 2020190116 A1 WO2020190116 A1 WO 2020190116A1 KR 2020095039 W KR2020095039 W KR 2020095039W WO 2020190116 A1 WO2020190116 A1 WO 2020190116A1
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PCT/KR2020/095039
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김민준
이동훈
서상덕
김동희
김서연
이다정
최승원
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주식회사 엘지화학
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Priority claimed from KR1020200030989A external-priority patent/KR102311643B1/en
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Priority to CN202080005872.0A priority Critical patent/CN113056831A/en
Publication of WO2020190116A1 publication Critical patent/WO2020190116A1/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
    • 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 an organic light-emitting device having a low driving voltage, high luminous efficiency, and excellent lifespan.
  • the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material.
  • An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.
  • the organic light emitting device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode.
  • the organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
  • a voltage is applied between the two electrodes
  • holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.
  • Patent Document 0001 Korean Patent Publication No. 10-2000-0051826
  • the present invention relates to an organic light-emitting device having a low driving voltage, high luminous efficiency, and excellent lifespan.
  • the present invention provides the following organic light emitting device.
  • a second electrode provided to face the first electrode
  • the emission layer includes a first compound represented by Formula 1 below and a second compound represented by Formula 2 below,
  • X 1 to X 3 are each independently N or CH, but at least two of X 1 to X 3 are N,
  • Ar 1 and Ar 2 are each independently deuterium; Substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,
  • Z is each independently hydrogen, or deuterium, or two adjacent ones of Z are bonded to each other to include a C 6-60 aromatic ring or any one or more heteroatoms selected from the group consisting of N, O and S Can form 2-60 heteroaromatic rings,
  • the C 6-60 aromatic ring and the C 2-60 heteroaromatic ring are unsubstituted or substituted with deuterium,
  • n is an integer from 0 to 6
  • A is a substituent represented by the following formula 1-1,
  • R 1 to R 4 are each independently hydrogen or deuterium, or two adjacent ones of R 1 to R 4 are bonded to each other to form a C 6-60 aromatic ring or any one selected from the group consisting of N, O and S Can form a C 2-60 heteroaromatic ring containing more than one heteroatom
  • the C 6-60 aromatic ring and the C 2-60 heteroaromatic ring are unsubstituted or substituted with deuterium,
  • n is an integer from 0 to 6
  • T 1 to T 4 are each independently a substituted or unsubstituted C 6-60 aromatic ring fused with a neighboring pentagonal ring; Or a substituted or unsubstituted C 2-60 heteroaromatic ring containing any one or more heteroatoms selected from the group consisting of N, O and S,
  • L 1 and L 2 are each independently a single bond; Substituted or unsubstituted C 6-60 arylene; Or substituted or unsubstituted C 2-60 heteroarylene including any one or more heteroatoms selected from the group consisting of N, O and S,
  • Ar 3 and Ar 4 are each independently a substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S.
  • the organic light-emitting device described above may simultaneously include the first compound and the second compound as a host material in the emission layer, thereby exhibiting low driving voltage, high luminous efficiency, and long lifespan characteristics.
  • 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 cathode 4 shows an example of an organic light emitting device.
  • 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 a heteroaryl group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two
  • a substituent to which two or more substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
  • the number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the ester group may be substituted with an oxygen of the ester group with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms.
  • it may be a compound of the following structural formula, but is not limited thereto.
  • the number of carbon atoms of the imide group is not particularly limited, but it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.
  • the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, but is not limited thereto.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms.
  • alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhex
  • the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.
  • the cycloalkyl group is not particularly limited, but is preferably 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms.
  • the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms.
  • the aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a 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 heterogeneous elements, and the number of carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms.
  • heteroaryl include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, Carbazole group, benzo
  • aromatic ring refers to condensation having a plurality of aromatics such as a fluorene ring as well as a condensed monocyclic or condensed polycyclic ring having only carbon as a ring-forming atom and having aromaticity in the entire molecule. It is understood that the monocyclic ring also includes a condensed polycyclic ring formed by linking adjacent substituents. At this time, the number of carbon atoms of the aromatic ring is 6 to 60, or 6 to 30, or 6 to 20, but is not limited thereto.
  • the aromatic ring may be a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a fluorene ring, and the like, but is not limited thereto.
  • heterocyclic ring refers to a hetero-condensed monocyclic or hetero-condensed ring containing at least one heteroatom among O, N, and S other than carbon as a ring-forming atom and having aromaticity in the entire molecule. It means a polycyclic ring.
  • the number of carbon atoms of the hetero ring is 2 to 60, or 2 to 30, or 2 to 20, but is not limited thereto.
  • the hetero ring may be a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and the like, but is not limited thereto.
  • the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above.
  • the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group.
  • heteroaryl among the heteroarylamines may be described above for heteroaryl.
  • 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 the heterocycle is formed by bonding of two substituents.
  • An organic light-emitting device includes a first electrode on a substrate and a second electrode provided opposite to the first electrode, and in this case, when the first electrode is an anode, the second electrode is a cathode and When the first electrode is a cathode, the second electrode is an anode.
  • the organic light-emitting device may be a normal type organic light-emitting device in which an anode, an emission layer, and a cathode are sequentially stacked on a substrate.
  • the organic light-emitting device may be an organic light-emitting device of an inverted type in which a cathode, an emission layer, and an anode are sequentially stacked on a substrate.
  • 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; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the cathode material is a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO 2 /Al, but are not limited thereto.
  • the organic light emitting device includes a light emitting layer provided between the first electrode and the second electrode, which is a layer that emits light in a visible light region by combining holes and electrons transported from the hole transport layer and the electron transport layer,
  • the emission layer includes a first compound represented by Formula 1 and a second compound represented by Formula 2.
  • both the first compound and the second compound are used as host materials.
  • the first compound is an N-type host material
  • the second compound is a P-type host material
  • the emission layer of the organic light emitting device includes the N-type host material and the P-type host material at the same time, a single material host Compared to the case of use, it can exhibit improved effects in terms of efficiency and life.
  • the first compound has a structure in which both an N-containing 6-membered heterocyclic group and an A substituent (benzocarbazolyl-based substituent) are bonded to one benzene ring of a dibenzothiophene-based core.
  • the first compound having such a structure includes a compound having a structure in which an N-containing 6-membered heterocyclic group and an A substituent (benzocarbazolyl-based substituent) are each bonded to another benzene ring of a dibenzothiophene-based core, and the A substituent (Compared to a compound in which a substituted/unsubstituted carbazolyl substituent instead of a benzocarbazolyl substituent) is bonded, stability against electrons and holes is high, and the balance between electrons and holes can be stably maintained.
  • an N-containing 6 membered-heterocyclic group and an A substituent are each bonded to another benzene ring of the dibenzothiophene-based core.
  • an organic light-emitting device employing a compound having a structure and a compound in which a substituted/unsubstituted carbazolyl substituent is combined instead of the A substituent (benzocarbazolyl-based substituent) the characteristics of low driving voltage, high efficiency and long life Show.
  • the first compound is represented by any one of the following Formulas 1A to 1D, depending on the bonding position of the N-containing 6-membered heterocyclic group in the dibenzothiophene-based core:
  • all of X 1 to X 3 are N.
  • each of Z is independently hydrogen or deuterium, or two adjacent to Z may be bonded to each other to form an unsubstituted or deuterated C 6-20 aromatic ring, for example a benzene ring. .
  • n which means the number of Z, is 0, 1, 2, 3, 4, 5, or 6.
  • the first compound may be represented by any one of the following Formulas 1A-1 to 1D-1:
  • Z 1 to Z 3 is a substituent A represented by Formula 1-1, and the others are each independently hydrogen or deuterium, or two of Z 1 to Z 3 that are adjacent to each other are unsubstituted or deuterium Can form a benzene ring substituted with,
  • Z 4 to Z 7 are each independently hydrogen or deuterium, or two adjacent two of Z 4 to Z 7 may be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium,
  • Ar 1 and Ar 2 are as defined in Chemical Formula 1.
  • Z 1 is A
  • Z 2 and Z 3 are each independently hydrogen or deuterium, or Z 2 and Z 3 are combined with each other to form a benzene ring unsubstituted or substituted with deuterium;
  • Z 2 is A, and Z 1 and Z 3 are each independently hydrogen or deuterium; or
  • Z 3 is A, and Z 1 and Z 2 are each independently hydrogen or deuterium, or Z 1 and Z 2 may be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium.
  • Z 1 is A
  • Z 2 and Z 3 are each independently hydrogen or deuterium, or Z 2 and Z 3 are combined with each other to form a benzene ring unsubstituted or substituted with deuterium;
  • Z 2 is A, and Z 1 and Z 3 are each independently hydrogen or deuterium; or
  • Z 3 is A, and Z 1 and Z 2 may each independently be hydrogen or deuterium.
  • Z 1 is A, and Z 2 and Z 3 are each independently hydrogen or deuterium;
  • Z 2 is A, and Z 1 and Z 3 are each independently hydrogen or deuterium; or
  • Z 3 is A, and Z 1 and Z 2 are each independently hydrogen or deuterium, or Z 1 and Z 2 may be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium.
  • Z 1 is A
  • Z 2 and Z 3 are each independently hydrogen or deuterium, or Z 2 and Z 3 are combined with each other to form a benzene ring unsubstituted or substituted with deuterium;
  • Z 2 is A, and Z 1 and Z 3 are each independently hydrogen or deuterium; or
  • Z 3 is A, and Z 1 and Z 2 are each independently hydrogen or deuterium, or Z 1 and Z 2 may be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium.
  • the first compound may be represented by any one of the following Formulas 3-1 to 3-7:
  • Each R is independently hydrogen or deuterium
  • Ar 1 and Ar 2 are as defined in Chemical Formula 1.
  • Ar 1 and Ar 2 are each independently unsubstituted or substituted with heavy hydrogen, or C 6-20 aryl C 6-20 aryl.
  • Ar 1 and Ar 2 are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzothiophenyl, dibenzofuranyl, or carbazolyl,
  • Ar 1 and Ar 2 may be unsubstituted or substituted with 1 to 5 substituents each independently selected from the group consisting of deuterium and C 6-20 aryl.
  • Ar 1 and Ar 2 are each independently any one selected from the group consisting of:
  • Ar 1 and Ar 2 may be the same as each other, or Ar 1 and Ar 2 may be different.
  • R 1 to R 4 are each independently hydrogen or deuterium, or two adjacent to R 1 to R 4 are bonded to each other to be unsubstituted or deuterium It can form a substituted benzene ring.
  • m which means the number of deuterium (D)
  • D deuterium
  • A is any one of the substituents represented by the following formulas a1 to a4:
  • the compound represented by Formula 1 may be prepared by a manufacturing method such as the following Scheme 1 as an example.
  • each of X is independently halogen, preferably bromo or chloro, and definitions for other substituents are as described above.
  • the compound represented by Formula 1 is prepared by combining starting materials SM1 and SM2 through an amine substitution reaction.
  • This amine substitution reaction is preferably carried out in the presence of a palladium catalyst and a base.
  • the reactor for the amine substitution reaction may be appropriately changed, and the method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.
  • the second compound is a biscarbazole-based compound, and preferably, T 1 to T 4 have a structure in which each independently a C 6-20 aromatic ring. More preferably, T 1 to T 4 are unsubstituted or deuterium-substituted benzene rings, or unsubstituted or deuterium-substituted naphthalene rings.
  • T 1 to T 4 are benzene rings, wherein the second compound is represented by the following formula 2-1:
  • r and s are each independently an integer of 0 to 7,
  • L 1 and L 2 are each independently a single bond or an unsubstituted C 6-20 arylene.
  • L 1 and L 2 are each independently a single bond, phenylene, or naphthylene.
  • Ar 3 and Ar 4 are each independently C 6-20 aryl unsubstituted or substituted with C 1-10 alkyl or C 6-20 aryl; Or C 2-20 heteroaryl including O or S.
  • Ar 3 and Ar 4 are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, fluorenyl, spirobifluorenyl, fluoranthenyl, Dibenzothiophenyl, dibenzofuranyl,
  • Ar 3 and Ar 4 may be unsubstituted or substituted with 1 to 4 substituents each independently selected from the group consisting of C 1-10 alkyl and C 6-20 aryl.
  • Ar 3 and Ar 4 are each independently any one selected from the group consisting of:
  • Ar 3 and Ar 4 may be the same as each other, or Ar 3 and Ar 4 may be different.
  • the second compound is represented by the following formula 2-2:
  • L 1 and L 2 are each independently a single bond, phenylene, or naphthylene,
  • Ar 3 and Ar 4 are as defined in Chemical Formula 2.
  • the compound represented by Formula 2 may be prepared by a manufacturing method as shown in Scheme 2 below, for example.
  • each of X is independently halogen, preferably bromo or chloro, and the definition of other substituents is as described above.
  • the compound represented by Formula 2 is prepared by combining the starting materials SM3 and SM4 through a Suzuki-coupling reaction.
  • This Suzuki-coupling reaction is preferably carried out in the presence of a palladium catalyst and a base.
  • the reactor for the Suzuki-coupling reaction may be appropriately changed, and the method of preparing the compound represented by Formula 2 may be more specific in Preparation Examples to be described later.
  • the first compound and the second compound are preferably included in the light-emitting layer in a weight ratio of 99:1 to 1:99, more preferably 50:50, to implement a device having high efficiency and long life.
  • the emission layer further includes a dopant material in addition to the host material.
  • 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
  • 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.
  • the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.
  • the light emitting layer may include the following iridium complex compound as a dopant material, but is not limited thereto.
  • the organic light emitting device may further include a hole injection layer on the anode.
  • the hole injection layer is made of a hole injection material, and the hole injection material has the ability to transport holes, and thus has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material.
  • a compound that prevents migration to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferable.
  • hole injection material examples include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene )-Based organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.
  • the organic light-emitting device may further include a hole transport layer on the anode or on the hole injection layer formed on the anode.
  • the hole transport layer is a layer that receives holes from an anode or a hole injection layer formed on the anode and transports holes to the emission layer, and the hole transport material included in the hole transport layer receives holes from the anode or the hole injection layer to the emission layer.
  • a transferable material a material with high mobility for holes is suitable.
  • the hole transport material include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion.
  • the organic light-emitting device may further include an electron suppression layer on the hole transport layer.
  • the electron suppression 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 means a layer that plays a role in improving
  • the electron-suppressing layer includes an electron-blocking material, and examples of such an electron-blocking material include a compound represented by Formula 1 or an arylamine-based organic material, but are not limited thereto.
  • the organic balsop device may further include a hole blocking layer 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 such hole-blocking materials include: a subazine derivative including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; A compound into which an electron withdrawing group such as a phosphine oxide derivative has been introduced may be used, but is not limited thereto.
  • the organic light-emitting device may include an electron transport layer on the emission layer or on the hole blocking layer.
  • the electron transport layer is a layer that receives electrons from a cathode or an electron injection layer to be described later and transports electrons to the emission layer.
  • an electron transport material included in the electron transport layer electrons capable of receiving electrons from the cathode and transferring them to the emission layer Materials with high mobility are suitable.
  • the electron transport material 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 transport layer can be used with any desired cathode material as used according to the prior art.
  • suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.
  • the organic light-emitting device may further include an electron injection layer between the electron transport layer and the cathode.
  • the electron injection layer is a layer that injects electrons from the cathode, and the electron injection material included in the electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and excellent electron injection to the light emitting layer or the light emitting material A compound having an effect, preventing the movement of excitons generated in the light emitting layer to the hole injection layer, and having excellent thin film formation ability is preferable.
  • materials that can be used as the electron injection layer include LiF, NaCl, CsF, Li 2 O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, tria Sol, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and the like, derivatives thereof, metal complex compounds, and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.
  • 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 injection and transport layer that simultaneously serves as an electron transport layer and an electron injection layer for transporting received electrons to the emission layer.
  • 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 first compound and the second compound may be included in the emission layer.
  • FIG. 2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron suppressing layer 7, a hole blocking layer 8, an electron injection and transport layer ( 8) and the cathode 4 shows an example of an organic light emitting device.
  • the first compound and the second compound may be included in the emission layer.
  • the organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described configurations. 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 each of the above-described layers thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
  • PVD physical vapor deposition
  • the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method of a host and a dopant.
  • the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.
  • an organic light-emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890).
  • the manufacturing method is not limited thereto.
  • the 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.
  • intermediate 2-1-1 (10g, 25.2mmol) and intermediate 2-1-2 (8g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water and added. After sufficient stirring, reflux was performed, and then bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-2-1 (10g, 25.2mmol) and intermediate 2-2-2 (8g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water and added. After sufficient stirring, reflux was performed, and then bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-4-1 (10g, 25.2mmol) and intermediate 2-4-2 (9.3g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.3mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-5-1 (10g, 25.2mmol) and intermediate 2-5-2 (10.1g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.3mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-6-1 (10g, 25.2mmol) and intermediate 2-6-2 (11.4g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.3mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-7-1 (10g, 22.4mmol) and intermediate 2-7-2 (10.2g, 24.6mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.4g, 89.5mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-8-1 (10g, 17.9mmol) and intermediate 2-8-2 (5.6g, 19.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (9.9g, 71.5mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-9-1 (10g, 21.1mmol) and intermediate 2-9-2 (6.7g, 23.3mmol) were added to 200 ml of THF, stirred, and potassium carbonate (11.7g, 84.6mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-10-1 (10g, 27mmol) and intermediate 2-10-2 (10g, 29.6mmol) were added to 200 ml of THF, stirred, and potassium carbonate (14.9g, 107.8mmol) was dissolved in water and added. After sufficiently stirring and refluxing, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-11-1 (10g, 27mmol) and intermediate 2-11-2 (11.5g, 29.6mmol) were added to 200 ml of THF, stirred, and potassium carbonate (14.9g, 107.8mmol) was dissolved in water and added. After sufficient stirring, reflux was performed, and then bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-12-1 (10g, 23.8mmol) and intermediate 2-12-2 (8.8g, 26.1mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.1g, 95mmol) was dissolved in water and added. Then, after sufficiently stirring, refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-13-1 (10g, 24.3mmol) and intermediate 2-13-2 (11.1g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-14-1 (10g, 24.3mmol) and intermediate 2-14-2 (7.7g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-15-1 (10g, 24.3mmol) and intermediate 2-15-2 (9g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water and added. Then, after sufficiently stirring, refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-16-1 (10g, 24.3mmol) and intermediate 2-16-2 (11.1g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-17-1 (10g, 24.3mmol) and intermediate 2-17-2 (10.1g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-18-1 (10g, 24.3mmol) and intermediate 2-18-2 (10.5g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-19-1 (10g, 24.3mmol) and intermediate 2-19-2 (10.5g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-20-1 (10g, 23.4mmol) and intermediate 2-20-2 (9.4g, 25.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.9g, 93.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-21-1 (10g, 23.4mmol) and intermediate 2-21-2 (10.6g, 25.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.9g, 93.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-22-1 (10g, 23.4mmol) and intermediate 2-22-2 (11.3g, 25.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.9g, 93.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • intermediate 2-23-1 (10g, 23.4mmol) and intermediate 2-23-2 (10.1g, 25.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.9g, 93.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • Comparative example 1 Fabrication of an organic light emitting device
  • a glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000 ⁇ was put in distilled water dissolved in a detergent and washed with ultrasonic waves.
  • ITO indium tin oxide
  • a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured by Millipore Co. was used as distilled water.
  • ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner.
  • the substrate was transported to a vacuum evaporator.
  • the following HI-1 compound was formed as a hole injection layer on the prepared ITO transparent electrode to a thickness of 1150 ⁇ , but the following compound A-1 was p-doping at a concentration of 1.5%.
  • the following HT-1 compound was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800 ⁇ .
  • an electron suppressing layer was formed by vacuum depositing the following EB-1 compound with a film thickness of 150 ⁇ on the hole transport layer.
  • the compound 1-1 prepared in Preparation Example 1-1 and the following Dp-7 compound were vacuum-deposited at a weight ratio of 98:2 on the EB-1 deposition film to form a red light emitting layer having a thickness of 400 ⁇ .
  • a hole blocking layer was formed by vacuum depositing the following HB-1 compound with a film thickness of 30 ⁇ on the emission layer. Subsequently, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300 ⁇ . Lithium fluoride (LiF) at a thickness of 12 ⁇ and aluminum at a thickness of 1,000 ⁇ were sequentially deposited on the electron injection and transport layer to form a negative electrode.
  • LiF lithium fluoride
  • the deposition rate of organic matter was maintained at 0.4 ⁇ 0.7 ⁇ /sec
  • the deposition rate of lithium fluoride at the cathode was 0.3 ⁇ /sec
  • the deposition rate of aluminum was 2 ⁇ /sec
  • the vacuum degree during deposition was 2 x 10 ⁇ Maintaining 7 to 5 x 10 -6 torr, an organic light emitting device was manufactured.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the compound shown in Table 1 below was used instead of compound 1-1 in the organic light-emitting device of Comparative Example 1.
  • the organic light-emitting device of the embodiment in which the first compound represented by Formula 1 and the second compound represented by Formula 2 were simultaneously used as the host material of the emission layer is a compound represented by Formulas 1 and 2 Compared to the organic light-emitting device of Comparative Example in which only one of or neither is employed, the same or superior luminous efficiency, low driving voltage, and remarkably improved lifetime characteristics are exhibited.
  • the device according to the example exhibited higher efficiency and longer life than the device of the comparative example employing the compound represented by Formula 1 as a single host.
  • the device according to the embodiment has improved efficiency and lifespan characteristics compared to the device of Comparative Example employing Comparative Examples Compounds C-1 to C-12 as a first host and a compound represented by Formula 2 as a second host. Became.
  • Comparative Example employing Comparative Examples Compounds C-1 to C-12 as a first host and a compound represented by Formula 2 as a second host. Became.
  • the combination of the first compound represented by Formula 1 and the second compound represented by Formula 2 was used as a cohost, it was confirmed that energy was effectively transferred to the red dopant in the red light emitting layer. This can be determined because the first compound has high stability against electrons and holes, and also because the amount of holes increased as the second compound was used simultaneously, and a more stable balance of electrons and holes was maintained in the red light emitting layer. It is judged as.
  • the organic light-emitting device when considering that the luminous efficiency and lifetime characteristics of the organic light-emitting device have a trade-off relationship with each other, the organic light-emitting device employing a combination of the compounds of the present invention has significantly improved device characteristics compared to the comparative example device. It can be seen as representing.
  • substrate 2 anode

Abstract

The present invention provides an organic light emitting diode.

Description

유기 발광 소자Organic light emitting element
본 출원은 2019년 3월 15일자 한국 특허 출원 제10-2019-0030168호 및 2020년 3월 12일자 한국 특허 출원 제10-2020-0030989호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌들에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0030168 filed March 15, 2019 and Korean Patent Application No. 10-2020-0030989 filed March 12, 2020. All contents disclosed in the documents are included as part of this specification.
본 발명은 구동 전압이 낮고, 발광 효율이 높으며, 수명이 우수한 유기 발광 소자에 관한 것이다. The present invention relates to an organic light-emitting device having a low driving voltage, high luminous efficiency, and excellent lifespan.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 넓은 시야각, 우수한 콘트라스트, 빠른 응답 시간을 가지며, 휘도, 구동 전압 및 응답 속도 특성이 우수하여 많은 연구가 진행되고 있다. In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.
유기 발광 소자는 일반적으로 양극과 음극 및 상기 양극과 음극 사이에 유기물 층을 포함하는 구조를 가진다. 상기 유기물 층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어질 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. The organic light emitting device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.
상기와 같은 유기 발광 소자에 사용되는 유기물에 대하여 새로운 재료의 개발이 지속적으로 요구되고 있다.Development of new materials for organic materials used in organic light emitting devices as described above is continuously required.
[선행기술문헌][Prior technical literature]
[특허문헌][Patent Literature]
(특허문헌 0001) 한국특허 공개번호 제10-2000-0051826호(Patent Document 0001) Korean Patent Publication No. 10-2000-0051826
본 발명은 구동 전압이 낮고, 발광 효율이 높으며, 수명이 우수한 유기 발광 소자에 관한 것이다. The present invention relates to an organic light-emitting device having a low driving voltage, high luminous efficiency, and excellent lifespan.
상기 과제를 해결하기 위하여, 본 발명은 하기의 유기 발광 소자를 제공한다.In order to solve the above problems, the present invention provides the following organic light emitting device.
본 발명에 따른 유기 발광 소자는,The organic light-emitting device according to the present invention,
제1 전극;A first electrode;
상기 제1 전극과 대향하여 구비된 제2 전극; 및A second electrode provided to face the first electrode; And
상기 제1 전극과 상기 제2 전극 사이에 구비된 발광층을 포함하고,Comprising a light emitting layer provided between the first electrode and the second electrode,
상기 발광층은 하기 화학식 1로 표시되는 제1 화합물 및 하기 화학식 2로 표시되는 제2 화합물을 포함하고,The emission layer includes a first compound represented by Formula 1 below and a second compound represented by Formula 2 below,
[화학식 1][Formula 1]
Figure PCTKR2020095039-appb-img-000001
Figure PCTKR2020095039-appb-img-000001
상기 화학식 1에서,In Formula 1,
X 1 내지 X 3는 각각 독립적으로, N 또는 CH이되, X 1 내지 X 3 중 적어도 둘은 N이고, X 1 to X 3 are each independently N or CH, but at least two of X 1 to X 3 are N,
Ar 1 및 Ar 2는 각각 독립적으로, 중수소; 치환 또는 비치환된 C 6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴이고,Ar 1 and Ar 2 are each independently deuterium; Substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,
Z는 각각 독립적으로, 수소, 또는 중수소이거나, 또는 Z 중 인접하는 둘은 서로 결합하여 C 6-60 방향족 고리 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로방향족 고리를 형성할 수 있고, Z is each independently hydrogen, or deuterium, or two adjacent ones of Z are bonded to each other to include a C 6-60 aromatic ring or any one or more heteroatoms selected from the group consisting of N, O and S Can form 2-60 heteroaromatic rings,
여기서, 상기 C 6-60 방향족 고리 및 상기 C 2-60 헤테로방향족 고리는 비치환되거나, 또는 중수소로 치환되고,Here, the C 6-60 aromatic ring and the C 2-60 heteroaromatic ring are unsubstituted or substituted with deuterium,
n은 0 내지 6의 정수이고,n is an integer from 0 to 6,
A는 하기 화학식 1-1로 표시되는 치환기이고,A is a substituent represented by the following formula 1-1,
[화학식 1-1][Formula 1-1]
Figure PCTKR2020095039-appb-img-000002
Figure PCTKR2020095039-appb-img-000002
상기 화학식 1-1에서,In Formula 1-1,
R 1 내지 R 4는 각각 독립적으로, 수소 또는 중수소이거나, 또는 R 1 내지 R 4 중 인접하는 둘은 서로 결합하여 C 6-60 방향족 고리 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로방향족 고리를 형성할 수 있고,R 1 to R 4 are each independently hydrogen or deuterium, or two adjacent ones of R 1 to R 4 are bonded to each other to form a C 6-60 aromatic ring or any one selected from the group consisting of N, O and S Can form a C 2-60 heteroaromatic ring containing more than one heteroatom
여기서, 상기 C 6-60 방향족 고리 및 상기 C 2-60 헤테로방향족 고리는 비치환되거나, 또는 중수소로 치환되고,Here, the C 6-60 aromatic ring and the C 2-60 heteroaromatic ring are unsubstituted or substituted with deuterium,
D는 중수소를 의미하고,D means deuterium,
m은 0 내지 6의 정수이고,m is an integer from 0 to 6,
[화학식 2] [Formula 2]
Figure PCTKR2020095039-appb-img-000003
Figure PCTKR2020095039-appb-img-000003
상기 화학식 2에서,In Chemical Formula 2,
T 1 내지 T 4는 각각 독립적으로, 이웃하는 오각고리와 융합되는, 치환 또는 비치환된 C 6-60 방향족 고리; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로방향족 고리이고,T 1 to T 4 are each independently a substituted or unsubstituted C 6-60 aromatic ring fused with a neighboring pentagonal ring; Or a substituted or unsubstituted C 2-60 heteroaromatic ring containing any one or more heteroatoms selected from the group consisting of N, O and S,
L 1 및 L 2는 각각 독립적으로, 단일 결합; 치환 또는 비치환된 C 6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴렌이고,L 1 and L 2 are each independently a single bond; Substituted or unsubstituted C 6-60 arylene; Or substituted or unsubstituted C 2-60 heteroarylene including any one or more heteroatoms selected from the group consisting of N, O and S,
Ar 3 및 Ar 4는 각각 독립적으로, 치환 또는 비치환된 C 6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴이다.Ar 3 and Ar 4 are each independently a substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S.
상술한 유기 발광 소자는 발광층에 호스트 물질로 제1 화합물 및 제2 화합물을 동시에 포함하여, 낮은 구동 전압, 높은 발광 효율 및 장수명 특성을 나타낼 수 있다. The organic light-emitting device described above may simultaneously include the first compound and the second compound as a host material in the emission layer, thereby exhibiting low driving voltage, high luminous efficiency, and long lifespan characteristics.
도 1은 기판(1), 양극(2), 발광층(3) 및 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(3), 전자억제층(7), 정공저지층(8), 전자주입 및 수송층(8) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron suppressing layer 7, a hole blocking layer 8, an electron injection and transport layer ( 8) and the cathode 4 shows an example of an organic light emitting device.
이하, 본 발명의 이해를 돕기 위하여 보다 상세히 설명한다.Hereinafter, it will be described in more detail to aid in understanding the present invention.
(용어의 정의)(Definition of Terms)
본 명세서에서,
Figure PCTKR2020095039-appb-img-000004
및
Figure PCTKR2020095039-appb-img-000005
는 다른 치환기에 연결되는 결합을 의미한다.In this specification,
Figure PCTKR2020095039-appb-img-000004
And
Figure PCTKR2020095039-appb-img-000005
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 헤테로아릴기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환되거나, 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환 또는 비치환된 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 비페닐기일 수 있다. 즉, 비페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수 있다.In the present specification, the term "substituted or unsubstituted" refers to deuterium; 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 a heteroaryl group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the aforementioned 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 PCTKR2020095039-appb-img-000006
Figure PCTKR2020095039-appb-img-000006
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 PCTKR2020095039-appb-img-000007
Figure PCTKR2020095039-appb-img-000007
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 PCTKR2020095039-appb-img-000008
Figure PCTKR2020095039-appb-img-000008
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, 비페닐기, 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 phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a 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 PCTKR2020095039-appb-img-000009
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 PCTKR2020095039-appb-img-000009
Etc. However, it is not limited thereto.
본 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 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 heterogeneous elements, and the number of carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of heteroaryl include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group (phenanthroline), isoxazolyl group, thiadiazolyl Group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.
본 명세서에서 사용되는 용어 "방향족 고리"는 고리 형성 원자로서 탄소만을 포함하면서 분자 전체가 방향족성(aromaticity)을 갖는 축합단환 또는 축합다환 고리뿐 아니라, 플루오렌 고리와 같은 복수 개의 방향족성을 갖는 축합단환 고리가 인접한 치환기끼리 연결되어 형성된 축합다환 고리 또한 포함하는 것으로 이해된다. 이때, 상기 방향족 고리의 탄소수는 6 내지 60, 또는 6 내지 30, 또는 6 내지 20이나, 이에 한정되는 것은 아니다. 또한, 상기 방향족 고리로는 벤젠 고리, 나프탈렌 고리, 안트라센 고리, 페난쓰렌 고리, 파이렌 고리, 플루오렌 고리 등이 될 수 있으나, 이에 한정되는 것은 아니다. The term "aromatic ring" as used herein refers to condensation having a plurality of aromatics such as a fluorene ring as well as a condensed monocyclic or condensed polycyclic ring having only carbon as a ring-forming atom and having aromaticity in the entire molecule. It is understood that the monocyclic ring also includes a condensed polycyclic ring formed by linking adjacent substituents. At this time, the number of carbon atoms of the aromatic ring is 6 to 60, or 6 to 30, or 6 to 20, but is not limited thereto. Further, the aromatic ring may be a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a fluorene ring, and the like, but is not limited thereto.
본 명세서에서 사용되는 용어 "헤테로방향족 고리(heterocyclic ring)"는 고리 형성 원자로서 탄소 외 O, N, 및 S 중 1개 이상의 헤테로원자를 포함하면서 분자 전체가 방향족성을 갖는 헤테로축합단환 또는 헤테로축합다환 고리를 의미한다. 상기 헤테로 고리의 탄소수는 2 내지 60, 또는 2 내지 30, 또는 2 내지 20이나, 이에 한정되는 것은 아니다. 또한, 상기 헤테로 고리로는 벤조퓨란 고리, 벤조티오펜 고리, 디벤조퓨란 고리, 디벤조티오펜 고리 등이 될 수 있으나, 이에 한정되는 것은 아니다. The term "heterocyclic ring" as used herein refers to a hetero-condensed monocyclic or hetero-condensed ring containing at least one heteroatom among O, N, and S other than carbon as a ring-forming atom and having aromaticity in the entire molecule. It means a polycyclic ring. The number of carbon atoms of the hetero ring is 2 to 60, or 2 to 30, or 2 to 20, but is not limited thereto. In addition, the hetero ring may be a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and the like, but is not limited thereto.
본 명세서에 있어서, 아르알킬기, 아르알케닐기, 알킬아릴기, 아릴아민기 중의 아릴기는 전술한 아릴기의 예시와 같다. 본 명세서에 있어서, 아르알킬기, 알킬아릴기, 알킬아민기 중 알킬기는 전술한 알킬기의 예시와 같다. 본 명세서에 있어서, 헤테로아릴아민 중 헤테로아릴은 전술한 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 among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group. In the present specification, heteroaryl among the heteroarylamines may be described above for heteroaryl. 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 the heterocycle is formed by bonding of two substituents.
이하, 각 구성 별로 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail for each configuration.
제1 전극 및 제2 전극First electrode and second electrode
일 구현예에 따른 유기 발광 소자는, 기판 상에 제1 전극 및 상기 제1 전극과 대향하여 구비된 제2 전극을 포함하고, 이때, 상기 제1 전극이 양극인 경우 상기 제2 전극은 음극이고, 상기 제1 전극이 음극인 경우 상기 제2 전극은 양극이다.An organic light-emitting device according to an embodiment includes a first electrode on a substrate and a second electrode provided opposite to the first electrode, and in this case, when the first electrode is an anode, the second electrode is a cathode and When the first electrode is a cathode, the second electrode is an anode.
구체적으로, 상기 유기 발광 소자는 기판 상에 양극, 발광층 및 음극이 순차적으로 적층된 정방향 구조(normal type)의 유기 발광 소자일 수 있다. 다르게는, 상기 유기 발광 소자는 기판 상에 음극, 발광층 및 양극이 순차적으로 적층된 역방향 구조(inverted type)의 유기 발광 소자일 수 있다. Specifically, the organic light-emitting device may be a normal type organic light-emitting device in which an anode, an emission layer, and a cathode are sequentially stacked on a substrate. Alternatively, the organic light-emitting device may be an organic light-emitting device of an inverted type in which a cathode, an emission layer, and an anode are sequentially stacked on a substrate.
상기 양극 물질로는 통상 유기물 층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 상기 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SNO 2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO:Al or SNO 2 :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.
상기 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 상기 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO 2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO 2 /Al, but are not limited thereto.
발광층Emitting layer
일 구현예에 따른 유기 발광 소자는 상기 제1 전극과 제2 전극 사이에 구비된, 정공 수송층과 전자 수송층으로부터 수송된 정공과 전자가 결합되어 가시광선 영역의 빛을 내는 층인 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 제1 화합물과 상기 화학식 2로 표시되는 제2 화합물을 포함한다.The organic light emitting device according to an embodiment includes a light emitting layer provided between the first electrode and the second electrode, which is a layer that emits light in a visible light region by combining holes and electrons transported from the hole transport layer and the electron transport layer, The emission layer includes a first compound represented by Formula 1 and a second compound represented by Formula 2.
이때, 상기 발광층 내에서 상기 제1 화합물과 상기 제2 화합물은 모두 호스트 재료로 사용된다. 구체적으로, 상기 제1 화합물은 N형 호스트 물질이고, 상기 제2 화합물은 P형 호스트 물질로, 유기 발광 소자의 발광층이 이러한 N형 호스트 물질과 P형 호스트 물질을 동시에 포함하는 경우 단일 물질 호스트를 사용하는 경우에 비하여, 효율 및 수명 측면에서 개선된 효과를 나타낼 수 있다. In this case, in the emission layer, both the first compound and the second compound are used as host materials. Specifically, the first compound is an N-type host material, and the second compound is a P-type host material, and when the emission layer of the organic light emitting device includes the N-type host material and the P-type host material at the same time, a single material host Compared to the case of use, it can exhibit improved effects in terms of efficiency and life.
특히, 상기 제1 화합물은 디벤조티오펜계 코어의 하나의 벤젠 고리에 N 함유 6원-헤테로고리기와 A 치환기(벤조카바졸일계 치환기)가 모두 결합된 구조를 갖는다. 이러한 구조를 갖는 제1 화합물은 N 함유 6원-헤테로고리기와 A 치환기(벤조카바졸일계 치환기)가 디벤조티오펜계 코어의 다른 벤젠 고리에 각각 결합되어 있는 구조를 갖는 화합물 및 상기 A 치환기(벤조카바졸일계 치환기) 대신 치환/비치환된 카바졸일 치환기가 결합된 화합물에 비하여, 전자와 정공에 대한 안정도가 높고, 전자와 정공의 균형을 안정적으로 유지할 수 있다. 따라서, 상기 제1 화합물을 채용한 유기 발광 소자는, (1) N 함유 6원-헤테로고리기와 A 치환기(벤조카바졸일계 치환기)가 디벤조티오펜계 코어의 다른 벤젠 고리에 각각 결합되어 있는 구조를 갖는 화합물 및 (2) 상기 A 치환기(벤조카바졸일계 치환기) 대신 치환/비치환된 카바졸일 치환기가 결합된 화합물을 채용한 유기 발광 소자에 비하여, 저구동 전압, 고효율 및 장수명의 특성을 나타낸다. In particular, the first compound has a structure in which both an N-containing 6-membered heterocyclic group and an A substituent (benzocarbazolyl-based substituent) are bonded to one benzene ring of a dibenzothiophene-based core. The first compound having such a structure includes a compound having a structure in which an N-containing 6-membered heterocyclic group and an A substituent (benzocarbazolyl-based substituent) are each bonded to another benzene ring of a dibenzothiophene-based core, and the A substituent ( Compared to a compound in which a substituted/unsubstituted carbazolyl substituent instead of a benzocarbazolyl substituent) is bonded, stability against electrons and holes is high, and the balance between electrons and holes can be stably maintained. Therefore, in the organic light emitting device employing the first compound, (1) an N-containing 6 membered-heterocyclic group and an A substituent (benzocarbazolyl-based substituent) are each bonded to another benzene ring of the dibenzothiophene-based core. Compared to an organic light-emitting device employing a compound having a structure and a compound in which a substituted/unsubstituted carbazolyl substituent is combined instead of the A substituent (benzocarbazolyl-based substituent), the characteristics of low driving voltage, high efficiency and long life Show.
바람직하게는, 상기 제1 화합물은 상기 디벤조티오펜계 코어에서의 N 함유 6원-헤테로고리기의 결합 위치에 따라 하기 화학식 1A 내지 1D 중 어느 하나로 표시된다:Preferably, the first compound is represented by any one of the following Formulas 1A to 1D, depending on the bonding position of the N-containing 6-membered heterocyclic group in the dibenzothiophene-based core:
[화학식 1A] [화학식 1B][Formula 1A] [Formula 1B]
Figure PCTKR2020095039-appb-img-000010
Figure PCTKR2020095039-appb-img-000010
[화학식 1C] [화학식 1D][Formula 1C] [Formula 1D]
Figure PCTKR2020095039-appb-img-000011
Figure PCTKR2020095039-appb-img-000011
상기 화학식 1A 내지 1D에서,In Formulas 1A to 1D,
각 치환기에 대한 설명은 상기 화학식 1에서 정의한 바와 같다.Description of each substituent is as defined in Chemical Formula 1.
바람직하게는, X 1 내지 X 3는 모두 N이다.Preferably, all of X 1 to X 3 are N.
바람직하게는, Z는 각각 독립적으로, 수소 또는 중수소이거나, 또는 Z 중 인접하는 둘은 서로 결합하여 비치환되거나 또는 중수소로 치환된 C 6-20 방향족 고리, 예를 들어 벤젠 고리를 형성할 수 있다.Preferably, each of Z is independently hydrogen or deuterium, or two adjacent to Z may be bonded to each other to form an unsubstituted or deuterated C 6-20 aromatic ring, for example a benzene ring. .
이때, Z의 개수를 의미하는 n은 0, 1, 2, 3, 4, 5, 또는 6이다.At this time, n, which means the number of Z, is 0, 1, 2, 3, 4, 5, or 6.
보다 구체적으로, 상기 제1 화합물은 하기 화학식 1A-1 내지 1D-1 중 어느 하나로 표시될 수 있다:More specifically, the first compound may be represented by any one of the following Formulas 1A-1 to 1D-1:
Figure PCTKR2020095039-appb-img-000012
Figure PCTKR2020095039-appb-img-000012
상기 화학식 1A-1 내지 1D-1에서,In Formulas 1A-1 to 1D-1,
Z 1 내지 Z 3 중 하나는 상기 화학식 1-1로 표시되는 치환기 A이고, 나머지는 각각 독립적으로, 수소 또는 중수소이거나, 또는 Z 1 내지 Z 3 중 인접하는 둘은 서로 결합하여 비치환되거나 또는 중수소로 치환된 벤젠 고리를 형성할 수 있고,One of Z 1 to Z 3 is a substituent A represented by Formula 1-1, and the others are each independently hydrogen or deuterium, or two of Z 1 to Z 3 that are adjacent to each other are unsubstituted or deuterium Can form a benzene ring substituted with,
Z 4 내지 Z 7은 각각 독립적으로, 수소 또는 중수소이거나, 또는 Z 4 내지 Z 7 중 인접하는 둘은 서로 결합하여 비치환되거나 또는 중수소로 치환된 벤젠 고리를 형성할 수 있고,Z 4 to Z 7 are each independently hydrogen or deuterium, or two adjacent two of Z 4 to Z 7 may be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium,
Ar 1 및 Ar 2는 상기 화학식 1에서 정의한 바와 같다.Ar 1 and Ar 2 are as defined in Chemical Formula 1.
구체적으로, 상기 화학식 1A-1에서는, Specifically, in Chemical Formula 1A-1,
Z 1이 A이고, Z 2 및 Z 3가 각각 독립적으로, 수소 또는 중수소이거나, 또는 Z 2 및 Z 3 둘이 서로 결합하여, 비치환되거나 또는 중수소로 치환된 벤젠 고리를 형성하거나;Z 1 is A, Z 2 and Z 3 are each independently hydrogen or deuterium, or Z 2 and Z 3 are combined with each other to form a benzene ring unsubstituted or substituted with deuterium;
Z 2가 A이고, Z 1 및 Z 3가 각각 독립적으로, 수소 또는 중수소이거나; 또는Z 2 is A, and Z 1 and Z 3 are each independently hydrogen or deuterium; or
Z 3가 A이고, Z 1 및 Z 2가 각각 독립적으로, 수소 또는 중수소이거나, 또는 Z 1 및 Z 2 둘이 서로 결합하여, 비치환되거나 또는 중수소로 치환된 벤젠 고리를 형성할 수 있다.Z 3 is A, and Z 1 and Z 2 are each independently hydrogen or deuterium, or Z 1 and Z 2 may be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium.
또한, 상기 화학식 1B-1에서는, In addition, in Formula 1B-1,
Z 1이 A이고, Z 2 및 Z 3가 각각 독립적으로, 수소 또는 중수소이거나, 또는 Z 2 및 Z 3 둘이 서로 결합하여, 비치환되거나 또는 중수소로 치환된 벤젠 고리를 형성하거나;Z 1 is A, Z 2 and Z 3 are each independently hydrogen or deuterium, or Z 2 and Z 3 are combined with each other to form a benzene ring unsubstituted or substituted with deuterium;
Z 2가 A이고, Z 1 및 Z 3가 각각 독립적으로, 수소 또는 중수소이거나; 또는Z 2 is A, and Z 1 and Z 3 are each independently hydrogen or deuterium; or
Z 3가 A이고, Z 1 및 Z 2가 각각 독립적으로, 수소 또는 중수소일 수 있다.Z 3 is A, and Z 1 and Z 2 may each independently be hydrogen or deuterium.
또한, 상기 화학식 1C-1에서는, In addition, in Formula 1C-1,
Z 1이 A이고, Z 2 및 Z 3가 각각 독립적으로, 수소 또는 중수소이거나;Z 1 is A, and Z 2 and Z 3 are each independently hydrogen or deuterium;
Z 2가 A이고, Z 1 및 Z 3가 각각 독립적으로, 수소 또는 중수소이거나; 또는Z 2 is A, and Z 1 and Z 3 are each independently hydrogen or deuterium; or
Z 3가 A이고, Z 1 및 Z 2가 각각 독립적으로, 수소 또는 중수소이거나, 또는 Z 1 및 Z 2 둘이 서로 결합하여, 비치환되거나 또는 중수소로 치환된 벤젠 고리를 형성할 수 있다.Z 3 is A, and Z 1 and Z 2 are each independently hydrogen or deuterium, or Z 1 and Z 2 may be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium.
구체적으로, 상기 화학식 1D-1에서는, Specifically, in Chemical Formula 1D-1,
Z 1이 A이고, Z 2 및 Z 3가 각각 독립적으로, 수소 또는 중수소이거나, 또는 Z 2 및 Z 3 둘이 서로 결합하여, 비치환되거나 또는 중수소로 치환된 벤젠 고리를 형성하거나;Z 1 is A, Z 2 and Z 3 are each independently hydrogen or deuterium, or Z 2 and Z 3 are combined with each other to form a benzene ring unsubstituted or substituted with deuterium;
Z 2가 A이고, Z 1 및 Z 3가 각각 독립적으로, 수소 또는 중수소이거나; 또는Z 2 is A, and Z 1 and Z 3 are each independently hydrogen or deuterium; or
Z 3가 A이고, Z 1 및 Z 2가 각각 독립적으로, 수소 또는 중수소이거나, 또는 Z 1 및 Z 2 둘이 서로 결합하여, 비치환되거나 또는 중수소로 치환된 벤젠 고리를 형성할 수 있다.Z 3 is A, and Z 1 and Z 2 are each independently hydrogen or deuterium, or Z 1 and Z 2 may be bonded to each other to form a benzene ring unsubstituted or substituted with deuterium.
또는, 상기 제1 화합물은 하기 화학식 3-1 내지 3-7 중 어느 하나로 표시될 수 있다:Alternatively, the first compound may be represented by any one of the following Formulas 3-1 to 3-7:
Figure PCTKR2020095039-appb-img-000013
Figure PCTKR2020095039-appb-img-000013
상기 화학식 3-1 내지 3-7에서,In Formulas 3-1 to 3-7,
R은 각각 독립적으로, 수소, 또는 중수소이고,Each R is independently hydrogen or deuterium,
A, Ar 1 및 Ar 2는 상기 화학식 1에서 정의한 바와 같다.A, Ar 1 and Ar 2 are as defined in Chemical Formula 1.
바람직하게는, Ar 1 및 Ar 2는 각각 독립적으로, 비치환되거나, 또는 중수소 또는 C 6-20 아릴로 치환된 C 6-20 아릴이다. Preferably, Ar 1 and Ar 2 are each independently unsubstituted or substituted with heavy hydrogen, or C 6-20 aryl C 6-20 aryl.
보다 바람직하게는, Ar 1 및 Ar 2는 각각 독립적으로, 페닐, 비페닐릴, 터페닐릴, 나프틸, 페난쓰레닐, 디벤조티오페닐, 디벤조퓨라닐, 또는 카바졸일이고, More preferably, Ar 1 and Ar 2 are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzothiophenyl, dibenzofuranyl, or carbazolyl,
여기서, Ar 1 및 Ar 2는 비치환되거나, 또는 중수소 및 C 6-20 아릴로 구성되는 군으로부터 각각 독립적으로 선택되는 1개 내지 5개의 치환기로 치환될 수 있다. Here, Ar 1 and Ar 2 may be unsubstituted or substituted with 1 to 5 substituents each independently selected from the group consisting of deuterium and C 6-20 aryl.
가장 바람직하게는, Ar 1 및 Ar 2는 각각 독립적으로, 하기로 구성되는 군으로부터 선택되는 어느 하나이다:Most preferably, Ar 1 and Ar 2 are each independently any one selected from the group consisting of:
Figure PCTKR2020095039-appb-img-000014
.
Figure PCTKR2020095039-appb-img-000014
.
이때, Ar 1 및 Ar 2는 서로 동일할 수 있고, 또는, Ar 1 및 Ar 2는 상이할 수 있다. At this time, Ar 1 and Ar 2 may be the same as each other, or Ar 1 and Ar 2 may be different.
또한, 상기 화학식 1-1로 표시되는 치환기인 A에서, R 1 내지 R 4는 각각 독립적으로, 수소 또는 중수소이거나, 또는 R 1 내지 R 4 중 인접하는 둘은 서로 결합하여 비치환되거나 또는 중수소로 치환된 벤젠 고리를 형성할 수 있다.In addition, in the substituent A represented by Formula 1-1, R 1 to R 4 are each independently hydrogen or deuterium, or two adjacent to R 1 to R 4 are bonded to each other to be unsubstituted or deuterium It can form a substituted benzene ring.
이때, 중수소(D)의 개수를 의미하는 m은 0, 1, 2, 3, 4, 5, 또는 6이다.At this time, m, which means the number of deuterium (D), is 0, 1, 2, 3, 4, 5, or 6.
예를 들어, A는 하기 화학식 a1 내지 a4로 표시되는 치환기 중 어느 하나이다:For example, A is any one of the substituents represented by the following formulas a1 to a4:
Figure PCTKR2020095039-appb-img-000015
.
Figure PCTKR2020095039-appb-img-000015
.
상기 제1 화합물의 구체적인 예는 다음과 같다:Specific examples of the first compound are as follows:
Figure PCTKR2020095039-appb-img-000016
Figure PCTKR2020095039-appb-img-000016
Figure PCTKR2020095039-appb-img-000017
Figure PCTKR2020095039-appb-img-000017
Figure PCTKR2020095039-appb-img-000018
Figure PCTKR2020095039-appb-img-000018
Figure PCTKR2020095039-appb-img-000019
Figure PCTKR2020095039-appb-img-000019
Figure PCTKR2020095039-appb-img-000020
Figure PCTKR2020095039-appb-img-000020
Figure PCTKR2020095039-appb-img-000021
Figure PCTKR2020095039-appb-img-000021
Figure PCTKR2020095039-appb-img-000022
Figure PCTKR2020095039-appb-img-000022
Figure PCTKR2020095039-appb-img-000023
Figure PCTKR2020095039-appb-img-000023
Figure PCTKR2020095039-appb-img-000024
Figure PCTKR2020095039-appb-img-000024
Figure PCTKR2020095039-appb-img-000025
Figure PCTKR2020095039-appb-img-000025
Figure PCTKR2020095039-appb-img-000026
Figure PCTKR2020095039-appb-img-000026
Figure PCTKR2020095039-appb-img-000027
Figure PCTKR2020095039-appb-img-000027
Figure PCTKR2020095039-appb-img-000028
Figure PCTKR2020095039-appb-img-000028
Figure PCTKR2020095039-appb-img-000029
Figure PCTKR2020095039-appb-img-000029
Figure PCTKR2020095039-appb-img-000030
Figure PCTKR2020095039-appb-img-000030
Figure PCTKR2020095039-appb-img-000031
Figure PCTKR2020095039-appb-img-000031
Figure PCTKR2020095039-appb-img-000032
Figure PCTKR2020095039-appb-img-000032
Figure PCTKR2020095039-appb-img-000033
Figure PCTKR2020095039-appb-img-000033
Figure PCTKR2020095039-appb-img-000034
Figure PCTKR2020095039-appb-img-000034
Figure PCTKR2020095039-appb-img-000035
Figure PCTKR2020095039-appb-img-000035
Figure PCTKR2020095039-appb-img-000036
Figure PCTKR2020095039-appb-img-000036
Figure PCTKR2020095039-appb-img-000037
Figure PCTKR2020095039-appb-img-000037
Figure PCTKR2020095039-appb-img-000038
Figure PCTKR2020095039-appb-img-000038
Figure PCTKR2020095039-appb-img-000039
Figure PCTKR2020095039-appb-img-000039
Figure PCTKR2020095039-appb-img-000040
Figure PCTKR2020095039-appb-img-000040
Figure PCTKR2020095039-appb-img-000041
Figure PCTKR2020095039-appb-img-000041
Figure PCTKR2020095039-appb-img-000042
Figure PCTKR2020095039-appb-img-000042
Figure PCTKR2020095039-appb-img-000043
Figure PCTKR2020095039-appb-img-000043
Figure PCTKR2020095039-appb-img-000044
Figure PCTKR2020095039-appb-img-000044
Figure PCTKR2020095039-appb-img-000045
Figure PCTKR2020095039-appb-img-000045
Figure PCTKR2020095039-appb-img-000046
Figure PCTKR2020095039-appb-img-000046
Figure PCTKR2020095039-appb-img-000047
Figure PCTKR2020095039-appb-img-000047
Figure PCTKR2020095039-appb-img-000048
Figure PCTKR2020095039-appb-img-000048
Figure PCTKR2020095039-appb-img-000049
Figure PCTKR2020095039-appb-img-000049
Figure PCTKR2020095039-appb-img-000050
Figure PCTKR2020095039-appb-img-000050
Figure PCTKR2020095039-appb-img-000051
Figure PCTKR2020095039-appb-img-000051
Figure PCTKR2020095039-appb-img-000052
Figure PCTKR2020095039-appb-img-000052
Figure PCTKR2020095039-appb-img-000053
Figure PCTKR2020095039-appb-img-000053
Figure PCTKR2020095039-appb-img-000054
Figure PCTKR2020095039-appb-img-000054
Figure PCTKR2020095039-appb-img-000055
Figure PCTKR2020095039-appb-img-000055
Figure PCTKR2020095039-appb-img-000056
Figure PCTKR2020095039-appb-img-000056
Figure PCTKR2020095039-appb-img-000057
Figure PCTKR2020095039-appb-img-000057
Figure PCTKR2020095039-appb-img-000058
Figure PCTKR2020095039-appb-img-000058
Figure PCTKR2020095039-appb-img-000059
Figure PCTKR2020095039-appb-img-000059
Figure PCTKR2020095039-appb-img-000060
Figure PCTKR2020095039-appb-img-000060
Figure PCTKR2020095039-appb-img-000061
Figure PCTKR2020095039-appb-img-000061
Figure PCTKR2020095039-appb-img-000062
Figure PCTKR2020095039-appb-img-000062
Figure PCTKR2020095039-appb-img-000063
Figure PCTKR2020095039-appb-img-000063
Figure PCTKR2020095039-appb-img-000064
Figure PCTKR2020095039-appb-img-000064
Figure PCTKR2020095039-appb-img-000065
Figure PCTKR2020095039-appb-img-000065
Figure PCTKR2020095039-appb-img-000066
Figure PCTKR2020095039-appb-img-000066
Figure PCTKR2020095039-appb-img-000067
Figure PCTKR2020095039-appb-img-000067
Figure PCTKR2020095039-appb-img-000068
Figure PCTKR2020095039-appb-img-000068
Figure PCTKR2020095039-appb-img-000069
Figure PCTKR2020095039-appb-img-000069
Figure PCTKR2020095039-appb-img-000070
Figure PCTKR2020095039-appb-img-000070
Figure PCTKR2020095039-appb-img-000071
Figure PCTKR2020095039-appb-img-000071
Figure PCTKR2020095039-appb-img-000072
Figure PCTKR2020095039-appb-img-000072
Figure PCTKR2020095039-appb-img-000073
Figure PCTKR2020095039-appb-img-000073
Figure PCTKR2020095039-appb-img-000074
Figure PCTKR2020095039-appb-img-000074
Figure PCTKR2020095039-appb-img-000075
Figure PCTKR2020095039-appb-img-000075
Figure PCTKR2020095039-appb-img-000076
Figure PCTKR2020095039-appb-img-000076
Figure PCTKR2020095039-appb-img-000077
Figure PCTKR2020095039-appb-img-000077
Figure PCTKR2020095039-appb-img-000078
Figure PCTKR2020095039-appb-img-000078
Figure PCTKR2020095039-appb-img-000079
Figure PCTKR2020095039-appb-img-000079
Figure PCTKR2020095039-appb-img-000080
Figure PCTKR2020095039-appb-img-000080
Figure PCTKR2020095039-appb-img-000081
Figure PCTKR2020095039-appb-img-000081
Figure PCTKR2020095039-appb-img-000082
Figure PCTKR2020095039-appb-img-000082
Figure PCTKR2020095039-appb-img-000083
Figure PCTKR2020095039-appb-img-000083
Figure PCTKR2020095039-appb-img-000084
Figure PCTKR2020095039-appb-img-000084
Figure PCTKR2020095039-appb-img-000085
Figure PCTKR2020095039-appb-img-000085
Figure PCTKR2020095039-appb-img-000086
Figure PCTKR2020095039-appb-img-000086
Figure PCTKR2020095039-appb-img-000087
Figure PCTKR2020095039-appb-img-000087
Figure PCTKR2020095039-appb-img-000088
Figure PCTKR2020095039-appb-img-000088
Figure PCTKR2020095039-appb-img-000089
Figure PCTKR2020095039-appb-img-000089
Figure PCTKR2020095039-appb-img-000090
Figure PCTKR2020095039-appb-img-000090
Figure PCTKR2020095039-appb-img-000091
Figure PCTKR2020095039-appb-img-000091
Figure PCTKR2020095039-appb-img-000092
Figure PCTKR2020095039-appb-img-000092
Figure PCTKR2020095039-appb-img-000093
Figure PCTKR2020095039-appb-img-000093
Figure PCTKR2020095039-appb-img-000094
Figure PCTKR2020095039-appb-img-000094
Figure PCTKR2020095039-appb-img-000095
Figure PCTKR2020095039-appb-img-000095
Figure PCTKR2020095039-appb-img-000096
Figure PCTKR2020095039-appb-img-000096
Figure PCTKR2020095039-appb-img-000097
Figure PCTKR2020095039-appb-img-000097
Figure PCTKR2020095039-appb-img-000098
Figure PCTKR2020095039-appb-img-000098
Figure PCTKR2020095039-appb-img-000099
Figure PCTKR2020095039-appb-img-000099
Figure PCTKR2020095039-appb-img-000100
Figure PCTKR2020095039-appb-img-000100
Figure PCTKR2020095039-appb-img-000101
Figure PCTKR2020095039-appb-img-000101
Figure PCTKR2020095039-appb-img-000102
Figure PCTKR2020095039-appb-img-000102
Figure PCTKR2020095039-appb-img-000103
Figure PCTKR2020095039-appb-img-000103
Figure PCTKR2020095039-appb-img-000104
Figure PCTKR2020095039-appb-img-000104
Figure PCTKR2020095039-appb-img-000105
Figure PCTKR2020095039-appb-img-000105
Figure PCTKR2020095039-appb-img-000106
Figure PCTKR2020095039-appb-img-000106
Figure PCTKR2020095039-appb-img-000107
Figure PCTKR2020095039-appb-img-000107
Figure PCTKR2020095039-appb-img-000108
Figure PCTKR2020095039-appb-img-000108
Figure PCTKR2020095039-appb-img-000109
Figure PCTKR2020095039-appb-img-000109
Figure PCTKR2020095039-appb-img-000110
Figure PCTKR2020095039-appb-img-000110
Figure PCTKR2020095039-appb-img-000111
Figure PCTKR2020095039-appb-img-000111
Figure PCTKR2020095039-appb-img-000112
Figure PCTKR2020095039-appb-img-000112
Figure PCTKR2020095039-appb-img-000113
Figure PCTKR2020095039-appb-img-000113
Figure PCTKR2020095039-appb-img-000114
Figure PCTKR2020095039-appb-img-000114
Figure PCTKR2020095039-appb-img-000115
Figure PCTKR2020095039-appb-img-000115
Figure PCTKR2020095039-appb-img-000116
Figure PCTKR2020095039-appb-img-000116
Figure PCTKR2020095039-appb-img-000117
Figure PCTKR2020095039-appb-img-000117
Figure PCTKR2020095039-appb-img-000118
Figure PCTKR2020095039-appb-img-000118
Figure PCTKR2020095039-appb-img-000119
Figure PCTKR2020095039-appb-img-000119
Figure PCTKR2020095039-appb-img-000120
Figure PCTKR2020095039-appb-img-000120
Figure PCTKR2020095039-appb-img-000121
Figure PCTKR2020095039-appb-img-000121
Figure PCTKR2020095039-appb-img-000122
Figure PCTKR2020095039-appb-img-000122
Figure PCTKR2020095039-appb-img-000123
Figure PCTKR2020095039-appb-img-000123
Figure PCTKR2020095039-appb-img-000124
Figure PCTKR2020095039-appb-img-000124
Figure PCTKR2020095039-appb-img-000125
Figure PCTKR2020095039-appb-img-000125
Figure PCTKR2020095039-appb-img-000126
Figure PCTKR2020095039-appb-img-000126
Figure PCTKR2020095039-appb-img-000127
Figure PCTKR2020095039-appb-img-000127
Figure PCTKR2020095039-appb-img-000128
Figure PCTKR2020095039-appb-img-000128
Figure PCTKR2020095039-appb-img-000129
Figure PCTKR2020095039-appb-img-000129
Figure PCTKR2020095039-appb-img-000130
Figure PCTKR2020095039-appb-img-000130
Figure PCTKR2020095039-appb-img-000131
Figure PCTKR2020095039-appb-img-000131
Figure PCTKR2020095039-appb-img-000132
Figure PCTKR2020095039-appb-img-000132
Figure PCTKR2020095039-appb-img-000133
Figure PCTKR2020095039-appb-img-000133
Figure PCTKR2020095039-appb-img-000134
Figure PCTKR2020095039-appb-img-000134
Figure PCTKR2020095039-appb-img-000135
Figure PCTKR2020095039-appb-img-000135
Figure PCTKR2020095039-appb-img-000136
Figure PCTKR2020095039-appb-img-000136
Figure PCTKR2020095039-appb-img-000137
Figure PCTKR2020095039-appb-img-000137
Figure PCTKR2020095039-appb-img-000138
Figure PCTKR2020095039-appb-img-000138
Figure PCTKR2020095039-appb-img-000139
Figure PCTKR2020095039-appb-img-000139
Figure PCTKR2020095039-appb-img-000140
Figure PCTKR2020095039-appb-img-000140
Figure PCTKR2020095039-appb-img-000141
Figure PCTKR2020095039-appb-img-000141
Figure PCTKR2020095039-appb-img-000142
Figure PCTKR2020095039-appb-img-000142
Figure PCTKR2020095039-appb-img-000143
Figure PCTKR2020095039-appb-img-000143
Figure PCTKR2020095039-appb-img-000144
Figure PCTKR2020095039-appb-img-000144
Figure PCTKR2020095039-appb-img-000145
Figure PCTKR2020095039-appb-img-000145
Figure PCTKR2020095039-appb-img-000146
Figure PCTKR2020095039-appb-img-000146
Figure PCTKR2020095039-appb-img-000147
Figure PCTKR2020095039-appb-img-000147
Figure PCTKR2020095039-appb-img-000148
Figure PCTKR2020095039-appb-img-000148
Figure PCTKR2020095039-appb-img-000149
Figure PCTKR2020095039-appb-img-000149
Figure PCTKR2020095039-appb-img-000150
Figure PCTKR2020095039-appb-img-000150
Figure PCTKR2020095039-appb-img-000151
Figure PCTKR2020095039-appb-img-000151
Figure PCTKR2020095039-appb-img-000152
Figure PCTKR2020095039-appb-img-000152
Figure PCTKR2020095039-appb-img-000153
Figure PCTKR2020095039-appb-img-000153
Figure PCTKR2020095039-appb-img-000154
Figure PCTKR2020095039-appb-img-000154
Figure PCTKR2020095039-appb-img-000155
Figure PCTKR2020095039-appb-img-000155
Figure PCTKR2020095039-appb-img-000156
Figure PCTKR2020095039-appb-img-000156
Figure PCTKR2020095039-appb-img-000157
Figure PCTKR2020095039-appb-img-000157
Figure PCTKR2020095039-appb-img-000158
Figure PCTKR2020095039-appb-img-000158
Figure PCTKR2020095039-appb-img-000159
Figure PCTKR2020095039-appb-img-000159
Figure PCTKR2020095039-appb-img-000160
Figure PCTKR2020095039-appb-img-000160
Figure PCTKR2020095039-appb-img-000161
Figure PCTKR2020095039-appb-img-000161
Figure PCTKR2020095039-appb-img-000162
Figure PCTKR2020095039-appb-img-000162
Figure PCTKR2020095039-appb-img-000163
Figure PCTKR2020095039-appb-img-000163
Figure PCTKR2020095039-appb-img-000164
Figure PCTKR2020095039-appb-img-000164
Figure PCTKR2020095039-appb-img-000165
Figure PCTKR2020095039-appb-img-000165
Figure PCTKR2020095039-appb-img-000166
Figure PCTKR2020095039-appb-img-000166
Figure PCTKR2020095039-appb-img-000167
Figure PCTKR2020095039-appb-img-000167
Figure PCTKR2020095039-appb-img-000168
Figure PCTKR2020095039-appb-img-000168
Figure PCTKR2020095039-appb-img-000169
Figure PCTKR2020095039-appb-img-000169
Figure PCTKR2020095039-appb-img-000170
Figure PCTKR2020095039-appb-img-000170
Figure PCTKR2020095039-appb-img-000171
Figure PCTKR2020095039-appb-img-000171
Figure PCTKR2020095039-appb-img-000172
Figure PCTKR2020095039-appb-img-000172
Figure PCTKR2020095039-appb-img-000173
Figure PCTKR2020095039-appb-img-000173
Figure PCTKR2020095039-appb-img-000174
Figure PCTKR2020095039-appb-img-000174
Figure PCTKR2020095039-appb-img-000175
Figure PCTKR2020095039-appb-img-000175
Figure PCTKR2020095039-appb-img-000176
Figure PCTKR2020095039-appb-img-000176
Figure PCTKR2020095039-appb-img-000177
Figure PCTKR2020095039-appb-img-000177
Figure PCTKR2020095039-appb-img-000178
Figure PCTKR2020095039-appb-img-000178
Figure PCTKR2020095039-appb-img-000179
Figure PCTKR2020095039-appb-img-000179
Figure PCTKR2020095039-appb-img-000180
Figure PCTKR2020095039-appb-img-000180
Figure PCTKR2020095039-appb-img-000181
Figure PCTKR2020095039-appb-img-000181
Figure PCTKR2020095039-appb-img-000182
Figure PCTKR2020095039-appb-img-000182
Figure PCTKR2020095039-appb-img-000183
Figure PCTKR2020095039-appb-img-000183
Figure PCTKR2020095039-appb-img-000184
Figure PCTKR2020095039-appb-img-000184
Figure PCTKR2020095039-appb-img-000185
Figure PCTKR2020095039-appb-img-000185
Figure PCTKR2020095039-appb-img-000186
Figure PCTKR2020095039-appb-img-000186
Figure PCTKR2020095039-appb-img-000187
Figure PCTKR2020095039-appb-img-000187
Figure PCTKR2020095039-appb-img-000188
Figure PCTKR2020095039-appb-img-000188
Figure PCTKR2020095039-appb-img-000189
Figure PCTKR2020095039-appb-img-000189
Figure PCTKR2020095039-appb-img-000190
Figure PCTKR2020095039-appb-img-000190
Figure PCTKR2020095039-appb-img-000191
Figure PCTKR2020095039-appb-img-000191
Figure PCTKR2020095039-appb-img-000192
Figure PCTKR2020095039-appb-img-000192
Figure PCTKR2020095039-appb-img-000193
Figure PCTKR2020095039-appb-img-000193
Figure PCTKR2020095039-appb-img-000194
Figure PCTKR2020095039-appb-img-000194
Figure PCTKR2020095039-appb-img-000195
Figure PCTKR2020095039-appb-img-000195
Figure PCTKR2020095039-appb-img-000196
Figure PCTKR2020095039-appb-img-000196
Figure PCTKR2020095039-appb-img-000197
Figure PCTKR2020095039-appb-img-000197
Figure PCTKR2020095039-appb-img-000198
Figure PCTKR2020095039-appb-img-000198
Figure PCTKR2020095039-appb-img-000199
Figure PCTKR2020095039-appb-img-000199
Figure PCTKR2020095039-appb-img-000200
Figure PCTKR2020095039-appb-img-000200
Figure PCTKR2020095039-appb-img-000201
Figure PCTKR2020095039-appb-img-000201
Figure PCTKR2020095039-appb-img-000202
Figure PCTKR2020095039-appb-img-000202
Figure PCTKR2020095039-appb-img-000203
Figure PCTKR2020095039-appb-img-000203
Figure PCTKR2020095039-appb-img-000204
Figure PCTKR2020095039-appb-img-000204
Figure PCTKR2020095039-appb-img-000205
Figure PCTKR2020095039-appb-img-000205
Figure PCTKR2020095039-appb-img-000206
Figure PCTKR2020095039-appb-img-000206
Figure PCTKR2020095039-appb-img-000207
Figure PCTKR2020095039-appb-img-000207
Figure PCTKR2020095039-appb-img-000208
Figure PCTKR2020095039-appb-img-000208
Figure PCTKR2020095039-appb-img-000209
Figure PCTKR2020095039-appb-img-000209
Figure PCTKR2020095039-appb-img-000210
Figure PCTKR2020095039-appb-img-000210
Figure PCTKR2020095039-appb-img-000211
Figure PCTKR2020095039-appb-img-000211
Figure PCTKR2020095039-appb-img-000212
Figure PCTKR2020095039-appb-img-000212
Figure PCTKR2020095039-appb-img-000213
Figure PCTKR2020095039-appb-img-000213
Figure PCTKR2020095039-appb-img-000214
Figure PCTKR2020095039-appb-img-000214
Figure PCTKR2020095039-appb-img-000215
Figure PCTKR2020095039-appb-img-000215
Figure PCTKR2020095039-appb-img-000216
Figure PCTKR2020095039-appb-img-000216
Figure PCTKR2020095039-appb-img-000217
Figure PCTKR2020095039-appb-img-000217
Figure PCTKR2020095039-appb-img-000218
Figure PCTKR2020095039-appb-img-000218
Figure PCTKR2020095039-appb-img-000219
Figure PCTKR2020095039-appb-img-000219
Figure PCTKR2020095039-appb-img-000220
Figure PCTKR2020095039-appb-img-000220
Figure PCTKR2020095039-appb-img-000221
Figure PCTKR2020095039-appb-img-000221
Figure PCTKR2020095039-appb-img-000222
Figure PCTKR2020095039-appb-img-000222
Figure PCTKR2020095039-appb-img-000223
Figure PCTKR2020095039-appb-img-000223
Figure PCTKR2020095039-appb-img-000224
Figure PCTKR2020095039-appb-img-000224
Figure PCTKR2020095039-appb-img-000225
Figure PCTKR2020095039-appb-img-000225
Figure PCTKR2020095039-appb-img-000226
Figure PCTKR2020095039-appb-img-000226
Figure PCTKR2020095039-appb-img-000227
Figure PCTKR2020095039-appb-img-000227
Figure PCTKR2020095039-appb-img-000228
Figure PCTKR2020095039-appb-img-000228
Figure PCTKR2020095039-appb-img-000229
Figure PCTKR2020095039-appb-img-000229
Figure PCTKR2020095039-appb-img-000230
Figure PCTKR2020095039-appb-img-000230
Figure PCTKR2020095039-appb-img-000231
Figure PCTKR2020095039-appb-img-000231
Figure PCTKR2020095039-appb-img-000232
Figure PCTKR2020095039-appb-img-000232
Figure PCTKR2020095039-appb-img-000233
Figure PCTKR2020095039-appb-img-000233
Figure PCTKR2020095039-appb-img-000234
Figure PCTKR2020095039-appb-img-000234
Figure PCTKR2020095039-appb-img-000235
Figure PCTKR2020095039-appb-img-000235
Figure PCTKR2020095039-appb-img-000236
Figure PCTKR2020095039-appb-img-000236
Figure PCTKR2020095039-appb-img-000237
Figure PCTKR2020095039-appb-img-000237
Figure PCTKR2020095039-appb-img-000238
Figure PCTKR2020095039-appb-img-000238
Figure PCTKR2020095039-appb-img-000239
Figure PCTKR2020095039-appb-img-000239
Figure PCTKR2020095039-appb-img-000240
Figure PCTKR2020095039-appb-img-000240
Figure PCTKR2020095039-appb-img-000241
Figure PCTKR2020095039-appb-img-000241
Figure PCTKR2020095039-appb-img-000242
Figure PCTKR2020095039-appb-img-000242
Figure PCTKR2020095039-appb-img-000243
Figure PCTKR2020095039-appb-img-000243
Figure PCTKR2020095039-appb-img-000244
Figure PCTKR2020095039-appb-img-000244
Figure PCTKR2020095039-appb-img-000245
Figure PCTKR2020095039-appb-img-000245
Figure PCTKR2020095039-appb-img-000246
Figure PCTKR2020095039-appb-img-000246
Figure PCTKR2020095039-appb-img-000247
Figure PCTKR2020095039-appb-img-000247
Figure PCTKR2020095039-appb-img-000248
Figure PCTKR2020095039-appb-img-000248
Figure PCTKR2020095039-appb-img-000249
Figure PCTKR2020095039-appb-img-000249
Figure PCTKR2020095039-appb-img-000250
Figure PCTKR2020095039-appb-img-000250
Figure PCTKR2020095039-appb-img-000251
Figure PCTKR2020095039-appb-img-000251
Figure PCTKR2020095039-appb-img-000252
Figure PCTKR2020095039-appb-img-000252
Figure PCTKR2020095039-appb-img-000253
Figure PCTKR2020095039-appb-img-000253
Figure PCTKR2020095039-appb-img-000254
Figure PCTKR2020095039-appb-img-000254
Figure PCTKR2020095039-appb-img-000255
Figure PCTKR2020095039-appb-img-000255
Figure PCTKR2020095039-appb-img-000256
Figure PCTKR2020095039-appb-img-000256
Figure PCTKR2020095039-appb-img-000257
Figure PCTKR2020095039-appb-img-000257
Figure PCTKR2020095039-appb-img-000258
Figure PCTKR2020095039-appb-img-000258
Figure PCTKR2020095039-appb-img-000259
Figure PCTKR2020095039-appb-img-000259
Figure PCTKR2020095039-appb-img-000260
Figure PCTKR2020095039-appb-img-000260
Figure PCTKR2020095039-appb-img-000261
Figure PCTKR2020095039-appb-img-000261
Figure PCTKR2020095039-appb-img-000262
Figure PCTKR2020095039-appb-img-000262
Figure PCTKR2020095039-appb-img-000263
Figure PCTKR2020095039-appb-img-000263
Figure PCTKR2020095039-appb-img-000264
Figure PCTKR2020095039-appb-img-000264
Figure PCTKR2020095039-appb-img-000265
Figure PCTKR2020095039-appb-img-000265
Figure PCTKR2020095039-appb-img-000266
Figure PCTKR2020095039-appb-img-000266
Figure PCTKR2020095039-appb-img-000267
Figure PCTKR2020095039-appb-img-000267
Figure PCTKR2020095039-appb-img-000268
Figure PCTKR2020095039-appb-img-000268
Figure PCTKR2020095039-appb-img-000269
Figure PCTKR2020095039-appb-img-000269
Figure PCTKR2020095039-appb-img-000270
Figure PCTKR2020095039-appb-img-000270
Figure PCTKR2020095039-appb-img-000271
Figure PCTKR2020095039-appb-img-000271
Figure PCTKR2020095039-appb-img-000272
Figure PCTKR2020095039-appb-img-000272
Figure PCTKR2020095039-appb-img-000273
Figure PCTKR2020095039-appb-img-000273
Figure PCTKR2020095039-appb-img-000274
Figure PCTKR2020095039-appb-img-000274
Figure PCTKR2020095039-appb-img-000275
Figure PCTKR2020095039-appb-img-000275
Figure PCTKR2020095039-appb-img-000276
Figure PCTKR2020095039-appb-img-000276
Figure PCTKR2020095039-appb-img-000277
Figure PCTKR2020095039-appb-img-000277
Figure PCTKR2020095039-appb-img-000278
Figure PCTKR2020095039-appb-img-000278
Figure PCTKR2020095039-appb-img-000279
Figure PCTKR2020095039-appb-img-000279
Figure PCTKR2020095039-appb-img-000280
Figure PCTKR2020095039-appb-img-000280
Figure PCTKR2020095039-appb-img-000281
Figure PCTKR2020095039-appb-img-000281
Figure PCTKR2020095039-appb-img-000282
Figure PCTKR2020095039-appb-img-000282
Figure PCTKR2020095039-appb-img-000283
Figure PCTKR2020095039-appb-img-000283
Figure PCTKR2020095039-appb-img-000284
Figure PCTKR2020095039-appb-img-000284
Figure PCTKR2020095039-appb-img-000285
Figure PCTKR2020095039-appb-img-000285
Figure PCTKR2020095039-appb-img-000286
Figure PCTKR2020095039-appb-img-000286
Figure PCTKR2020095039-appb-img-000287
Figure PCTKR2020095039-appb-img-000287
Figure PCTKR2020095039-appb-img-000288
Figure PCTKR2020095039-appb-img-000288
Figure PCTKR2020095039-appb-img-000289
Figure PCTKR2020095039-appb-img-000289
Figure PCTKR2020095039-appb-img-000290
Figure PCTKR2020095039-appb-img-000290
Figure PCTKR2020095039-appb-img-000291
Figure PCTKR2020095039-appb-img-000291
Figure PCTKR2020095039-appb-img-000292
Figure PCTKR2020095039-appb-img-000292
Figure PCTKR2020095039-appb-img-000293
Figure PCTKR2020095039-appb-img-000293
Figure PCTKR2020095039-appb-img-000294
Figure PCTKR2020095039-appb-img-000294
Figure PCTKR2020095039-appb-img-000295
Figure PCTKR2020095039-appb-img-000295
Figure PCTKR2020095039-appb-img-000296
Figure PCTKR2020095039-appb-img-000296
Figure PCTKR2020095039-appb-img-000297
Figure PCTKR2020095039-appb-img-000297
Figure PCTKR2020095039-appb-img-000298
Figure PCTKR2020095039-appb-img-000298
Figure PCTKR2020095039-appb-img-000299
Figure PCTKR2020095039-appb-img-000299
Figure PCTKR2020095039-appb-img-000300
Figure PCTKR2020095039-appb-img-000300
Figure PCTKR2020095039-appb-img-000301
Figure PCTKR2020095039-appb-img-000301
Figure PCTKR2020095039-appb-img-000302
Figure PCTKR2020095039-appb-img-000302
Figure PCTKR2020095039-appb-img-000303
Figure PCTKR2020095039-appb-img-000303
Figure PCTKR2020095039-appb-img-000304
Figure PCTKR2020095039-appb-img-000304
Figure PCTKR2020095039-appb-img-000305
Figure PCTKR2020095039-appb-img-000305
Figure PCTKR2020095039-appb-img-000306
Figure PCTKR2020095039-appb-img-000306
Figure PCTKR2020095039-appb-img-000307
Figure PCTKR2020095039-appb-img-000307
Figure PCTKR2020095039-appb-img-000308
Figure PCTKR2020095039-appb-img-000308
Figure PCTKR2020095039-appb-img-000309
Figure PCTKR2020095039-appb-img-000309
Figure PCTKR2020095039-appb-img-000310
Figure PCTKR2020095039-appb-img-000310
Figure PCTKR2020095039-appb-img-000311
Figure PCTKR2020095039-appb-img-000311
Figure PCTKR2020095039-appb-img-000312
Figure PCTKR2020095039-appb-img-000312
Figure PCTKR2020095039-appb-img-000313
Figure PCTKR2020095039-appb-img-000313
Figure PCTKR2020095039-appb-img-000314
Figure PCTKR2020095039-appb-img-000314
Figure PCTKR2020095039-appb-img-000315
Figure PCTKR2020095039-appb-img-000315
Figure PCTKR2020095039-appb-img-000316
Figure PCTKR2020095039-appb-img-000316
Figure PCTKR2020095039-appb-img-000317
Figure PCTKR2020095039-appb-img-000317
Figure PCTKR2020095039-appb-img-000318
Figure PCTKR2020095039-appb-img-000318
Figure PCTKR2020095039-appb-img-000319
Figure PCTKR2020095039-appb-img-000319
Figure PCTKR2020095039-appb-img-000320
Figure PCTKR2020095039-appb-img-000320
Figure PCTKR2020095039-appb-img-000321
Figure PCTKR2020095039-appb-img-000321
Figure PCTKR2020095039-appb-img-000322
Figure PCTKR2020095039-appb-img-000322
Figure PCTKR2020095039-appb-img-000323
Figure PCTKR2020095039-appb-img-000323
Figure PCTKR2020095039-appb-img-000324
Figure PCTKR2020095039-appb-img-000324
Figure PCTKR2020095039-appb-img-000325
Figure PCTKR2020095039-appb-img-000325
Figure PCTKR2020095039-appb-img-000326
Figure PCTKR2020095039-appb-img-000326
Figure PCTKR2020095039-appb-img-000327
Figure PCTKR2020095039-appb-img-000327
..
한편, 상기 화학식 1로 표시되는 화합물은 일례로 하기 반응식 1과 같은 제조 방법으로 제조할 수 있다. On the other hand, the compound represented by Formula 1 may be prepared by a manufacturing method such as the following Scheme 1 as an example.
[반응식 1][Scheme 1]
Figure PCTKR2020095039-appb-img-000328
Figure PCTKR2020095039-appb-img-000328
상기 반응식 1에서, X는 각각 독립적으로, 할로겐이고, 바람직하게는 브로모, 또는 클로로이고, 다른 치환기에 대한 정의는 앞서 설명한 바와 같다.In Reaction Scheme 1, each of X is independently halogen, preferably bromo or chloro, and definitions for other substituents are as described above.
구체적으로, 상기 화학식 1로 표시되는 화합물은 아민 치환 반응을 통해 출발물질 SM1 및 SM2가 결합하여 제조된다. 이러한 아민 치환 반응은 팔라듐 촉매와 염기의 존재 하에 수행하는 것이 바람직하다. 또한, 상기 아민 치환 반응을 위한 반응기는 적절히 변경될 수 있고, 화학식 1로 표시되는 화합물의 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.Specifically, the compound represented by Formula 1 is prepared by combining starting materials SM1 and SM2 through an amine substitution reaction. This amine substitution reaction is preferably carried out in the presence of a palladium catalyst and a base. In addition, the reactor for the amine substitution reaction may be appropriately changed, and the method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.
한편, 상기 제2 화합물은 비스카바졸계 화합물로, 바람직하게는, T 1 내지 T 4가 각각 독립적으로 C 6-20 방향족 고리인 구조를 갖는다. 보다 바람직하게는, T 1 내지 T 4는 비치환되거나 또는 중수소로 치환된 벤젠 고리, 또는 비치환되거나 또는 중수소로 치환된 나프탈렌 고리이다. Meanwhile, the second compound is a biscarbazole-based compound, and preferably, T 1 to T 4 have a structure in which each independently a C 6-20 aromatic ring. More preferably, T 1 to T 4 are unsubstituted or deuterium-substituted benzene rings, or unsubstituted or deuterium-substituted naphthalene rings.
가장 바람직하게는, T 1 내지 T 4는 모두 벤젠 고리로, 이때 상기 제2 화합물은 하기 화학식 2-1로 표시된다:Most preferably, all of T 1 to T 4 are benzene rings, wherein the second compound is represented by the following formula 2-1:
[화학식 2-1][Formula 2-1]
Figure PCTKR2020095039-appb-img-000329
Figure PCTKR2020095039-appb-img-000329
상기 화학식 2-1에서,In Formula 2-1,
D는 중수소를 의미하고,D means deuterium,
r 및 s는 각각 독립적으로, 0 내지 7의 정수이고,r and s are each independently an integer of 0 to 7,
각 치환기에 대한 설명은 상기 화학식 2에서 정의한 바와 같다.Description of each substituent is as defined in Chemical Formula 2.
바람직하게는, L 1 및 L 2는 각각 독립적으로, 단일결합, 또는 비치환된 C 6-20 아릴렌이다.Preferably, L 1 and L 2 are each independently a single bond or an unsubstituted C 6-20 arylene.
보다 바람직하게는, L 1 및 L 2는 각각 독립적으로, 단일 결합, 페닐렌, 또는 나프틸렌이다.More preferably, L 1 and L 2 are each independently a single bond, phenylene, or naphthylene.
바람직하게는, Ar 3 및 Ar 4는 각각 독립적으로, 비치환되거나, 또는 C 1-10 알킬 또는 C 6-20 아릴로 치환된 C 6-20 아릴; 또는 O 또는 S를 포함하는 C 2-20 헤테로아릴이다.Preferably, Ar 3 and Ar 4 are each independently C 6-20 aryl unsubstituted or substituted with C 1-10 alkyl or C 6-20 aryl; Or C 2-20 heteroaryl including O or S.
보다 바람직하게는, Ar 3 및 Ar 4는 각각 독립적으로, 페닐, 비페닐릴, 터페닐릴, 나프틸, 페난쓰레닐, 트리페닐레닐, 플루오레닐, 스피로비플루오레닐, 플루오란테닐, 디벤조티오페닐, 디벤조퓨라닐이고, More preferably, Ar 3 and Ar 4 are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, fluorenyl, spirobifluorenyl, fluoranthenyl, Dibenzothiophenyl, dibenzofuranyl,
여기서, Ar 3 및 Ar 4는 비치환되거나, 또는 C 1-10 알킬 및 C 6-20 아릴로 구성되는 군으로부터 각각 독립적으로 선택되는 1개 내지 4개의 치환기로 치환될 수 있다. Here, Ar 3 and Ar 4 may be unsubstituted or substituted with 1 to 4 substituents each independently selected from the group consisting of C 1-10 alkyl and C 6-20 aryl.
가장 바람직하게는, Ar 3 및 Ar 4는 각각 독립적으로, 하기로 구성되는 군으로부터 선택되는 어느 하나이다:Most preferably, Ar 3 and Ar 4 are each independently any one selected from the group consisting of:
Figure PCTKR2020095039-appb-img-000330
.
Figure PCTKR2020095039-appb-img-000330
.
이때, Ar 3 및 Ar 4는 서로 동일할 수 있고, 또는, Ar 3 및 Ar 4는 상이할 수 있다. At this time, Ar 3 and Ar 4 may be the same as each other, or Ar 3 and Ar 4 may be different.
바람직하게는, 상기 제2 화합물은 하기 화학식 2-2로 표시된다:Preferably, the second compound is represented by the following formula 2-2:
[화학식 2-2][Formula 2-2]
Figure PCTKR2020095039-appb-img-000331
Figure PCTKR2020095039-appb-img-000331
상기 화학식 2-2에서,In Formula 2-2,
L 1 및 L 2는 각각 독립적으로, 단일 결합, 페닐렌, 또는 나프틸렌이고,L 1 and L 2 are each independently a single bond, phenylene, or naphthylene,
Ar 3 및 Ar 4는 상기 화학식 2에서 정의한 바와 같다.Ar 3 and Ar 4 are as defined in Chemical Formula 2.
상기 제2 화합물의 구체적인 예는 다음과 같다:Specific examples of the second compound are as follows:
Figure PCTKR2020095039-appb-img-000332
Figure PCTKR2020095039-appb-img-000332
Figure PCTKR2020095039-appb-img-000333
Figure PCTKR2020095039-appb-img-000333
Figure PCTKR2020095039-appb-img-000334
Figure PCTKR2020095039-appb-img-000334
Figure PCTKR2020095039-appb-img-000335
Figure PCTKR2020095039-appb-img-000335
Figure PCTKR2020095039-appb-img-000336
Figure PCTKR2020095039-appb-img-000336
Figure PCTKR2020095039-appb-img-000337
Figure PCTKR2020095039-appb-img-000337
Figure PCTKR2020095039-appb-img-000338
Figure PCTKR2020095039-appb-img-000338
Figure PCTKR2020095039-appb-img-000339
Figure PCTKR2020095039-appb-img-000339
Figure PCTKR2020095039-appb-img-000340
Figure PCTKR2020095039-appb-img-000340
Figure PCTKR2020095039-appb-img-000341
Figure PCTKR2020095039-appb-img-000341
Figure PCTKR2020095039-appb-img-000342
Figure PCTKR2020095039-appb-img-000342
Figure PCTKR2020095039-appb-img-000343
Figure PCTKR2020095039-appb-img-000343
Figure PCTKR2020095039-appb-img-000344
Figure PCTKR2020095039-appb-img-000344
Figure PCTKR2020095039-appb-img-000345
Figure PCTKR2020095039-appb-img-000345
Figure PCTKR2020095039-appb-img-000346
Figure PCTKR2020095039-appb-img-000346
Figure PCTKR2020095039-appb-img-000347
Figure PCTKR2020095039-appb-img-000347
Figure PCTKR2020095039-appb-img-000348
Figure PCTKR2020095039-appb-img-000348
Figure PCTKR2020095039-appb-img-000349
Figure PCTKR2020095039-appb-img-000349
Figure PCTKR2020095039-appb-img-000350
Figure PCTKR2020095039-appb-img-000350
Figure PCTKR2020095039-appb-img-000351
Figure PCTKR2020095039-appb-img-000351
Figure PCTKR2020095039-appb-img-000352
Figure PCTKR2020095039-appb-img-000352
..
한편, 상기 화학식 2로 표시되는 화합물은 일례로 하기 반응식 2와 같은 제조 방법으로 제조할 수 있다. On the other hand, the compound represented by Formula 2 may be prepared by a manufacturing method as shown in Scheme 2 below, for example.
[반응식 2][Scheme 2]
Figure PCTKR2020095039-appb-img-000353
Figure PCTKR2020095039-appb-img-000353
상기 반응식 2에서, X는 각각 독립적으로, 할로겐이고, 바람직하게는 브로모, 또는 클로로이고, 다른 치환기에 대한 정의는 앞서 설명한 바와 같다.In Scheme 2, each of X is independently halogen, preferably bromo or chloro, and the definition of other substituents is as described above.
구체적으로, 상기 화학식 2로 표시되는 화합물은 Suzuki-coupling 반응을 통해 출발물질 SM3 및 SM4가 결합하여 제조된다. 이러한 Suzuki-coupling 반응은 팔라듐 촉매와 염기의 존재 하에 수행하는 것이 바람직하다. 또한, 상기 Suzuki-coupling 반응을 위한 반응기는 적절히 변경될 수 있고, 화학식 2로 표시되는 화합물의 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.Specifically, the compound represented by Formula 2 is prepared by combining the starting materials SM3 and SM4 through a Suzuki-coupling reaction. This Suzuki-coupling reaction is preferably carried out in the presence of a palladium catalyst and a base. In addition, the reactor for the Suzuki-coupling reaction may be appropriately changed, and the method of preparing the compound represented by Formula 2 may be more specific in Preparation Examples to be described later.
이러한 제1 화합물 및 상기 제2 화합물은 상기 발광층 내에 99:1 내지 1:99의 중량비, 보다 바람직하게는 50:50의 중량비로 포함되는 것이 고효율 및 장수명의 소자 구현에 바람직하다.The first compound and the second compound are preferably included in the light-emitting layer in a weight ratio of 99:1 to 1:99, more preferably 50:50, to implement a device having high efficiency and long life.
한편, 상기 발광층은 상기 호스트 재료 외 도펀트 재료를 더 포함한다. 이러한 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.Meanwhile, the emission layer further includes a dopant material in addition to the host material. Examples of such dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of an aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.
바람직하게는, 상기 발광층은 하기와 같은 이리듐 착체 화합물을 도펀트 재료로 포함할 수 있으나, 이에 한정되는 것은 아니다.Preferably, the light emitting layer may include the following iridium complex compound as a dopant material, but is not limited thereto.
Figure PCTKR2020095039-appb-img-000354
Figure PCTKR2020095039-appb-img-000354
Figure PCTKR2020095039-appb-img-000355
Figure PCTKR2020095039-appb-img-000355
Figure PCTKR2020095039-appb-img-000356
Figure PCTKR2020095039-appb-img-000356
Figure PCTKR2020095039-appb-img-000357
Figure PCTKR2020095039-appb-img-000357
정공주입층Hole injection layer
일 구현예에 따른 유기 발광 소자는 상기 양극 상에 정공 주입층을 추가로 포함할 수 있다. 상기 정공 주입층은 정공 주입 물질로 이루어져 있으며, 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. The organic light emitting device according to an embodiment may further include a hole injection layer on the anode. The hole injection layer is made of a hole injection material, and the hole injection material has the ability to transport holes, and thus has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material. A compound that prevents migration to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferable.
상기 정공 주입 물질의 구체적인 예로는, 금속 포피린(porphyrin), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone)계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이에 한정되지 않는다.Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene )-Based organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.
정공수송층Hole transport layer
일 구현예에 따른 유기 발광 소자는 상기 양극 상에, 또는 상기 양극 상에 형성된 정공주입층 상에 정공수송층을 더 포함할 수 있다. 상기 정공수송층은 양극 또는 양극 상에 형성된 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로, 상기 정공수송층에 포함되는 정공 수송 물질로는 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. The organic light-emitting device according to an embodiment may further include a hole transport layer on the anode or on the hole injection layer formed on the anode. The hole transport layer is a layer that receives holes from an anode or a hole injection layer formed on the anode and transports holes to the emission layer, and the hole transport material included in the hole transport layer receives holes from the anode or the hole injection layer to the emission layer. As a transferable material, a material with high mobility for holes is suitable.
상기 정공 수송 물질의 구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이에 한정되지 않는다.Specific examples of the hole transport material include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion.
전자억제층Electron suppression layer
일 구현예에 따른 유기 발광 소자는 상기 정공수송층 상에 전자억제층을 더 포함할 수 있다. 상기 전자억제층은 상기 정공수송층 상에 형성되어, 바람직하게는 발광층에 접하여 구비되어, 정공이동도를 조절하고, 전자의 과다한 이동을 방지하여 정공-전자간 결합 확률을 높여줌으로써 유기 발광 소자의 효율을 개선하는 역할을 하는 층을 의미한다. 상기 전자억제층은 전자저지물질을 포함하고, 이러한 전자저지물질의 예로 상기 화학식 1로 표시되는 화합물을 사용하거나, 또는 아릴아민 계열의 유기물 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.The organic light-emitting device according to an embodiment may further include an electron suppression layer on the hole transport layer. The electron suppression 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 means a layer that plays a role in improving The electron-suppressing layer includes an electron-blocking material, and examples of such an electron-blocking material include a compound represented by Formula 1 or an arylamine-based organic material, but are not limited thereto.
정공저지층Hole bottom
일 구현예에 따른 유기 발솽 소자는 상기 발광층 상에 정공저지층을 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.The organic balsop device according to an embodiment may further include a hole blocking layer 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 such hole-blocking materials 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.
전자수송층Electron transport layer
일 구현예에 따른 유기 발광 소자는 상기 발광층 상에, 또는 상기 정공저지층 상에 전자수송층을 포함할 수 있다. 상기 전자수송층은 음극 또는 후술하는 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하는 층으로, 상기 전자수송층에 포함되는 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 전자에 대한 이동성이 큰 물질이 적합하다. The organic light-emitting device according to an embodiment may include an electron transport layer on the emission layer or on the hole blocking layer. The electron transport layer is a layer that receives electrons from a cathode or an electron injection layer to be described later and transports electrons to the emission layer. As an electron transport material included in the electron transport layer, electrons capable of receiving electrons from the cathode and transferring them to the emission layer Materials with high mobility are suitable.
상기 전자 수송 물질의 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. 전자 수송층은 종래기술에 따라 사용된 바와 같이 임의의 원하는 캐소드 물질과 함께 사용할 수 있다. 특히, 적절한 캐소드 물질의 예는 낮은 일함수를 가지고 알루미늄층 또는 실버층이 뒤따르는 통상적인 물질이다. 구체적으로 세슘, 바륨, 칼슘, 이테르븀 및 사마륨이고, 각 경우 알루미늄 층 또는 실버층이 뒤따른다.Specific examples of the electron transport material 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 transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.
전자주입층Electron injection layer
일 구현예에 따른 유기 발광 소자는 상기 전자수송층과 음극 사이에 전자주입층을 추가로 포함할 수 있다. 상기 전자주입층은 음극으로부터 전자를 주입하는 층으로, 상기 전자주입층에 포함되는 전자 주입 물질로는 전자를 수송하는 능력을 갖고, 음극으로부터의 전자 주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자주입 효과를 가지며, 발광층에서 생성된 여기자의 정공주입층에의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물이 바람직하다. The organic light-emitting device according to an embodiment may further include an electron injection layer between the electron transport layer and the cathode. The electron injection layer is a layer that injects electrons from the cathode, and the electron injection material included in the electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and excellent electron injection to the light emitting layer or the light emitting material A compound having an effect, preventing the movement of excitons generated in the light emitting layer to the hole injection layer, and having excellent thin film formation ability is preferable.
상기 전자주입층으로 사용될 수 있는 물질의 구체적인 예로는, 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. Specific examples of materials that can be used as the electron injection layer include LiF, NaCl, CsF, Li 2 O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, tria Sol, imidazole, perylenetetracarboxylic acid, preorenylidene 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 전자수송층 및 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 injection and transport layer that simultaneously serves as an electron transport layer and an electron injection layer for transporting received electrons to the emission layer.
유기 발광 소자Organic light emitting element
일 구현예에 따라 상기 제1 전극이 양극이고, 상기 제2 전극이 음극인 유기 발광 소자의 구조를 도 1에 예시하였다. 도 1은 기판(1), 양극(2), 발광층(3) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 제1 화합물 및 상기 제2 화합물은 상기 발광층에 포함될 수 있다. According to an embodiment, the structure of an organic light-emitting device in which the first electrode is an anode and the second electrode is a cathode is illustrated in FIG. 1. 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 first compound and the second compound may be included in the emission layer.
다른 구현예에 따라 상기 제1 전극이 양극이고, 상기 제2 전극이 음극인 유기 발광 소자의 구조를 도 2에 예시하였다. 도 2는 기판(1), 양극(2), 정공주입층(5), 정공수송층(6), 발광층(3), 전자억제층(7), 정공저지층(8), 전자주입 및 수송층(8) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 제1 화합물 및 상기 제2 화합물은 상기 발광층에 포함될 수 있다. According to another embodiment, the structure of an organic light-emitting device in which the first electrode is an anode and the second electrode is a cathode is illustrated in FIG. 2. 2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron suppressing layer 7, a hole blocking layer 8, an electron injection and transport layer ( 8) and the cathode 4 shows an example of an organic light emitting device. In such a structure, the first compound and the second compound may be included in the emission layer.
본 발명에 따른 유기 발광 소자는 상술한 구성을 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 상술한 각 층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시켜 제조할 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수 있다. 또한, 발광층은 호스트 및 도펀트를 진공 증착법 뿐만 아니라 용액 도포법에 의하여 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described configurations. 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 each of the above-described layers thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method of a host and a dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.
이와 같은 방법 외에도, 기판 상에 음극 물질로부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 제조할 수 있다(WO 2003/012890). 다만, 제조 방법이 이에 한정되는 것은 아니다. In addition to such a method, an organic light-emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.
한편, 본 발명에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.Meanwhile, 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.
상기 유기 발광 소자의 제조는 이하 실시예에서 구체적으로 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범위가 이들에 의하여 한정되는 것은 아니다.The fabrication of the organic light emitting device 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.
합성예Synthesis example 1-1: 화합물 1-1의 제조 1-1: Preparation of compound 1-1
Figure PCTKR2020095039-appb-img-000358
Figure PCTKR2020095039-appb-img-000358
질소 분위기에서 중간체 1-1-1(10 g, 22.2mmol), 화합물 a(5.3g, 24.4 mmol), sodium tert-butoxide(4.3 g, 44.4 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-1을 7.3 g 제조하였다. (수율: 52%, MS: [M+H]+= 631)In a nitrogen atmosphere, intermediate 1-1-1 (10 g, 22.2 mmol), compound a (5.3 g, 24.4 mmol), sodium tert-butoxide (4.3 g, 44.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.3 g of compound 1-1. (Yield: 52%, MS: [M+H]+= 631)
합성예 1-2: 화합물 1-2의 제조Synthesis Example 1-2: Preparation of Compound 1-2
Figure PCTKR2020095039-appb-img-000359
Figure PCTKR2020095039-appb-img-000359
질소 분위기에서 중간체 1-2-1(10 g, 20mmol), 화합물 a(4.8g, 22 mmol), sodium tert-butoxide(3.8 g, 40 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-2를 6.9 g 제조하였다. (수율: 51%, MS: [M+H]+= 681)In a nitrogen atmosphere, intermediate 1-2-1 (10 g, 20 mmol), compound a (4.8 g, 22 mmol), sodium tert-butoxide (3.8 g, 40 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.9 g of compound 1-2. (Yield: 51%, MS: [M+H]+= 681)
합성예 1-3: 화합물 1-3의 제조Synthesis Example 1-3: Preparation of Compound 1-3
Figure PCTKR2020095039-appb-img-000360
Figure PCTKR2020095039-appb-img-000360
질소 분위기에서 중간체 1-3-1(10 g, 16.3mmol), 화합물 a(3.9g, 17.9 mmol), sodium tert-butoxide(3.1 g, 32.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-3을 8.9 g 제조하였다. (수율: 69%, MS: [M+H]+= 796)In a nitrogen atmosphere, intermediate 1-3-1 (10 g, 16.3 mmol), compound a (3.9 g, 17.9 mmol), sodium tert-butoxide (3.1 g, 32.5 mmol) was added to 200 ml of Xylene, followed by stirring and refluxing. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.9 g of compound 1-3. (Yield: 69%, MS: [M+H]+= 796)
합성예Synthesis example 1-4: 화합물 1-4의 제조 1-4: Preparation of compound 1-4
Figure PCTKR2020095039-appb-img-000361
Figure PCTKR2020095039-appb-img-000361
질소 분위기에서 중간체 1-4-1(10 g, 17.1mmol), 화합물 a(4.1g, 18.8 mmol), sodium tert-butoxide(3.3 g, 34.2 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-4를 7.1 g 제조하였다. (수율: 54%, MS: [M+H]+= 765)In a nitrogen atmosphere, intermediate 1-4-1 (10 g, 17.1 mmol), compound a (4.1 g, 18.8 mmol), sodium tert-butoxide (3.3 g, 34.2 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.1 g of compound 1-4. (Yield: 54%, MS: [M+H]+= 765)
합성예 1-5: 화합물 1-5의 제조Synthesis Example 1-5: Preparation of compound 1-5
Figure PCTKR2020095039-appb-img-000362
Figure PCTKR2020095039-appb-img-000362
질소 분위기에서 중간체 1-5-1(10 g, 17.9mmol), 화합물 a(4.3g, 19.6 mmol), sodium tert-butoxide(3.4 g, 35.7 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-5를 8.9 g 제조하였다. (수율: 67%, MS: [M+H]+= 741)In a nitrogen atmosphere, intermediate 1-5-1 (10 g, 17.9 mmol), compound a (4.3 g, 19.6 mmol), sodium tert-butoxide (3.4 g, 35.7 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.9 g of compound 1-5. (Yield: 67%, MS: [M+H]+= 741)
합성예 1-6: 화합물 1-6의 제조Synthesis Example 1-6: Preparation of compound 1-6
Figure PCTKR2020095039-appb-img-000363
Figure PCTKR2020095039-appb-img-000363
질소 분위기에서 중간체 1-6-1(10 g, 15.4mmol), 화합물 a(3.7g, 16.9 mmol), sodium tert-butoxide(3 g, 30.8 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-6을 7.4 g 제조하였다. (수율: 58%, MS: [M+H]+= 831)In a nitrogen atmosphere, intermediate 1-6-1 (10 g, 15.4 mmol), compound a (3.7 g, 16.9 mmol), sodium tert-butoxide (3 g, 30.8 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.4 g of compound 1-6. (Yield: 58%, MS: [M+H]+= 831)
합성예 1-7: 화합물 1-7의 제조Synthesis Example 1-7: Preparation of Compound 1-7
Figure PCTKR2020095039-appb-img-000364
Figure PCTKR2020095039-appb-img-000364
질소 분위기에서 중간체 1-7-1(10 g, 16.4mmol), 화합물 d(4.8g, 18 mmol), sodium tert-butoxide(3.2 g, 32.8 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-7을 7 g 제조하였다. (수율: 51%, MS: [M+H]+= 841)In a nitrogen atmosphere, intermediate 1-7-1 (10 g, 16.4 mmol), compound d (4.8 g, 18 mmol), sodium tert-butoxide (3.2 g, 32.8 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7 g of compound 1-7. (Yield: 51%, MS: [M+H]+= 841)
합성예 1-8: 화합물 1-8의 제조Synthesis Example 1-8: Preparation of compound 1-8
Figure PCTKR2020095039-appb-img-000365
Figure PCTKR2020095039-appb-img-000365
질소 분위기에서 중간체 1-8-1(10 g, 16mmol), 화합물 d(4.7g, 17.6 mmol), sodium tert-butoxide(3.1 g, 32 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-8을 6.8 g 제조하였다. (수율: 50%, MS: [M+H]+= 855)In a nitrogen atmosphere, intermediate 1-8-1 (10 g, 16 mmol), compound d (4.7 g, 17.6 mmol), sodium tert-butoxide (3.1 g, 32 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.8 g of compound 1-8. (Yield: 50%, MS: [M+H]+= 855)
합성예 1-9: 화합물 1-9의 제조Synthesis Example 1-9: Preparation of Compound 1-9
Figure PCTKR2020095039-appb-img-000366
Figure PCTKR2020095039-appb-img-000366
질소 분위기에서 중간체 1-9-1(10 g, 14.6mmol), 화합물 c(4.3g, 16.1 mmol), sodium tert-butoxide(2.8 g, 29.2 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-9를 6.7 g 제조하였다. (수율: 50%, MS: [M+H]+= 915)In a nitrogen atmosphere, intermediate 1-9-1 (10 g, 14.6 mmol), compound c (4.3 g, 16.1 mmol), sodium tert-butoxide (2.8 g, 29.2 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.7 g of compound 1-9. (Yield: 50%, MS: [M+H]+= 915)
합성예 1-10: 화합물 1-10의 제조Synthesis Example 1-10: Preparation of Compound 1-10
Figure PCTKR2020095039-appb-img-000367
Figure PCTKR2020095039-appb-img-000367
질소 분위기에서 중간체 1-10-1(10 g, 17.4mmol), 화합물 b(5.1g, 19.2 mmol), sodium tert-butoxide(3.3 g, 34.8 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-10을 8.8 g 제조하였다. (수율: 63%, MS: [M+H]+= 805)In a nitrogen atmosphere, intermediate 1-10-1 (10 g, 17.4 mmol), compound b (5.1 g, 19.2 mmol), sodium tert-butoxide (3.3 g, 34.8 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.8 g of compound 1-10. (Yield: 63%, MS: [M+H]+= 805)
합성예 1-11: 화합물 1-11의 제조Synthesis Example 1-11: Preparation of Compound 1-11
Figure PCTKR2020095039-appb-img-000368
Figure PCTKR2020095039-appb-img-000368
질소 분위기에서 중간체 1-11-1(10 g, 16.5mmol), 화합물 a(3.9g, 18.1 mmol), sodium tert-butoxide(3.2 g, 33 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-11을 8.4 g 제조하였다. (수율: 65%, MS: [M+H]+= 787)In a nitrogen atmosphere, intermediate 1-11-1 (10 g, 16.5 mmol), compound a (3.9 g, 18.1 mmol), sodium tert-butoxide (3.2 g, 33 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.4 g of compound 1-11. (Yield: 65%, MS: [M+H]+= 787)
합성예 1-12: 화합물 1-12의 제조Synthesis Example 1-12: Preparation of Compound 1-12
Figure PCTKR2020095039-appb-img-000369
Figure PCTKR2020095039-appb-img-000369
질소 분위기에서 중간체 1-12-1(10 g, 19mmol), 화합물 a(4.5g, 20.9 mmol), sodium tert-butoxide(3.7 g, 38 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-12를 7.1 g 제조하였다. (수율: 53%, MS: [M+H]+= 707)In a nitrogen atmosphere, intermediate 1-12-1 (10 g, 19 mmol), compound a (4.5 g, 20.9 mmol), sodium tert-butoxide (3.7 g, 38 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.1 g of compound 1-12. (Yield: 53%, MS: [M+H]+= 707)
합성예 1-13: 화합물 1-13의 제조Synthesis Example 1-13: Preparation of Compound 1-13
Figure PCTKR2020095039-appb-img-000370
Figure PCTKR2020095039-appb-img-000370
질소 분위기에서 중간체 1-13-1(10 g, 15.4mmol), 화합물 a(3.7g, 16.9 mmol), sodium tert-butoxide(3 g, 30.8 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-13을 6.8 g 제조하였다. (수율: 53%, MS: [M+H]+= 831)In a nitrogen atmosphere, intermediate 1-13-1 (10 g, 15.4 mmol), compound a (3.7 g, 16.9 mmol), sodium tert-butoxide (3 g, 30.8 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.8 g of compound 1-13. (Yield: 53%, MS: [M+H]+= 831)
합성예 1-14: 화합물 1-14의 제조Synthesis Example 1-14: Preparation of Compound 1-14
Figure PCTKR2020095039-appb-img-000371
Figure PCTKR2020095039-appb-img-000371
질소 분위기에서 중간체 1-14-1(10 g, 20mmol), 화합물 b(5.9g, 22 mmol), sodium tert-butoxide(3.8 g, 40 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-14를 7.9 g 제조하였다. (수율: 54%, MS: [M+H]+= 731)In a nitrogen atmosphere, intermediate 1-14-1 (10 g, 20 mmol), compound b (5.9 g, 22 mmol), sodium tert-butoxide (3.8 g, 40 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.9 g of compound 1-14. (Yield: 54%, MS: [M+H]+= 731)
합성예 1-15: 화합물 1-15의 제조Synthesis Example 1-15: Preparation of Compound 1-15
Figure PCTKR2020095039-appb-img-000372
Figure PCTKR2020095039-appb-img-000372
질소 분위기에서 중간체 1-15-1(10 g, 15.3mmol), 화합물 c(4.5g, 16.9 mmol), sodium tert-butoxide(2.9 g, 30.7 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-15를 9.3 g 제조하였다. (수율: 69%, MS: [M+H]+= 883)In a nitrogen atmosphere, intermediate 1-15-1 (10 g, 15.3 mmol), compound c (4.5 g, 16.9 mmol), sodium tert-butoxide (2.9 g, 30.7 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.3 g of compound 1-15. (Yield: 69%, MS: [M+H]+= 883)
합성예 1-16: 화합물 1-16의 제조Synthesis Example 1-16: Preparation of Compound 1-16
Figure PCTKR2020095039-appb-img-000373
Figure PCTKR2020095039-appb-img-000373
질소 분위기에서 중간체 1-16-1(10 g, 14.4mmol), 화합물 a(3.4g, 15.8 mmol), sodium tert-butoxide(2.8 g, 28.7 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-16을 6.4 g 제조하였다. (수율: 51%, MS: [M+H]+= 877)In a nitrogen atmosphere, intermediate 1-16-1 (10 g, 14.4 mmol), compound a (3.4 g, 15.8 mmol), sodium tert-butoxide (2.8 g, 28.7 mmol) was added to 200 ml of Xylene, followed by stirring and refluxing. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.4 g of compound 1-16. (Yield: 51%, MS: [M+H]+= 877)
합성예 1-17: 화합물 1-17의 제조Synthesis Example 1-17: Preparation of Compound 1-17
Figure PCTKR2020095039-appb-img-000374
Figure PCTKR2020095039-appb-img-000374
질소 분위기에서 중간체 1-17-1(10 g, 20mmol), 화합물 a(4.8g, 22 mmol), sodium tert-butoxide(3.8 g, 40 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-17을 7.9 g 제조하였다. (수율: 58%, MS: [M+H]+= 681)In a nitrogen atmosphere, intermediate 1-17-1 (10 g, 20 mmol), compound a (4.8 g, 22 mmol), sodium tert-butoxide (3.8 g, 40 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.9 g of compound 1-17. (Yield: 58%, MS: [M+H]+= 681)
합성예 1-18: 화합물 1-18의 제조Synthesis Example 1-18: Preparation of compound 1-18
Figure PCTKR2020095039-appb-img-000375
Figure PCTKR2020095039-appb-img-000375
질소 분위기에서 중간체 1-18-1(10 g, 16mmol), 화합물 b(4.7g, 17.6 mmol), sodium tert-butoxide(3.1 g, 31.9 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-18을 7.2 g 제조하였다. (수율: 53%, MS: [M+H]+= 857)In a nitrogen atmosphere, intermediate 1-18-1 (10 g, 16 mmol), compound b (4.7 g, 17.6 mmol), sodium tert-butoxide (3.1 g, 31.9 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.2 g of compound 1-18. (Yield: 53%, MS: [M+H]+= 857)
합성예 1-19: 화합물 1-19의 제조Synthesis Example 1-19: Preparation of Compound 1-19
Figure PCTKR2020095039-appb-img-000376
Figure PCTKR2020095039-appb-img-000376
질소 분위기에서 중간체 1-19-1(10 g, 15.2mmol), 화합물 c(4.5g, 16.8 mmol), sodium tert-butoxide(2.9 g, 30.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-19를 8.5 g 제조하였다. (수율: 63%, MS: [M+H]+= 887)In a nitrogen atmosphere, intermediate 1-19-1 (10 g, 15.2 mmol), compound c (4.5 g, 16.8 mmol), sodium tert-butoxide (2.9 g, 30.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.5 g of compound 1-19. (Yield: 63%, MS: [M+H]+= 887)
합성예 1-20: 화합물 1-20의 제조Synthesis Example 1-20: Preparation of Compound 1-20
Figure PCTKR2020095039-appb-img-000377
Figure PCTKR2020095039-appb-img-000377
질소 분위기에서 중간체 1-20-1(10 g, 15.2mmol), 화합물 d(4.5g, 16.8 mmol), sodium tert-butoxide(2.9 g, 30.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-20을 7.4 g 제조하였다. (수율: 55%, MS: [M+H]+= 887)In a nitrogen atmosphere, intermediate 1-20-1 (10 g, 15.2 mmol), compound d (4.5 g, 16.8 mmol), sodium tert-butoxide (2.9 g, 30.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.4 g of compound 1-20. (Yield: 55%, MS: [M+H]+= 887)
합성예 1-21: 화합물 1-21의 제조Synthesis Example 1-21: Preparation of Compound 1-21
Figure PCTKR2020095039-appb-img-000378
Figure PCTKR2020095039-appb-img-000378
질소 분위기에서 중간체 1-21-1(10 g, 19mmol), 화합물 a(4.5g, 20.9 mmol), sodium tert-butoxide(3.7 g, 38 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-21을 9.4 g 제조하였다. (수율: 70%, MS: [M+H]+= 707)In a nitrogen atmosphere, intermediate 1-21-1 (10 g, 19 mmol), compound a (4.5 g, 20.9 mmol), sodium tert-butoxide (3.7 g, 38 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.4 g of compound 1-21. (Yield: 70%, MS: [M+H]+= 707)
합성예 1-22: 화합물 1-22의 제조Synthesis Example 1-22: Preparation of Compound 1-22
Figure PCTKR2020095039-appb-img-000379
Figure PCTKR2020095039-appb-img-000379
질소 분위기에서 중간체 1-22-1(10 g, 22.2mmol), 화합물 a(5.3g, 24.4 mmol), sodium tert-butoxide(4.3 g, 44.4 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-22를 7.1 g 제조하였다. (수율: 51%, MS: [M+H]+= 631)In a nitrogen atmosphere, intermediate 1-22-1 (10 g, 22.2 mmol), compound a (5.3 g, 24.4 mmol), sodium tert-butoxide (4.3 g, 44.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.1 g of compound 1-22. (Yield: 51%, MS: [M+H]+= 631)
합성예 1-23: 화합물 1-23의 제조Synthesis Example 1-23: Preparation of Compound 1-23
Figure PCTKR2020095039-appb-img-000380
Figure PCTKR2020095039-appb-img-000380
질소 분위기에서 중간체 1-23-1(10 g, 16.2mmol), 화합물 a(3.9g, 17.9 mmol), sodium tert-butoxide(3.1 g, 32.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-23을 6.8 g 제조하였다. (수율: 53%, MS: [M+H]+= 797)In a nitrogen atmosphere, intermediate 1-23-1 (10 g, 16.2 mmol), compound a (3.9 g, 17.9 mmol), sodium tert-butoxide (3.1 g, 32.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.8 g of compound 1-23. (Yield: 53%, MS: [M+H]+= 797)
합성예 1-24: 화합물 1-24의 제조Synthesis Example 1-24: Preparation of Compound 1-24
Figure PCTKR2020095039-appb-img-000381
Figure PCTKR2020095039-appb-img-000381
질소 분위기에서 중간체 1-24-1(10 g, 16mmol), 화합물 b(4.7g, 17.6 mmol), sodium tert-butoxide(3.1 g, 31.9 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-24를 8.3 g 제조하였다. (수율: 61%, MS: [M+H]+= 857)In a nitrogen atmosphere, intermediate 1-24-1 (10 g, 16 mmol), compound b (4.7 g, 17.6 mmol), sodium tert-butoxide (3.1 g, 31.9 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.3 g of compound 1-24. (Yield: 61%, MS: [M+H]+= 857)
합성예 1-25: 화합물 1-25의 제조Synthesis Example 1-25: Preparation of Compound 1-25
Figure PCTKR2020095039-appb-img-000382
Figure PCTKR2020095039-appb-img-000382
질소 분위기에서 중간체 1-25-1(10 g, 15mmol), 화합물 d(4.4g, 16.5 mmol), sodium tert-butoxide(2.9 g, 30 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-25을 8.7 g 제조하였다. (수율: 65%, MS: [M+H]+= 897)In a nitrogen atmosphere, intermediate 1-25-1 (10 g, 15 mmol), compound d (4.4 g, 16.5 mmol), sodium tert-butoxide (2.9 g, 30 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.7 g of compounds 1-25. (Yield: 65%, MS: [M+H]+= 897)
합성예 1-26: 화합물 1-26의 제조Synthesis Example 1-26: Preparation of Compound 1-26
Figure PCTKR2020095039-appb-img-000383
Figure PCTKR2020095039-appb-img-000383
질소 분위기에서 중간체 1-26-1(10 g, 20mmol), 화합물 a(4.8g, 22 mmol), sodium tert-butoxide(3.8 g, 40 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-26을 6.9 g 제조하였다. (수율: 51%, MS: [M+H]+= 681)In a nitrogen atmosphere, intermediate 1-26-1 (10 g, 20 mmol), compound a (4.8 g, 22 mmol), sodium tert-butoxide (3.8 g, 40 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.9 g of compound 1-26. (Yield: 51%, MS: [M+H]+= 681)
합성예 1-27: 화합물 1-27의 제조Synthesis Example 1-27: Preparation of Compound 1-27
Figure PCTKR2020095039-appb-img-000384
Figure PCTKR2020095039-appb-img-000384
질소 분위기에서 중간체 1-27-1(10 g, 16.7mmol), 화합물 a(4g, 18.3 mmol), sodium tert-butoxide(3.2 g, 33.3 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-27을 6.6 g 제조하였다. (수율: 51%, MS: [M+H]+= 781)In a nitrogen atmosphere, intermediate 1-27-1 (10 g, 16.7 mmol), compound a (4 g, 18.3 mmol), sodium tert-butoxide (3.2 g, 33.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.6 g of compound 1-27. (Yield: 51%, MS: [M+H]+= 781)
합성예 1-28: 화합물 1-28의 제조Synthesis Example 1-28: Preparation of Compound 1-28
Figure PCTKR2020095039-appb-img-000385
Figure PCTKR2020095039-appb-img-000385
질소 분위기에서 중간체 1-28-1(10 g, 15.4mmol), 화합물 c(4.5g, 16.9 mmol), sodium tert-butoxide(3 g, 30.8 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-28을 7 g 제조하였다. (수율: 52%, MS: [M+H]+= 881)In a nitrogen atmosphere, intermediate 1-28-1 (10 g, 15.4 mmol), compound c (4.5 g, 16.9 mmol), sodium tert-butoxide (3 g, 30.8 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7 g of compound 1-28. (Yield: 52%, MS: [M+H]+= 881)
합성예 1-29: 화합물 1-29의 제조Synthesis Example 1-29: Preparation of Compound 1-29
Figure PCTKR2020095039-appb-img-000386
Figure PCTKR2020095039-appb-img-000386
질소 분위기에서 중간체 1-29-1(10 g, 16.7mmol), 화합물 a(4g, 18.3 mmol), sodium tert-butoxide(3.2 g, 33.3 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-29를 6.9 g 제조하였다. (수율: 53%, MS: [M+H]+= 781)In a nitrogen atmosphere, intermediate 1-29-1 (10 g, 16.7 mmol), compound a (4 g, 18.3 mmol), sodium tert-butoxide (3.2 g, 33.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.9 g of compound 1-29. (Yield: 53%, MS: [M+H]+= 781)
합성예 1-30: 화합물 1-30의 제조Synthesis Example 1-30: Preparation of Compound 1-30
Figure PCTKR2020095039-appb-img-000387
Figure PCTKR2020095039-appb-img-000387
질소 분위기에서 중간체 1-30-1(10 g, 14mmol), 화합물 a(3.4g, 15.4 mmol), sodium tert-butoxide(2.7 g, 28.1 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-30을 7.1 g 제조하였다. (수율: 57%, MS: [M+H]+= 893)In a nitrogen atmosphere, intermediates 1-30-1 (10 g, 14 mmol), compound a (3.4 g, 15.4 mmol), sodium tert-butoxide (2.7 g, 28.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.1 g of compound 1-30. (Yield: 57%, MS: [M+H]+= 893)
합성예 1-31: 화합물 1-31의 제조Synthesis Example 1-31: Preparation of Compound 1-31
Figure PCTKR2020095039-appb-img-000388
Figure PCTKR2020095039-appb-img-000388
질소 분위기에서 중간체 1-31-1(10 g, 22.2mmol), 화합물 a(5.3g, 24.4 mmol), sodium tert-butoxide(4.3 g, 44.4 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-31을 7.8 g 제조하였다. (수율: 56%, MS: [M+H]+= 631)In a nitrogen atmosphere, intermediate 1-31-1 (10 g, 22.2 mmol), compound a (5.3 g, 24.4 mmol), sodium tert-butoxide (4.3 g, 44.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.8 g of compound 1-31. (Yield: 56%, MS: [M+H]+= 631)
합성예 1-32: 화합물 1-32의 제조Synthesis Example 1-32: Preparation of Compound 1-32
Figure PCTKR2020095039-appb-img-000389
Figure PCTKR2020095039-appb-img-000389
질소 분위기에서 중간체 1-32-1(10 g, 16.6mmol), 화합물 a(4g, 18.3 mmol), sodium tert-butoxide(3.2 g, 33.3 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-32를 8.1 g 제조하였다. (수율: 62%, MS: [M+H]+= 783)In a nitrogen atmosphere, intermediate 1-32-1 (10 g, 16.6 mmol), compound a (4 g, 18.3 mmol), sodium tert-butoxide (3.2 g, 33.3 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.1 g of compound 1-32. (Yield: 62%, MS: [M+H]+= 783)
합성예 1-33: 화합물 1-33의 제조Synthesis Example 1-33: Preparation of Compound 1-33
Figure PCTKR2020095039-appb-img-000390
Figure PCTKR2020095039-appb-img-000390
질소 분위기에서 중간체 1-33-1(10 g, 19mmol), 화합물 a(4.6g, 20.9 mmol), sodium tert-butoxide(3.7 g, 38.1 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-33을 7 g 제조하였다. (수율: 52%, MS: [M+H]+= 707)In a nitrogen atmosphere, intermediate 1-33-1 (10 g, 19 mmol), compound a (4.6 g, 20.9 mmol), sodium tert-butoxide (3.7 g, 38.1 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7 g of compound 1-33. (Yield: 52%, MS: [M+H]+= 707)
합성예Synthesis example 1-34: 화합물 1-34의 제조 1-34: Preparation of compound 1-34
Figure PCTKR2020095039-appb-img-000391
Figure PCTKR2020095039-appb-img-000391
질소 분위기에서 중간체 1-34-1(10 g, 18.2mmol), 화합물 a(4.4g, 20 mmol), sodium tert-butoxide(3.5 g, 36.4 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-34를 8.2 g 제조하였다. (수율: 62%, MS: [M+H]+= 731)In a nitrogen atmosphere, intermediate 1-34-1 (10 g, 18.2 mmol), compound a (4.4 g, 20 mmol), sodium tert-butoxide (3.5 g, 36.4 mmol) was added to 200 ml of Xylene, followed by stirring and refluxing. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.2 g of compound 1-34. (Yield: 62%, MS: [M+H]+= 731)
합성예 1-35: 화합물 1-35의 제조Synthesis Example 1-35: Preparation of compound 1-35
Figure PCTKR2020095039-appb-img-000392
Figure PCTKR2020095039-appb-img-000392
질소 분위기에서 중간체 1-35-1(10 g, 15.6mmol), 화합물 d(4.6g, 17.2 mmol), sodium tert-butoxide(3 g, 31.3 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-35을 9.4 g 제조하였다. (수율: 69%, MS: [M+H]+= 871)In a nitrogen atmosphere, intermediate 1-35-1 (10 g, 15.6 mmol), compound d (4.6 g, 17.2 mmol), sodium tert-butoxide (3 g, 31.3 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.4 g of compound 1-35. (Yield: 69%, MS: [M+H]+= 871)
합성예 1-36: 화합물 1-36의 제조Synthesis Example 1-36: Preparation of Compound 1-36
Figure PCTKR2020095039-appb-img-000393
Figure PCTKR2020095039-appb-img-000393
질소 분위기에서 중간체 1-36-1(10 g, 22.3mmol), 화합물 c(6.5g, 24.5 mmol), sodium tert-butoxide(4.3 g, 44.5 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-36을 8 g 제조하였다. (수율: 53%, MS: [M+H]+= 681)In a nitrogen atmosphere, intermediate 1-36-1 (10 g, 22.3 mmol), compound c (6.5 g, 24.5 mmol), sodium tert-butoxide (4.3 g, 44.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8 g of compound 1-36. (Yield: 53%, MS: [M+H]+= 681)
합성예 1-37: 화합물 1-37의 제조Synthesis Example 1-37: Preparation of Compound 1-37
Figure PCTKR2020095039-appb-img-000394
Figure PCTKR2020095039-appb-img-000394
질소 분위기에서 중간체 1-37-1(10 g, 18.2mmol), 화합물 b(5.4g, 20 mmol), sodium tert-butoxide(3.5 g, 36.4 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-37을 37 9 g 제조하였다. (수율: 63%, MS: [M+H]+= 781)In a nitrogen atmosphere, intermediate 1-37-1 (10 g, 18.2 mmol), compound b (5.4 g, 20 mmol), and sodium tert-butoxide (3.5 g, 36.4 mmol) were added to 200 ml of Xylene, followed by stirring and refluxing. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 37 9 g of compound 1-37. (Yield: 63%, MS: [M+H]+= 781)
합성예 1-38: 화합물 1-38의 제조Synthesis Example 1-38: Preparation of Compound 1-38
Figure PCTKR2020095039-appb-img-000395
Figure PCTKR2020095039-appb-img-000395
질소 분위기에서 중간체 1-38-1(10 g, 14.7mmol), 화합물 c(4.3g, 16.2 mmol), sodium tert-butoxide(2.8 g, 29.4 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-38을 8.6 g 제조하였다. (수율: 64%, MS: [M+H]+= 913)In a nitrogen atmosphere, intermediate 1-38-1 (10 g, 14.7 mmol), compound c (4.3 g, 16.2 mmol), sodium tert-butoxide (2.8 g, 29.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.6 g of compound 1-38. (Yield: 64%, MS: [M+H]+= 913)
합성예 1-39: 화합물 1-39의 제조Synthesis Example 1-39: Preparation of Compound 1-39
Figure PCTKR2020095039-appb-img-000396
Figure PCTKR2020095039-appb-img-000396
질소 분위기에서 중간체 1-39-1(10 g, 16mmol), 화합물 b(4.7g, 17.6 mmol), sodium tert-butoxide(3.1 g, 32 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-39를 9.3 g 제조하였다. (수율: 68%, MS: [M+H]+= 857)In a nitrogen atmosphere, intermediate 1-39-1 (10 g, 16 mmol), compound b (4.7 g, 17.6 mmol), sodium tert-butoxide (3.1 g, 32 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.3 g of compound 1-39. (Yield: 68%, MS: [M+H]+= 857)
합성예 1-40: 화합물 1-40의 제조Synthesis Example 1-40: Preparation of Compound 1-40
Figure PCTKR2020095039-appb-img-000397
Figure PCTKR2020095039-appb-img-000397
질소 분위기에서 중간체 1-40-1(10 g, 18.2mmol), 화합물 a(4.4g, 20 mmol), sodium tert-butoxide(3.5 g, 36.4 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-40을 8 g 제조하였다. (수율: 60%, MS: [M+H]+= 731)In a nitrogen atmosphere, intermediate 1-40-1 (10 g, 18.2 mmol), compound a (4.4 g, 20 mmol), sodium tert-butoxide (3.5 g, 36.4 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8 g of compound 1-40. (Yield: 60%, MS: [M+H]+= 731)
합성예 1-41: 화합물 1-41의 제조Synthesis Example 1-41: Preparation of Compound 1-41
Figure PCTKR2020095039-appb-img-000398
Figure PCTKR2020095039-appb-img-000398
질소 분위기에서 중간체 1-41-1(10 g, 16.5mmol), 화합물 d(4.9g, 18.2 mmol), sodium tert-butoxide(3.2 g, 33.1 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입하였다. 2시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-41을 8.2 g 제조하였다. (수율: 59%, MS: [M+H]+= 837)In a nitrogen atmosphere, intermediate 1-41-1 (10 g, 16.5 mmol), compound d (4.9 g, 18.2 mmol), sodium tert-butoxide (3.2 g, 33.1 mmol) was added to 200 ml of Xylene and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was terminated after 2 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.2 g of compound 1-41. (Yield: 59%, MS: [M+H]+= 837)
합성예 1-42: 화합물 1-42의 제조Synthesis Example 1-42: Preparation of Compound 1-42
Figure PCTKR2020095039-appb-img-000399
Figure PCTKR2020095039-appb-img-000399
질소 분위기에서 중간체 1-42-1(10 g, 14.4mmol), 화합물 c(4.2g, 15.8 mmol), sodium tert-butoxide(2.8 g, 28.8 mmol)을 Xylene 200 ml에 넣고 교반 및 환류하였다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol)을 투입하였다. 3시간 후 반응이 종결되면 상온으로 식히고 감압하여 용매를 제거하였다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 1-42를 7.1 g 제조하였다. (수율: 53%, MS: [M+H]+= 927)In a nitrogen atmosphere, intermediate 1-42-1 (10 g, 14.4 mmol), compound c (4.2 g, 15.8 mmol), sodium tert-butoxide (2.8 g, 28.8 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. When the reaction was terminated after 3 hours, it was cooled to room temperature and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.1 g of compound 1-42. (Yield: 53%, MS: [M+H]+= 927)
합성예Synthesis example 2-1: 화합물 2-1의 제조 2-1: Preparation of compound 2-1
Figure PCTKR2020095039-appb-img-000400
Figure PCTKR2020095039-appb-img-000400
질소 분위기에서 중간체 2-1-1(10g, 25.2mmol)와 중간체 2-1-2(8g, 27.7mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.9g, 100.7mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol)을 투입하였다. 3시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-1를 9g 제조하였다. (수율: 64%, MS: [M+H]+= 561)In a nitrogen atmosphere, intermediate 2-1-1 (10g, 25.2mmol) and intermediate 2-1-2 (8g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water and added. After sufficient stirring, reflux was performed, and then bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound 2-1. (Yield: 64%, MS: [M+H]+= 561)
합성예Synthesis example 2-2: 화합물 2-2의 제조 2-2: Preparation of compound 2-2
Figure PCTKR2020095039-appb-img-000401
Figure PCTKR2020095039-appb-img-000401
질소 분위기에서 중간체 2-2-1(10g, 25.2mmol)와 중간체 2-2-2(8g, 27.7mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.9g, 100.7mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol)을 투입하였다. 4시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-2를 10.6g 제조하였다. (수율: 66%, MS: [M+H]+= 637)In a nitrogen atmosphere, intermediate 2-2-1 (10g, 25.2mmol) and intermediate 2-2-2 (8g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water and added. After sufficient stirring, reflux was performed, and then bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of compound 2-2. (Yield: 66%, MS: [M+H]+= 637)
합성예 2-3: 화합물 2-3의 제조Synthesis Example 2-3: Preparation of Compound 2-3
Figure PCTKR2020095039-appb-img-000402
Figure PCTKR2020095039-appb-img-000402
질소 분위기에서 중간체 2-3-1(10g, 25.2mmol)와 중간체 2-3-2(10.1g, 27.7mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.9g, 100.7mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol)을 투입하였다. 4시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-3을 9g 제조하였다. (수율: 56%, MS: [M+H]+= 637)In a nitrogen atmosphere, add Intermediate 2-3-1 (10g, 25.2mmol) and Intermediate 2-3-2 (10.1g, 27.7mmol) to 200 ml of THF, stir, and dissolve potassium carbonate (13.9g, 100.7mmol) in water. The mixture was added, stirred sufficiently, and refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.3mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound 2-3. (Yield: 56%, MS: [M+H]+= 637)
합성예 2-4: 화합물 2-4의 제조Synthesis Example 2-4: Preparation of compound 2-4
Figure PCTKR2020095039-appb-img-000403
Figure PCTKR2020095039-appb-img-000403
질소 분위기에서 중간체 2-4-1(10g, 25.2mmol)와 중간체 2-4-2(9.3g, 27.7mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.9g, 100.7mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol)을 투입하였다. 2시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-4를 7.8g 제조하였다. (수율: 51%, MS: [M+H]+= 611)In a nitrogen atmosphere, intermediate 2-4-1 (10g, 25.2mmol) and intermediate 2-4-2 (9.3g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.3mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.8 g of compound 2-4. (Yield: 51%, MS: [M+H]+= 611)
합성예 2-5: 화합물 2-5의 제조Synthesis Example 2-5: Preparation of compound 2-5
Figure PCTKR2020095039-appb-img-000404
Figure PCTKR2020095039-appb-img-000404
질소 분위기에서 중간체 2-5-1(10g, 25.2mmol)와 중간체 2-5-2(10.1g, 27.7mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.9g, 100.7mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol)을 투입하였다. 4시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-5를 10.4g 제조하였다. (수율: 65%, MS: [M+H]+= 637)In a nitrogen atmosphere, intermediate 2-5-1 (10g, 25.2mmol) and intermediate 2-5-2 (10.1g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.3mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4 g of compound 2-5. (Yield: 65%, MS: [M+H]+= 637)
합성예 2-6: 화합물 2-6의 제조Synthesis Example 2-6: Preparation of Compound 2-6
Figure PCTKR2020095039-appb-img-000405
Figure PCTKR2020095039-appb-img-000405
질소 분위기에서 중간체 2-6-1(10g, 25.2mmol)와 중간체 2-6-2(11.4g, 27.7mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.9g, 100.7mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol)을 투입하였다. 2시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-6을 10.5g 제조하였다. (수율: 61%, MS: [M+H]+= 687)In a nitrogen atmosphere, intermediate 2-6-1 (10g, 25.2mmol) and intermediate 2-6-2 (11.4g, 27.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.9g, 100.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.3mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of compound 2-6. (Yield: 61%, MS: [M+H]+= 687)
합성예 2-7: 화합물 2-7의 제조Synthesis Example 2-7: Preparation of Compound 2-7
Figure PCTKR2020095039-appb-img-000406
Figure PCTKR2020095039-appb-img-000406
질소 분위기에서 중간체 2-7-1(10g, 22.4mmol)와 중간체 2-7-2(10.2g, 24.6mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(12.4g, 89.5mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 3시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-7을 11g 제조하였다. (수율: 67%, MS: [M+H]+= 737)In a nitrogen atmosphere, intermediate 2-7-1 (10g, 22.4mmol) and intermediate 2-7-2 (10.2g, 24.6mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.4g, 89.5mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11 g of compound 2-7. (Yield: 67%, MS: [M+H]+= 737)
합성예Synthesis example 2-8: 화합물 2-8의 제조 2-8: Preparation of compound 2-8
Figure PCTKR2020095039-appb-img-000407
Figure PCTKR2020095039-appb-img-000407
질소 분위기에서 중간체 2-8-1(10g, 17.9mmol)와 중간체 2-8-2(5.6g, 19.7mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(9.9g, 71.5mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 3시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-8를 7.8g 제조하였다. (수율: 60%, MS: [M+H]+= 723)In a nitrogen atmosphere, intermediate 2-8-1 (10g, 17.9mmol) and intermediate 2-8-2 (5.6g, 19.7mmol) were added to 200 ml of THF, stirred, and potassium carbonate (9.9g, 71.5mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.8 g of compound 2-8. (Yield: 60%, MS: [M+H]+= 723)
합성예 2-9: 화합물 2-9의 제조Synthesis Example 2-9: Preparation of Compound 2-9
Figure PCTKR2020095039-appb-img-000408
Figure PCTKR2020095039-appb-img-000408
질소 분위기에서 중간체 2-9-1(10g, 21.1mmol)와 중간체 2-9-2(6.7g, 23.3mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(11.7g, 84.6mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 3시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-9를 7.4g 제조하였다. (수율: 55%, MS: [M+H]+= 637)In a nitrogen atmosphere, intermediate 2-9-1 (10g, 21.1mmol) and intermediate 2-9-2 (6.7g, 23.3mmol) were added to 200 ml of THF, stirred, and potassium carbonate (11.7g, 84.6mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.4 g of compound 2-9. (Yield: 55%, MS: [M+H]+= 637)
합성예 2-10: 화합물 2-10의 제조Synthesis Example 2-10: Preparation of Compound 2-10
Figure PCTKR2020095039-appb-img-000409
Figure PCTKR2020095039-appb-img-000409
질소 분위기에서 중간체 2-10-1(10g, 27mmol)와 중간체 2-10-2(10g, 29.6mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(14.9g, 107.8mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol)을 투입하였다. 2시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-10을 11g 제조하였다. (수율: 70%, MS: [M+H]+= 585)In a nitrogen atmosphere, intermediate 2-10-1 (10g, 27mmol) and intermediate 2-10-2 (10g, 29.6mmol) were added to 200 ml of THF, stirred, and potassium carbonate (14.9g, 107.8mmol) was dissolved in water and added. After sufficiently stirring and refluxing, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11 g of compound 2-10. (Yield: 70%, MS: [M+H]+= 585)
합성예 2-11: 화합물 2-11의 제조Synthesis Example 2-11: Preparation of Compound 2-11
Figure PCTKR2020095039-appb-img-000410
Figure PCTKR2020095039-appb-img-000410
질소 분위기에서 중간체 2-11-1(10g, 27mmol)와 중간체 2-11-2(11.5g, 29.6mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(14.9g, 107.8mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol)을 투입하였다. 2시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-11을 11.5g 제조하였다. (수율: 67%, MS: [M+H]+= 635)In a nitrogen atmosphere, intermediate 2-11-1 (10g, 27mmol) and intermediate 2-11-2 (11.5g, 29.6mmol) were added to 200 ml of THF, stirred, and potassium carbonate (14.9g, 107.8mmol) was dissolved in water and added. After sufficient stirring, reflux was performed, and then bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5 g of compound 2-11. (Yield: 67%, MS: [M+H]+= 635)
합성예 2-12: 화합물 2-12의 제조Synthesis Example 2-12: Preparation of Compound 2-12
Figure PCTKR2020095039-appb-img-000411
Figure PCTKR2020095039-appb-img-000411
질소 분위기에서 중간체 2-12-1(10g, 23.8mmol)와 중간체 2-12-2(8.8g, 26.1mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.1g, 95mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 3시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-12를 10.4g 제조하였다. (수율: 69%, MS: [M+H]+= 635)In a nitrogen atmosphere, intermediate 2-12-1 (10g, 23.8mmol) and intermediate 2-12-2 (8.8g, 26.1mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.1g, 95mmol) was dissolved in water and added. Then, after sufficiently stirring, refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4 g of compound 2-12. (Yield: 69%, MS: [M+H]+= 635)
합성예 2-13: 화합물 2-13의 제조Synthesis Example 2-13: Preparation of Compound 2-13
Figure PCTKR2020095039-appb-img-000412
Figure PCTKR2020095039-appb-img-000412
질소 분위기에서 중간체 2-13-1(10g, 24.3mmol)와 중간체 2-13-2(11.1g, 26.8mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.5g, 97.3mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 2시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-13을 9g 제조하였다. (수율: 53%, MS: [M+H]+= 701)In a nitrogen atmosphere, intermediate 2-13-1 (10g, 24.3mmol) and intermediate 2-13-2 (11.1g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound 2-13. (Yield: 53%, MS: [M+H]+= 701)
합성예 2-14: 화합물 2-14의 제조Synthesis Example 2-14: Preparation of Compound 2-14
Figure PCTKR2020095039-appb-img-000413
Figure PCTKR2020095039-appb-img-000413
질소 분위기에서 중간체 2-14-1(10g, 24.3mmol)와 중간체 2-14-2(7.7g, 26.8mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.5g, 97.3mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 3시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-14를 8.9g 제조하였다. (수율: 64%, MS: [M+H]+= 575)In a nitrogen atmosphere, intermediate 2-14-1 (10g, 24.3mmol) and intermediate 2-14-2 (7.7g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.9 g of compound 2-14. (Yield: 64%, MS: [M+H]+= 575)
합성예 2-15: 화합물 2-15의 제조Synthesis Example 2-15: Preparation of Compound 2-15
Figure PCTKR2020095039-appb-img-000414
Figure PCTKR2020095039-appb-img-000414
질소 분위기에서 중간체 2-15-1(10g, 24.3mmol)와 중간체 2-15-2(9g, 26.8mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.5g, 97.3mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 4시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-15를 8.4g 제조하였다. (수율: 55%, MS: [M+H]+= 625)In a nitrogen atmosphere, intermediate 2-15-1 (10g, 24.3mmol) and intermediate 2-15-2 (9g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water and added. Then, after sufficiently stirring, refluxed, and then bis (tri-tert-butylphosphine) palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.4 g of compound 2-15. (Yield: 55%, MS: [M+H]+= 625)
합성예 2-16: 화합물 2-16의 제조Synthesis Example 2-16: Preparation of Compound 2-16
Figure PCTKR2020095039-appb-img-000415
Figure PCTKR2020095039-appb-img-000415
질소 분위기에서 중간체 2-16-1(10g, 24.3mmol)와 중간체 2-16-2(11.1g, 26.8mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.5g, 97.3mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 2시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-16을 11.2g 제조하였다. (수율: 66%, MS: [M+H]+= 701)In a nitrogen atmosphere, intermediate 2-16-1 (10g, 24.3mmol) and intermediate 2-16-2 (11.1g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound 2-16. (Yield: 66%, MS: [M+H]+= 701)
합성예 2-17: 화합물 2-17의 제조Synthesis Example 2-17: Preparation of Compound 2-17
Figure PCTKR2020095039-appb-img-000416
Figure PCTKR2020095039-appb-img-000416
질소 분위기에서 중간체 2-17-1(10g, 24.3mmol)와 중간체 2-17-2(10.1g, 26.8mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.5g, 97.3mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 3시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-17을 10g 제조하였다. (수율: 62%, MS: [M+H]+= 665)In a nitrogen atmosphere, intermediate 2-17-1 (10g, 24.3mmol) and intermediate 2-17-2 (10.1g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10 g of compound 2-17. (Yield: 62%, MS: [M+H]+= 665)
합성예 2-18: 화합물 2-18의 제조Synthesis Example 2-18: Preparation of Compound 2-18
Figure PCTKR2020095039-appb-img-000417
Figure PCTKR2020095039-appb-img-000417
질소 분위기에서 중간체 2-18-1(10g, 24.3mmol)와 중간체 2-18-2(10.5g, 26.8mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.5g, 97.3mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 2시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-18을 9.8g 제조하였다. (수율: 59%, MS: [M+H]+= 681)In a nitrogen atmosphere, intermediate 2-18-1 (10g, 24.3mmol) and intermediate 2-18-2 (10.5g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.8 g of compound 2-18. (Yield: 59%, MS: [M+H]+= 681)
합성예 2-19: 화합물 2-19의 제조Synthesis Example 2-19: Preparation of Compound 2-19
Figure PCTKR2020095039-appb-img-000418
Figure PCTKR2020095039-appb-img-000418
질소 분위기에서 중간체 2-19-1(10g, 24.3mmol)와 중간체 2-19-2(10.5g, 26.8mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(13.5g, 97.3mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 3시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-19를 11.4g 제조하였다. (수율: 69%, MS: [M+H]+= 681)In a nitrogen atmosphere, intermediate 2-19-1 (10g, 24.3mmol) and intermediate 2-19-2 (10.5g, 26.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (13.5g, 97.3mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of compound 2-19. (Yield: 69%, MS: [M+H]+= 681)
합성예 2-20: 화합물 2-20의 제조Synthesis Example 2-20: Preparation of Compound 2-20
Figure PCTKR2020095039-appb-img-000419
Figure PCTKR2020095039-appb-img-000419
질소 분위기에서 중간체 2-20-1(10g, 23.4mmol)와 중간체 2-20-2(9.4g, 25.8mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(12.9g, 93.7mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 2시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-20을 9g 제조하였다. (수율: 58%, MS: [M+H]+= 667)In a nitrogen atmosphere, intermediate 2-20-1 (10g, 23.4mmol) and intermediate 2-20-2 (9.4g, 25.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.9g, 93.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound 2-20. (Yield: 58%, MS: [M+H]+= 667)
합성예 2-21: 화합물 2-21의 제조Synthesis Example 2-21: Preparation of Compound 2-21
Figure PCTKR2020095039-appb-img-000420
Figure PCTKR2020095039-appb-img-000420
질소 분위기에서 중간체 2-21-1(10g, 23.4mmol)와 중간체 2-21-2(10.6g, 25.8mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(12.9g, 93.7mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 4시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-21을 10.7g 제조하였다. (수율: 64%, MS: [M+H]+= 717)In a nitrogen atmosphere, intermediate 2-21-1 (10g, 23.4mmol) and intermediate 2-21-2 (10.6g, 25.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.9g, 93.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7 g of compound 2-21. (Yield: 64%, MS: [M+H]+= 717)
합성예 2-22: 화합물 2-22의 제조Synthesis Example 2-22: Preparation of Compound 2-22
Figure PCTKR2020095039-appb-img-000421
Figure PCTKR2020095039-appb-img-000421
질소 분위기에서 중간체 2-22-1(10g, 23.4mmol)와 중간체 2-22-2(11.3g, 25.8mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(12.9g, 93.7mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 3시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-22를 9g 제조하였다. (수율: 52%, MS: [M+H]+= 743)In a nitrogen atmosphere, intermediate 2-22-1 (10g, 23.4mmol) and intermediate 2-22-2 (11.3g, 25.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.9g, 93.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound 2-22. (Yield: 52%, MS: [M+H]+= 743)
합성예 2-23: 화합물 2-23의 제조Synthesis Example 2-23: Preparation of Compound 2-23
Figure PCTKR2020095039-appb-img-000422
Figure PCTKR2020095039-appb-img-000422
질소 분위기에서 중간체 2-23-1(10g, 23.4mmol)와 중간체 2-23-2(10.1g, 25.8mmol)를 THF 200 ml에 넣고 교반하고 potassium carbonate(12.9g, 93.7mmol)를 물에 녹여 투입하고 충분히 교반한 후 환류한 다음 bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol)을 투입하였다. 4시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-23을 9.1g 제조하였다. (수율: 56%, MS: [M+H]+= 697)In a nitrogen atmosphere, intermediate 2-23-1 (10g, 23.4mmol) and intermediate 2-23-2 (10.1g, 25.8mmol) were added to 200 ml of THF, stirred, and potassium carbonate (12.9g, 93.7mmol) was dissolved in water. The mixture was added, stirred sufficiently, and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.1 g of compound 2-23. (Yield: 56%, MS: [M+H]+= 697)
비교예Comparative example 1: 유기 발광 소자의 제조 1: Fabrication of an organic light emitting device
ITO(indium tin oxide)가 1,000Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척했다. 이때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀러포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용했다. ITO를 30분간 세척한 후 증류수로 2회 반복하여 초음파 세척을 10분간 진행했다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다.A glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000Å 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 cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 정공주입층으로 하기 HI-1 화합물을 1150Å의 두께로 형성하되 하기 A-1 화합물을 1.5% 농도로 p-doping 했다. 상기 정공주입층 위에 하기 HT-1 화합물을 진공 증착하여 막 두께 800Å 의 정공수송층을 형성하였다. 이어서, 상기 정공수송층 위에 막 두께 150Å으로 하기 EB-1 화합물을 진공 증착하여 전자억제층을 형성하였다. The following HI-1 compound was formed as a hole injection layer on the prepared ITO transparent electrode to a thickness of 1150Å, but the following compound A-1 was p-doping at a concentration of 1.5%. The following HT-1 compound was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800Å. Subsequently, an electron suppressing layer was formed by vacuum depositing the following EB-1 compound with a film thickness of 150Å on the hole transport layer.
이어서, 상기 EB-1 증착막 위에 상기 제조예 1-1에서 제조한 화합물 1-1 과 하기 Dp-7 화합물을 98:2의 중량비로 진공 증착하여 400Å 두께의 적색 발광층을 형성하였다. Subsequently, the compound 1-1 prepared in Preparation Example 1-1 and the following Dp-7 compound were vacuum-deposited at a weight ratio of 98:2 on the EB-1 deposition film to form a red light emitting layer having a thickness of 400Å.
상기 발광층 위에 막 두께 30Å으로 하기 HB-1 화합물을 진공 증착하여 정공저지층을 형성하였다. 이어서, 상기 정공저지층 위에 하기 ET-1 화합물과 하기 LiQ 화합물을 2:1의 중량비로 진공 증착하여 300Å의 두께로 전자 주입 및 수송층을 형성하였다. 상기 전자 주입 및 수송층 위에 순차적으로 12Å 두께로 리튬플로라이드(LiF)와 1,000Å 두께로 알루미늄을 증착하여 음극을 형성하였다. A hole blocking layer was formed by vacuum depositing the following HB-1 compound with a film thickness of 30Å on the emission layer. Subsequently, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300Å. Lithium fluoride (LiF) at a thickness of 12Å and aluminum at a thickness of 1,000Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.
Figure PCTKR2020095039-appb-img-000423
Figure PCTKR2020095039-appb-img-000423
상기의 과정에서 유기물의 증착속도는 0.4~0.7Å/sec를 유지하였고, 음극의 리튬플로라이드는 0.3Å/sec, 알루미늄은 2Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 2 x 10 -7 ~ 5 x 10 -6 torr를 유지하여, 유기 발광 소자를 제작했다.In the above process, the deposition rate of organic matter was maintained at 0.4~0.7Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum degree during deposition was 2 x 10 − Maintaining 7 to 5 x 10 -6 torr, an organic light emitting device was manufactured.
비교예Comparative example 2 내지 2 to 비교예Comparative example 15 15
비교예 1의 유기 발광 소자에서 화합물 1-1 대신 하기 표 1에 기재된 화합물을 사용하는 것을 제외하고는, 상기 비교예 1과 동일한 방법으로 유기 발광 소자를 제조하였다. An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the compound shown in Table 1 below was used instead of compound 1-1 in the organic light-emitting device of Comparative Example 1.
실시예Example 1 내지 1 to 실시예Example 120 120
비교예 1의 유기 발광 소자에서 화합물 1-1 대신 표 2 내지 4에 기재된 제1 호스트로 화학식 1의 화합물과 제2호스트로 화학식 2의 화합물을 1:1의 중량비로 공증착하여 사용하는 것을 제외하고는, 상기 비교예 1과 동일한 방법으로 유기 발광 소자를 제조하였다. In the organic light-emitting device of Comparative Example 1, instead of compound 1-1, the first host described in Tables 2 to 4 was used by co-depositing the compound of Formula 1 and the compound of Formula 2 as a second host in a weight ratio of 1:1. Then, an organic light-emitting device was manufactured in the same manner as in Comparative Example 1.
비교예Comparative example 16 내지 16 to 비교예Comparative example 63 63
비교예 1의 유기 발광 소자에서 화합물 1-1 대신 하기 표 5 및 6에 기재된 제1 호스트로 비교 화합물 C-1 내지 C-12 화합물과 제2 호스트로 화학식2의 화합물을 1:1로 공증착하여 사용하는 것을 제외하고는, 상기 비교예 1과 동일한 방법으로 유기 발광 소자를 제조하였다. In the organic light-emitting device of Comparative Example 1, instead of compound 1-1, a 1:1 co-deposition of the compound of Formula 2 to the first host described in Tables 5 and 6 below and the compound of Comparative Compound C-1 to C-12 and the second host An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except for using it.
Figure PCTKR2020095039-appb-img-000424
Figure PCTKR2020095039-appb-img-000424
실험예Experimental example 1: 소자 특성 평가 1: element characteristics evaluation
상기 실시예 1 내지 실시예 120 및 비교예 1 내지 비교예 63에서 제작된 유기 발광 소자에 전류를 인가하였을 때, 전압, 효율, 수명을 측정(15mA/cm 2 기준)하고 그 결과를 하기 표 1 내지 6에 나타냈다. 수명 T95는 휘도가 초기 휘도(10,000 nit)에서 95%로 감소되는데 소요되는 시간을 의미한다.When a current was applied to the organic light-emitting devices prepared in Examples 1 to 120 and Comparative Examples 1 to 63, voltage, efficiency, and lifetime were measured (15 mA/cm 2 basis) and the results are shown in Table 1 below. It is shown in to 6. The lifetime T95 refers to the time it takes for the luminance to decrease from the initial luminance (10,000 nit) to 95%.
구분division 호스트Host 구동전압(V)Driving voltage (V) 효율(cd/A)Efficiency (cd/A) 수명 T95(hr)Life T95(hr) 발광색Luminous color
비교예 1Comparative Example 1 화합물 1-1Compound 1-1 3.913.91 16.016.0 141141 적색Red
비교예 2Comparative Example 2 화합물 1-2Compound 1-2 3.843.84 16.116.1 143143 적색Red
비교예 3Comparative Example 3 화합물 1-3Compound 1-3 3.763.76 17.517.5 141141 적색Red
비교예 4Comparative Example 4 화합물 1-12Compound 1-12 3.973.97 16.316.3 144144 적색Red
비교예 5Comparative Example 5 화합물 1-13Compound 1-13 3.933.93 16.116.1 147147 적색Red
비교예 6Comparative Example 6 화합물 1-14Compound 1-14 3.943.94 16.116.1 140140 적색Red
비교예 7Comparative Example 7 화합물 1-22Compound 1-22 4.024.02 16.516.5 141141 적색Red
비교예 8Comparative Example 8 화합물 1-23Compound 1-23 3.983.98 15.315.3 145145 적색Red
비교예 9Comparative Example 9 화합물 1-24Compound 1-24 4.044.04 16.116.1 137137 적색Red
비교예 10Comparative Example 10 화합물 1-32Compound 1-32 3.823.82 16.316.3 134134 적색Red
비교예 11Comparative Example 11 화합물 1-33Compound 1-33 3.983.98 17.417.4 153153 적색Red
비교예 12Comparative Example 12 화합물 1-34Compound 1-34 3.913.91 17.217.2 151151 적색Red
비교예 13Comparative Example 13 화합물 1-36Compound 1-36 3.943.94 18.418.4 157157 적색Red
비교예 14Comparative Example 14 화합물 1-37Compound 1-37 3.923.92 17.717.7 157157 적색Red
비교예 15Comparative Example 15 화합물 1-40Compound 1-40 3.933.93 18.718.7 160160 적색Red
구분division 제1호스트Host 1 제2호스트2nd host 구동전압(V)Driving voltage (V) 효율(cd/A)Efficiency (cd/A) 수명 T95(hr)Life T95(hr) 발광색Luminous color
실시예 1Example 1 화합물 1-1Compound 1-1 화합물 2-1Compound 2-1 3.993.99 21.321.3 241241 적색Red
실시예 2Example 2 화합물 2-2Compound 2-2 3.973.97 20.420.4 234234 적색Red
실시예 3Example 3 화합물 2-8Compound 2-8 3.983.98 20.420.4 230230 적색Red
실시예 4Example 4 화합물 2-19Compound 2-19 3.993.99 21.721.7 227227 적색Red
실시예 5Example 5 화합물 1-2Compound 1-2 화합물 2-1Compound 2-1 3.883.88 20.720.7 225225 적색Red
실시예 6Example 6 화합물 2-2Compound 2-2 3.913.91 20.620.6 206206 적색Red
실시예 7Example 7 화합물 2-8Compound 2-8 3.943.94 20.420.4 209209 적색Red
실시예 8Example 8 화합물 2-19Compound 2-19 3.923.92 20.320.3 212212 적색Red
실시예 8Example 8 화합물 1-3Compound 1-3 화합물 2-1Compound 2-1 3.883.88 21.421.4 218218 적색Red
실시예 10Example 10 화합물 2-2Compound 2-2 3.853.85 19.419.4 220220 적색Red
실시예 11Example 11 화합물 2-8Compound 2-8 3.863.86 19.519.5 212212 적색Red
실시예 12Example 12 화합물 2-19Compound 2-19 3.903.90 20.120.1 215215 적색Red
실시예 13Example 13 화합물 1-5Compound 1-5 화합물 2-1Compound 2-1 3.843.84 20.020.0 210210 적색Red
실시예 14Example 14 화합물 2-2Compound 2-2 3.823.82 21.121.1 219219 적색Red
실시예 15Example 15 화합물 2-8Compound 2-8 3.913.91 19.919.9 227227 적색Red
실시예 16Example 16 화합물 2-19Compound 2-19 3.903.90 20.820.8 203203 적색Red
실시예 17Example 17 화합물 1-7Compound 1-7 화합물 2-1Compound 2-1 3.923.92 21.021.0 200200 적색Red
실시예 18Example 18 화합물 2-2Compound 2-2 3.903.90 20.120.1 218218 적색Red
실시예 19Example 19 화합물 2-8Compound 2-8 3.943.94 19.719.7 221221 적색Red
실시예 20Example 20 화합물 2-19Compound 2-19 3.993.99 20.620.6 220220 적색Red
실시예 21Example 21 화합물 1-8Compound 1-8 화합물 2-1Compound 2-1 3.903.90 19.419.4 203203 적색Red
실시예 22Example 22 화합물 2-2Compound 2-2 3.913.91 19.319.3 200200 적색Red
실시예 23Example 23 화합물 2-8Compound 2-8 3.943.94 20.520.5 202202 적색Red
실시예 24Example 24 화합물 2-19Compound 2-19 3.953.95 20.720.7 199199 적색Red
실시예 25Example 25 화합물 1-12Compound 1-12 화합물 2-1Compound 2-1 4.014.01 20.320.3 186186 적색Red
실시예 26Example 26 화합물 2-2Compound 2-2 4.054.05 20.220.2 203203 적색Red
실시예 27Example 27 화합물 2-8Compound 2-8 4.034.03 20.720.7 200200 적색Red
실시예 28Example 28 화합물 2-19Compound 2-19 4.054.05 20.420.4 209209 적색Red
실시예 29Example 29 화합물 1-13Compound 1-13 화합물 2-1Compound 2-1 4.034.03 18.818.8 204204 적색Red
실시예 30Example 30 화합물 2-2Compound 2-2 4.074.07 19.119.1 210210 적색Red
실시예 31Example 31 화합물 2-8Compound 2-8 4.044.04 19.619.6 201201 적색Red
실시예 32Example 32 화합물 2-19Compound 2-19 4.034.03 20.120.1 212212 적색Red
실시예 33Example 33 화합물 1-14Compound 1-14 화합물 2-1Compound 2-1 4.054.05 19.319.3 205205 적색Red
실시예 34Example 34 화합물 2-2Compound 2-2 4.104.10 19.519.5 198198 적색Red
실시예 35Example 35 화합물 2-8Compound 2-8 4.124.12 19.019.0 199199 적색Red
실시예 36Example 36 화합물 2-19Compound 2-19 4.094.09 19.719.7 203203 적색Red
실시예 37Example 37 화합물 1-15Compound 1-15 화합물 2-1Compound 2-1 4.084.08 19.319.3 210210 적색Red
실시예 38Example 38 화합물 2-2Compound 2-2 4.064.06 19.019.0 216216 적색Red
실시예 39Example 39 화합물 2-8Compound 2-8 4.104.10 18.418.4 204204 적색Red
실시예 40Example 40 화합물 2-19Compound 2-19 4.124.12 19.019.0 201201 적색Red
구분division 제1호스트Host 1 제2호스트2nd host 구동전압(V)Driving voltage (V) 효율(cd/A)Efficiency (cd/A) 수명 T95(hr)Life T95(hr) 발광색Luminous color
실시예 41Example 41 화합물 1-16Compound 1-16 화합물 2-1Compound 2-1 4.114.11 18.118.1 197197 적색Red
실시예 42Example 42 화합물 2-2Compound 2-2 4.084.08 19.319.3 199199 적색Red
실시예 43Example 43 화합물 2-8Compound 2-8 4.104.10 19.619.6 203203 적색Red
실시예 44Example 44 화합물 2-19Compound 2-19 4.124.12 19.119.1 201201 적색Red
실시예 45Example 45 화합물 1-22Compound 1-22 화합물 2-9Compound 2-9 4.134.13 18.618.6 205205 적색Red
실시예 46Example 46 화합물 2-10Compound 2-10 4.094.09 19.019.0 199199 적색Red
실시예 47Example 47 화합물 2-12Compound 2-12 4.124.12 19.219.2 198198 적색Red
실시예 48Example 48 화합물 2-16Compound 2-16 4.144.14 19.019.0 210210 적색Red
실시예 49Example 49 화합물 1-23Compound 1-23 화합물 2-9Compound 2-9 4.074.07 17.817.8 197197 적색Red
실시예 50Example 50 화합물 2-10Compound 2-10 4.104.10 17.917.9 204204 적색Red
실시예 51Example 51 화합물 2-12Compound 2-12 4.054.05 18.018.0 207207 적색Red
실시예 52Example 52 화합물 2-16Compound 2-16 4.084.08 18.218.2 206206 적색Red
실시예 53Example 53 화합물 1-24Compound 1-24 화합물 2-9Compound 2-9 4.134.13 18.318.3 208208 적색Red
실시예 54Example 54 화합물 2-10Compound 2-10 4.114.11 18.918.9 207207 적색Red
실시예 55Example 55 화합물 2-12Compound 2-12 4.154.15 19.119.1 203203 적색Red
실시예 56Example 56 화합물 2-16Compound 2-16 4.144.14 19.219.2 194194 적색Red
실시예 57Example 57 화합물 1-25Compound 1-25 화합물 2-9Compound 2-9 4.154.15 18.118.1 191191 적색Red
실시예 58Example 58 화합물 2-10Compound 2-10 4.134.13 18.018.0 201201 적색Red
실시예 59Example 59 화합물 2-12Compound 2-12 4.144.14 18.718.7 203203 적색Red
실시예 60Example 60 화합물 2-16Compound 2-16 4.174.17 19.019.0 208208 적색Red
실시예 61Example 61 화합물 1-26Compound 1-26 화합물 2-9Compound 2-9 4.184.18 18.718.7 205205 적색Red
실시예 62Example 62 화합물 2-10Compound 2-10 4.194.19 18.618.6 204204 적색Red
실시예 63Example 63 화합물 2-12Compound 2-12 4.144.14 18.918.9 203203 적색Red
실시예 64Example 64 화합물 2-16Compound 2-16 4.154.15 18.018.0 211211 적색Red
실시예 65Example 65 화합물 1-27Compound 1-27 화합물 2-9Compound 2-9 4.114.11 18.718.7 216216 적색Red
실시예 66Example 66 화합물 2-10Compound 2-10 4.134.13 18.618.6 214214 적색Red
실시예 67Example 67 화합물 2-12Compound 2-12 4.154.15 18.918.9 210210 적색Red
실시예 68Example 68 화합물 2-16Compound 2-16 4.174.17 18.018.0 208208 적색Red
실시예 69Example 69 화합물 1-29Compound 1-29 화합물 2-9Compound 2-9 4.184.18 18.018.0 207207 적색Red
실시예 70Example 70 화합물 2-10Compound 2-10 4.214.21 18.718.7 206206 적색Red
실시예 71Example 71 화합물 2-12Compound 2-12 4.194.19 18.418.4 201201 적색Red
실시예 72Example 72 화합물 2-16Compound 2-16 4.184.18 18.918.9 197197 적색Red
실시예 73Example 73 화합물 1-30Compound 1-30 화합물 2-9Compound 2-9 4.204.20 18.518.5 191191 적색Red
실시예 74Example 74 화합물 2-10Compound 2-10 4.174.17 18.318.3 198198 적색Red
실시예 75Example 75 화합물 2-12Compound 2-12 4.154.15 19.119.1 204204 적색Red
실시예 76Example 76 화합물 2-16Compound 2-16 4.164.16 19.419.4 206206 적색Red
실시예 77Example 77 화합물 1-31Compound 1-31 화합물 2-9Compound 2-9 4.194.19 19.319.3 190190 적색Red
실시예 78Example 78 화합물 2-10Compound 2-10 4.214.21 19.219.2 196196 적색Red
실시예 79Example 79 화합물 2-12Compound 2-12 4.154.15 19.319.3 194194 적색Red
실시예 80Example 80 화합물 2-16Compound 2-16 4.134.13 18.818.8 208208 적색Red
구분division 제1호스트Host 1 제2호스트2nd host 구동전압(V)Driving voltage (V) 효율(cd/A)Efficiency (cd/A) 수명 T95(hr)Life T95(hr) 발광색Luminous color
실시예 81Example 81 화합물 1-32Compound 1-32 화합물 2-3Compound 2-3 3.943.94 20.320.3 226226 적색Red
실시예 82Example 82 화합물 2-4Compound 2-4 3.973.97 21.321.3 211211 적색Red
실시예 83Example 83 화합물 2-14Compound 2-14 3.923.92 23.323.3 234234 적색Red
실시예 84Example 84 화합물 2-21Compound 2-21 3.963.96 22.722.7 227227 적색Red
실시예 85Example 85 화합물 1-33Compound 1-33 화합물 2-3Compound 2-3 3.933.93 22.422.4 256256 적색Red
실시예 86Example 86 화합물 2-4Compound 2-4 3.953.95 23.623.6 267267 적색Red
실시예 87Example 87 화합물 2-14Compound 2-14 3.973.97 22.922.9 248248 적색Red
실시예 88Example 88 화합물 2-21Compound 2-21 3.963.96 22.522.5 272272 적색Red
실시예 89Example 89 화합물 1-34Compound 1-34 화합물 2-3Compound 2-3 3.903.90 24.724.7 238238 적색Red
실시예 90Example 90 화합물 2-4Compound 2-4 3.913.91 24.624.6 222222 적색Red
실시예 91Example 91 화합물 2-14Compound 2-14 3.953.95 24.624.6 218218 적색Red
실시예 92Example 92 화합물 2-21Compound 2-21 3.973.97 24.324.3 231231 적색Red
실시예 93Example 93 화합물 1-35Compound 1-35 화합물 2-3Compound 2-3 3.933.93 22.922.9 225225 적색Red
실시예 94Example 94 화합물 2-4Compound 2-4 3.973.97 22.422.4 219219 적색Red
실시예 95Example 95 화합물 2-14Compound 2-14 4.014.01 23.623.6 224224 적색Red
실시예 96Example 96 화합물 2-21Compound 2-21 3.983.98 22.722.7 216216 적색Red
실시예 97Example 97 화합물 1-36Compound 1-36 화합물 2-3Compound 2-3 3.993.99 22.822.8 217217 적색Red
실시예 98Example 98 화합물 2-4Compound 2-4 3.973.97 23.023.0 205205 적색Red
실시예 99Example 99 화합물 2-14Compound 2-14 3.993.99 24.124.1 215215 적색Red
실시예 100Example 100 화합물 2-21Compound 2-21 3.953.95 22.822.8 224224 적색Red
실시예 101Example 101 화합물 1-37Compound 1-37 화합물 2-3Compound 2-3 4.034.03 22.022.0 231231 적색Red
실시예 102Example 102 화합물 2-4Compound 2-4 3.993.99 21.721.7 244244 적색Red
실시예 103Example 103 화합물 2-14Compound 2-14 4.054.05 21.621.6 249249 적색Red
실시예 104Example 104 화합물 2-21Compound 2-21 4.024.02 22.022.0 271271 적색Red
실시예 105Example 105 화합물 1-38Compound 1-38 화합물 2-3Compound 2-3 3.903.90 25.325.3 268268 적색Red
실시예 106Example 106 화합물 2-4Compound 2-4 3.953.95 25.425.4 248248 적색Red
실시예 107Example 107 화합물 2-14Compound 2-14 3.933.93 25.725.7 251251 적색Red
실시예 108Example 108 화합물 2-21Compound 2-21 3.973.97 25.025.0 255255 적색Red
실시예 109Example 109 화합물 1-39Compound 1-39 화합물 2-3Compound 2-3 3.953.95 22.822.8 203203 적색Red
실시예 110Example 110 화합물 2-4Compound 2-4 3.983.98 21.921.9 201201 적색Red
실시예 111Example 111 화합물 2-14Compound 2-14 3.963.96 21.721.7 197197 적색Red
실시예 112Example 112 화합물 2-21Compound 2-21 3.993.99 21.321.3 205205 적색Red
실시예 113Example 113 화합물 1-40Compound 1-40 화합물 2-3Compound 2-3 3.813.81 22.722.7 277277 적색Red
실시예 114Example 114 화합물 2-4Compound 2-4 3.853.85 22.922.9 285285 적색Red
실시예 115Example 115 화합물 2-14Compound 2-14 3.843.84 23.623.6 279279 적색Red
실시예 116Example 116 화합물 2-21Compound 2-21 3.803.80 23.823.8 288288 적색Red
실시예 117Example 117 화합물 1-42Compound 1-42 화합물 2-3Compound 2-3 3.903.90 25.025.0 271271 적색Red
실시예 118Example 118 화합물 2-4Compound 2-4 3.873.87 24.924.9 265265 적색Red
실시예 119Example 119 화합물 2-14Compound 2-14 3.843.84 25.025.0 269269 적색Red
실시예 120Example 120 화합물 2-21Compound 2-21 3.893.89 24.524.5 258258 적색Red
구분division 제1호스트Host 1 제2호스트2nd host 구동전압(V)Driving voltage (V) 효율(cd/A)Efficiency (cd/A) 수명 T95(hr)Life T95(hr) 발광색Luminous color
비교예 16Comparative Example 16 화합물 C-1Compound C-1 화합물 2-1Compound 2-1 4.024.02 12.712.7 128128 적색Red
비교예 17Comparative Example 17 화합물 2-2Compound 2-2 4.034.03 12.312.3 123123 적색Red
비교예 18Comparative Example 18 화합물 2-8Compound 2-8 3.993.99 12.412.4 120120 적색Red
비교예 19Comparative Example 19 화합물 2-19Compound 2-19 4.014.01 12.512.5 111111 적색Red
비교예 20Comparative Example 20 화합물 C-2Compound C-2 화합물 2-1Compound 2-1 4.054.05 13.613.6 116116 적색Red
비교예 21Comparative Example 21 화합물 2-2Compound 2-2 3.993.99 13.813.8 120120 적색Red
비교예 22Comparative Example 22 화합물 2-8Compound 2-8 4.104.10 13.713.7 127127 적색Red
비교예 23Comparative Example 23 화합물 2-19Compound 2-19 3.973.97 13.213.2 104104 적색Red
비교예 24Comparative Example 24 화합물 C-3Compound C-3 화합물 2-1Compound 2-1 4.024.02 14.114.1 119119 적색Red
비교예 25Comparative Example 25 화합물 2-2Compound 2-2 4.004.00 14.514.5 121121 적색Red
비교예 26Comparative Example 26 화합물 2-8Compound 2-8 4.074.07 13.413.4 121121 적색Red
비교예 27Comparative Example 27 화합물 2-19Compound 2-19 3.993.99 14.314.3 134134 적색Red
비교예 28Comparative Example 28 화합물 C-4Compound C-4 화합물 2-1Compound 2-1 4.014.01 13.713.7 115115 적색Red
비교예 29Comparative Example 29 화합물 2-2Compound 2-2 4.114.11 14.614.6 103103 적색Red
비교예 30Comparative Example 30 화합물 2-8Compound 2-8 4.134.13 13.413.4 101101 적색Red
비교예 31Comparative Example 31 화합물 2-19Compound 2-19 4.084.08 12.812.8 109109 적색Red
비교예 32Comparative Example 32 화합물 C-5Compound C-5 화합물 2-9Compound 2-9 4.124.12 14.014.0 108108 적색Red
비교예 33Comparative Example 33 화합물 2-10Compound 2-10 4.134.13 13.313.3 103103 적색Red
비교예 34Comparative Example 34 화합물 2-12Compound 2-12 4.154.15 14.114.1 110110 적색Red
비교예 35Comparative Example 35 화합물 2-16Compound 2-16 4.104.10 14.414.4 111111 적색Red
비교예 36Comparative Example 36 화합물 C-6Compound C-6 화합물 2-9Compound 2-9 4.024.02 15.915.9 104104 적색Red
비교예 37Comparative Example 37 화합물 2-10Compound 2-10 4.004.00 14.814.8 105105 적색Red
비교예 38Comparative Example 38 화합물 2-12Compound 2-12 4.104.10 14.914.9 107107 적색Red
비교예 39Comparative Example 39 화합물 2-16Compound 2-16 4.044.04 14.514.5 114114 적색Red
비교예 40Comparative Example 40 화합물 C-7Compound C-7 화합물 2-9Compound 2-9 3.973.97 14.014.0 111111 적색Red
비교예 41Comparative Example 41 화합물 2-10Compound 2-10 3.953.95 14.114.1 113113 적색Red
비교예 42Comparative Example 42 화합물 2-12Compound 2-12 4.984.98 15.515.5 108108 적색Red
비교예 43Comparative Example 43 화합물 2-16Compound 2-16 3.993.99 14.314.3 111111 적색Red
비교예 44Comparative Example 44 화합물 C-8Compound C-8 화합물 2-9Compound 2-9 4.014.01 16.516.5 108108 적색Red
비교예 45Comparative Example 45 화합물 2-10Compound 2-10 4.054.05 15.215.2 106106 적색Red
비교예 46Comparative Example 46 화합물 2-12Compound 2-12 4.114.11 15.515.5 105105 적색Red
비교예 47Comparative Example 47 화합물 2-16Compound 2-16 4.134.13 15.315.3 104104 적색Red
비교예 48Comparative Example 48 화합물 C-9Compound C-9 화합물 2-3Compound 2-3 4.054.05 15.715.7 107107 적색Red
비교예 49Comparative Example 49 화합물 2-4Compound 2-4 4.074.07 14.514.5 106106 적색Red
비교예 50Comparative Example 50 화합물 2-14Compound 2-14 4.064.06 14.914.9 104104 적색Red
비교예 51Comparative Example 51 화합물 2-21Compound 2-21 4.054.05 14.014.0 108108 적색Red
비교예 52Comparative Example 52 화합물 C-10Compound C-10 화합물 2-3Compound 2-3 4.104.10 13.913.9 115115 적색Red
비교예 53Comparative Example 53 화합물 2-4Compound 2-4 4.124.12 13.313.3 113113 적색Red
비교예 54Comparative Example 54 화합물 2-14Compound 2-14 4.114.11 13.713.7 104104 적색Red
비교예 55Comparative Example 55 화합물 2-21Compound 2-21 4.154.15 14.514.5 107107 적색Red
구분 division 제1호스트Host 1 제2호스트2nd host 구동전압(V)Driving voltage (V) 효율(cd/A)Efficiency (cd/A) 수명 T95(hr)Life T95(hr) 발광색Luminous color
비교예 56Comparative Example 56 화합물 C-11Compound C-11 화합물 2-3Compound 2-3 4.074.07 14.314.3 110110 적색Red
비교예 57Comparative Example 57 화합물 2-4Compound 2-4 4.114.11 14.014.0 114114 적색Red
비교예 58Comparative Example 58 화합물 2-14Compound 2-14 4.084.08 14.114.1 110110 적색Red
비교예 59Comparative Example 59 화합물 2-21Compound 2-21 4.094.09 15.815.8 118118 적색Red
비교예 60Comparative Example 60 화합물 C-12Compound C-12 화합물 2-9Compound 2-9 4.174.17 13.213.2 111111 적색Red
비교예 61Comparative Example 61 화합물 2-10Compound 2-10 4.154.15 13.013.0 115115 적색Red
비교예 62Comparative Example 62 화합물 2-12Compound 2-12 4.184.18 14.214.2 122122 적색Red
비교예 63Comparative Example 63 화합물 2-16Compound 2-16 4.114.11 14.314.3 118118 적색Red
상기 표에 나타난 바와 같이, 발광층의 호스트 물질로 상기 화학식 1로 표시되는 제1 화합물 및 상기 화학식 2로 표시되는 제2 화합물을 동시에 사용한 실시예의 유기 발광 소자는, 상기 화학식 1 및 2로 표시되는 화합물 중 하나만을 채용하거나, 둘 다 채용하지 않는 비교예의 유기 발광 소자에 비하여, 동등 또는 우수한 발광 효율, 낮은 구동 전압 및 현저히 향상된 수명 특성을 나타내었다. As shown in the above table, the organic light-emitting device of the embodiment in which the first compound represented by Formula 1 and the second compound represented by Formula 2 were simultaneously used as the host material of the emission layer is a compound represented by Formulas 1 and 2 Compared to the organic light-emitting device of Comparative Example in which only one of or neither is employed, the same or superior luminous efficiency, low driving voltage, and remarkably improved lifetime characteristics are exhibited.
구체적으로, 실시예에 따른 소자는, 상기 화학식 1로 표시되는 화합물을 단일 호스트로 채용한 비교예의 소자에 비하여, 높은 효율 및 긴 수명을 나타내었다. 또한, 실시예에 따른 소자는, 비교예 화합물 C-1 내지 C-12를 제1 호스트로, 상기 화학식 2로 표시되는 화합물을 제2 호스트로 채용한 비교예의 소자에 비해서도 효율 및 수명 특성이 개선되었다. 이를 통해, 상기 화학식 1로 표시되는 제1 화합물 및 상기 화학식 2로 표시되는 제2 화합물의 조합을 코호스트로 사용 시에, 적색 발광층 내에서 적색 도펀트로의 에너지 전달이 효과적으로 이루어졌음이 확인된다. 이는, 제1 화합물이 전자와 정공에 대한 안정도가 높기 때문이라 판단 할 수 있으며, 또한 제2 화합물을 동시에 사용함에 따라 정공의 양이 많아지면서 적색 발광층내에 전자와 정공이 더 안정적인 균형을 유지하였기 때문으로 판단된다.Specifically, the device according to the example exhibited higher efficiency and longer life than the device of the comparative example employing the compound represented by Formula 1 as a single host. In addition, the device according to the embodiment has improved efficiency and lifespan characteristics compared to the device of Comparative Example employing Comparative Examples Compounds C-1 to C-12 as a first host and a compound represented by Formula 2 as a second host. Became. Through this, when the combination of the first compound represented by Formula 1 and the second compound represented by Formula 2 was used as a cohost, it was confirmed that energy was effectively transferred to the red dopant in the red light emitting layer. This can be determined because the first compound has high stability against electrons and holes, and also because the amount of holes increased as the second compound was used simultaneously, and a more stable balance of electrons and holes was maintained in the red light emitting layer. It is judged as.
따라서, 유기 발광 소자의 호스트 물질로 상기 제1 화합물과 상기 제2 화합물을 동시에 채용하는 경우, 유기 발광 소자의 구동 전압, 발광 효율 및/또는 수명 특성이 향상시킬 수 있음을 확인할 수 있었다. 이는 일반적으로 유기 발광 소자의 발광 효율 및 수명 특성은 서로 트레이드-오프(Trade-off) 관계를 갖는 점을 고려할 때 본 발명의 화합물간의 조합을 채용한 유기 발광 소자는 비교예 소자 대비 현저히 향상된 소자 특성을 나타낸다고 볼 수 있다.Accordingly, it was confirmed that when the first compound and the second compound are simultaneously employed as host materials of the organic light-emitting device, driving voltage, luminous efficiency, and/or lifetime characteristics of the organic light-emitting device can be improved. In general, when considering that the luminous efficiency and lifetime characteristics of the organic light-emitting device have a trade-off relationship with each other, the organic light-emitting device employing a combination of the compounds of the present invention has significantly improved device characteristics compared to the comparative example device. It can be seen as representing.
[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: 전자억제층 8: 정공저지층7: electron suppression layer 8: hole blocking layer
9: 전자 주입 및 수송층 9: electron injection and transport layer

Claims (12)

  1. 제1 전극;A first electrode;
    상기 제1 전극과 대향하여 구비된 제2 전극; 및A second electrode provided to face the first electrode; And
    상기 제1 전극과 제2 전극 사이에 구비된 발광층을 포함하고,Including a light emitting layer provided between the first electrode and the second electrode,
    상기 발광층은 하기 화학식 1로 표시되는 제1 화합물 및 하기 화학식 2로 표시되는 제2 화합물을 포함하는,The emission layer comprises a first compound represented by the following formula 1 and a second compound represented by the following formula 2,
    유기 발광 소자:Organic light emitting element:
    [화학식 1][Formula 1]
    Figure PCTKR2020095039-appb-img-000425
    Figure PCTKR2020095039-appb-img-000425
    상기 화학식 1에서,In Formula 1,
    X 1 내지 X 3는 각각 독립적으로, N 또는 CH이되, X 1 내지 X 3 중 적어도 둘은 N이고, X 1 to X 3 are each independently N or CH, but at least two of X 1 to X 3 are N,
    Ar 1 및 Ar 2는 각각 독립적으로, 중수소; 치환 또는 비치환된 C 6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴이고,Ar 1 and Ar 2 are each independently deuterium; Substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,
    Z는 각각 독립적으로, 수소, 또는 중수소이거나, 또는 Z 중 인접하는 둘은 서로 결합하여 C 6-60 방향족 고리 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로방향족 고리를 형성할 수 있고, Z is each independently hydrogen, or deuterium, or two adjacent ones of Z are bonded to each other to include a C 6-60 aromatic ring or any one or more heteroatoms selected from the group consisting of N, O and S Can form 2-60 heteroaromatic rings,
    여기서, 상기 C 6-60 방향족 고리 및 상기 C 2-60 헤테로방향족 고리는 비치환되거나, 또는 중수소로 치환되고,Here, the C 6-60 aromatic ring and the C 2-60 heteroaromatic ring are unsubstituted or substituted with deuterium,
    n은 0 내지 6의 정수이고,n is an integer from 0 to 6,
    A는 하기 화학식 1-1로 표시되는 치환기이고,A is a substituent represented by the following formula 1-1,
    [화학식 1-1][Formula 1-1]
    Figure PCTKR2020095039-appb-img-000426
    Figure PCTKR2020095039-appb-img-000426
    상기 화학식 1-1에서,In Formula 1-1,
    R 1 내지 R 4는 각각 독립적으로, 수소 또는 중수소이거나, 또는 R 1 내지 R 4 중 인접하는 둘은 서로 결합하여 C 6-60 방향족 고리 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로방향족 고리를 형성할 수 있고,R 1 to R 4 are each independently hydrogen or deuterium, or two adjacent ones of R 1 to R 4 are bonded to each other to form a C 6-60 aromatic ring or any one selected from the group consisting of N, O and S Can form a C 2-60 heteroaromatic ring containing more than one heteroatom
    여기서, 상기 C 6-60 방향족 고리 및 상기 C 2-60 헤테로방향족 고리는 비치환되거나, 또는 중수소로 치환되고,Here, the C 6-60 aromatic ring and the C 2-60 heteroaromatic ring are unsubstituted or substituted with deuterium,
    D는 중수소를 의미하고,D means deuterium,
    m은 0 내지 6의 정수이고,m is an integer from 0 to 6,
    [화학식 2][Formula 2]
    Figure PCTKR2020095039-appb-img-000427
    Figure PCTKR2020095039-appb-img-000427
    상기 화학식 2에서,In Chemical Formula 2,
    T 1 내지 T 4는 각각 독립적으로, 치환 또는 비치환된 C 6-60 방향족 고리; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로방향족 고리이고,T 1 to T 4 are each independently a substituted or unsubstituted C 6-60 aromatic ring; Or a substituted or unsubstituted C 2-60 heteroaromatic ring containing any one or more heteroatoms selected from the group consisting of N, O and S,
    L 1 및 L 2는 각각 독립적으로, 단일 결합; 치환 또는 비치환된 C 6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴렌이고,L 1 and L 2 are each independently a single bond; Substituted or unsubstituted C 6-60 arylene; Or substituted or unsubstituted C 2-60 heteroarylene including any one or more heteroatoms selected from the group consisting of N, O and S,
    Ar 3 및 Ar 4는 각각 독립적으로, 치환 또는 비치환된 C 6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C 2-60 헤테로아릴이다.Ar 3 and Ar 4 are each independently a substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S.
  2. 제1항에 있어서,The method of claim 1,
    X 1 내지 X 3는 모두 N인,X 1 to X 3 are all N,
    유기 발광 소자.Organic light emitting device.
  3. 제1항에 있어서,The method of claim 1,
    상기 제1 화합물은 하기 화학식 3-1 내지 3-7 중 어느 하나로 표시되는,The first compound is represented by any one of the following Formulas 3-1 to 3-7,
    유기 발광 소자:Organic light emitting element:
    Figure PCTKR2020095039-appb-img-000428
    Figure PCTKR2020095039-appb-img-000428
    상기 화학식 3-1 내지 3-7에서,In Formulas 3-1 to 3-7,
    R은 각각 독립적으로, 수소, 또는 중수소이고,Each R is independently hydrogen or deuterium,
    A, Ar 1 및 Ar 2는 제1항에서 정의한 바와 같다.A, Ar 1 and Ar 2 are as defined in claim 1.
  4. 제1항에 있어서,The method of claim 1,
    Ar 1 및 Ar 2는 각각 독립적으로, 하기로 구성되는 군으로부터 선택되는 어느 하나인, Ar 1 and Ar 2 are each independently, any one selected from the group consisting of,
    유기 발광 소자:Organic light emitting element:
    Figure PCTKR2020095039-appb-img-000429
    .
    Figure PCTKR2020095039-appb-img-000429
    .
  5. 제1항에 있어서,The method of claim 1,
    A는 하기 화학식 a1 내지 a4로 표시되는 치환기 중 어느 하나인,A is any one of the substituents represented by the following formulas a1 to a4,
    유기 발광 소자:Organic light emitting element:
    Figure PCTKR2020095039-appb-img-000430
    .
    Figure PCTKR2020095039-appb-img-000430
    .
  6. 제1항에 있어서,The method of claim 1,
    상기 제1 화합물은 하기로 구성되는 군으로부터 선택되는 어느 하나인,The first compound is any one selected from the group consisting of,
    유기 발광 소자:Organic light emitting element:
    Figure PCTKR2020095039-appb-img-000431
    Figure PCTKR2020095039-appb-img-000431
    Figure PCTKR2020095039-appb-img-000432
    Figure PCTKR2020095039-appb-img-000432
    Figure PCTKR2020095039-appb-img-000433
    Figure PCTKR2020095039-appb-img-000433
    Figure PCTKR2020095039-appb-img-000434
    Figure PCTKR2020095039-appb-img-000434
    Figure PCTKR2020095039-appb-img-000435
    Figure PCTKR2020095039-appb-img-000435
    Figure PCTKR2020095039-appb-img-000436
    Figure PCTKR2020095039-appb-img-000436
    Figure PCTKR2020095039-appb-img-000437
    Figure PCTKR2020095039-appb-img-000437
    Figure PCTKR2020095039-appb-img-000438
    Figure PCTKR2020095039-appb-img-000438
    Figure PCTKR2020095039-appb-img-000439
    Figure PCTKR2020095039-appb-img-000439
    Figure PCTKR2020095039-appb-img-000440
    Figure PCTKR2020095039-appb-img-000440
    Figure PCTKR2020095039-appb-img-000441
    Figure PCTKR2020095039-appb-img-000441
    Figure PCTKR2020095039-appb-img-000442
    Figure PCTKR2020095039-appb-img-000442
    Figure PCTKR2020095039-appb-img-000443
    Figure PCTKR2020095039-appb-img-000443
    Figure PCTKR2020095039-appb-img-000444
    Figure PCTKR2020095039-appb-img-000444
    Figure PCTKR2020095039-appb-img-000445
    Figure PCTKR2020095039-appb-img-000445
    Figure PCTKR2020095039-appb-img-000446
    Figure PCTKR2020095039-appb-img-000446
    Figure PCTKR2020095039-appb-img-000447
    Figure PCTKR2020095039-appb-img-000447
    Figure PCTKR2020095039-appb-img-000448
    Figure PCTKR2020095039-appb-img-000448
    Figure PCTKR2020095039-appb-img-000449
    Figure PCTKR2020095039-appb-img-000449
    Figure PCTKR2020095039-appb-img-000450
    Figure PCTKR2020095039-appb-img-000450
    Figure PCTKR2020095039-appb-img-000451
    Figure PCTKR2020095039-appb-img-000451
    Figure PCTKR2020095039-appb-img-000452
    Figure PCTKR2020095039-appb-img-000452
    Figure PCTKR2020095039-appb-img-000453
    Figure PCTKR2020095039-appb-img-000453
    Figure PCTKR2020095039-appb-img-000454
    Figure PCTKR2020095039-appb-img-000454
    Figure PCTKR2020095039-appb-img-000455
    Figure PCTKR2020095039-appb-img-000455
    Figure PCTKR2020095039-appb-img-000456
    Figure PCTKR2020095039-appb-img-000456
    Figure PCTKR2020095039-appb-img-000457
    Figure PCTKR2020095039-appb-img-000457
    Figure PCTKR2020095039-appb-img-000458
    Figure PCTKR2020095039-appb-img-000458
    Figure PCTKR2020095039-appb-img-000459
    Figure PCTKR2020095039-appb-img-000459
    Figure PCTKR2020095039-appb-img-000460
    Figure PCTKR2020095039-appb-img-000460
    Figure PCTKR2020095039-appb-img-000461
    Figure PCTKR2020095039-appb-img-000461
    Figure PCTKR2020095039-appb-img-000462
    Figure PCTKR2020095039-appb-img-000462
    Figure PCTKR2020095039-appb-img-000463
    Figure PCTKR2020095039-appb-img-000463
    Figure PCTKR2020095039-appb-img-000464
    Figure PCTKR2020095039-appb-img-000464
    Figure PCTKR2020095039-appb-img-000465
    Figure PCTKR2020095039-appb-img-000465
    Figure PCTKR2020095039-appb-img-000466
    Figure PCTKR2020095039-appb-img-000466
    Figure PCTKR2020095039-appb-img-000467
    Figure PCTKR2020095039-appb-img-000467
    Figure PCTKR2020095039-appb-img-000468
    Figure PCTKR2020095039-appb-img-000468
    Figure PCTKR2020095039-appb-img-000469
    Figure PCTKR2020095039-appb-img-000469
    Figure PCTKR2020095039-appb-img-000470
    Figure PCTKR2020095039-appb-img-000470
    Figure PCTKR2020095039-appb-img-000471
    Figure PCTKR2020095039-appb-img-000471
    Figure PCTKR2020095039-appb-img-000472
    Figure PCTKR2020095039-appb-img-000472
    Figure PCTKR2020095039-appb-img-000473
    Figure PCTKR2020095039-appb-img-000473
    Figure PCTKR2020095039-appb-img-000474
    Figure PCTKR2020095039-appb-img-000474
    Figure PCTKR2020095039-appb-img-000475
    Figure PCTKR2020095039-appb-img-000475
    Figure PCTKR2020095039-appb-img-000476
    Figure PCTKR2020095039-appb-img-000476
    Figure PCTKR2020095039-appb-img-000477
    Figure PCTKR2020095039-appb-img-000477
    Figure PCTKR2020095039-appb-img-000478
    Figure PCTKR2020095039-appb-img-000478
    Figure PCTKR2020095039-appb-img-000479
    Figure PCTKR2020095039-appb-img-000479
    Figure PCTKR2020095039-appb-img-000480
    Figure PCTKR2020095039-appb-img-000480
    Figure PCTKR2020095039-appb-img-000481
    Figure PCTKR2020095039-appb-img-000481
    Figure PCTKR2020095039-appb-img-000482
    Figure PCTKR2020095039-appb-img-000482
    Figure PCTKR2020095039-appb-img-000483
    Figure PCTKR2020095039-appb-img-000483
    Figure PCTKR2020095039-appb-img-000484
    Figure PCTKR2020095039-appb-img-000484
    Figure PCTKR2020095039-appb-img-000485
    Figure PCTKR2020095039-appb-img-000485
    Figure PCTKR2020095039-appb-img-000486
    Figure PCTKR2020095039-appb-img-000486
    Figure PCTKR2020095039-appb-img-000487
    Figure PCTKR2020095039-appb-img-000487
    Figure PCTKR2020095039-appb-img-000488
    Figure PCTKR2020095039-appb-img-000488
    Figure PCTKR2020095039-appb-img-000489
    Figure PCTKR2020095039-appb-img-000489
    Figure PCTKR2020095039-appb-img-000490
    Figure PCTKR2020095039-appb-img-000490
    Figure PCTKR2020095039-appb-img-000491
    Figure PCTKR2020095039-appb-img-000491
    Figure PCTKR2020095039-appb-img-000492
    Figure PCTKR2020095039-appb-img-000492
    Figure PCTKR2020095039-appb-img-000493
    Figure PCTKR2020095039-appb-img-000493
    Figure PCTKR2020095039-appb-img-000494
    Figure PCTKR2020095039-appb-img-000494
    Figure PCTKR2020095039-appb-img-000495
    Figure PCTKR2020095039-appb-img-000495
    Figure PCTKR2020095039-appb-img-000496
    Figure PCTKR2020095039-appb-img-000496
    Figure PCTKR2020095039-appb-img-000497
    Figure PCTKR2020095039-appb-img-000497
    Figure PCTKR2020095039-appb-img-000498
    Figure PCTKR2020095039-appb-img-000498
    Figure PCTKR2020095039-appb-img-000499
    Figure PCTKR2020095039-appb-img-000499
    Figure PCTKR2020095039-appb-img-000500
    Figure PCTKR2020095039-appb-img-000500
    Figure PCTKR2020095039-appb-img-000501
    Figure PCTKR2020095039-appb-img-000501
    Figure PCTKR2020095039-appb-img-000502
    Figure PCTKR2020095039-appb-img-000502
    Figure PCTKR2020095039-appb-img-000503
    Figure PCTKR2020095039-appb-img-000503
    Figure PCTKR2020095039-appb-img-000504
    Figure PCTKR2020095039-appb-img-000504
    Figure PCTKR2020095039-appb-img-000505
    Figure PCTKR2020095039-appb-img-000505
    Figure PCTKR2020095039-appb-img-000506
    Figure PCTKR2020095039-appb-img-000506
    Figure PCTKR2020095039-appb-img-000507
    Figure PCTKR2020095039-appb-img-000507
    Figure PCTKR2020095039-appb-img-000508
    Figure PCTKR2020095039-appb-img-000508
    Figure PCTKR2020095039-appb-img-000509
    Figure PCTKR2020095039-appb-img-000509
    Figure PCTKR2020095039-appb-img-000510
    Figure PCTKR2020095039-appb-img-000510
    Figure PCTKR2020095039-appb-img-000511
    Figure PCTKR2020095039-appb-img-000511
    Figure PCTKR2020095039-appb-img-000512
    Figure PCTKR2020095039-appb-img-000512
    Figure PCTKR2020095039-appb-img-000513
    Figure PCTKR2020095039-appb-img-000513
    Figure PCTKR2020095039-appb-img-000514
    Figure PCTKR2020095039-appb-img-000514
    Figure PCTKR2020095039-appb-img-000515
    Figure PCTKR2020095039-appb-img-000515
    Figure PCTKR2020095039-appb-img-000516
    Figure PCTKR2020095039-appb-img-000516
    Figure PCTKR2020095039-appb-img-000517
    Figure PCTKR2020095039-appb-img-000517
    Figure PCTKR2020095039-appb-img-000518
    Figure PCTKR2020095039-appb-img-000518
    Figure PCTKR2020095039-appb-img-000519
    Figure PCTKR2020095039-appb-img-000519
    Figure PCTKR2020095039-appb-img-000520
    Figure PCTKR2020095039-appb-img-000520
    Figure PCTKR2020095039-appb-img-000521
    Figure PCTKR2020095039-appb-img-000521
    Figure PCTKR2020095039-appb-img-000522
    Figure PCTKR2020095039-appb-img-000522
    Figure PCTKR2020095039-appb-img-000523
    Figure PCTKR2020095039-appb-img-000523
    Figure PCTKR2020095039-appb-img-000524
    Figure PCTKR2020095039-appb-img-000524
    Figure PCTKR2020095039-appb-img-000525
    Figure PCTKR2020095039-appb-img-000525
    Figure PCTKR2020095039-appb-img-000526
    Figure PCTKR2020095039-appb-img-000526
    Figure PCTKR2020095039-appb-img-000527
    Figure PCTKR2020095039-appb-img-000527
    Figure PCTKR2020095039-appb-img-000528
    Figure PCTKR2020095039-appb-img-000528
    Figure PCTKR2020095039-appb-img-000529
    Figure PCTKR2020095039-appb-img-000529
    Figure PCTKR2020095039-appb-img-000530
    Figure PCTKR2020095039-appb-img-000530
    Figure PCTKR2020095039-appb-img-000531
    Figure PCTKR2020095039-appb-img-000531
    Figure PCTKR2020095039-appb-img-000532
    Figure PCTKR2020095039-appb-img-000532
    Figure PCTKR2020095039-appb-img-000533
    Figure PCTKR2020095039-appb-img-000533
    Figure PCTKR2020095039-appb-img-000534
    Figure PCTKR2020095039-appb-img-000534
    Figure PCTKR2020095039-appb-img-000535
    Figure PCTKR2020095039-appb-img-000535
    Figure PCTKR2020095039-appb-img-000536
    Figure PCTKR2020095039-appb-img-000536
    Figure PCTKR2020095039-appb-img-000537
    Figure PCTKR2020095039-appb-img-000537
    Figure PCTKR2020095039-appb-img-000538
    Figure PCTKR2020095039-appb-img-000538
    Figure PCTKR2020095039-appb-img-000539
    Figure PCTKR2020095039-appb-img-000539
    Figure PCTKR2020095039-appb-img-000540
    Figure PCTKR2020095039-appb-img-000540
    Figure PCTKR2020095039-appb-img-000541
    Figure PCTKR2020095039-appb-img-000541
    Figure PCTKR2020095039-appb-img-000542
    Figure PCTKR2020095039-appb-img-000542
    Figure PCTKR2020095039-appb-img-000543
    Figure PCTKR2020095039-appb-img-000543
    Figure PCTKR2020095039-appb-img-000544
    Figure PCTKR2020095039-appb-img-000544
    Figure PCTKR2020095039-appb-img-000545
    Figure PCTKR2020095039-appb-img-000545
    Figure PCTKR2020095039-appb-img-000546
    Figure PCTKR2020095039-appb-img-000546
    Figure PCTKR2020095039-appb-img-000547
    Figure PCTKR2020095039-appb-img-000547
    Figure PCTKR2020095039-appb-img-000548
    Figure PCTKR2020095039-appb-img-000548
    Figure PCTKR2020095039-appb-img-000549
    Figure PCTKR2020095039-appb-img-000549
    Figure PCTKR2020095039-appb-img-000550
    Figure PCTKR2020095039-appb-img-000550
    Figure PCTKR2020095039-appb-img-000551
    Figure PCTKR2020095039-appb-img-000551
    Figure PCTKR2020095039-appb-img-000552
    Figure PCTKR2020095039-appb-img-000552
    Figure PCTKR2020095039-appb-img-000553
    Figure PCTKR2020095039-appb-img-000553
    Figure PCTKR2020095039-appb-img-000554
    Figure PCTKR2020095039-appb-img-000554
    Figure PCTKR2020095039-appb-img-000555
    Figure PCTKR2020095039-appb-img-000555
    Figure PCTKR2020095039-appb-img-000556
    Figure PCTKR2020095039-appb-img-000556
    Figure PCTKR2020095039-appb-img-000557
    Figure PCTKR2020095039-appb-img-000557
    Figure PCTKR2020095039-appb-img-000558
    Figure PCTKR2020095039-appb-img-000558
    Figure PCTKR2020095039-appb-img-000559
    Figure PCTKR2020095039-appb-img-000559
    Figure PCTKR2020095039-appb-img-000560
    Figure PCTKR2020095039-appb-img-000560
    Figure PCTKR2020095039-appb-img-000561
    Figure PCTKR2020095039-appb-img-000561
    Figure PCTKR2020095039-appb-img-000562
    Figure PCTKR2020095039-appb-img-000562
    Figure PCTKR2020095039-appb-img-000563
    Figure PCTKR2020095039-appb-img-000563
    Figure PCTKR2020095039-appb-img-000564
    Figure PCTKR2020095039-appb-img-000564
    Figure PCTKR2020095039-appb-img-000565
    Figure PCTKR2020095039-appb-img-000565
    Figure PCTKR2020095039-appb-img-000566
    Figure PCTKR2020095039-appb-img-000566
    Figure PCTKR2020095039-appb-img-000567
    Figure PCTKR2020095039-appb-img-000567
    Figure PCTKR2020095039-appb-img-000568
    Figure PCTKR2020095039-appb-img-000568
    Figure PCTKR2020095039-appb-img-000569
    Figure PCTKR2020095039-appb-img-000569
    Figure PCTKR2020095039-appb-img-000570
    Figure PCTKR2020095039-appb-img-000570
    Figure PCTKR2020095039-appb-img-000571
    Figure PCTKR2020095039-appb-img-000571
    Figure PCTKR2020095039-appb-img-000572
    Figure PCTKR2020095039-appb-img-000572
    Figure PCTKR2020095039-appb-img-000573
    Figure PCTKR2020095039-appb-img-000573
    Figure PCTKR2020095039-appb-img-000574
    Figure PCTKR2020095039-appb-img-000574
    Figure PCTKR2020095039-appb-img-000575
    Figure PCTKR2020095039-appb-img-000575
    Figure PCTKR2020095039-appb-img-000576
    Figure PCTKR2020095039-appb-img-000576
    Figure PCTKR2020095039-appb-img-000577
    Figure PCTKR2020095039-appb-img-000577
    Figure PCTKR2020095039-appb-img-000578
    Figure PCTKR2020095039-appb-img-000578
    Figure PCTKR2020095039-appb-img-000579
    Figure PCTKR2020095039-appb-img-000579
    Figure PCTKR2020095039-appb-img-000580
    Figure PCTKR2020095039-appb-img-000580
    Figure PCTKR2020095039-appb-img-000581
    Figure PCTKR2020095039-appb-img-000581
    Figure PCTKR2020095039-appb-img-000582
    Figure PCTKR2020095039-appb-img-000582
    Figure PCTKR2020095039-appb-img-000583
    Figure PCTKR2020095039-appb-img-000583
    Figure PCTKR2020095039-appb-img-000584
    Figure PCTKR2020095039-appb-img-000584
    Figure PCTKR2020095039-appb-img-000585
    Figure PCTKR2020095039-appb-img-000585
    Figure PCTKR2020095039-appb-img-000586
    Figure PCTKR2020095039-appb-img-000586
    Figure PCTKR2020095039-appb-img-000587
    Figure PCTKR2020095039-appb-img-000587
    Figure PCTKR2020095039-appb-img-000588
    Figure PCTKR2020095039-appb-img-000588
    Figure PCTKR2020095039-appb-img-000589
    Figure PCTKR2020095039-appb-img-000589
    Figure PCTKR2020095039-appb-img-000590
    Figure PCTKR2020095039-appb-img-000590
    Figure PCTKR2020095039-appb-img-000591
    Figure PCTKR2020095039-appb-img-000591
    Figure PCTKR2020095039-appb-img-000592
    Figure PCTKR2020095039-appb-img-000592
    Figure PCTKR2020095039-appb-img-000593
    Figure PCTKR2020095039-appb-img-000593
    Figure PCTKR2020095039-appb-img-000594
    Figure PCTKR2020095039-appb-img-000594
    Figure PCTKR2020095039-appb-img-000595
    Figure PCTKR2020095039-appb-img-000595
    Figure PCTKR2020095039-appb-img-000596
    Figure PCTKR2020095039-appb-img-000596
    Figure PCTKR2020095039-appb-img-000597
    Figure PCTKR2020095039-appb-img-000597
    Figure PCTKR2020095039-appb-img-000598
    Figure PCTKR2020095039-appb-img-000598
    Figure PCTKR2020095039-appb-img-000599
    Figure PCTKR2020095039-appb-img-000599
    Figure PCTKR2020095039-appb-img-000600
    Figure PCTKR2020095039-appb-img-000600
    Figure PCTKR2020095039-appb-img-000601
    Figure PCTKR2020095039-appb-img-000601
    Figure PCTKR2020095039-appb-img-000602
    Figure PCTKR2020095039-appb-img-000602
    Figure PCTKR2020095039-appb-img-000603
    Figure PCTKR2020095039-appb-img-000603
    Figure PCTKR2020095039-appb-img-000604
    Figure PCTKR2020095039-appb-img-000604
    Figure PCTKR2020095039-appb-img-000605
    Figure PCTKR2020095039-appb-img-000605
    Figure PCTKR2020095039-appb-img-000606
    Figure PCTKR2020095039-appb-img-000606
    Figure PCTKR2020095039-appb-img-000607
    Figure PCTKR2020095039-appb-img-000607
    Figure PCTKR2020095039-appb-img-000608
    Figure PCTKR2020095039-appb-img-000608
    Figure PCTKR2020095039-appb-img-000609
    Figure PCTKR2020095039-appb-img-000609
    Figure PCTKR2020095039-appb-img-000610
    Figure PCTKR2020095039-appb-img-000610
    Figure PCTKR2020095039-appb-img-000611
    Figure PCTKR2020095039-appb-img-000611
    Figure PCTKR2020095039-appb-img-000612
    Figure PCTKR2020095039-appb-img-000612
    Figure PCTKR2020095039-appb-img-000613
    Figure PCTKR2020095039-appb-img-000613
    Figure PCTKR2020095039-appb-img-000614
    Figure PCTKR2020095039-appb-img-000614
    Figure PCTKR2020095039-appb-img-000615
    Figure PCTKR2020095039-appb-img-000615
    Figure PCTKR2020095039-appb-img-000616
    Figure PCTKR2020095039-appb-img-000616
    Figure PCTKR2020095039-appb-img-000617
    Figure PCTKR2020095039-appb-img-000617
    Figure PCTKR2020095039-appb-img-000618
    Figure PCTKR2020095039-appb-img-000618
    Figure PCTKR2020095039-appb-img-000619
    Figure PCTKR2020095039-appb-img-000619
    Figure PCTKR2020095039-appb-img-000620
    Figure PCTKR2020095039-appb-img-000620
    Figure PCTKR2020095039-appb-img-000621
    Figure PCTKR2020095039-appb-img-000621
    Figure PCTKR2020095039-appb-img-000622
    Figure PCTKR2020095039-appb-img-000622
    Figure PCTKR2020095039-appb-img-000623
    Figure PCTKR2020095039-appb-img-000623
    Figure PCTKR2020095039-appb-img-000624
    Figure PCTKR2020095039-appb-img-000624
    Figure PCTKR2020095039-appb-img-000625
    Figure PCTKR2020095039-appb-img-000625
    Figure PCTKR2020095039-appb-img-000626
    Figure PCTKR2020095039-appb-img-000626
    Figure PCTKR2020095039-appb-img-000627
    Figure PCTKR2020095039-appb-img-000627
    Figure PCTKR2020095039-appb-img-000628
    Figure PCTKR2020095039-appb-img-000628
    Figure PCTKR2020095039-appb-img-000629
    Figure PCTKR2020095039-appb-img-000629
    Figure PCTKR2020095039-appb-img-000630
    Figure PCTKR2020095039-appb-img-000630
    Figure PCTKR2020095039-appb-img-000631
    Figure PCTKR2020095039-appb-img-000631
    Figure PCTKR2020095039-appb-img-000632
    Figure PCTKR2020095039-appb-img-000632
    Figure PCTKR2020095039-appb-img-000633
    Figure PCTKR2020095039-appb-img-000633
    Figure PCTKR2020095039-appb-img-000634
    Figure PCTKR2020095039-appb-img-000634
    Figure PCTKR2020095039-appb-img-000635
    Figure PCTKR2020095039-appb-img-000635
    Figure PCTKR2020095039-appb-img-000636
    Figure PCTKR2020095039-appb-img-000636
    Figure PCTKR2020095039-appb-img-000637
    Figure PCTKR2020095039-appb-img-000637
    Figure PCTKR2020095039-appb-img-000638
    Figure PCTKR2020095039-appb-img-000638
    Figure PCTKR2020095039-appb-img-000639
    Figure PCTKR2020095039-appb-img-000639
    Figure PCTKR2020095039-appb-img-000640
    Figure PCTKR2020095039-appb-img-000640
    Figure PCTKR2020095039-appb-img-000641
    Figure PCTKR2020095039-appb-img-000641
    Figure PCTKR2020095039-appb-img-000642
    Figure PCTKR2020095039-appb-img-000642
    Figure PCTKR2020095039-appb-img-000643
    Figure PCTKR2020095039-appb-img-000643
    Figure PCTKR2020095039-appb-img-000644
    Figure PCTKR2020095039-appb-img-000644
    Figure PCTKR2020095039-appb-img-000645
    Figure PCTKR2020095039-appb-img-000645
    Figure PCTKR2020095039-appb-img-000646
    Figure PCTKR2020095039-appb-img-000646
    Figure PCTKR2020095039-appb-img-000647
    Figure PCTKR2020095039-appb-img-000647
    Figure PCTKR2020095039-appb-img-000648
    Figure PCTKR2020095039-appb-img-000648
    Figure PCTKR2020095039-appb-img-000649
    Figure PCTKR2020095039-appb-img-000649
    Figure PCTKR2020095039-appb-img-000650
    Figure PCTKR2020095039-appb-img-000650
    Figure PCTKR2020095039-appb-img-000651
    Figure PCTKR2020095039-appb-img-000651
    Figure PCTKR2020095039-appb-img-000652
    Figure PCTKR2020095039-appb-img-000652
    Figure PCTKR2020095039-appb-img-000653
    Figure PCTKR2020095039-appb-img-000653
    Figure PCTKR2020095039-appb-img-000654
    Figure PCTKR2020095039-appb-img-000654
    Figure PCTKR2020095039-appb-img-000655
    Figure PCTKR2020095039-appb-img-000655
    Figure PCTKR2020095039-appb-img-000656
    Figure PCTKR2020095039-appb-img-000656
    Figure PCTKR2020095039-appb-img-000657
    Figure PCTKR2020095039-appb-img-000657
    Figure PCTKR2020095039-appb-img-000658
    Figure PCTKR2020095039-appb-img-000658
    Figure PCTKR2020095039-appb-img-000659
    Figure PCTKR2020095039-appb-img-000659
    Figure PCTKR2020095039-appb-img-000660
    Figure PCTKR2020095039-appb-img-000660
    Figure PCTKR2020095039-appb-img-000661
    Figure PCTKR2020095039-appb-img-000661
    Figure PCTKR2020095039-appb-img-000662
    Figure PCTKR2020095039-appb-img-000662
    Figure PCTKR2020095039-appb-img-000663
    Figure PCTKR2020095039-appb-img-000663
    Figure PCTKR2020095039-appb-img-000664
    Figure PCTKR2020095039-appb-img-000664
    Figure PCTKR2020095039-appb-img-000665
    Figure PCTKR2020095039-appb-img-000665
    Figure PCTKR2020095039-appb-img-000666
    Figure PCTKR2020095039-appb-img-000666
    Figure PCTKR2020095039-appb-img-000667
    Figure PCTKR2020095039-appb-img-000667
    Figure PCTKR2020095039-appb-img-000668
    Figure PCTKR2020095039-appb-img-000668
    Figure PCTKR2020095039-appb-img-000669
    Figure PCTKR2020095039-appb-img-000669
    Figure PCTKR2020095039-appb-img-000670
    Figure PCTKR2020095039-appb-img-000670
    Figure PCTKR2020095039-appb-img-000671
    Figure PCTKR2020095039-appb-img-000671
    Figure PCTKR2020095039-appb-img-000672
    Figure PCTKR2020095039-appb-img-000672
    Figure PCTKR2020095039-appb-img-000673
    Figure PCTKR2020095039-appb-img-000673
    Figure PCTKR2020095039-appb-img-000674
    Figure PCTKR2020095039-appb-img-000674
    Figure PCTKR2020095039-appb-img-000675
    Figure PCTKR2020095039-appb-img-000675
    Figure PCTKR2020095039-appb-img-000676
    Figure PCTKR2020095039-appb-img-000676
    Figure PCTKR2020095039-appb-img-000677
    Figure PCTKR2020095039-appb-img-000677
    Figure PCTKR2020095039-appb-img-000678
    Figure PCTKR2020095039-appb-img-000678
    Figure PCTKR2020095039-appb-img-000679
    Figure PCTKR2020095039-appb-img-000679
    Figure PCTKR2020095039-appb-img-000680
    Figure PCTKR2020095039-appb-img-000680
    Figure PCTKR2020095039-appb-img-000681
    Figure PCTKR2020095039-appb-img-000681
    Figure PCTKR2020095039-appb-img-000682
    Figure PCTKR2020095039-appb-img-000682
    Figure PCTKR2020095039-appb-img-000683
    Figure PCTKR2020095039-appb-img-000683
    Figure PCTKR2020095039-appb-img-000684
    Figure PCTKR2020095039-appb-img-000684
    Figure PCTKR2020095039-appb-img-000685
    Figure PCTKR2020095039-appb-img-000685
    Figure PCTKR2020095039-appb-img-000686
    Figure PCTKR2020095039-appb-img-000686
    Figure PCTKR2020095039-appb-img-000687
    Figure PCTKR2020095039-appb-img-000687
    Figure PCTKR2020095039-appb-img-000688
    Figure PCTKR2020095039-appb-img-000688
    Figure PCTKR2020095039-appb-img-000689
    Figure PCTKR2020095039-appb-img-000689
    Figure PCTKR2020095039-appb-img-000690
    Figure PCTKR2020095039-appb-img-000690
    Figure PCTKR2020095039-appb-img-000691
    Figure PCTKR2020095039-appb-img-000691
    Figure PCTKR2020095039-appb-img-000692
    Figure PCTKR2020095039-appb-img-000692
    Figure PCTKR2020095039-appb-img-000693
    Figure PCTKR2020095039-appb-img-000693
    Figure PCTKR2020095039-appb-img-000694
    Figure PCTKR2020095039-appb-img-000694
    Figure PCTKR2020095039-appb-img-000695
    Figure PCTKR2020095039-appb-img-000695
    Figure PCTKR2020095039-appb-img-000696
    Figure PCTKR2020095039-appb-img-000696
    Figure PCTKR2020095039-appb-img-000697
    Figure PCTKR2020095039-appb-img-000697
    Figure PCTKR2020095039-appb-img-000698
    Figure PCTKR2020095039-appb-img-000698
    Figure PCTKR2020095039-appb-img-000699
    Figure PCTKR2020095039-appb-img-000699
    Figure PCTKR2020095039-appb-img-000700
    Figure PCTKR2020095039-appb-img-000700
    Figure PCTKR2020095039-appb-img-000701
    Figure PCTKR2020095039-appb-img-000701
    Figure PCTKR2020095039-appb-img-000702
    Figure PCTKR2020095039-appb-img-000702
    Figure PCTKR2020095039-appb-img-000703
    Figure PCTKR2020095039-appb-img-000703
    Figure PCTKR2020095039-appb-img-000704
    Figure PCTKR2020095039-appb-img-000704
    Figure PCTKR2020095039-appb-img-000705
    Figure PCTKR2020095039-appb-img-000705
    Figure PCTKR2020095039-appb-img-000706
    Figure PCTKR2020095039-appb-img-000706
    Figure PCTKR2020095039-appb-img-000707
    Figure PCTKR2020095039-appb-img-000707
    Figure PCTKR2020095039-appb-img-000708
    Figure PCTKR2020095039-appb-img-000708
    Figure PCTKR2020095039-appb-img-000709
    Figure PCTKR2020095039-appb-img-000709
    Figure PCTKR2020095039-appb-img-000710
    Figure PCTKR2020095039-appb-img-000710
    Figure PCTKR2020095039-appb-img-000711
    Figure PCTKR2020095039-appb-img-000711
    Figure PCTKR2020095039-appb-img-000712
    Figure PCTKR2020095039-appb-img-000712
    Figure PCTKR2020095039-appb-img-000713
    Figure PCTKR2020095039-appb-img-000713
    Figure PCTKR2020095039-appb-img-000714
    Figure PCTKR2020095039-appb-img-000714
    Figure PCTKR2020095039-appb-img-000715
    Figure PCTKR2020095039-appb-img-000715
    Figure PCTKR2020095039-appb-img-000716
    Figure PCTKR2020095039-appb-img-000716
    Figure PCTKR2020095039-appb-img-000717
    Figure PCTKR2020095039-appb-img-000717
    Figure PCTKR2020095039-appb-img-000718
    Figure PCTKR2020095039-appb-img-000718
    Figure PCTKR2020095039-appb-img-000719
    Figure PCTKR2020095039-appb-img-000719
    Figure PCTKR2020095039-appb-img-000720
    Figure PCTKR2020095039-appb-img-000720
    Figure PCTKR2020095039-appb-img-000721
    Figure PCTKR2020095039-appb-img-000721
    Figure PCTKR2020095039-appb-img-000722
    Figure PCTKR2020095039-appb-img-000722
    Figure PCTKR2020095039-appb-img-000723
    Figure PCTKR2020095039-appb-img-000723
    Figure PCTKR2020095039-appb-img-000724
    Figure PCTKR2020095039-appb-img-000724
    Figure PCTKR2020095039-appb-img-000725
    Figure PCTKR2020095039-appb-img-000725
    Figure PCTKR2020095039-appb-img-000726
    Figure PCTKR2020095039-appb-img-000726
    Figure PCTKR2020095039-appb-img-000727
    Figure PCTKR2020095039-appb-img-000727
    Figure PCTKR2020095039-appb-img-000728
    Figure PCTKR2020095039-appb-img-000728
    Figure PCTKR2020095039-appb-img-000729
    Figure PCTKR2020095039-appb-img-000729
    Figure PCTKR2020095039-appb-img-000730
    Figure PCTKR2020095039-appb-img-000730
    Figure PCTKR2020095039-appb-img-000731
    Figure PCTKR2020095039-appb-img-000731
    Figure PCTKR2020095039-appb-img-000732
    Figure PCTKR2020095039-appb-img-000732
    Figure PCTKR2020095039-appb-img-000733
    Figure PCTKR2020095039-appb-img-000733
    Figure PCTKR2020095039-appb-img-000734
    Figure PCTKR2020095039-appb-img-000734
    Figure PCTKR2020095039-appb-img-000735
    Figure PCTKR2020095039-appb-img-000735
    Figure PCTKR2020095039-appb-img-000736
    Figure PCTKR2020095039-appb-img-000736
    Figure PCTKR2020095039-appb-img-000737
    Figure PCTKR2020095039-appb-img-000737
    Figure PCTKR2020095039-appb-img-000738
    Figure PCTKR2020095039-appb-img-000738
    Figure PCTKR2020095039-appb-img-000739
    Figure PCTKR2020095039-appb-img-000739
    Figure PCTKR2020095039-appb-img-000740
    Figure PCTKR2020095039-appb-img-000740
    Figure PCTKR2020095039-appb-img-000741
    Figure PCTKR2020095039-appb-img-000741
    Figure PCTKR2020095039-appb-img-000742
    Figure PCTKR2020095039-appb-img-000742
    ..
  7. 제1항에 있어서,The method of claim 1,
    상기 제2 화합물은 하기 화학식 2-1로 표시되는,The second compound is represented by the following formula 2-1,
    유기 발광 소자:Organic light emitting element:
    [화학식 2-1][Formula 2-1]
    Figure PCTKR2020095039-appb-img-000743
    Figure PCTKR2020095039-appb-img-000743
    상기 화학식 2-1에서,In Formula 2-1,
    D는 중수소를 의미하고,D means deuterium,
    r 및 s는 각각 독립적으로, 0 내지 7의 정수이고,r and s are each independently an integer of 0 to 7,
    L 1, L 2, Ar 3 및 Ar 4에 대한 설명은 제1항에서 정의한 바와 같다.Descriptions of L 1 , L 2 , Ar 3 and Ar 4 are as defined in claim 1.
  8. 제1항에 있어서,The method of claim 1,
    L 1 및 L 2는 각각 독립적으로, 단일 결합, 페닐렌, 또는 나프틸렌인,L 1 and L 2 are each independently a single bond, phenylene, or naphthylene,
    유기 발광 소자.Organic light emitting device.
  9. 제1항에 있어서,The method of claim 1,
    Ar 3 및 Ar 4는 각각 독립적으로, 하기로 구성되는 군으로부터 선택되는 어느 하나인,Ar 3 and Ar 4 are each independently, any one selected from the group consisting of,
    유기 발광 소자:Organic light emitting element:
    Figure PCTKR2020095039-appb-img-000744
    .
    Figure PCTKR2020095039-appb-img-000744
    .
  10. 제1항에 있어서,The method of claim 1,
    상기 제2 화합물은 하기 화학식 2-2로 표시되는,The second compound is represented by the following formula 2-2,
    유기 발광 소자:Organic light emitting element:
    [화학식 2-2][Formula 2-2]
    Figure PCTKR2020095039-appb-img-000745
    Figure PCTKR2020095039-appb-img-000745
    상기 화학식 2-2에서,In Formula 2-2,
    L 1 및 L 2는 각각 독립적으로, 단일 결합, 페닐렌, 또는 나프틸렌이고,L 1 and L 2 are each independently a single bond, phenylene, or naphthylene,
    Ar 3 및 Ar 4는 제1항에서 정의한 바와 같다.Ar 3 and Ar 4 are as defined in claim 1.
  11. 제1항에 있어서,The method of claim 1,
    상기 제2 화합물은 하기로 구성되는 군으로부터 선택되는 어느 하나인,The second compound is any one selected from the group consisting of,
    유기 발광 소자:Organic light emitting element:
    Figure PCTKR2020095039-appb-img-000746
    Figure PCTKR2020095039-appb-img-000746
    Figure PCTKR2020095039-appb-img-000747
    Figure PCTKR2020095039-appb-img-000747
    Figure PCTKR2020095039-appb-img-000748
    Figure PCTKR2020095039-appb-img-000748
    Figure PCTKR2020095039-appb-img-000749
    Figure PCTKR2020095039-appb-img-000749
    Figure PCTKR2020095039-appb-img-000750
    Figure PCTKR2020095039-appb-img-000750
    Figure PCTKR2020095039-appb-img-000751
    Figure PCTKR2020095039-appb-img-000751
    Figure PCTKR2020095039-appb-img-000752
    Figure PCTKR2020095039-appb-img-000752
    Figure PCTKR2020095039-appb-img-000753
    Figure PCTKR2020095039-appb-img-000753
    Figure PCTKR2020095039-appb-img-000754
    Figure PCTKR2020095039-appb-img-000754
    Figure PCTKR2020095039-appb-img-000755
    Figure PCTKR2020095039-appb-img-000755
    Figure PCTKR2020095039-appb-img-000756
    Figure PCTKR2020095039-appb-img-000756
    Figure PCTKR2020095039-appb-img-000757
    Figure PCTKR2020095039-appb-img-000757
    Figure PCTKR2020095039-appb-img-000758
    Figure PCTKR2020095039-appb-img-000758
    Figure PCTKR2020095039-appb-img-000759
    Figure PCTKR2020095039-appb-img-000759
    Figure PCTKR2020095039-appb-img-000760
    Figure PCTKR2020095039-appb-img-000760
    Figure PCTKR2020095039-appb-img-000761
    Figure PCTKR2020095039-appb-img-000761
    Figure PCTKR2020095039-appb-img-000762
    Figure PCTKR2020095039-appb-img-000762
    Figure PCTKR2020095039-appb-img-000763
    Figure PCTKR2020095039-appb-img-000763
    Figure PCTKR2020095039-appb-img-000764
    Figure PCTKR2020095039-appb-img-000764
    Figure PCTKR2020095039-appb-img-000765
    Figure PCTKR2020095039-appb-img-000765
    Figure PCTKR2020095039-appb-img-000766
    Figure PCTKR2020095039-appb-img-000766
    ..
  12. 제1항에 있어서,The method of claim 1,
    상기 제1 화합물 및 상기 제2 화합물은 99:1 내지 1:99의 중량비로 포함되는,The first compound and the second compound are included in a weight ratio of 99:1 to 1:99,
    유기 발광 소자.Organic light emitting device.
PCT/KR2020/095039 2019-03-15 2020-03-13 Organic light emitting diode WO2020190116A1 (en)

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KR20190030168 2019-03-15
KR10-2020-0030989 2020-03-12
KR1020200030989A KR102311643B1 (en) 2019-03-15 2020-03-12 Organic light emitting device

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150126756A (en) * 2014-05-02 2015-11-13 삼성디스플레이 주식회사 Organic light emitting device
KR20170111387A (en) * 2016-03-28 2017-10-12 에스에프씨 주식회사 Organic light-emitting compounds and Organic light-emitting device comprising the same
KR20190007789A (en) * 2017-07-13 2019-01-23 에스에프씨 주식회사 organic light-emitting diode with high efficiency and long lifetime
KR20190013139A (en) * 2017-07-31 2019-02-11 엘티소재주식회사 Heterocyclic compound and organic light emitting device comprising the same
KR20190024772A (en) * 2017-08-28 2019-03-08 주식회사 엘지화학 Heterocyclic compound and organic light emitting device comprising same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150126756A (en) * 2014-05-02 2015-11-13 삼성디스플레이 주식회사 Organic light emitting device
KR20170111387A (en) * 2016-03-28 2017-10-12 에스에프씨 주식회사 Organic light-emitting compounds and Organic light-emitting device comprising the same
KR20190007789A (en) * 2017-07-13 2019-01-23 에스에프씨 주식회사 organic light-emitting diode with high efficiency and long lifetime
KR20190013139A (en) * 2017-07-31 2019-02-11 엘티소재주식회사 Heterocyclic compound and organic light emitting device comprising the same
KR20190024772A (en) * 2017-08-28 2019-03-08 주식회사 엘지화학 Heterocyclic compound and organic light emitting device comprising same

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