WO2021107678A1 - Compound and organic light-emitting device comprising same - Google Patents

Compound and organic light-emitting device comprising same Download PDF

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WO2021107678A1
WO2021107678A1 PCT/KR2020/017069 KR2020017069W WO2021107678A1 WO 2021107678 A1 WO2021107678 A1 WO 2021107678A1 KR 2020017069 W KR2020017069 W KR 2020017069W WO 2021107678 A1 WO2021107678 A1 WO 2021107678A1
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group
substituted
unsubstituted
compound
mmol
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PCT/KR2020/017069
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French (fr)
Korean (ko)
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김선우
홍완표
금수정
김명곤
김경희
조혜민
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주식회사 엘지화학
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Priority claimed from KR1020200060597A external-priority patent/KR20210067844A/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN202080009134.3A priority Critical patent/CN113366002B/en
Priority to US17/428,032 priority patent/US20220089617A1/en
Priority to JP2021539575A priority patent/JP7143570B2/en
Priority to EP20891826.8A priority patent/EP3909958B1/en
Publication of WO2021107678A1 publication Critical patent/WO2021107678A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • 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
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K99/00—Subject matter not provided for in other groups of this subclass
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups

Definitions

  • the present specification relates to a compound and an organic light emitting device including the same.
  • the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material.
  • An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween.
  • the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
  • the present specification provides a compound and an organic light emitting device including the same.
  • An exemplary embodiment of the present specification provides a compound represented by the following formula (1).
  • A1 is a substituted or unsubstituted monocyclic or polycyclic heterocycle including a 5-membered ring including O or S,
  • R1 to R7, R′ and R′′ are the same as or different from each other, and each independently represents hydrogen; deuterium; halogen group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted haloalkyl group; substituted or unsubstituted cyclo Alkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted haloalkoxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted
  • the present specification is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one organic material layer includes the compound.
  • the compound described herein may be used as a material for an organic material layer of an organic light emitting device.
  • the compound according to another exemplary embodiment may improve efficiency, low driving voltage, and/or lifespan characteristics in an organic light emitting device.
  • the compounds described herein can be used as hole injection, hole transport, hole injection and hole transport, electron blocking, light emission, hole blocking, electron transport, or electron injection material.
  • the organic light emitting device according to an exemplary embodiment of the present specification has effects of low driving voltage, high efficiency, or long lifespan.
  • 1 to 3 show examples of an organic light emitting device according to an exemplary embodiment of the present specification.
  • FIG. 4 is a diagram illustrating a photoluminescence analysis graph according to Experimental Example 1 of the present specification.
  • thermogravimetric analysis graph of Compound 19 is a diagram showing a thermogravimetric analysis graph of Compound 19 according to Experimental Example 3 of the present specification.
  • thermogravimetric analysis graph of compound BD-A according to Experimental Example 3 of the present specification.
  • thermogravimetric analysis graph of compound BD-C according to Experimental Example 3 of the present specification.
  • Conventional boron compounds have a half width of about 23 to 30 nm, and a wavelength of a basic core structure of about 453 nm, but the stability of the material is relatively lower than that of the amine compound, and thus the lifespan is lowered. Therefore, there is a need for a method for securing a long lifespan by increasing the stability of a material while maintaining excellent optical properties by controlling the substituents of the boron compound.
  • the compound of Formula 1 is a compound using electrons abundant in a structure including a monocyclic or polycyclic heterocycle including a 5-membered ring including O or S, in which A1 is substituted or unsubstituted. Structural stability and excellent electrochemical properties can be secured.
  • substitution means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is not limited, and when two or more are substituted , two or more substituents may be the same as or different from each other.
  • substituted or unsubstituted refers to deuterium; halogen group; cyano group; an alkyl group; cycloalkyl group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; alkenyl group; haloalkyl group; haloalkoxy group; an arylalkyl group; silyl group; boron group; amine group; aryl group; Condensed ring groups of aromatic hydrocarbons and aliphatic hydrocarbons; And it means that it is substituted with one or more substituents selected from the group consisting of a heterocyclic group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents.
  • that two or more substituents are connected means that the hydrogen of any one substituent is connected with another substituent.
  • a phenyl group and a naphthyl group are connected. or may be a substituent of
  • the connection of three substituents means that (substituent 1)-(substituent 2)-(substituent 3) is continuously connected, as well as (substituent 2) and (substituent 3) are connected to (substituent 1).
  • a phenyl group, a naphthyl group and an isopropyl group are connected, , or may be a substituent of The above definition applies equally to the case where 4 or more substituents are connected.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30.
  • Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl,
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and 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, adamantyl group, bicyclo [2.2.1] octyl group, norbornyl group, etc., but is not limited thereto.
  • the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. may be It is not limited.
  • the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30.
  • 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 is not limited thereto.
  • haloalkyl group means that at least one halogen group is substituted for hydrogen in the alkyl group in the definition of the alkyl group.
  • the haloalkoxy group means that at least one halogen group is substituted for hydrogen of the alkoxy group in the definition of the alkoxy group.
  • the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.
  • the aryl group is a monocyclic aryl group
  • the number of carbon atoms is not particularly limited, but preferably 6 to 30 carbon atoms.
  • the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto.
  • the aryl group is a polycyclic aryl group
  • the number of carbon atoms is not particularly limited. It is preferable that it is C10-30.
  • the polycyclic aryl group may be a naphthyl group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a phenalene group, a perylene group, a chrysene group, a fluorene group, and the like, but is not limited thereto.
  • the fluorene group may be substituted, and adjacent groups may combine with each other to form a ring.
  • the "adjacent" group refers to a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom in which the substituent is substituted.
  • two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups.
  • the arylalkyl group means that the alkyl group is substituted with an aryl group, and examples of the aryl group and the alkyl group described above may be applied to the aryl group and the alkyl group of the arylalkyl group.
  • the aryloxy group means substituted with an aryl group instead of an alkyl group of the alkoxy group in the definition of the alkoxy group
  • the aryloxy group includes a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5- Dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3-biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4 -Methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group, 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenane a toryloxy group, a 9-phenanthryloxy group, and the like, but is not limited thereto.
  • the alkyl group of the alkyltioxy group is the same as the example of the alkyl group described above.
  • the alkyl thiooxy group includes, but is not limited to, methyl thiooxy group, ethyl thiooxy group, tert-butyl thiooxy group, hexyl thiooxy group, octyl thiooxy group, and the like.
  • the aryl group in the arylthioxy group is the same as the example of the aryl group described above.
  • the arylthioxy group includes, but is not limited to, a phenylthioxy group, a 2-methylphenylthioxy group, a 4-tert-butylphenylthioxy group, and the like.
  • the heterocyclic group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se and S, and the like.
  • the number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic.
  • heterocyclic group examples include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group, a triazole group, an acridine group.
  • pyridazine group pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazine group, pyrido pyrimidine group, pyrido pyrazine group, pyrazino pyrazine group, isoquinoline group, indole group, carbazole group, benz Oxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, phenanthridine group, phenanthridine group, phenanthroline group, isoxazole group, thia Diazole group, dibenzofuran group, dibenzosilol group, phenoxanthine group (phenoxathiine), phenoxazine group (phenoxazine), phenothiazine group (phenothiazine), dihydroindenoc
  • the silyl group may be an alkylsilyl group, an arylsilyl group, an alkylarylsilyl group, a heteroarylsilyl group, or the like.
  • Examples of the above-described alkyl group may be applied to the alkyl group in the alkylsilyl group
  • the examples of the aryl group may be applied to the aryl group in the arylsilyl group
  • the alkyl group and aryl group in the alkylarylsilyl group may include the alkyl group and the aryl group.
  • Examples of can be applied, the heteroaryl group among the heteroarylsilyl group, the examples of the heterocyclic group can be applied.
  • the boron group may be -BR 100 R 101 , wherein R 100 and R 101 are the same or different, and each independently hydrogen; heavy hydrogen; halogen; nitrile group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And it may be selected from the group consisting of a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
  • the boron group includes a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like, but is not limited thereto.
  • the amine group is -NH 2 , an alkylamine group, an N-alkylarylamine group, an arylamine group, an N-arylheteroarylamine group, an N-alkylheteroarylamine group, and a heteroarylamine group from the group consisting of may be selected, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30.
  • the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, and a 9-methyl-anthracenylamine group.
  • the N-alkylarylamine group refers to an amine group in which an alkyl group and an aryl group are substituted with N of the amine group.
  • the alkyl group and the aryl group in the N-alkylarylamine group are the same as the examples of the alkyl group and the aryl group described above.
  • the N-arylheteroarylamine group refers to an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.
  • the aryl group and the heteroaryl group in the N-arylheteroarylamine group are the same as the examples of the above-described aryl group and heterocyclic group.
  • the N-alkylheteroarylamine group refers to an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group.
  • the alkyl group and the heteroaryl group in the N-alkylheteroarylamine group are the same as the examples of the above-described alkyl group and heterocyclic group.
  • examples of the alkylamine group include a substituted or unsubstituted monoalkylamine group, or a substituted or unsubstituted dialkylamine group.
  • the alkyl group in the alkylamine group may be a straight-chain or branched alkyl group.
  • the alkylamine group including two or more alkyl groups may include a straight-chain alkyl group, a branched-chain alkyl group, or a straight-chain alkyl group and a branched alkyl group at the same time.
  • the alkyl group in the alkylamine group may be selected from the examples of the alkyl group described above.
  • examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, or a substituted or unsubstituted diheteroarylamine group.
  • the heteroarylamine group including two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time.
  • the heteroaryl group in the heteroarylamine group may be selected from the examples of the heterocyclic group described above.
  • adjacent two of the substituents combine with each other to form a ring means a substituted or unsubstituted hydrocarbon ring by bonding with adjacent groups; Or it means to form a substituted or unsubstituted heterocyclic ring.
  • ring is a substituted or unsubstituted hydrocarbon ring; Or it means a substituted or unsubstituted heterocyclic ring.
  • the hydrocarbon ring group may be an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, or a condensed ring group of an aromatic hydrocarbon and an aliphatic hydrocarbon, and may be selected from examples of the cycloalkyl group, an aryl group, and combinations thereof, and the hydrocarbon
  • the cyclic group includes, but is not limited to, a phenyl group, a cyclohexyl group, an adamantyl group, a tetrahydronaphthalene group, and a tetrahydroanthracene group.
  • the hydrocarbon ring may be an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, or a condensed ring of an aromatic hydrocarbon and an aliphatic hydrocarbon, and may be selected from among the examples of the cycloalkyl group or the aryl group, except that it is not monovalent.
  • the hydrocarbon ring may include, but is not limited to, benzene, cyclohexane, adamantane, tetrahydronaphthalene, tetrahydroanthracene, and the like.
  • the heterocycle includes atoms other than carbon and one or more heteroatoms, specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se and S, and the like.
  • the heterocycle may be monocyclic or polycyclic, and may be an aromatic, aliphatic, or condensed ring of aromatic and aliphatic, and the aromatic heterocycle may be selected from examples of the heterocyclic group, except that it is not monovalent.
  • the aliphatic heterocycle refers to an aliphatic ring including one or more heteroatoms.
  • aliphatic heterocycles include oxirane, tetrahydrofuran, 1,4-dioxane, pyrrolidine, piperidine, morpholine, oxepane, azocaine , thiocaine, tetrahydronaphthothiophene, tetrahydronaphthofuran, tetrahydrobenzothiophene, and tetrahydrobenzofuran, but are not limited thereto.
  • the arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied.
  • the heteroarylene group means that the heteroaryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the heterocyclic group described above may be applied.
  • Chemical Formula 1 includes at least one condensed aliphatic hydrocarbon ring substituted or unsubstituted with an alkyl group.
  • A1 is a substituted or unsubstituted 5-membered monocyclic heterocycle including O, or S; Or a substituted or unsubstituted, O, or a polycyclic heterocycle including a 5-membered heterocycle including S.
  • A1 is a substituted or unsubstituted 5-membered aromatic or aliphatic monocyclic heterocycle including O, or S; Or a substituted or unsubstituted, aromatic, aliphatic, or polycyclic heterocycle of condensed aromatic and aliphatic containing a 5-membered heterocycle containing O, or S.
  • Chemical Formula A1 is represented by the following Chemical Formula A1-1 or A1-2.
  • Y1 and Y3 are the same as or different from each other, and each independently O; or S;
  • G1, G2 and G7 to G10 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubsti
  • A1 is a structure represented by any one of the following Chemical Formulas A1-3 to Al-5.
  • Y2, Y4 and Y5 are the same as or different from each other, and each independently O; or S;
  • G3 to G6 and G11 to G28 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsub
  • n11 and n12 are each an integer of 0 to 2
  • Chemical Formula A1-1 is represented by the following Chemical Formula A1-1-1 or A1-1-2.
  • Y1 is O; or S;
  • Z1 is O; S; CR201R202; or NR203;
  • G301 to G304 and R201 to R203 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsub
  • Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-5.
  • R', R" and R1 to R7 are the same as those defined in Formula 1 above,
  • Y1 to Y5 are the same as or different from each other, and each independently O; or S;
  • G1 to G28 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted sily
  • n11 and n12 are each an integer of 0 to 2
  • Chemical Formula 1 is represented by the following Chemical Formulas 1-1-1, 1-1-2, 1-1-3, 1-1-4, 1-1-5, 1-1-6 , any of 1-2-1, 1-2-2, 1-3-1, 1-3-2, 1-4-1, 1-4-2, 1-5-1, and 1-5-2 displayed as one
  • R', R" and R1 to R7 are the same as those defined in Formula 1 above,
  • Y1 to Y5 are the same as or different from each other, and each independently O; or S;
  • Z1 is O; S; CR201R202; or NR203;
  • G1 to G28, G301 to G304 and R201 to R203 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group;
  • n11 and n12 are each an integer of 0 to 2
  • adjacent groups of R1 to R4 may be bonded to each other to form a substituted or unsubstituted 5-membered monocyclic heterocycle; Or substituted or unsubstituted, to form a polycyclic heterocycle including a 5-membered heterocycle.
  • adjacent groups of R1 to R4 are bonded to each other, a substituted or unsubstituted 5-membered monocyclic heterocycle including N, O, or S; Or substituted or unsubstituted, to form a polycyclic heterocycle including a 5-membered heterocycle including N, O, or S.
  • adjacent groups of R1 to R4 may be bonded to each other, may be substituted or unsubstituted, and may include a 5-membered aromatic or aliphatic monocyclic heterocycle including N, O, or S; Or a substituted or unsubstituted, aromatic, aliphatic, or polycyclic heterocycle containing a 5-membered heterocycle containing N, O, or S is formed by condensation of aromatic and aliphatic.
  • adjacent groups of R1 to R4 are bonded to each other to form a ring represented by the following Chemical Formula B1-1 or B1-2.
  • Y101 and Y103 are the same as or different from each other, and each independently O; S; or NR"';
  • R"', G101, G102, and G107 to G110 are the same as or different from each other, and each independently represents hydrogen; deuterium; halogen group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted haloalkyl group; substituted or unsubstituted a cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkylthioxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; substituted or unsubstituted boron group; substituted or unsubstituted amine group; substituted or unsubstituted arylalkyl group; substituted or unsubstituted
  • adjacent groups of R1 to R4 are bonded to each other to form a ring represented by any one of Formulas B1-3 to Bl-5.
  • Y102, Y104 and Y105 are the same as or different from each other, and each independently O; S; or NR"';
  • R"', G103 to G106 and G111 to G128 are the same as or different from each other, and each independently represents hydrogen; deuterium; halogen group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted haloalkyl group; substituted or unsubstituted a cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkylthioxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; substituted or unsubstituted boron group; substituted or unsubstituted amine group; substituted or unsubstituted arylalkyl group; substituted or unsubstituted
  • n111 and n112 are each an integer from 0 to 2
  • Chemical Formula B1-1 is represented by the following Chemical Formula B1-1-1 or B1-1-2.
  • Y101 is O; S; or NR304;
  • Z101 is O; S; CR301R302; or NR303;
  • G401 to G404 and R301 to R304 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsub
  • Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-6 to 1-30.
  • R', R" and R1 to R7 are the same as those defined in Formula 1 above,
  • Y1 to Y5 are the same as or different from each other, and each independently O; or S;
  • Y101 to Y105 are the same as or different from each other, and each independently O; S; or NR"';
  • R"', R101, G1 to G28 and G101 to G128 are the same as or different from each other, and each independently represents hydrogen; deuterium; halogen group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted haloalkyl group; substituted or an unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkylthioxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; A substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a
  • n11, n12, n111 and n112 are each an integer from 0 to 2
  • r101 is 1 or 2
  • Y2 is O or S.
  • a group in which adjacent groups of R1 to R4 do not form a substituted or unsubstituted ring with each other is hydrogen.
  • R1 to R4 are hydrogen.
  • R101 is hydrogen
  • R1 to R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkylsilyl group; a substituted or unsubstituted C1-C30 linear or branched haloalkyl group; a substituted or unsubstituted C1-C30 linear or branched haloalkoxy group; a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic diarylamine group having 6 to 30 carbon atoms; a substituted or unsubstituted
  • R1 to R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a linear or branched alkylsilyl group having 1 to 30 carbon atoms; a linear or branched haloalkyl group having 1 to 30 carbon atoms; a linear or branched haloalkoxy group having 1 to 30 carbon atoms; an arylalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic diarylamine group having 6 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, and the substituents are deuterium, a halogen group,
  • R1 to R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; methyl group; tert-butyl group; -CD 3 ; -CF 3 ; -OCF 3 ; queuing; trimethylsilyl group; diphenylamine group; cyclohexyl group; phenyl group; adamantyl group; or a carbazole group, and the substituent is unsubstituted or substituted with one or more selected from the group consisting of deuterium, -F, a cyano group, a methyl group, a trimethylsilyl group, a tert-butyl group, and combinations thereof.
  • R6 is deuterium; cyano group; methyl group; tert-butyl group; -CD 3 ; -CF 3 ; -OCF 3 ; queuing; trimethylsilyl group; diphenylamine group; cyclohexyl group; phenyl group; adamantyl group; or a carbazole group, and the substituent is unsubstituted or substituted with one or more selected from the group consisting of deuterium, -F, a cyano group, a methyl group, a trimethylsilyl group, a tert-butyl group, and combinations thereof.
  • R1 to R5 and R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; methyl group; tert-butyl group; -CD 3 ; -CF 3 ; -OCF 3 ; queuing; trimethylsilyl group; diphenylamine group; cyclohexyl group; phenyl group; adamantyl group; or a carbazole group, and the substituent is unsubstituted or substituted with one or more selected from the group consisting of deuterium, -F, a cyano group, a methyl group, a trimethylsilyl group, a tert-butyl group, and combinations thereof.
  • R1 to R7 are the same as or different from each other, and are each independently a group represented by any one of the structures of Group C below.
  • R10 and R11 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
  • r10 is an integer from 1 to 10
  • r11 is an integer from 1 to 8;
  • r1 is 0 or 1
  • r2 is 0 or 1
  • R1 to R7 are the same as or different from each other, and are each independently a group represented by any one of the structures of Group D below.
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
  • r100, r101, r108 and r109 are each an integer from 1 to 8;
  • r102 and r107 are each an integer from 1 to 12,
  • r103 and r104 are each an integer from 1 to 10,
  • r105 is an integer from 1 to 6
  • r106 and r110 to r113 are each an integer of 1 to 4,
  • r114 is an integer from 1 to 14;
  • r115 is an integer from 1 to 18,
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; or a substituted or unsubstituted aryl group.
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkylsilyl group; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C20 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted C1-C20 linear or branched alkylsilyl group; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a linear or branched alkyl group having 1 to 30 carbon atoms substituted or unsubstituted with deuterium; a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms that is unsubstituted or substituted with deuterium; a linear or branched alkylsilyl group having 1 to 30 carbon atoms that is unsubstituted or substituted with deuterium; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms that is unsubstituted or substituted with deuterium.
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a linear or branched alkyl group having 1 to 20 carbon atoms that is unsubstituted or substituted with deuterium; a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms that is unsubstituted or substituted with deuterium; a linear or branched alkylsilyl group having 1 to 20 carbon atoms that is unsubstituted or substituted with deuterium; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms that is unsubstituted or substituted with deuterium.
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; methyl group; -CD 3 ; tert-butyl group; cyclohexyl group; trimethyl silyl group; Or a phenyl group unsubstituted or substituted with deuterium.
  • adjacent groups of R1 to R4 are bonded to each other to form a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted heterocycle is formed.
  • adjacent groups of R1 to R4 are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocycle having 2 to 30 carbon atoms is formed.
  • adjacent groups of R1 to R4 are bonded to each other and include a substituted or unsubstituted monocyclic or polycyclic aliphatic, aromatic, or aliphatic and aromatic condensed hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic aliphatic heterocycle having 2 to 30 carbon atoms is formed.
  • adjacent groups of R1 to R4 are bonded to each other to form a monocyclic or polycyclic aliphatic, aromatic, or aliphatic and aromatic condensed hydrocarbon ring having 3 to 30 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic aliphatic heterocycle having 2 to 30 carbon atoms, wherein the ring is a linear or branched alkyl group having 1 to 30 carbon atoms, and a linear or branched haloalkyl group having 1 to 30 carbon atoms It is substituted or unsubstituted with one or more selected from the group consisting of.
  • adjacent groups of R1 to R4 are bonded to each other to form a cyclopentane ring; cyclohexane ring; cycloheptane ring; bicyclo[2.2.1]octane ring; norbornane ring; adamantane ring; indene ring; phenanthrene ring; tetrahydrofuran ring; tetrahydrothiophene ring; pyrrolidine ring; tetrahydrobenzofuran ring; tetrahydrobenzothiophene ring; octahydrobenzofuran ring; octahydrobenzothiophene ring; octahydrocycloheptaindole ring; octahydroheptapyrrole ring; octahydroindene ring; benzene ring; phenanthrene ring;
  • R' is a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
  • R' is a linear or branched alkyl group having 1 to 30 carbon atoms; an arylalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic hydrocarbon ring group having 3 to 30 carbon atoms; or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, the substituents being deuterium, a halogen group, a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms, A linear or branched alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 3 to 30 carbon atoms, a linear or branched alkoxy group having 1 to 30 carbon atoms, a linear or branched haloalkyl group having 1 to 30 carbon atoms, a haloalkyl
  • R' is a methyl group; tert-butyl group; phenyl group; biphenyl group; terphenyl group; naphthyl group; fluorene group; triphenylene group; dibenzofuran group; cumyl group; adamantyl group; tetrahydronaphthyl group; or a hexahydrodibenzofuran group, and the substituents are deuterium, F, cyano group, methyl group, tert-butyl group, -CD 3 , -CF 3 , -OCF 3 , cyclohexyl group, phenyl group, diphenylamine group, pyridine It is unsubstituted or substituted with one or more selected from the group consisting of a group, a pyrimidine group, a methoxy group, an i-propyl group, a phenoxy group, a triphenyl
  • R" is a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms; substituted or unsubstituted C3 to 30 monocyclic or polycyclic hydrocarbon ring group, or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
  • R" is a linear or branched alkyl group having 1 to 30 carbon atoms; an arylalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic hydrocarbon ring group having 3 to 30 carbon atoms; or 2 to carbon atoms 30 is a monocyclic or polycyclic heterocyclic group, and the substituents are deuterium, a halogen group, a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms, and a cycloalkyl group having 1 to 30 carbon atoms.
  • a linear or branched alkylsilyl group an arylsilyl group having 3 to 30 carbon atoms, a straight or branched chain alkoxy group having 1 to 30 carbon atoms, a straight or branched chain haloalkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms
  • a linear or branched haloalkoxy group an aryloxy group having 6 to 30 carbon atoms, a monocyclic or polycyclic arylalkyl group having 6 to 30 carbon atoms, a monocyclic or polycyclic diarylamine group having 6 to 30 carbon atoms, a monocyclic group having 6 to 30 carbon atoms Or a polycyclic aryl group, a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, a monocyclic or polycyclic aliphatic group having 3 to 30 carbon atoms, and a monocyclic or polycyclic aromatic condensed
  • R" is a methyl group; a tert-butyl group; a phenyl group; a biphenyl group; a terphenyl group; a naphthyl group; a fluorene group; a triphenylene group; a dibenzofuran group; a cumyl group; adamantyl group; tetrahydronaphthyl group; or hexahydrodibenzofuran group, wherein the substituents are deuterium, F, cyano group, methyl group, tert-butyl group, -CD 3 , -CF 3 , -OCF 3 , cyclohexyl group , a phenyl group, a diphenylamine group, a pyridine group, a pyrimidine group, a methoxy group, an i-propyl group, a phenoxy group, a triphenyl
  • Y1 is O.
  • Y1 is S.
  • Y2 is O.
  • Y2 is S.
  • Y3 is O.
  • Y3 is S.
  • Y4 is O.
  • Y4 is S.
  • Y5 is O.
  • Y5 is S.
  • Y101 is O.
  • Y101 is S.
  • Y101 is NR"'.
  • Y102 is O.
  • Y102 is S.
  • Y102 is NR"'.
  • Y103 is O.
  • Y103 is S.
  • Y103 is NR"'.
  • Y104 is O.
  • Y104 is S.
  • Y104 is NR"'.
  • Y105 is O.
  • Y105 is S.
  • Y105 is NR"'.
  • R1 and G2 are combined with each other to form a substituted or unsubstituted heterocycle.
  • R1 and G2 are combined with each other to form a heterocycle including substituted or unsubstituted B and N.
  • R1 and G2 are combined with each other to form a 6-membered heterocycle including substituted or unsubstituted B and N.
  • R1 and G2 are combined with each other to form a heterocycle substituted with an aryl group.
  • R1 and G2 are combined with each other to form a heterocycle including B and N substituted with an aryl group.
  • R1 and G2 are combined with each other to form a 6-membered heterocycle including B and Si substituted with a phenyl group.
  • R4 and R' are bonded to each other to form a ring in any one of the structures represented by the following Group A.
  • R10 to R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
  • r10 is an integer from 1 to 10
  • r11 is an integer from 1 to 8;
  • r12 is an integer from 1 to 6
  • each of the r10 to r12 is 2 or more, the structures in the two or more parentheses are the same as or different from each other,
  • r1 is 0 or 1
  • r2 is 0 or 1.
  • R4 and R' combine with each other to form a ring in any one of the structures represented by Group B below.
  • R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
  • r100, r101, r108, r109 and r116 to r118 are each an integer of 1 to 8;
  • r102 and r107 are each an integer of 1 to 12,
  • r103 and r104 are each an integer from 1 to 10,
  • r105 is an integer from 1 to 6
  • r106 and r110 to r113 are each an integer of 1 to 4,
  • r114 is an integer from 1 to 14;
  • r115 is an integer from 1 to 18,
  • each of r100 to r118 is two or more, the structures in the two or more parentheses are the same as or different from each other.
  • R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; or a substituted or unsubstituted aryl group.
  • R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkylsilyl group; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.
  • R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C20 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted C1-C20 linear or branched alkylsilyl group; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.
  • R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a linear or branched alkyl group having 1 to 30 carbon atoms substituted or unsubstituted with deuterium; a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms that is unsubstituted or substituted with deuterium; a linear or branched alkylsilyl group having 1 to 30 carbon atoms that is unsubstituted or substituted with deuterium; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms that is unsubstituted or substituted with deuterium.
  • R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a linear or branched alkyl group having 1 to 20 carbon atoms that is unsubstituted or substituted with deuterium; a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms that is unsubstituted or substituted with deuterium; a linear or branched alkylsilyl group having 1 to 20 carbon atoms that is unsubstituted or substituted with deuterium; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms that is unsubstituted or substituted with deuterium.
  • R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; methyl group; -CD 3 ; tert-butyl group; cyclohexyl group; trimethyl silyl group; Or a phenyl group unsubstituted or substituted with deuterium.
  • the G1 to G28 and G101 and G128 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted C1-C30 linear or branched haloalkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkylsilyl group; a substituted or unsubstituted monocyclic or polycyclic arylsilyl group having 6 to 30 carbon atoms; a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic diarylamine group having 6 to 30 carbon atom
  • the G1 to G28 and G101 and G128 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a linear or branched alkyl group having 1 to 30 carbon atoms; a linear or branched haloalkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a linear or branched alkylsilyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic arylsilyl group having 6 to 30 carbon atoms; an arylalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic diarylamine group having 6 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, and the substituent is substituted with
  • the G1 to G28 and G101 and G128 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; methyl group; i-propyl group; tert-butyl group; -CF 3 ; adamantyl group; trimethylsilyl group; triphenylsilyl group; diphenylamine group; phenyl group; naphthyl group; cumyl group; pyridyl group; or a carbazole group, and the substituent is unsubstituted or substituted with one or more selected from the group consisting of deuterium, F, a methyl group, a tert-butyl group, and combinations thereof.
  • R"' is a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms; substituted or unsubstituted monocyclic or polycyclic aliphatic, aromatic, or A condensed hydrocarbon ring group of an aliphatic and an aromatic, or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
  • R"' is a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic aliphatic, aromatic, or aliphatic and aromatic condensed hydrocarbon ring group having 6 to 30 carbon atoms; or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, and the substituents are deuterium, a halogen group, a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched chain haloalkyl group having 1 to 30 carbon atoms, and their It is substituted or unsubstituted with one or more selected from the group consisting of combinations.
  • R"' is a tert-butyl group; a phenyl group; a biphenyl group; a tetrahydrobenzofuran group; a pyridine group; or a triazine group
  • the substituents are deuterium, F, -CF 3 , a methyl group , tert- butyl group, and unsubstituted or substituted with one or more selected from the group consisting of combinations thereof.
  • G1 to G28 and G101 and G128 are the same as or different from each other, and are each independently a group represented by any one of the structures of Group C below.
  • R10 and R11 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
  • r10 is an integer from 1 to 10
  • r11 is an integer from 1 to 8;
  • r1 is 0 or 1
  • r2 is 0 or 1
  • G1 to G28 and G101 and G128 are the same as or different from each other, and are each independently a group represented by any one of the structures of Group D below.
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
  • r100, r101, r108 and r109 are each an integer from 1 to 8;
  • r102 and r107 are each an integer from 1 to 12,
  • r103 and r104 are each an integer from 1 to 10,
  • r105 is an integer from 1 to 6
  • r106 and r110 to r113 are each an integer of 1 to 4,
  • r114 is an integer from 1 to 14;
  • r115 is an integer from 1 to 18,
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; or a substituted or unsubstituted aryl group.
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkylsilyl group; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C20 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted C1-C20 linear or branched alkylsilyl group; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a linear or branched alkyl group having 1 to 30 carbon atoms substituted or unsubstituted with deuterium; a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms that is unsubstituted or substituted with deuterium; a linear or branched alkylsilyl group having 1 to 30 carbon atoms that is unsubstituted or substituted with deuterium; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms that is unsubstituted or substituted with deuterium.
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a linear or branched alkyl group having 1 to 20 carbon atoms that is unsubstituted or substituted with deuterium; a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms that is unsubstituted or substituted with deuterium; a linear or branched alkylsilyl group having 1 to 20 carbon atoms that is unsubstituted or substituted with deuterium; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms that is unsubstituted or substituted with deuterium.
  • R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; methyl group; -CD 3 ; tert-butyl group; cyclohexyl group; trimethyl silyl group; Or a phenyl group unsubstituted or substituted with deuterium.
  • adjacent groups of G1 to G28 and G101 and G128 are bonded to each other to form a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted heterocycle is formed.
  • adjacent groups of G1 to G28 and G101 and G128 are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocycle having 2 to 30 carbon atoms is formed.
  • adjacent groups of G1 to G28 and G101 and G128 are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic aliphatic, aromatic, or aliphatic and aromatic condensed hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic aliphatic heterocycle having 2 to 30 carbon atoms is formed.
  • adjacent groups of G1 to G28 and G101 and G128 are bonded to each other to form a monocyclic or polycyclic aliphatic, aromatic, or aliphatic and aromatic condensed hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic aliphatic heterocycle having 2 to 30 carbon atoms is formed, and the ring is monocyclic or polycyclic having 6 to 30 carbon atoms unsubstituted or substituted with a linear or branched alkyl group having 1 to 30 carbon atoms.
  • adjacent groups of G1 to G28 and G101 and G128 are bonded to each other to form a cyclopentane ring; cyclohexane ring; cycloheptane ring; bicyclo[2.2.1]octane ring; norbornane ring; adamantane ring; indene ring; phenanthrene ring; tetrahydrofuran ring; tetrahydrothiophene ring; tetrahydronaphthofuran ring; tetrahydranaphthothiophene ring; pyrrolidine ring; octahydrobenzofuran ring; octahydrobenzothiophene ring; octahydroindene ring; benzene ring; phenanthrene ring; benzofuran ring; fluorene ring; dihydroanthracene
  • R"' and G102 are combined with each other to form a substituted or unsubstituted heterocycle.
  • the R"' and G102 are combined with each other to form a heterocycle including substituted or unsubstituted B and N.
  • the R"' and G102 are combined with each other to form a 6-membered heterocycle including substituted or unsubstituted B and N.
  • the R"' and G102 are bonded to each other to form a heterocycle.
  • the R"' and G102 are combined with each other to form a heterocycle including B and N.
  • the R"' and G102 are combined with each other to form a 6-membered heterocycle including B and N.
  • Formula 1 is any one selected from the following compounds.
  • Ph means a phenyl group
  • A1 of Formula 1 is benzofuran substituted with a t-butyl group or benzothiophene substituted with a t-butyl group
  • R′ and R′′ are each independently a t-butyl group or iso
  • a compound in which a phenyl group substituted with a propyl group or a biphenyl group substituted with a t-butyl group and R2 or R3 is a t-butyl group or hydrogen, R6 is a terbutyl group, a phenyl group, or an adamantyl group is excluded.
  • A1 of Formula 1 is benzofuran or dibenzofuran
  • a compound that is a diphenylamine group unsubstituted or substituted with a t-butyl group in R2 is excluded.
  • R′ and R′′ are each independently a phenyl group substituted with a t-butyl group, and R3 is a t-butyl group, R6 The compound which is this methyl group or a cyclohexyl group is excluded.
  • A1 of Formula 1 is benzofuran or dibenzofuran
  • R' and R" are each independently a biphenyl group substituted with a t-butyl group
  • R3 is a substituted with a t-butyl group
  • R6 is a methyl group
  • A1 of Formula 1 is benzofuran or dibenzofuran
  • R' and R" are each independently a biphenyl group or a phenyl group substituted with a diphenylamine group
  • R1 to R4 are hydrogen
  • R6 is a cyclohexyl group
  • Formula 1 when A1 of Formula 1 includes a 5-membered aliphatic or aromatic heterocycle, and A1 of Formula 1 includes a 5-membered aromatic heterocycle, Formula 1 is an aliphatic hydrocarbon condensed ring includes at least one.
  • the present specification provides an organic light emitting device including the above-described compound.
  • the 'layer' means compatible with the 'film' mainly used in the present technical field, and refers to a coating covering a desired area.
  • the size of the 'layers' is not limited, and each 'layer' may have the same size or different sizes. According to an exemplary embodiment, the size of the 'layer' may be the same as the entire device, may correspond to the size of a specific functional area, and may be as small as a single sub-pixel.
  • the meaning that a specific material A is included in layer B means that i) one or more types of material A are included in one layer B, and ii) layer B is composed of one or more layers, and material A is multi-layered B. It includes everything included in one or more floors among the floors.
  • the meaning that a specific material A is included in the C layer or the D layer means i) is included in one or more of the one or more layers C, ii) is included in one or more of the one or more layers D, or iii) ) means all of which are included in one or more C-layers and one or more D-layers, respectively.
  • the present specification includes a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound represented by Formula 1 above. do.
  • the organic material layer of the organic light emitting device of the present specification may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked.
  • it may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, and the like.
  • the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by Formula 1 above.
  • the organic material layer includes an emission layer
  • the emission layer includes the compound represented by Formula 1 as a dopant of the emission layer.
  • the organic material layer includes an emission layer
  • the emission layer includes the compound represented by Formula 1 as a blue fluorescent dopant of the emission layer.
  • the organic light emitting device includes a hole injection layer and a hole transport layer. It further includes one or more layers selected from the group consisting of a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer.
  • the light emitting layer further includes a host compound.
  • the light emitting layer further includes a host compound, wherein at least one hydrogen at a substitutable position is substituted with deuterium in the host compound.
  • the host compound when the host compound is substituted with deuterium, it is substituted with deuterium by 30% or more. In another exemplary embodiment, the host compound is substituted with deuterium by 40% or more. In another exemplary embodiment, the host compound is substituted with deuterium by 60% or more. In another exemplary embodiment, the host compound is substituted with deuterium by 80% or more. In another exemplary embodiment, the host compound is 100% substituted with deuterium.
  • the light emitting layer further includes a compound represented by the following formula (H).
  • L20 and L21 are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heterocyclic group,
  • Ar20 and Ar21 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
  • R20 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • L20 and L21 are the same as or different from each other, and each independently a direct bond; a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms; or a monocyclic or polycyclic heteroarylene group having 2 to 30 carbon atoms.
  • L20 and L21 are the same as or different from each other, and each independently a direct bond; a monocyclic or polycyclic arylene group having 6 to 20 carbon atoms; or a monocyclic or polycyclic heteroarylene group having 2 to 20 carbon atoms.
  • L20 and L21 are the same as or different from each other, and each independently a direct bond; phenylene group; biphenylrylene group; naphthylene group; a divalent dibenzofuran group; or a divalent dibenzothiophene group.
  • Ar20 and Ar21 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
  • Ar20 and Ar21 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 20 carbon atoms.
  • Ar20 and Ar21 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic to 4cyclic aryl group having 6 to 20 carbon atoms; or a substituted or unsubstituted monocyclic to 4cyclic heterocyclic group having 6 to 20 carbon atoms.
  • Ar20 and Ar21 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted anthracene group; a substituted or unsubstituted phenanthrene group; a substituted or unsubstituted phenalene group; a substituted or unsubstituted fluorene group; a substituted or unsubstituted benzofluorene group; a substituted or unsubstituted furan group; a substituted or unsubstituted thiophene group; A substituted or unsubstituted dibenzofuran group; a substituted or unsubstituted naphthobenzofur
  • Ar20 and Ar21 are the same as or different from each other, and each independently represent a phenyl group unsubstituted or substituted with deuterium or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; a biphenyl group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; a naphthyl group unsubstituted or substituted with deuterium or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; a dibenzofuran group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; a naphthobenzofuran group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; a dibenzothiophene group unsubstituted or
  • Ar20 and Ar21 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with deuterium; biphenyl group; a naphthyl group unsubstituted or substituted with deuterium; dibenzofuran group; naphthobenzofuran group; dibenzothiophene group; or a naphthobenzothiophene group.
  • Ar20 is a substituted or unsubstituted heterocyclic group
  • Ar21 is a substituted or unsubstituted aryl group.
  • R 20 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
  • R 20 is hydrogen; heavy hydrogen; fluorine; a substituted or unsubstituted C1-C10 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 10 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
  • R 20 is hydrogen; heavy hydrogen; a phenyl group unsubstituted or substituted with deuterium, a phenyl group, or a naphthyl group; a naphthyl group unsubstituted or substituted with deuterium or a phenyl group; biphenyl group; dibenzofuran group; or a dibenzothiophene group.
  • the compound represented by Formula H is any one selected from the following compounds.
  • the compound represented by Formula 1 is used as a dopant in the emission layer, and the compound represented by Formula H is used as a host.
  • the content of the dopant may be selected from 0.01 to 10 parts by weight based on 100 parts by weight of the light emitting layer, but is not limited thereto.
  • the light emitting layer includes a host and a dopant, and the host and the dopant are 99:1 to 1:99 by weight, preferably 99:1 to 70:30 by weight, even more preferably 99 It is included in a weight ratio of :1 to 90:10.
  • the light emitting layer may further include a host material, and the host may include a condensed aromatic ring derivative or a heterocyclic compound containing compound.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc.
  • heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type and a furan compound, a pyrimidine derivative, or a triazine derivative, and may be a mixture of two or more thereof, but is not limited thereto.
  • the organic material layer includes an emission layer, and the emission layer includes one or more dopants and a host.
  • the organic material layer includes an emission layer, and the emission layer includes two or more mixed dopants and a host.
  • At least one of the two or more mixed dopants includes Formula 1, and the host includes a compound represented by Formula H.
  • At least one of the two or more mixed dopants may include Chemical Formula 1, and for the rest, a dopant material known in the art may be used, but the present invention is not limited thereto.
  • At least one of the two or more mixed dopants includes Formula 1, and the remainder uses at least one of a boron-based compound, a pyrene-based compound, and a delayed fluorescence-based compound different from Formula 1
  • the present invention is not limited thereto.
  • the organic material layer includes an emission layer, and the emission layer includes at least one host.
  • the organic material layer includes an emission layer, and the emission layer includes two or more types of mixed hosts.
  • At least one of the two or more types of mixed hosts is a compound represented by Formula H.
  • the two or more types of mixed hosts are different from each other, and each independently represent a compound represented by Formula H.
  • the organic material layer includes an emission layer, and the emission layer includes two types of mixed hosts.
  • the organic material layer includes a light emitting layer
  • the light emitting layer includes two types of mixed hosts
  • the two types of mixed hosts are different from each other
  • the two types of hosts are represented by Formula H is a compound that becomes
  • the organic material layer includes a light emitting layer, the first host represented by the formula (H); and a second host represented by Formula H, wherein the first host and the second host are different from each other.
  • the first host the second host is included in a weight ratio of 95:5 to 5:95, preferably 70:30 to 30:70 by weight.
  • the organic material layer includes an emission layer, and the emission layer includes at least one host and a dopant.
  • the organic material layer includes a light emitting layer, the light emitting layer includes at least one host and a dopant, the host includes a compound represented by Formula H, and the dopant includes the above formula The compound represented by 1 is included.
  • the organic material layer includes an emission layer, and the emission layer includes two or more mixed hosts, and a dopant.
  • At least one of the two or more mixed hosts includes the compound represented by Formula H, and the dopant includes the compound represented by Formula 1 above.
  • the two or more types of mixed hosts are different from each other.
  • the organic material layer includes an emission layer, and the emission layer includes two types of mixed hosts, and a dopant.
  • the two types of mixed hosts are different from each other, and each independently include a compound represented by Formula H, and the dopant includes a compound represented by Formula 1 above.
  • the organic material layer includes a light emitting layer, the first host represented by the formula (H); a second host represented by the formula (H); and a dopant represented by Formula 1, wherein the first host and the second host are different from each other.
  • the organic material layer uses at least one host and at least one dopant, and the at least one host includes a compound represented by Formula H, and the at least one dopant is and a compound represented by the formula (1).
  • the organic material layer uses two or more types of mixed hosts, and two or more types of mixed dopants, and the two or more types of mixed hosts may use the same material as described above, and a mixture of the two or more types The dopant may use the same material as described above.
  • the organic light emitting device includes a first electrode; a second electrode; a light emitting layer provided between the first electrode and the second electrode; and two or more organic material layers provided between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, wherein at least one of the two or more organic material layers includes a compound represented by Formula 1 above.
  • the two or more organic material layers may be selected from the group consisting of a light emitting layer, a hole transport layer, a hole injection layer, a layer for simultaneously transporting and injecting holes, and an electron blocking layer.
  • the organic light emitting device may include two or more electron transport layers, but is not limited thereto.
  • the organic material layer includes two or more electron transport layers, and at least one of the two or more electron transport layers includes the compound represented by Formula 1 above.
  • the compound represented by Formula 1 may be included in one of the two or more electron transport layers, and may be included in each of the two or more electron transport layers.
  • materials other than the compound represented by Formula 1 may be the same or different from each other.
  • the electron transport layer may further include an n-type dopant.
  • the n-type dopant those known in the art may be used, for example, a metal or a metal complex may be used.
  • the electron transport layer including the compound represented by Formula 1 may further include lithium quinolate (LiQ).
  • the organic material layer includes two or more hole transport layers, and at least one of the two or more hole transport layers includes the compound represented by Formula 1 above.
  • the compound represented by Formula 1 may be included in one of the two or more hole transport layers, and may be included in each of the two or more hole transport layers.
  • the organic material layer includes a hole injection layer or a hole transport layer containing a compound including an arylamine group, a carbazolyl group or a benzocarbazolyl group in addition to the organic material layer including the compound represented by Formula 1 above.
  • a hole injection layer or a hole transport layer containing a compound including an arylamine group, a carbazolyl group or a benzocarbazolyl group in addition to the organic material layer including the compound represented by Formula 1 above. may include
  • the first electrode is an anode or a cathode.
  • the second electrode is a cathode or an anode.
  • the organic light emitting device may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.
  • the organic light emitting device may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.
  • FIGS. 1 to 3 illustrate an organic light emitting device, but is not limited thereto.
  • FIG. 1 illustrates a structure of an organic light emitting device in which a substrate 1, a first electrode 2, a light emitting layer 3, and a second electrode 4 are sequentially stacked.
  • the compound may be included in the light emitting layer 3 .
  • the compound is included in one or more of the light emitting layer 3 , the hole blocking layer 6 , the electron injection and transport layer 7 , and the hole injection layer 8 .
  • the 3 is a substrate (1), a first electrode (2), a hole injection layer (5), a hole transport layer (8), an electron blocking layer (9), a light emitting layer (3), a first electron transport layer (10), the second
  • the compound may be included in the light emitting layer 3 .
  • the organic light emitting device of the present specification may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound, that is, the compound represented by Formula 1 above.
  • the organic material layers may be formed of the same material or different materials.
  • the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate.
  • a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation
  • a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode.
  • It may be prepared by forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.
  • an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
  • the compound represented by Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device.
  • the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, 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 (International Patent Application Laid-Open No. 2003/012890).
  • the manufacturing method is not limited thereto.
  • a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer.
  • metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO:Al or SnO 2 : a combination of a metal such as Sb and an oxide; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
  • the second electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer.
  • metals or alloys thereof such as, for example, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead; LiF/Al or a multi-layered material such as LiO 2 /Al, but is not limited thereto.
  • the emission layer may include a host material and a dopant material.
  • the host material include a condensed aromatic ring derivative or a heterocyclic compound containing compound.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like
  • heterocyclic-containing compounds include dibenzofuran derivatives, ladder-type furan compounds, and pyrimidine derivatives, but is not limited thereto.
  • the dopant material examples include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex, in addition to the compound represented by Formula 1 above.
  • the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamine group, and includes pyrene, anthracene, chrysene, periplanthene, and the like, having an arylamine group.
  • the styrylamine compound is a compound in which at least one arylvinyl group is substituted with a substituted or unsubstituted arylamine, and one or two or more selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamine group A substituent is substituted or unsubstituted.
  • the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.
  • the light emitting material of the light emitting layer receives and bonds holes and electrons from the hole transport layer and the electron transport layer, respectively.
  • a material capable of emitting light in the visible light region a material having good quantum efficiency for fluorescence or phosphorescence is preferable.
  • 8-hydroxy-quinoline aluminum complex Alq 3
  • carbazole-based compounds dimerized styryl compounds
  • BAlq 10-hydroxybenzo quinoline-metal compounds
  • compounds of the benzoxazole, benzthiazole and benzimidazole series Poly(p-phenylenevinylene) (PPV)-based polymers
  • spiro compounds polyfluorene; and rubrene, but is not limited thereto.
  • the hole injection layer is a layer for injecting holes from the electrode. It is preferable that the hole injection material has the ability to transport holes and thus has a hole injection effect at the first electrode and an excellent hole injection effect on the light emitting layer or the light emitting material. Also, a material excellent in the ability to prevent movement of excitons generated in the light emitting layer to the electron injection layer or the electron injection material is preferable. In addition, a material excellent in the ability to form a thin film is preferable. In addition, it is preferable that the highest ocupied molecular orbital (HOMO) of the hole injection material is between the work function of the first electrode material and the HOMO of the surrounding organic material layer.
  • HOMO highest ocupied molecular orbital
  • the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material; carbazole-based organics; nitrile-based organics; hexanitrile hexaazatriphenylene-based organic substances; quinacridone-based organic substances; perylene-based organic materials; Polythiophene-based conductive polymers such as anthraquinone and polyaniline or mixtures of two or more of the above examples, but are not limited thereto.
  • the hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer.
  • the hole transport material is a material capable of transporting holes from the first electrode or the hole injection layer to the light emitting layer, and a material having high hole mobility is preferable. Specific examples include, but are not limited to, an arylamine-based organic material, a carbazole-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.
  • the electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer.
  • the electron transport material is a material capable of well injecting electrons from the second electrode and transferring them to the light emitting layer, and a material having high electron mobility is preferable. Specific examples include an Al complex of 8-hydroxyquinoline; complexes containing Alq 3 ; organic radical compounds; hydroxyflavone-metal complexes; triazine derivatives; LiQ, etc., but is not limited thereto.
  • the electron transport layer may be used with any desired first electrode material, as used in accordance with the prior art.
  • suitable first electrode materials are conventional materials having a low work function, followed by a layer of aluminum or silver. Specifically, there are cesium, barium, calcium, ytterbium, samarium, and the like, followed by an aluminum layer or a silver layer in each case.
  • the electron injection layer is a layer that injects electrons from the electrode. It is preferable that the electron injection material has excellent electron transporting ability and has excellent electron injection effect from the second electrode and electron injection effect with respect to the light emitting layer or the light emitting material. In addition, a material that prevents excitons generated in the light emitting layer from moving to the hole injection layer and has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, triazine, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. derivatives thereof, metal complex compounds and nitrogen-containing 5-membered ring derivatives, and mixtures of two or more of the above examples, but are not limited thereto.
  • Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, and bis(8-hydroxyquinolinato)manganese. , tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h ]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato) (o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. , but is not limited thereto.
  • the electron blocking layer is a layer capable of improving the lifetime and efficiency of the device by preventing electrons injected from the electron injection layer from entering the hole injection layer through the emission layer.
  • a known material can be used without limitation, and may be formed between the light emitting layer and the hole injection layer, or between the light emitting layer and the layer that simultaneously injects and transports holes.
  • the hole blocking layer is a layer that blocks holes from reaching the cathode through the light emitting layer, and may be generally formed under the same conditions as the electron injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, aluminum complexes, pyridine, pyrimidine or triazine derivatives, but is not limited thereto.
  • the organic light emitting device may be a top emission type, a back emission type, or a double side emission type depending on the material used.
  • the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
  • the compound according to the present specification may act on a principle similar to that applied to an organic light emitting device in an organic light emitting device including an organic phosphorescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and the like.
  • the organic solar cell may have a structure including a negative electrode, a positive electrode, and a photoactive layer provided between the negative electrode and the positive electrode, and the photoactive layer may include the compound.
  • the organic light emitting device of the present specification may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except for forming one or more organic material layers using the above-described compound.
  • N 1 , N 1 -bis(phenyl- d 5 ) -N 3 -(4-trimethylsilylphenyl)benzene-1,3-diamine 47.8 mmol, 20 g
  • 1-bromo-3- Chloro-5-methylbenzene 47.8 mmol, 9.82 g
  • toluene 0.2 M, 240 ml
  • sodium terbutoxide 7.17 mmol, 6.89 g
  • bis (tri-terbutylphosphine) palladium (0) 0.478 mmol, 0.244 g
  • N -(4-terbutylphenyl)-5'-methyl-[1,1',3',1''-terphenyl]-2'-amine 76.6 mmol, 30 g
  • 1- Bromo-3-chloro-5-terbutylbenzene 76.6 mmol, 19.0 g
  • toluene 0.2 M, 380 ml
  • sodium terbutoxide 115 mmol, 11.0 g
  • bis(tri-terbutylphosphine) After adding palladium (0) (0.766 mmol, 0.392 g), the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere.
  • N- (4-terphenyl)-1,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-amine 114 mmol, 40 g
  • 1 -Bromo-3-chloro-5-methylbenzene 114 mmol, 23.5 g
  • toluene 0.2 M, 572 ml
  • sodium terbutoxide 172 mmol, 16.5 g
  • bis(tri-terbutylphosphine) After adding palladium (0) (1.14 mmol, 0.585 g), the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere.
  • N,N -bis(2-fluorophenyl)-4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro- 1H -carbazol-5-amine (34.1 mmol, 13.8 g) and 1-bromo-3-chloro-5-methylbenzene (34.1 mmol, 7 g) were dissolved in toluene (0.2 M, 170 ml), and sodium terbutoxide (51.1 mmol, 4.91 g), bis(tri -terbutylphosphine)palladium(0) (0.341 mmol, 0.174 g) was added, and the mixture was stirred under reflux conditions in an argon atmosphere for 4 hours.
  • compound 22-b (18.2 mmol, 16.5 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 180 ml), boron triiodide (29.1 mmol, 11.4 g) was added, and argon atmosphere 140 The mixture was stirred at °C for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (164 mmol, 21.1 g) was added, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O.
  • 5-tertbutyl- N- (4-triphenylsilylphenyl)-[1,1'-biphenyl]-2-amine (53.6 mmol, 30 g) and 1-bromo-3-chloro- Dissolve 5-methylbenzene (53.6 mmol, 11.0 g) in toluene (0.2 M, 270 ml), sodium terbutoxide (80.4 mmol, 7.72 g), bis(tri-terbutylphosphine)palladium(0) (0.536 mmol) , 0.274 g), and stirred for 12 hours under reflux conditions in an argon atmosphere.

Abstract

The present specification provides a compound of chemical formula 1 and an organic light-emitting device comprising same.

Description

화합물 및 이를 포함하는 유기 발광 소자Compound and organic light emitting device comprising same
본 출원은 2019년 11월 29일에 한국특허청에 제출된 한국 특허 출원 제10-2019-0156840호 및 2020년 5월 20일에 한국특허청에 제출된 한국 특허 출원 제10-2020-0060597호의 출원일의 이익을 주장하며, 그 내용 전부는 본 명세서에 포함된다.This application is based on the filing date of Korean Patent Application No. 10-2019-0156840, filed with the Korean Intellectual Property Office on November 29, 2019, and Korean Patent Application No. 10-2020-0060597, filed with the Korean Intellectual Property Office on May 20, 2020 claims, the entire contents of which are incorporated herein by reference.
본 명세서는 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다.The present specification relates to a compound and an organic light emitting device including the same.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층 등으로 이루어 질 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. In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and these excitons are When it falls back to the ground state, it lights up.
상기와 같은 유기 발광 소자를 위한 새로운 재료의 개발이 계속 요구되고 있다.The development of new materials for the organic light emitting device as described above is continuously required.
본 명세서는 화합물 및 이를 포함하는 유기 발광 소자를 제공한다.The present specification provides a compound and an organic light emitting device including the same.
본 명세서의 일 실시상태는 하기 화학식 1로 표시되는 화합물을 제공한다.An exemplary embodiment of the present specification provides a compound represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2020017069-appb-I000001
Figure PCTKR2020017069-appb-I000001
상기 화학식 1에 있어서,In Formula 1,
A1은 치환 또는 비치환되고, O 또는 S를 포함하는 5원 고리를 포함하는 단환 또는 다환의 헤테로고리이고,A1 is a substituted or unsubstituted monocyclic or polycyclic heterocycle including a 5-membered ring including O or S,
R1 내지 R7, R' 및 R"은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성한다.R1 to R7, R′ and R″ are the same as or different from each other, and each independently represents hydrogen; deuterium; halogen group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted haloalkyl group; substituted or unsubstituted cyclo Alkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted haloalkoxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted a heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group.
또한, 본 명세서는 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 1층 이상은 상기 화합물을 포함하는 것인 유기 발광 소자를 제공한다.In addition, the present specification is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one organic material layer includes the compound.
본 명세서에 기재된 화합물은 유기 발광 소자의 유기물층의 재료로서 사용될 수 있다. 또 하나의 실시상태에 따른 화합물은 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다. 특히, 본 명세서에 기재된 화합물은 정공주입, 정공수송, 정공주입과 정공수송, 전자차단, 발광, 정공차단, 전자수송, 또는 전자주입 재료로 사용될 수 있다. 또한, 본 명세서의 일 실시상태에 따른 유기 발광 소자는 낮은 구동전압, 고효율 또는 장수명의 효과가 있다.The compound described herein may be used as a material for an organic material layer of an organic light emitting device. The compound according to another exemplary embodiment may improve efficiency, low driving voltage, and/or lifespan characteristics in an organic light emitting device. In particular, the compounds described herein can be used as hole injection, hole transport, hole injection and hole transport, electron blocking, light emission, hole blocking, electron transport, or electron injection material. In addition, the organic light emitting device according to an exemplary embodiment of the present specification has effects of low driving voltage, high efficiency, or long lifespan.
도 1 내지 3은 본 명세서의 일 실시상태에 따른 유기 발광 소자의 예를 도시한 것이다.1 to 3 show examples of an organic light emitting device according to an exemplary embodiment of the present specification.
도 4는 본 명세서의 실험예 1에 따른 광발광 분석 그래프 도시한 도이다.4 is a diagram illustrating a photoluminescence analysis graph according to Experimental Example 1 of the present specification.
도 5는 본 명세서의 실험예 3에 따른 화합물 19의 열중량 분석 그래프를 나타낸 도이다.5 is a diagram showing a thermogravimetric analysis graph of Compound 19 according to Experimental Example 3 of the present specification.
도 6은 본 명세서의 실험예 3에 따른 화합물 BD-A의 열중량 분석 그래프를 나타낸 도이다.6 is a diagram showing a thermogravimetric analysis graph of compound BD-A according to Experimental Example 3 of the present specification.
도 7은 본 명세서의 실험예 3에 따른 화합물 BD-C의 열중량 분석 그래프를 나타낸 도이다.7 is a diagram showing a thermogravimetric analysis graph of compound BD-C according to Experimental Example 3 of the present specification.
[부호의 설명][Explanation of code]
1: 기판1: substrate
2: 제1 전극2: first electrode
3: 발광층3: light emitting layer
4: 제2 전극4: second electrode
5: 정공주입층5: hole injection layer
6: 정공차단층6: hole blocking layer
7: 전자주입 및 수송층7: Electron injection and transport layer
8: 정공수송층8: hole transport layer
9: 전자차단층9: Electronic blocking layer
10: 제1 전자수송층10: first electron transport layer
11: 제2 전자수송층11: second electron transport layer
12: 전자주입층12: electron injection layer
이하, 본 명세서에 대하여 더욱 상세히 설명한다.Hereinafter, the present specification will be described in more detail.
종래의 보론 화합물은 반치폭이 23 내지 30nm 정도이고, 기본 코어구조의 파장은 453nm 정도이나, 물질의 안정성이 아민 화합물에 비해 상대적으로 떨어져 수명이 낮아지는 한계를 가지고 있다. 따라서, 보론 화합물의 치환기 조절을 통해 우수한 광학적 특성을 유지하면서 물질의 안정성을 높여 긴 수명을 확보하는 방법이 요구된다.Conventional boron compounds have a half width of about 23 to 30 nm, and a wavelength of a basic core structure of about 453 nm, but the stability of the material is relatively lower than that of the amine compound, and thus the lifespan is lowered. Therefore, there is a need for a method for securing a long lifespan by increasing the stability of a material while maintaining excellent optical properties by controlling the substituents of the boron compound.
본 명세서의 일 실시상태에 따른 화학식 1의 화합물은 A1이 치환 또는 비치환되고, O 또는 S를 포함하는 5원 고리를 포함하는 단환 또는 다환의 헤테로고리를 포함하는 구조로 풍부한 전자를 이용하여 화합물의 구조적 안정성과 우수한 전기 화학적 특성을 확보할 수 있다.The compound of Formula 1 according to an exemplary embodiment of the present specification is a compound using electrons abundant in a structure including a monocyclic or polycyclic heterocycle including a 5-membered ring including O or S, in which A1 is substituted or unsubstituted. Structural stability and excellent electrochemical properties can be secured.
본원 명세서 전체에서, 마쿠시 형식의 표현에 포함된 "이들의 조합"의 용어는 마쿠시 형식의 표현에 기재된 구성 요소들로 이루어진 군에서 선택되는 하나 이상의 혼합 또는 조합을 의미하는 것으로서, 상기 구성 요소들로 이루어진 군에서 선택되는 하나 이상을 포함하는 것을 의미한다.Throughout this specification, the term "combination of these" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, and the components It is meant to include one or more selected from the group consisting of.
본 명세서에서 치환기의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다. Examples of substituents in the present specification are described below, but are not limited thereto.
본 명세서에 있어서,
Figure PCTKR2020017069-appb-I000002
는 연결되는 부위를 의미한다.In this specification,
Figure PCTKR2020017069-appb-I000002
means the part to be connected.
상기 "치환"이라는 용어는 화합물의 탄소 원자에 결합된 수소 원자가 다른 치환기로 바뀌는 것을 의미하며, 치환되는 위치는 수소 원자가 치환되는 위치 즉, 치환기가 치환 가능한 위치라면 한정하지 않으며, 2 이상 치환되는 경우, 2 이상의 치환기는 서로 같거나 상이할 수 있다.The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is not limited, and when two or more are substituted , two or more substituents may be the same as or different from each other.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 할로겐기; 시아노기; 알킬기; 시클로알킬기; 알콕시기; 아릴옥시기; 알킬티옥시기; 아릴티옥시기; 알케닐기; 할로알킬기; 할로알콕시기; 아릴알킬기; 실릴기; 붕소기; 아민기; 아릴기; 방향족 탄화수소와 지방족 탄화수소의 축합고리기; 및 헤테로고리기로 이루어진 군으로부터 선택되는 1 이상의 치환기로 치환되었거나, 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환기로 치환되거나, 또는 어떠한 치환기도 갖지 않는 것을 의미한다.As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; an alkyl group; cycloalkyl group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; alkenyl group; haloalkyl group; haloalkoxy group; an arylalkyl group; silyl group; boron group; amine group; aryl group; Condensed ring groups of aromatic hydrocarbons and aliphatic hydrocarbons; And it means that it is substituted with one or more substituents selected from the group consisting of a heterocyclic group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents.
본 명세서에 있어서, 2 이상의 치환기가 연결된다는 것은 어느 하나의 치환기의 수소가 다른 치환기와 연결된 것을 말한다. 예컨대, 2개의 치환기가 연결되는 것은 페닐기와 나프틸기가 연결되어
Figure PCTKR2020017069-appb-I000003
또는
Figure PCTKR2020017069-appb-I000004
의 치환기가 될 수 있다. 또한, 3개의 치환기가 연결되는 것은 (치환기 1)-(치환기 2)-(치환기 3)이 연속하여 연결되는 것뿐만 아니라, (치환기 1)에 (치환기 2) 및 (치환기 3)이 연결되는 것도 포함한다. 예컨대, 페닐기, 나프틸기 및 이소프로필기가 연결되어,
Figure PCTKR2020017069-appb-I000005
,
Figure PCTKR2020017069-appb-I000006
또는
Figure PCTKR2020017069-appb-I000007
의 치환기가 될 수 있다. 4 이상의 치환기가 연결되는 것에도 전술한 정의가 동일하게 적용된다.In the present specification, that two or more substituents are connected means that the hydrogen of any one substituent is connected with another substituent. For example, when two substituents are connected, a phenyl group and a naphthyl group are connected.
Figure PCTKR2020017069-appb-I000003
or
Figure PCTKR2020017069-appb-I000004
may be a substituent of In addition, the connection of three substituents means that (substituent 1)-(substituent 2)-(substituent 3) is continuously connected, as well as (substituent 2) and (substituent 3) are connected to (substituent 1). include For example, a phenyl group, a naphthyl group and an isopropyl group are connected,
Figure PCTKR2020017069-appb-I000005
,
Figure PCTKR2020017069-appb-I000006
or
Figure PCTKR2020017069-appb-I000007
may be a substituent of The above definition applies equally to the case where 4 or more substituents are connected.
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 30인 것이 바람직하다. 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, 시클로펜틸메틸, 시클로헥실메틸, 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, 이에 한정되는 것은 아니다.In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like.
본 명세서에 있어서, 시클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 30인 것이 바람직하며, 구체적으로 시클로프로필, 시클로부틸, 시클로펜틸, 3-메틸시클로펜틸, 2,3-디메틸시클로펜틸, 시클로헥실, 3-메틸시클로헥실, 4-메틸시클로헥실, 2,3-디메틸시클로헥실, 3,4,5-트리메틸시클로헥실, 4-tert-부틸시클로헥실, 시클로헵틸, 시클로옥틸, 아다만틸기, 바이시클로[2.2.1]옥틸기, 노보닐기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and 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, adamantyl group, bicyclo [2.2.1] octyl group, norbornyl group, etc., but is not limited thereto.
본 명세서에 있어서, 상기 알콕시기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 알콕시기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 30인 것이 바람직하다. 구체적으로, 메톡시, 에톡시, n-프로폭시, 이소프로폭시, n-부톡시, 이소부톡시, tert-부톡시, sec-부톡시, n-펜틸옥시, 네오펜틸옥시, 이소펜틸옥시, n-헥실옥시, 3,3-디메틸부틸옥시, 2-에틸부틸옥시, n-옥틸옥시, n-노닐옥시, n-데실옥시, 벤질옥시, p-메틸벤질옥시 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. may be It is not limited.
본 명세서에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 30인 것이 바람직하다. 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, 이에 한정되는 것은 아니다.In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. 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 is not limited thereto.
본 명세서에 있어서, 상기 할로알킬기는 상기 알킬기의 정의 중 알킬기의 수소 대신 적어도 하나의 할로겐기가 치환되는 것을 의미한다.In the present specification, the haloalkyl group means that at least one halogen group is substituted for hydrogen in the alkyl group in the definition of the alkyl group.
본 명세서에 있어서, 상기 할로알콕시기는 상기 알콕시기의 정의 중 알콕시기의 수소 대신 적어도 하나의 할로겐기가 치환되는 것을 의미한다.In the present specification, the haloalkoxy group means that at least one halogen group is substituted for hydrogen of the alkoxy group in the definition of the alkoxy group.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나, 탄소수 6 내지 30인 것이 바람직하며, 상기 아릴기는 단환식 또는 다환식일 수 있다.In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.
상기 아릴기가 단환식 아릴기인 경우 탄소수는 특별히 한정되지 않으나, 탄소수 6 내지 30인 것이 바람직하다. 구체적으로 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto.
상기 아릴기가 다환식 아릴기인 경우 탄소수는 특별히 한정되지 않으나. 탄소수 10 내지 30인 것이 바람직하다. 구체적으로 다환식 아릴기로는 나프틸기, 안트라센기, 페난트렌기, 트리페닐렌기, 파이렌기, 페날렌기, 페릴렌기, 크라이센기, 플루오렌기 등이 될 수 있으나, 이에 한정되는 것은 아니다. When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it is C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a phenalene group, a perylene group, a chrysene group, a fluorene group, and the like, but is not limited thereto.
본 명세서에 있어서, 상기 플루오렌기는 치환될 수 있으며, 인접한 기들이 서로 결합하여 고리를 형성할 수 있다. In the present specification, the fluorene group may be substituted, and adjacent groups may combine with each other to form a ring.
상기 플루오렌기가 치환되는 경우,
Figure PCTKR2020017069-appb-I000008
등이 있으나, 이에 한정되지 않는다.When the fluorene group is substituted,
Figure PCTKR2020017069-appb-I000008
and the like, but is not limited thereto.
본 명세서에 있어서, "인접한" 기는 해당 치환기가 치환된 원자와 직접 연결된 원자에 치환된 치환기, 해당 치환기와 입체구조적으로 가장 가깝게 위치한 치환기, 또는 해당 치환기가 치환된 원자에 치환된 다른 치환기를 의미할 수 있다. 예컨대, 벤젠고리에서 오르토(ortho)위치로 치환된 2개의 치환기 및 지방족 고리에서 동일 탄소에 치환된 2개의 치환기는 서로 "인접한" 기로 해석될 수 있다.As used herein, the "adjacent" group refers to a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom in which the substituent is substituted. can For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups.
본 명세서에 있어서, 아릴알킬기는 상기 알킬기가 아릴기로 치환된 것을 의미하며, 상기 아릴알킬기의 아릴기 및 알킬기는 전술한 아릴기 및 알킬기의 예시가 적용될 수 있다.In the present specification, the arylalkyl group means that the alkyl group is substituted with an aryl group, and examples of the aryl group and the alkyl group described above may be applied to the aryl group and the alkyl group of the arylalkyl group.
본 명세서에 있어서, 아릴옥시기는 상기 알콕시기의 정의 중 알콕시기의 알킬기 대신 아릴기로 치환되는 것을 의미하며, 아릴옥시기로는 페녹시기, p-토릴옥시기, m-토릴옥시기, 3,5-디메틸-페녹시기, 2,4,6-트리메틸페녹시기, p-tert-부틸페녹시기, 3-바이페닐옥시기, 4-바이페닐옥시기, 1-나프틸옥시기, 2-나프틸옥시기, 4-메틸-1-나프틸옥시기, 5-메틸-2-나프틸옥시기, 1-안트릴옥시기, 2-안트릴옥시기, 9-안트릴옥시기, 1-페난트릴옥시기, 3-페난트릴옥시기, 9-페난트릴옥시기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryloxy group means substituted with an aryl group instead of an alkyl group of the alkoxy group in the definition of the alkoxy group, and the aryloxy group includes a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5- Dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3-biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4 -Methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group, 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenane a toryloxy group, a 9-phenanthryloxy group, and the like, but is not limited thereto.
본 명세서에 있어서, 알킬티옥시기의 알킬기는 전술한 알킬기의 예시와 같다. 구체적으로 알킬티옥시기로는 메틸티옥시기, 에틸티옥시기, tert－부틸티옥시기, 헥실티옥시기, 옥틸티옥시기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkyl group of the alkyltioxy group is the same as the example of the alkyl group described above. Specifically, the alkyl thiooxy group includes, but is not limited to, methyl thiooxy group, ethyl thiooxy group, tert-butyl thiooxy group, hexyl thiooxy group, octyl thiooxy group, and the like.
본 명세서에 있어서, 아릴티옥시기 중의 아릴기는 전술한 아릴기의 예시와 같다. 구체적으로 아릴티옥시기로는 페닐티옥시기, 2－메틸페닐티옥시기, 4－tert－부틸페닐티옥시기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group in the arylthioxy group is the same as the example of the aryl group described above. Specifically, the arylthioxy group includes, but is not limited to, a phenylthioxy group, a 2-methylphenylthioxy group, a 4-tert-butylphenylthioxy group, and the like.
본 명세서에 있어서, 헤테로고리기는 탄소가 아닌 원자, 이종원자를 1 이상 포함하는 것으로서, 구체적으로 상기 이종 원자는 O, N, Se 및 S 등으로 이루어진 군에서 선택되는 원자를 1 이상 포함할 수 있다. 탄소수는 특별히 한정되지 않으나, 탄소수 2 내지 30인 것이 바람직하며, 상기 헤테로고리기는 단환식 또는 다환식일 수 있다. 헤테로고리기의 예로는 티오펜기, 퓨란기, 피롤기, 이미다졸기, 티아졸기, 옥사졸기, 옥사디아졸기, 피리딘기, 바이피리딘기, 피리미딘기, 트리아진기, 트리아졸기, 아크리딘기, 피리다진기, 피라진기, 퀴놀린기, 퀴나졸린기, 퀴녹살린기, 프탈라진기, 피리도 피리미딘기, 피리도 피라진기, 피라지노 피라진기, 이소퀴놀린기, 인돌기, 카바졸기, 벤즈옥사졸기, 벤즈이미다졸기, 벤조티아졸기, 벤조카바졸기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨란기, 페난트리딘기(phenanthridine), 페난쓰롤린기(phenanthroline), 이소옥사졸기, 티아디아졸기, 디벤조퓨란기, 디벤조실롤기, 페노크산틴기(phenoxathiine), 페녹사진기(phenoxazine), 페노티아진기(phenothiazine), 디하이드로인데노카바졸기, 스피로플루오렌잔텐기, 스피로플루오렌티옥산텐기, 테트라하이드로나프토티오펜기, 테트라하이드로나프토퓨란기, 테트라하이드로벤조티오펜기, 및 테트라하이드로벤조퓨란기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the heterocyclic group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group, a triazole group, an acridine group. , pyridazine group, pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazine group, pyrido pyrimidine group, pyrido pyrazine group, pyrazino pyrazine group, isoquinoline group, indole group, carbazole group, benz Oxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, phenanthridine group, phenanthridine group, phenanthroline group, isoxazole group, thia Diazole group, dibenzofuran group, dibenzosilol group, phenoxanthine group (phenoxathiine), phenoxazine group (phenoxazine), phenothiazine group (phenothiazine), dihydroindenocarbazole group, spirofluorene xanthene group, spirofluorene thioxanthene group, tetrahydronaphthothiophene group, tetrahydronaphthofuran group, tetrahydrobenzothiophene group, and tetrahydrobenzofuran group, but is not limited thereto.
본 명세서 있어서, 상기 실릴기는 알킬실릴기, 아릴실릴기, 알킬아릴실릴기, 헤테로아릴실릴기 등일 수 있다. 상기 알킬실릴기 중 알킬기는 전술한 알킬기의 예시가 적용될 수 있고, 상기 아릴실릴기 중 아릴기는 전술한 아릴기의 예시가 적용될 수 있으며, 상기 알킬아릴실릴기 중의 알킬기 및 아릴기는 상기 알킬기 및 아릴기의 예시가 적용될 수 있고, 상기 헤테로아릴실릴기 중 헤테로아릴기는 상기 헤테로고리기의 예시가 적용될 수 있다.In the present specification, the silyl group may be an alkylsilyl group, an arylsilyl group, an alkylarylsilyl group, a heteroarylsilyl group, or the like. Examples of the above-described alkyl group may be applied to the alkyl group in the alkylsilyl group, the examples of the aryl group may be applied to the aryl group in the arylsilyl group, and the alkyl group and aryl group in the alkylarylsilyl group may include the alkyl group and the aryl group. Examples of can be applied, the heteroaryl group among the heteroarylsilyl group, the examples of the heterocyclic group can be applied.
본 명세서에 있어서, 붕소기는 -BR100R101일 수 있으며, 상기 R100 및 R101은 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 니트릴기; 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기; 및 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기로 이루어진 군으로부터 선택될 수 있다. 상기 붕소기는 구체적으로 트리메틸붕소기, 트리에틸붕소기, t-부틸디메틸붕소기, 트리페닐붕소기, 페닐붕소기 등이 있으나 이에 한정되지 않는다.In the present specification, the boron group may be -BR 100 R 101 , wherein R 100 and R 101 are the same or different, and each independently hydrogen; heavy hydrogen; halogen; nitrile group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And it may be selected from the group consisting of a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms. Specifically, the boron group includes a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like, but is not limited thereto.
본 명세서에 있어서, 아민기는 -NH2, 알킬아민기, N-알킬아릴아민기, 아릴아민기, N-아릴헤테로아릴아민기, N-알킬헤테로아릴아민기, 및 헤테로아릴아민기로 이루어진 군으로부터 선택될 수 있으며, 탄소수는 특별히 한정되지 않으나, 1 내지 30인 것이 바람직하다. 아민기의 구체적인 예로는 메틸아민기, 디메틸아민기, 에틸아민기, 디에틸아민기, 페닐아민기, 나프틸아민기, 바이페닐아민기, 안트라세닐아민기, 9-메틸-안트라세닐아민기, 디페닐아민기, 디톨릴아민기, N-페닐톨릴아민기, 트리페닐아민기, N-페닐바이페닐아민기, N-페닐나프틸아민기, N-바이페닐나프틸아민기; N-나프틸플루오레닐아민기, N-페닐페난트레닐아민기, N-바이페닐페난트레닐아민기, N-페닐플루오레닐아민기, N-페닐터페닐아민기, N-페난트레닐플루오레닐아민기, N-바이페닐플루오레닐아민기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the amine group is -NH 2 , an alkylamine group, an N-alkylarylamine group, an arylamine group, an N-arylheteroarylamine group, an N-alkylheteroarylamine group, and a heteroarylamine group from the group consisting of may be selected, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, and a 9-methyl-anthracenylamine group. , diphenylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-biphenylnaphthylamine group; N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine group, N-phenanthre nylfluorenylamine group, N-biphenylfluorenylamine group, and the like, but is not limited thereto.
본 명세서에 있어서, N-알킬아릴아민기는 아민기의 N에 알킬기 및 아릴기가 치환된 아민기를 의미한다. 상기 N-알킬아릴아민기 중의 알킬기와 아릴기는 전술한 알킬기 및 아릴기의 예시와 같다.In the present specification, the N-alkylarylamine group refers to an amine group in which an alkyl group and an aryl group are substituted with N of the amine group. The alkyl group and the aryl group in the N-alkylarylamine group are the same as the examples of the alkyl group and the aryl group described above.
본 명세서에 있어서, N-아릴헤테로아릴아민기는 아민기의 N에 아릴기 및 헤테로아릴기가 치환된 아민기를 의미한다. 상기 N-아릴헤테로아릴아민기 중의 아릴기와 헤테로아릴기는 전술한 아릴기 및 헤테로고리기의 예시와 같다.In the present specification, the N-arylheteroarylamine group refers to an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group. The aryl group and the heteroaryl group in the N-arylheteroarylamine group are the same as the examples of the above-described aryl group and heterocyclic group.
본 명세서에 있어서, N-알킬헤테로아릴아민기는 아민기의 N에 알킬기 및 헤테로아릴기가 치환된 아민기를 의미한다. 상기 N-알킬헤테로아릴아민기 중의 알킬기와 헤테로아릴기는 전술한 알킬기 및 헤테로고리기의 예시와 같다.In the present specification, the N-alkylheteroarylamine group refers to an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group. The alkyl group and the heteroaryl group in the N-alkylheteroarylamine group are the same as the examples of the above-described alkyl group and heterocyclic group.
본 명세서에 있어서, 알킬아민기의 예로는 치환 또는 비치환된 모노알킬아민기, 또는 치환 또는 비치환된 디알킬아민기가 있다. 상기 알킬아민기 중의 알킬기는 직쇄 또는 분지쇄의 알킬기일 수 있다. 상기 알킬기를 2 이상 포함하는 알킬아민기는 직쇄의 알킬기, 분지쇄의 알킬기, 또는 직쇄의 알킬기와 분지쇄의 알킬기를 동시에 포함할 수 있다. 예컨대, 상기 알킬아민기 중의 알킬기는 전술한 알킬기의 예시 중에서 선택될 수 있다.In the present specification, examples of the alkylamine group include a substituted or unsubstituted monoalkylamine group, or a substituted or unsubstituted dialkylamine group. The alkyl group in the alkylamine group may be a straight-chain or branched alkyl group. The alkylamine group including two or more alkyl groups may include a straight-chain alkyl group, a branched-chain alkyl group, or a straight-chain alkyl group and a branched alkyl group at the same time. For example, the alkyl group in the alkylamine group may be selected from the examples of the alkyl group described above.
본 명세서에 있어서, 헤테로아릴아민기의 예로는 치환 또는 비치환된 모노헤테로아릴아민기, 또는 치환 또는 비치환된 디헤테로아릴아민기가 있다. 상기 헤테로아릴기가 2 이상을 포함하는 헤테로아릴아민기는 단환식 헤테로아릴기, 다환식 헤테로아릴기, 또는 단환식 헤테로아릴기와 다환식 헤테로아릴기를 동시에 포함할 수 있다. 예컨대, 상기 헤테로아릴아민기 중의 헤테로아릴기는 전술한 헤테로고리기의 예시 중에서 선택될 수 있다.In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, or a substituted or unsubstituted diheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heterocyclic group described above.
본 명세서에 있어서, 치환기 중 "인접한 2개는 서로 결합하여 고리를 형성한다"는 의미는 인접한 기와 서로 결합하여 치환 또는 비치환된 탄화수소고리; 또는 치환 또는 비치환된 헤테로고리를 형성하는 것을 의미한다.In the present specification, the meaning of "adjacent two of the substituents combine with each other to form a ring" means a substituted or unsubstituted hydrocarbon ring by bonding with adjacent groups; Or it means to form a substituted or unsubstituted heterocyclic ring.
본 명세서에 있어서, 서로 결합하여 형성되는 치환 또는 비치환된 고리에서, "고리"는 치환 또는 비치환된 탄화수소고리; 또는 치환 또는 비치환된 헤테로고리를 의미한다.In the present specification, in a substituted or unsubstituted ring formed by bonding to each other, "ring" is a substituted or unsubstituted hydrocarbon ring; Or it means a substituted or unsubstituted heterocyclic ring.
본 명세서에 있어서, 탄화수소고리기는 방향족 탄화수소 고리, 지방족 탄화수소고리, 또는 방향족 탄화수소와 지방족 탄화수소의 축합고리기일 수 있으며, 상기 시클로알킬기, 아릴기, 및 이들의 조합의 예시 중에서 선택될 수 있으며, 상기 탄화수소고리기는 페닐기, 시클로헥실기, 아다만틸기, 테트라하이드로나프탈렌기, 테트라하이드로안트라센기 등이 있으나, 이에만 한정되는 것은 아니다In the present specification, the hydrocarbon ring group may be an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, or a condensed ring group of an aromatic hydrocarbon and an aliphatic hydrocarbon, and may be selected from examples of the cycloalkyl group, an aryl group, and combinations thereof, and the hydrocarbon The cyclic group includes, but is not limited to, a phenyl group, a cyclohexyl group, an adamantyl group, a tetrahydronaphthalene group, and a tetrahydroanthracene group.
본 명세서에 있어서, 탄화수소고리는 방향족 탄화수소 고리, 지방족 탄화수소고리, 또는 방향족 탄화수소와 지방족 탄화수소의 축합고리일 수 있으며, 상기 1가가 아닌 것을 제외하고 상기 시클로알킬기 또는 아릴기의 예시 중에서 선택될 수 있으며, 상기 탄화수소고리는 상기 탄화수소고리는 벤젠, 시클로헥산, 아다만탄, 테트라하이드로나프탈렌, 테트라하이드로안트라센 등이 있으나, 이에만 한정되는 것은 아니다.In the present specification, the hydrocarbon ring may be an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, or a condensed ring of an aromatic hydrocarbon and an aliphatic hydrocarbon, and may be selected from among the examples of the cycloalkyl group or the aryl group, except that it is not monovalent. The hydrocarbon ring may include, but is not limited to, benzene, cyclohexane, adamantane, tetrahydronaphthalene, tetrahydroanthracene, and the like.
본 명세서에 있어서, 헤테로고리는 탄소가 아닌 원자, 이종원자를 1 이상 포함하는 것으로서, 구체적으로 상기 이종 원자는 O, N, Se 및 S 등으로 이루어진 군에서 선택되는 원자를 1 이상 포함할 수 있다. 상기 헤테로고리는 단환 또는 다환일 수 있으며, 방향족, 지방족 또는 방향족과 지방족의 축합고리일 수 있으며, 상기 방향족 헤테로고리는 1가가 아닌 것을 제외하고 상기 헤테로고리기의 예시 중에서 선택될 수 있다.In the present specification, the heterocycle includes atoms other than carbon and one or more heteroatoms, specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se and S, and the like. The heterocycle may be monocyclic or polycyclic, and may be an aromatic, aliphatic, or condensed ring of aromatic and aliphatic, and the aromatic heterocycle may be selected from examples of the heterocyclic group, except that it is not monovalent.
본 명세서에 있어서, 지방족 헤테로고리란 헤테로원자 중 1개 이상을 포함하는 지방족 고리를 의미한다. 지방족 헤테로고리의 예로는, 옥시레인(oxirane), 테트라하이드로퓨란, 1,4-디옥세인(1,4-dioxane), 피롤리딘, 피페리딘, 모르폴린(morpholine), 옥세판, 아조케인, 티오케인, 테트라하이드로나프토티오펜, 테트라하이드로나프토퓨란, 테트라하이드로벤조티오펜, 및 테트라하이드로벤조퓨란 등이 있으나, 이에 한정되지 않는다.In the present specification, the aliphatic heterocycle refers to an aliphatic ring including one or more heteroatoms. Examples of aliphatic heterocycles include oxirane, tetrahydrofuran, 1,4-dioxane, pyrrolidine, piperidine, morpholine, oxepane, azocaine , thiocaine, tetrahydronaphthothiophene, tetrahydronaphthofuran, tetrahydrobenzothiophene, and tetrahydrobenzofuran, but are not limited thereto.
본 명세서에 있어서, 아릴렌기는 아릴기에 결합 위치가 두 개 있는 것 즉 2가기를 의미한다. 이들은 각각 2가기인 것을 제외하고는 전술한 아릴기의 설명이 적용될 수 있다.In the present specification, the arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied.
본 명세서에 있어서, 헤테로아릴렌기는 헤테로아릴기에 결합 위치가 두 개 있는 것 즉 2가기를 의미한다. 이들은 각각 2가기인 것을 제외하고는 전술한 헤테로고리기의 설명이 적용될 수 있다.In the present specification, the heteroarylene group means that the heteroaryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the heterocyclic group described above may be applied.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 알킬기로 치환 또는 비치환된 지방족 탄화수소 축합고리를 적어도 하나 포함한다.According to an exemplary embodiment of the present specification, Chemical Formula 1 includes at least one condensed aliphatic hydrocarbon ring substituted or unsubstituted with an alkyl group.
본 명세서의 일 실시상태에 따르면, 상기 A1은 치환 또는 비치환되고 O, 또는 S를 포함하는 5원의 단환 헤테로고리; 또는 치환 또는 비치환되고, O, 또는 S를 포함하는 5원 헤테로고리를 포함하는 다환의 헤테로고리이다.According to an exemplary embodiment of the present specification, A1 is a substituted or unsubstituted 5-membered monocyclic heterocycle including O, or S; Or a substituted or unsubstituted, O, or a polycyclic heterocycle including a 5-membered heterocycle including S.
본 명세서의 일 실시상태에 따르면, 상기 A1은 치환 또는 비치환되고 O, 또는 S를 포함하는 5원의 방향족 또는 지방족의 단환 헤테로고리; 또는 치환 또는 비치환되고, O, 또는 S를 포함하는 5원 헤테로고리를 포함하는 방향족, 지방족 또는 방향족과 지방족의 축합의 다환의 헤테로고리이다.According to an exemplary embodiment of the present specification, A1 is a substituted or unsubstituted 5-membered aromatic or aliphatic monocyclic heterocycle including O, or S; Or a substituted or unsubstituted, aromatic, aliphatic, or polycyclic heterocycle of condensed aromatic and aliphatic containing a 5-membered heterocycle containing O, or S.
본 명세서의 일 실시상태에 따르면, 상기 화학식 A1은 하기 화학식 A1-1 또는 A1-2로 표시된다.According to an exemplary embodiment of the present specification, the Chemical Formula A1 is represented by the following Chemical Formula A1-1 or A1-2.
[화학식 A1-1][Formula A1-1]
Figure PCTKR2020017069-appb-I000009
Figure PCTKR2020017069-appb-I000009
[화학식 A1-2][Formula A1-2]
Figure PCTKR2020017069-appb-I000010
Figure PCTKR2020017069-appb-I000010
상기 화학식 A1-1 및 A1-2에 있어서,In Formulas A1-1 and A1-2,
Y1 및 Y3는 서로 같거나 상이하고, 각각 독립적으로 O; 또는 S이며,Y1 and Y3 are the same as or different from each other, and each independently O; or S;
G1, G2 및 G7 내지 G10은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,G1, G2 and G7 to G10 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted silyl group; A substituted or unsubstituted hydrocarbon ring group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
Figure PCTKR2020017069-appb-I000011
는 상기 화학식 1에 결합되는 부위를 의미한다.
Figure PCTKR2020017069-appb-I000011
denotes a site bound to Formula 1 above.
본 명세서의 일 실시상태에 따르면, 상기 A1은 하기 화학식 A1-3 내지 Al-5 중 어느 하나로 표시되는 구조이다.According to an exemplary embodiment of the present specification, A1 is a structure represented by any one of the following Chemical Formulas A1-3 to Al-5.
[화학식 A1-3][Formula A1-3]
Figure PCTKR2020017069-appb-I000012
Figure PCTKR2020017069-appb-I000012
[화학식 A1-4][Formula A1-4]
Figure PCTKR2020017069-appb-I000013
Figure PCTKR2020017069-appb-I000013
[화학식 A1-5][Formula A1-5]
Figure PCTKR2020017069-appb-I000014
Figure PCTKR2020017069-appb-I000014
상기 화학식 A1-3 내지 A1-5에 있어서,In Formulas A1-3 to A1-5,
Y2, Y4 및 Y5는 서로 같거나 상이하고, 각각 독립적으로 O; 또는 S이며,Y2, Y4 and Y5 are the same as or different from each other, and each independently O; or S;
G3 내지 G6 및 G11 내지 G28은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,G3 to G6 and G11 to G28 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted silyl group; A substituted or unsubstituted hydrocarbon ring group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
n11 및 n12는 각각 0 내지 2의 정수이며,n11 and n12 are each an integer of 0 to 2,
상기 n11 및 n12가 2인 경우, 상기 두 개의 괄호 내의 구조는 서로 같거나 상이하고,When n11 and n12 are 2, the structures in the two parentheses are the same as or different from each other,
Figure PCTKR2020017069-appb-I000015
는 상기 화학식 1에 결합되는 부위를 의미한다.
Figure PCTKR2020017069-appb-I000015
denotes a site bound to Formula 1 above.
본 명세서의 일 실시상태에 따르면, 상기 화학식 A1-1은 하기 화학식 A1-1-1 또는 A1-1-2로 표시된다.According to an exemplary embodiment of the present specification, the Chemical Formula A1-1 is represented by the following Chemical Formula A1-1-1 or A1-1-2.
[화학식 A1-1-1][Formula A1-1-1]
Figure PCTKR2020017069-appb-I000016
Figure PCTKR2020017069-appb-I000016
[화학식 A1-1-2][Formula A1-1-2]
Figure PCTKR2020017069-appb-I000017
Figure PCTKR2020017069-appb-I000017
상기 화학식 A1-1-1 및 A1-1-2에 있어서,In the formulas A1-1-1 and A1-1-2,
Y1은 O; 또는 S이고,Y1 is O; or S;
Z1은 O; S; CR201R202; 또는 NR203이며,Z1 is O; S; CR201R202; or NR203;
G301 내지 G304 및 R201 내지 R203은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,G301 to G304 and R201 to R203 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted silyl group; A substituted or unsubstituted hydrocarbon ring group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
Figure PCTKR2020017069-appb-I000018
는 상기 화학식 1에 결합되는 부위를 의미한다.
Figure PCTKR2020017069-appb-I000018
denotes a site bound to Formula 1 above.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 1-1 내지 1-5 중 어느 하나로 표시된다.According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-5.
[화학식 1-1][Formula 1-1]
Figure PCTKR2020017069-appb-I000019
Figure PCTKR2020017069-appb-I000019
[화학식 1-2][Formula 1-2]
Figure PCTKR2020017069-appb-I000020
Figure PCTKR2020017069-appb-I000020
[화학식 1-3][Formula 1-3]
Figure PCTKR2020017069-appb-I000021
Figure PCTKR2020017069-appb-I000021
[화학식 1-4][Formula 1-4]
Figure PCTKR2020017069-appb-I000022
Figure PCTKR2020017069-appb-I000022
[화학식 1-5][Formula 1-5]
Figure PCTKR2020017069-appb-I000023
Figure PCTKR2020017069-appb-I000023
상기 화학식 1-1 내지 1-5에 있어서,In Formulas 1-1 to 1-5,
R', R" 및 R1 내지 R7의 정의는 상기 화학식 1에서 정의한 바와 동일하고,The definitions of R', R" and R1 to R7 are the same as those defined in Formula 1 above,
Y1 내지 Y5는 서로 같거나 상이하고, 각각 독립적으로 O; 또는 S이며,Y1 to Y5 are the same as or different from each other, and each independently O; or S;
G1 내지 G28은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,G1 to G28 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted silyl group; A substituted or unsubstituted hydrocarbon ring group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
n11 및 n12는 각각 0 내지 2의 정수이며,n11 and n12 are each an integer of 0 to 2,
상기 n11 및 n12가 2인 경우, 상기 두 개의 괄호 내의 구조는 서로 같거나 상이하다.When n11 and n12 are 2, structures within the two parentheses are the same as or different from each other.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 1-1-1, 1-1-2, 1-1-3, 1-1-4, 1-1-5, 1-1-6, 1-2-1, 1-2-2, 1-3-1, 1-3-2, 1-4-1, 1-4-2, 1-5-1 및 1-5-2 중 어느 하나로 표시된다.According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formulas 1-1-1, 1-1-2, 1-1-3, 1-1-4, 1-1-5, 1-1-6 , any of 1-2-1, 1-2-2, 1-3-1, 1-3-2, 1-4-1, 1-4-2, 1-5-1, and 1-5-2 displayed as one
[화학식 1-1-1][Formula 1-1-1]
Figure PCTKR2020017069-appb-I000024
Figure PCTKR2020017069-appb-I000024
[화학식 1-1-2][Formula 1-1-2]
Figure PCTKR2020017069-appb-I000025
Figure PCTKR2020017069-appb-I000025
[화학식 1-1-3][Formula 1-1-3]
Figure PCTKR2020017069-appb-I000026
Figure PCTKR2020017069-appb-I000026
[화학식 1-1-4][Formula 1-1-4]
Figure PCTKR2020017069-appb-I000027
Figure PCTKR2020017069-appb-I000027
[화학식 1-1-5][Formula 1-1-5]
Figure PCTKR2020017069-appb-I000028
Figure PCTKR2020017069-appb-I000028
[화학식 1-1-6][Formula 1-1-6]
Figure PCTKR2020017069-appb-I000029
Figure PCTKR2020017069-appb-I000029
[화학식 1-2-1][Formula 1-2-1]
Figure PCTKR2020017069-appb-I000030
Figure PCTKR2020017069-appb-I000030
[화학식 1-2-2][Formula 1-2-2]
Figure PCTKR2020017069-appb-I000031
Figure PCTKR2020017069-appb-I000031
[화학식 1-3-1][Formula 1-3-1]
Figure PCTKR2020017069-appb-I000032
Figure PCTKR2020017069-appb-I000032
[화학식 1-3-2][Formula 1-3-2]
Figure PCTKR2020017069-appb-I000033
Figure PCTKR2020017069-appb-I000033
[화학식 1-4-1][Formula 1-4-1]
Figure PCTKR2020017069-appb-I000034
Figure PCTKR2020017069-appb-I000034
[화학식 1-4-2][Formula 1-4-2]
Figure PCTKR2020017069-appb-I000035
Figure PCTKR2020017069-appb-I000035
[화학식 1-5-1][Formula 1-5-1]
Figure PCTKR2020017069-appb-I000036
Figure PCTKR2020017069-appb-I000036
[화학식 1-5-2][Formula 1-5-2]
Figure PCTKR2020017069-appb-I000037
Figure PCTKR2020017069-appb-I000037
상기 화학식 1-1-1, 1-1-2, 1-1-3, 1-1-4, 1-1-5, 1-1-6, 1-2-1, 1-2-2, 1-3-1, 1-3-2, 1-4-1, 1-4-2, 1-5-1 및 1-5-2에 있어서,Formula 1-1-1, 1-1-2, 1-1-3, 1-1-4, 1-1-5, 1-1-6, 1-2-1, 1-2-2, In 1-3-1, 1-3-2, 1-4-1, 1-4-2, 1-5-1 and 1-5-2,
R', R" 및 R1 내지 R7의 정의는 상기 화학식 1에서 정의한 바와 동일하고,The definitions of R', R" and R1 to R7 are the same as those defined in Formula 1 above,
Y1 내지 Y5는 서로 같거나 상이하고, 각각 독립적으로 O; 또는 S이며,Y1 to Y5 are the same as or different from each other, and each independently O; or S;
Z1은 O; S; CR201R202; 또는 NR203이며,Z1 is O; S; CR201R202; or NR203;
G1 내지 G28, G301 내지 G304 및 R201 내지 R203은 서로 같거 나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,G1 to G28, G301 to G304 and R201 to R203 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted silyl group; A substituted or unsubstituted hydrocarbon ring group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
n11 및 n12는 각각 0 내지 2의 정수이며,n11 and n12 are each an integer of 0 to 2,
상기 n11 및 n12가 2인 경우, 상기 두 개의 괄호 내의 구조는 서로 같거나 상이하다.When n11 and n12 are 2, structures within the two parentheses are the same as or different from each other.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여, 치환 또는 비치환된 5원의 단환 헤테로고리; 또는 치환 또는 비치환되고, 5원 헤테로고리를 포함하는 다환의 헤테로고리를 형성한다. According to an exemplary embodiment of the present specification, adjacent groups of R1 to R4 may be bonded to each other to form a substituted or unsubstituted 5-membered monocyclic heterocycle; Or substituted or unsubstituted, to form a polycyclic heterocycle including a 5-membered heterocycle.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여, 치환 또는 비치환되고 N, O, 또는 S를 포함하는 5원의 단환 헤테로고리; 또는 치환 또는 비치환되고, N, O, 또는 S를 포함하는 5원 헤테로고리를 포함하는 다환의 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, adjacent groups of R1 to R4 are bonded to each other, a substituted or unsubstituted 5-membered monocyclic heterocycle including N, O, or S; Or substituted or unsubstituted, to form a polycyclic heterocycle including a 5-membered heterocycle including N, O, or S.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여, 치환 또는 비치환되고 N, O, 또는 S를 포함하는 5원의 방향족 또는 지방족의 단환 헤테로고리; 또는 치환 또는 비치환되고, N, O, 또는 S를 포함하는 5원 헤테로고리를 포함하는 방향족, 지방족 또는 방향족과 지방족의 축합의 다환의 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, adjacent groups of R1 to R4 may be bonded to each other, may be substituted or unsubstituted, and may include a 5-membered aromatic or aliphatic monocyclic heterocycle including N, O, or S; Or a substituted or unsubstituted, aromatic, aliphatic, or polycyclic heterocycle containing a 5-membered heterocycle containing N, O, or S is formed by condensation of aromatic and aliphatic.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여, 하기 화학식 B1-1 또는 B1-2로 표시되는 고리를 형성한다.According to an exemplary embodiment of the present specification, adjacent groups of R1 to R4 are bonded to each other to form a ring represented by the following Chemical Formula B1-1 or B1-2.
[화학식 B1-1][Formula B1-1]
Figure PCTKR2020017069-appb-I000038
Figure PCTKR2020017069-appb-I000038
[화학식 B1-2][Formula B1-2]
Figure PCTKR2020017069-appb-I000039
Figure PCTKR2020017069-appb-I000039
상기 화학식 B1-1 및 B1-2에 있어서,In the formulas B1-1 and B1-2,
Y101 및 Y103는 서로 같거나 상이하고, 각각 독립적으로 O; S; 또는 NR"'이며,Y101 and Y103 are the same as or different from each other, and each independently O; S; or NR"';
R"', G101, G102 및 G107 내지 G110은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,R"', G101, G102, and G107 to G110 are the same as or different from each other, and each independently represents hydrogen; deuterium; halogen group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted haloalkyl group; substituted or unsubstituted a cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkylthioxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; substituted or unsubstituted boron group; substituted or unsubstituted amine group; substituted or unsubstituted arylalkyl group; substituted or unsubstituted silyl group; substituted or unsubstituted hydrocarbon ring group; or substituted or or an unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
Figure PCTKR2020017069-appb-I000040
는 상기 화학식 1에 결합되는 부위를 의미한다.
Figure PCTKR2020017069-appb-I000040
denotes a site bound to Formula 1 above.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여, 하기 화학식 B1-3 내지 Bl-5 중 어느 하나로 표시되는 고리를 형성한다.According to an exemplary embodiment of the present specification, adjacent groups of R1 to R4 are bonded to each other to form a ring represented by any one of Formulas B1-3 to Bl-5.
[화학식 B1-3][Formula B1-3]
Figure PCTKR2020017069-appb-I000041
Figure PCTKR2020017069-appb-I000041
[화학식 B1-4][Formula B1-4]
Figure PCTKR2020017069-appb-I000042
Figure PCTKR2020017069-appb-I000042
[화학식 B1-5][Formula B1-5]
Figure PCTKR2020017069-appb-I000043
Figure PCTKR2020017069-appb-I000043
상기 화학식 B1-3 내지 B1-5에 있어서,In the formulas B1-3 to B1-5,
Y102, Y104 및 Y105는 서로 같거나 상이하고, 각각 독립적으로 O; S; 또는 NR"'이며,Y102, Y104 and Y105 are the same as or different from each other, and each independently O; S; or NR"';
R"', G103 내지 G106 및 G111 내지 G128은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,R"', G103 to G106 and G111 to G128 are the same as or different from each other, and each independently represents hydrogen; deuterium; halogen group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted haloalkyl group; substituted or unsubstituted a cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkylthioxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; substituted or unsubstituted boron group; substituted or unsubstituted amine group; substituted or unsubstituted arylalkyl group; substituted or unsubstituted silyl group; substituted or unsubstituted hydrocarbon ring group; or substituted or or an unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
n111 및 n112는 각각 0 내지 2의 정수이며,n111 and n112 are each an integer from 0 to 2,
상기 n111 및 n112가 2인 경우, 상기 두 개의 괄호 내의 구조는 서로 같거나 상이하고,When n111 and n112 are 2, the structures in the two parentheses are the same as or different from each other,
Figure PCTKR2020017069-appb-I000044
는 상기 화학식 1에 결합되는 부위를 의미한다.
Figure PCTKR2020017069-appb-I000044
denotes a site bound to Formula 1 above.
본 명세서의 일 실시상태에 따르면, 상기 화학식 B1-1은 하기 화학식 B1-1-1 또는 B1-1-2로 표시된다.According to an exemplary embodiment of the present specification, the Chemical Formula B1-1 is represented by the following Chemical Formula B1-1-1 or B1-1-2.
[화학식 B1-1-1][Formula B1-1-1]
Figure PCTKR2020017069-appb-I000045
Figure PCTKR2020017069-appb-I000045
[화학식 B1-1-2][Formula B1-1-2]
Figure PCTKR2020017069-appb-I000046
Figure PCTKR2020017069-appb-I000046
상기 화학식 B1-1-1 및 B1-1-2에 있어서,In the formulas B1-1-1 and B1-1-2,
Y101은 O; S; 또는 NR304이고,Y101 is O; S; or NR304;
Z101은 O; S; CR301R302; 또는 NR303이며,Z101 is O; S; CR301R302; or NR303;
G401 내지 G404 및 R301 내지 R304은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,G401 to G404 and R301 to R304 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted silyl group; A substituted or unsubstituted hydrocarbon ring group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
Figure PCTKR2020017069-appb-I000047
는 상기 화학식 1에 결합되는 부위를 의미한다.
Figure PCTKR2020017069-appb-I000047
denotes a site bound to Formula 1 above.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 1-6 내지 1-30 중 어느 하나로 표시된다.According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-6 to 1-30.
[화학식 1-6][Formula 1-6]
Figure PCTKR2020017069-appb-I000048
Figure PCTKR2020017069-appb-I000048
[화학식 1-7][Formula 1-7]
Figure PCTKR2020017069-appb-I000049
Figure PCTKR2020017069-appb-I000049
[화학식 1-8][Formula 1-8]
Figure PCTKR2020017069-appb-I000050
Figure PCTKR2020017069-appb-I000050
[화학식 1-9][Formula 1-9]
Figure PCTKR2020017069-appb-I000051
Figure PCTKR2020017069-appb-I000051
[화학식 1-10][Formula 1-10]
Figure PCTKR2020017069-appb-I000052
Figure PCTKR2020017069-appb-I000052
[화학식 1-11][Formula 1-11]
Figure PCTKR2020017069-appb-I000053
Figure PCTKR2020017069-appb-I000053
[화학식 1-12][Formula 1-12]
Figure PCTKR2020017069-appb-I000054
Figure PCTKR2020017069-appb-I000054
[화학식 1-13][Formula 1-13]
Figure PCTKR2020017069-appb-I000055
Figure PCTKR2020017069-appb-I000055
[화학식 1-14][Formula 1-14]
Figure PCTKR2020017069-appb-I000056
Figure PCTKR2020017069-appb-I000056
[화학식 1-15][Formula 1-15]
Figure PCTKR2020017069-appb-I000057
Figure PCTKR2020017069-appb-I000057
[화학식 1-16][Formula 1-16]
Figure PCTKR2020017069-appb-I000058
Figure PCTKR2020017069-appb-I000058
[화학식 1-17][Formula 1-17]
Figure PCTKR2020017069-appb-I000059
Figure PCTKR2020017069-appb-I000059
[화학식 1-18][Formula 1-18]
Figure PCTKR2020017069-appb-I000060
Figure PCTKR2020017069-appb-I000060
[화학식 1-19][Formula 1-19]
Figure PCTKR2020017069-appb-I000061
Figure PCTKR2020017069-appb-I000061
[화학식 1-20][Formula 1-20]
Figure PCTKR2020017069-appb-I000062
Figure PCTKR2020017069-appb-I000062
[화학식 1-21][Formula 1-21]
Figure PCTKR2020017069-appb-I000063
Figure PCTKR2020017069-appb-I000063
[화학식 1-22][Formula 1-22]
Figure PCTKR2020017069-appb-I000064
Figure PCTKR2020017069-appb-I000064
[화학식 1-23][Formula 1-23]
Figure PCTKR2020017069-appb-I000065
Figure PCTKR2020017069-appb-I000065
[화학식 1-24][Formula 1-24]
Figure PCTKR2020017069-appb-I000066
Figure PCTKR2020017069-appb-I000066
[화학식 1-25][Formula 1-25]
Figure PCTKR2020017069-appb-I000067
Figure PCTKR2020017069-appb-I000067
[화학식 1-26][Formula 1-26]
Figure PCTKR2020017069-appb-I000068
Figure PCTKR2020017069-appb-I000068
[화학식 1-27][Formula 1-27]
Figure PCTKR2020017069-appb-I000069
Figure PCTKR2020017069-appb-I000069
[화학식 1-28][Formula 1-28]
Figure PCTKR2020017069-appb-I000070
Figure PCTKR2020017069-appb-I000070
[화학식 1-29][Formula 1-29]
Figure PCTKR2020017069-appb-I000071
Figure PCTKR2020017069-appb-I000071
[화학식 1-30][Formula 1-30]
Figure PCTKR2020017069-appb-I000072
Figure PCTKR2020017069-appb-I000072
상기 화학식 1-6 내지 1-30에 있어서,In Formulas 1-6 to 1-30,
R', R" 및 R1 내지 R7의 정의는 상기 화학식 1에서 정의한 바와 동일하고,The definitions of R', R" and R1 to R7 are the same as those defined in Formula 1 above,
Y1 내지 Y5는 서로 같거나 상이하고, 각각 독립적으로 O; 또는 S이고,Y1 to Y5 are the same as or different from each other, and each independently O; or S;
Y101 내지 Y105는 서로 같거나 상이하고, 각각 독립적으로 O; S; 또는 NR"'이며,Y101 to Y105 are the same as or different from each other, and each independently O; S; or NR"';
R"', R101, G1 내지 G28 및 G101 내지 G128은 서로 같거 나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,R"', R101, G1 to G28 and G101 to G128 are the same as or different from each other, and each independently represents hydrogen; deuterium; halogen group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted haloalkyl group; substituted or an unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkylthioxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; A substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted hydrocarbon ring group; or A substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
n11, n12, n111 및 n112는 각각 0 내지 2의 정수이며,n11, n12, n111 and n112 are each an integer from 0 to 2,
r101은 1 또는 2이며,r101 is 1 or 2,
상기 r101, n11, n12, n111 및 n112이 2인 경우, 상기 2개의 괄호 내의 구조는 서로 같거나 상이하다.When r101, n11, n12, n111, and n112 are 2, structures within the two parentheses are the same as or different from each other.
본 명세서의 일 실시상태에 따르면, 상기 Y2는 O 또는 S이다.According to an exemplary embodiment of the present specification, Y2 is O or S.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4 중 인접한 기가 서로 치환 또는 비치환된 고리를 형성하지 않는 기는 수소이다.According to an exemplary embodiment of the present specification, a group in which adjacent groups of R1 to R4 do not form a substituted or unsubstituted ring with each other is hydrogen.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4는 수소이다.According to an exemplary embodiment of the present specification, R1 to R4 are hydrogen.
본 명세서의 일 실시상태에 따르면, 상기 R101은 수소이다.According to an exemplary embodiment of the present specification, R101 is hydrogen.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R7은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 시아노기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알킬기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알콕시기; 치환 또는 비치환된 탄소수 6 내지 30의 아릴알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 디아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단화 또는 다환의 헤테로고리기이다.According to an exemplary embodiment of the present specification, R1 to R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkylsilyl group; a substituted or unsubstituted C1-C30 linear or branched haloalkyl group; a substituted or unsubstituted C1-C30 linear or branched haloalkoxy group; a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic diarylamine group having 6 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R7은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 시아노기; 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기; 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알킬기; 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알콕시기; 탄소수 6 내지 30의 아릴알킬기; 탄소수 6 내지 30의 단환 또는 다환의 디아릴아민기; 탄소수 6 내지 30의 단환 또는 다환의 아릴기; 또는 탄소수 2 내지 30의 단화 또는 다환의 헤테로고리기이고, 상기 치환기는 중수소, 할로겐기, 시아노기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기, 탄소수 6 내지 30의 단환 또는 다환의 아릴기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, R1 to R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a linear or branched alkylsilyl group having 1 to 30 carbon atoms; a linear or branched haloalkyl group having 1 to 30 carbon atoms; a linear or branched haloalkoxy group having 1 to 30 carbon atoms; an arylalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic diarylamine group having 6 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, and the substituents are deuterium, a halogen group, a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkylsilyl having 1 to 30 carbon atoms. It is substituted or unsubstituted with one or more selected from the group consisting of a group, a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, and combinations thereof.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R7은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 시아노기; 메틸기; tert-부틸기; -CD3; -CF3; -OCF3; 큐밀기; 트리메틸실릴기; 디페닐아민기; 시클로헥실기; 페닐기; 아다만틸기; 또는 카바졸기이고, 상기 치환기는 중수소, -F, 시아노기, 메틸기, 트리메틸실릴기, tert-부틸기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, R1 to R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; methyl group; tert-butyl group; -CD 3 ; -CF 3 ; -OCF 3 ; queuing; trimethylsilyl group; diphenylamine group; cyclohexyl group; phenyl group; adamantyl group; or a carbazole group, and the substituent is unsubstituted or substituted with one or more selected from the group consisting of deuterium, -F, a cyano group, a methyl group, a trimethylsilyl group, a tert-butyl group, and combinations thereof.
본 명세서의 일 실시상태에 따르면, 상기 R6은 중수소; 시아노기; 메틸기; tert-부틸기; -CD3; -CF3; -OCF3; 큐밀기; 트리메틸실릴기; 디페닐아민기; 시클로헥실기; 페닐기; 아다만틸기; 또는 카바졸기이고, 상기 치환기는 중수소, -F, 시아노기, 메틸기, 트리메틸실릴기, tert-부틸기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, R6 is deuterium; cyano group; methyl group; tert-butyl group; -CD 3 ; -CF 3 ; -OCF 3 ; queuing; trimethylsilyl group; diphenylamine group; cyclohexyl group; phenyl group; adamantyl group; or a carbazole group, and the substituent is unsubstituted or substituted with one or more selected from the group consisting of deuterium, -F, a cyano group, a methyl group, a trimethylsilyl group, a tert-butyl group, and combinations thereof.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1의 코어인 보론 코어의 파라(para)위치인 R6에 작용기가 치환되는 경우, 상기 화합물 내에서 전자가 부족한 헤테로 원자인 보론에 전자를 공여하여 화합물의 안정성을 높여줄 수 있으며, 효과적으로 HOMO 및 LUMO 에너지 준위를 적절하게 조절하여 화합물의 광학적 특성을 조절하기 용이하다.According to an exemplary embodiment of the present specification, when a functional group is substituted in R6, which is the para position of the boron core, which is the core of Formula 1, electrons are donated to boron, which is a hetero atom lacking electrons in the compound, It can increase stability, and it is easy to control the optical properties of the compound by effectively controlling the HOMO and LUMO energy levels appropriately.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R5 및 R7은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 시아노기; 메틸기; tert-부틸기; -CD3; -CF3; -OCF3; 큐밀기; 트리메틸실릴기; 디페닐아민기; 시클로헥실기; 페닐기; 아다만틸기; 또는 카바졸기이고, 상기 치환기는 중수소, -F, 시아노기, 메틸기, 트리메틸실릴기, tert-부틸기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, R1 to R5 and R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; methyl group; tert-butyl group; -CD 3 ; -CF 3 ; -OCF 3 ; queuing; trimethylsilyl group; diphenylamine group; cyclohexyl group; phenyl group; adamantyl group; or a carbazole group, and the substituent is unsubstituted or substituted with one or more selected from the group consisting of deuterium, -F, a cyano group, a methyl group, a trimethylsilyl group, a tert-butyl group, and combinations thereof.
상기 큐밀기는
Figure PCTKR2020017069-appb-I000073
를 의미한다.The cumulus
Figure PCTKR2020017069-appb-I000073
means
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R7은 서로 같거나 상이하고, 각각 독립적으로 하기 Group C의 구조 중 어느 하나로 표시되는 기이다.According to an exemplary embodiment of the present specification, R1 to R7 are the same as or different from each other, and are each independently a group represented by any one of the structures of Group C below.
<Group C><Group C>
Figure PCTKR2020017069-appb-I000074
Figure PCTKR2020017069-appb-I000074
상기 구조에 있어서, In the structure,
R10 및 R11은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,R10 and R11 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
r10은 1 내지 10의 정수이며, r10 is an integer from 1 to 10,
r11은 1 내지 8의 정수이고,r11 is an integer from 1 to 8;
상기 r10 및 r11이 각각 2 이상인 경우, 2 이상의 괄호내의 구조는 서로 같거나 상이하며,When r10 and r11 are each 2 or more, the structures in parentheses of 2 or more are the same as or different from each other,
r1은 0 또는 1이고,r1 is 0 or 1,
r2는 0 또는 1이며,r2 is 0 or 1,
Figure PCTKR2020017069-appb-I000075
는 상기 화학식 1에 결합되는 부위이다.
Figure PCTKR2020017069-appb-I000075
is a site bound to Formula 1 above.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R7은 서로 같거나 상이하고, 각각 독립적으로 하기 Group D의 구조 중 어느 하나로 표시되는 기이다.According to an exemplary embodiment of the present specification, R1 to R7 are the same as or different from each other, and are each independently a group represented by any one of the structures of Group D below.
<Group D><Group D>
Figure PCTKR2020017069-appb-I000076
Figure PCTKR2020017069-appb-I000076
상기 구조에 있어서, In the structure,
R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고,R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
r100, r101, r108 및 r109은 각각 1 내지 8의 정수이고,r100, r101, r108 and r109 are each an integer from 1 to 8;
r102 및 r107는 각각 1 내지 12의 정수이며,r102 and r107 are each an integer from 1 to 12,
r103 및 r104는 각각 1 내지 10의 정수이고,r103 and r104 are each an integer from 1 to 10,
r105는 1 내지 6의 정수이며,r105 is an integer from 1 to 6,
r106 및 r110 내지 r113는 각각 1 내지 4의 정수이며,r106 and r110 to r113 are each an integer of 1 to 4,
r114는 1 내지 14의 정수이고,r114 is an integer from 1 to 14;
r115는 1 내지 18의 정수이며,r115 is an integer from 1 to 18,
상기 r100 내지 r115가 각각 2 이상인 경우, 상기 2 이상의 괄호 내의 구조는 서로 같거나 상이하며,When each of the r100 to r115 is 2 or more, the structures in the two or more parentheses are the same as or different from each other,
Figure PCTKR2020017069-appb-I000077
는 상기 화학식 1에 결합되는 부위이다.
Figure PCTKR2020017069-appb-I000077
is a site bound to Formula 1 above.
본 명세서의 일 실시상태에 따르면, 상기 Group D에서 상기 R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 실릴기; 또는 치환 또는 비치환된 아릴기이다.According to an exemplary embodiment of the present specification, in Group D, R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; or a substituted or unsubstituted aryl group.
본 명세서의 일 실시상태에 따르면, 상기 Group D에서 상기 R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기; 또는 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기이다.According to an exemplary embodiment of the present specification, in Group D, R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkylsilyl group; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 Group D에서 상기 R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 3 내지 20의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬실릴기; 또는 치환 또는 비치환된 탄소수 6 내지 20의 단환 또는 다환의 아릴기이다.According to an exemplary embodiment of the present specification, in Group D, R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C20 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted C1-C20 linear or branched alkylsilyl group; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 Group D에서 상기 R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 중수소로 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 중수소로 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 중수소로 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기; 또는 중수소로 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기이다.According to an exemplary embodiment of the present specification, in Group D, R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a linear or branched alkyl group having 1 to 30 carbon atoms substituted or unsubstituted with deuterium; a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms that is unsubstituted or substituted with deuterium; a linear or branched alkylsilyl group having 1 to 30 carbon atoms that is unsubstituted or substituted with deuterium; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms that is unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 따르면, 상기 Group D에서 상기 R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 중수소로 치환 또는 비치환된 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬기; 중수소로 치환 또는 비치환된 탄소수 3 내지 20의 단환 또는 다환의 시클로알킬기; 중수소로 치환 또는 비치환된 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬실릴기; 또는 중수소로 치환 또는 비치환된 탄소수 6 내지 20의 단환 또는 다환의 아릴기이다.According to an exemplary embodiment of the present specification, in Group D, R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a linear or branched alkyl group having 1 to 20 carbon atoms that is unsubstituted or substituted with deuterium; a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms that is unsubstituted or substituted with deuterium; a linear or branched alkylsilyl group having 1 to 20 carbon atoms that is unsubstituted or substituted with deuterium; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms that is unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 따르면, 상기 Group D에서 상기 R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 메틸기; -CD3; tert-부틸기; 시클로헥실기; 트리메틸 실릴기; 또는 중수소로 치환 또는 비치환된 페닐기이다.According to an exemplary embodiment of the present specification, in Group D, R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; methyl group; -CD 3 ; tert-butyl group; cyclohexyl group; trimethyl silyl group; Or a phenyl group unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여 치환 또는 비치환된 탄화수소고리; 또는 치환 또는 비치환된 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, adjacent groups of R1 to R4 are bonded to each other to form a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted heterocycle is formed.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 탄화수소고리; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, adjacent groups of R1 to R4 are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocycle having 2 to 30 carbon atoms is formed.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 지방족, 방향족, 또는 지방족 및 방향족 축합 탄화수소고리; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 지방족 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, adjacent groups of R1 to R4 are bonded to each other and include a substituted or unsubstituted monocyclic or polycyclic aliphatic, aromatic, or aliphatic and aromatic condensed hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic aliphatic heterocycle having 2 to 30 carbon atoms is formed.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여 탄소수 3 내지 30의 단환 또는 다환의 지방족, 방향족, 또는 지방족 및 방향족 축합 탄화수소고리; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 지방족 헤테로고리를 형성하고, 상기 고리는 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기, 및 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알킬기로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, adjacent groups of R1 to R4 are bonded to each other to form a monocyclic or polycyclic aliphatic, aromatic, or aliphatic and aromatic condensed hydrocarbon ring having 3 to 30 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic aliphatic heterocycle having 2 to 30 carbon atoms, wherein the ring is a linear or branched alkyl group having 1 to 30 carbon atoms, and a linear or branched haloalkyl group having 1 to 30 carbon atoms It is substituted or unsubstituted with one or more selected from the group consisting of.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여 시클로펜탄고리; 시클로헥산고리; 시클로헵탄고리; 바이시클로[2.2.1]옥탄고리; 노보넨(norbornane)고리; 아다만탄고리; 인덴고리; 페난트렌고리; 테트라하이드로퓨란고리; 테트라하이드로티오펜고리; 피롤리딘고리; 테트라하이드로벤조퓨란고리; 테트라하이드로벤조티오펜고리; 옥타하이드로벤조퓨란고리; 옥타하이드로벤조티오펜고리; 옥타하이드로시클로헵타인돌고리; 옥타하이드로헵타피롤고리; 옥타하이드로인덴고리; 벤젠고리; 페난트렌고리; 벤조퓨란고리; 플루오렌고리; 디하이드로아크리딘고리; 테트라하이드로퀴놀린고리; 디하이드로안트라센고리; 크로멘(chroman)고리; 카바졸고리; 또는 인돌로카바졸고리를 형성하고, 상기 고리는 메틸기, tert-부틸기, 및 -CF3로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, adjacent groups of R1 to R4 are bonded to each other to form a cyclopentane ring; cyclohexane ring; cycloheptane ring; bicyclo[2.2.1]octane ring; norbornane ring; adamantane ring; indene ring; phenanthrene ring; tetrahydrofuran ring; tetrahydrothiophene ring; pyrrolidine ring; tetrahydrobenzofuran ring; tetrahydrobenzothiophene ring; octahydrobenzofuran ring; octahydrobenzothiophene ring; octahydrocycloheptaindole ring; octahydroheptapyrrole ring; octahydroindene ring; benzene ring; phenanthrene ring; benzofuran ring; fluorene ring; dihydroacridine ring; tetrahydroquinoline ring; dihydroanthracene ring; chroman ring; carbazole ring; Or an indolocarbazole ring is formed, and the ring is unsubstituted or substituted with one or more selected from the group consisting of a methyl group, a tert-butyl group, and -CF 3 .
본 명세서의 일 실시상태에 따르면, 상기 R'는 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 아릴알킬기; 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 탄화수소고리기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기이다.According to an exemplary embodiment of the present specification, R' is a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 R'는 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 탄소수 6 내지 30의 아릴알킬기; 탄소수 3 내지 30의 단환 또는 다환의 탄화수소고리기; 또는 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기이며, 상기 치환기는 중수소, 할로겐기, 시아노기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기, 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기, 탄소수 3 내지 30의 아릴실릴기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알콕시기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알킬기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알콕시기, 탄소수 6 내지 30의 아릴옥시기, 탄소수 6 내지 30의 단환 또는 다환의 아릴알킬기, 탄소수 6 내지 30의 단환 또는 다환의 디아릴아민기, 탄소수 6 내지 30의 단환 또는 다환의 아릴기, 탄소수 2 내지 30의 단화 또는 다환의 헤테로고리기, 탄소수 6 내지 30의 단환 또는 다환의 방향족 탄화수소와 탄소수 3 내지 30의 단환 또는 다환의 지방족 탄화수소의 축합고리기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, R' is a linear or branched alkyl group having 1 to 30 carbon atoms; an arylalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic hydrocarbon ring group having 3 to 30 carbon atoms; or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, the substituents being deuterium, a halogen group, a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms, A linear or branched alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 3 to 30 carbon atoms, a linear or branched alkoxy group having 1 to 30 carbon atoms, a linear or branched haloalkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms A linear or branched haloalkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, a monocyclic or polycyclic arylalkyl group having 6 to 30 carbon atoms, a monocyclic or polycyclic diarylamine group having 6 to 30 carbon atoms, and 6 carbon atoms to 30 monocyclic or polycyclic aryl group, monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, condensed ring group of monocyclic or polycyclic aromatic hydrocarbon having 6 to 30 carbon atoms and monocyclic or polycyclic aliphatic hydrocarbon having 3 to 30 carbon atoms , and is unsubstituted or substituted with one or more selected from the group consisting of combinations thereof.
본 명세서의 일 실시상태에 따르면, 상기 R'는 메틸기; tert-부틸기; 페닐기; 바이페닐기; 터페닐기; 나프틸기; 플루오렌기; 트리페닐렌기; 디벤조퓨란기; 큐밀(cumyl)기; 아다만틸기; 테트라하이드로나프틸기; 또는 헥사하이드로디벤조퓨란기이고, 상기 치환기는 중수소, F, 시아노기, 메틸기, tert-부틸기, -CD3, -CF3, -OCF3, 시클로헥실기, 페닐기, 디페닐아민기, 피리딘기, 피리미딘기, 메톡시기, i-프로필기, 페녹시기, 트리페닐실릴기, 트리메틸실릴기, 테트라하이드로나프틸기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, R' is a methyl group; tert-butyl group; phenyl group; biphenyl group; terphenyl group; naphthyl group; fluorene group; triphenylene group; dibenzofuran group; cumyl group; adamantyl group; tetrahydronaphthyl group; or a hexahydrodibenzofuran group, and the substituents are deuterium, F, cyano group, methyl group, tert-butyl group, -CD 3 , -CF 3 , -OCF 3 , cyclohexyl group, phenyl group, diphenylamine group, pyridine It is unsubstituted or substituted with one or more selected from the group consisting of a group, a pyrimidine group, a methoxy group, an i-propyl group, a phenoxy group, a triphenylsilyl group, a trimethylsilyl group, a tetrahydronaphthyl group, and combinations thereof.
본 명세서의 일 실시상태에 따르면, 상기 R"는 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 아릴알킬기; 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 탄화수소고리기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기이다.According to an exemplary embodiment of the present specification, R" is a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms; substituted or unsubstituted C3 to 30 monocyclic or polycyclic hydrocarbon ring group, or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 R"는 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 탄소수 6 내지 30의 아릴알킬기; 탄소수 3 내지 30의 단환 또는 다환의 탄화수소고리기; 또는 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기이며, 상기 치환기는 중수소, 할로겐기, 시아노기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기, 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기, 탄소수 3 내지 30의 아릴실릴기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알콕시기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알킬기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알콕시기, 탄소수 6 내지 30의 아릴옥시기, 탄소수 6 내지 30의 단환 또는 다환의 아릴알킬기, 탄소수 6 내지 30의 단환 또는 다환의 디아릴아민기, 탄소수 6 내지 30의 단환 또는 다환의 아릴기, 탄소수 2 내지 30의 단화 또는 다환의 헤테로고리기, 탄소수 3 내지 30의 단환 또는 다환의 지방족 및 탄소수 6 내지 30의 단환 또는 다환의 방향족 축합 탄화수소고리기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, R" is a linear or branched alkyl group having 1 to 30 carbon atoms; an arylalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic hydrocarbon ring group having 3 to 30 carbon atoms; or 2 to carbon atoms 30 is a monocyclic or polycyclic heterocyclic group, and the substituents are deuterium, a halogen group, a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms, and a cycloalkyl group having 1 to 30 carbon atoms. of a linear or branched alkylsilyl group, an arylsilyl group having 3 to 30 carbon atoms, a straight or branched chain alkoxy group having 1 to 30 carbon atoms, a straight or branched chain haloalkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms A linear or branched haloalkoxy group, an aryloxy group having 6 to 30 carbon atoms, a monocyclic or polycyclic arylalkyl group having 6 to 30 carbon atoms, a monocyclic or polycyclic diarylamine group having 6 to 30 carbon atoms, a monocyclic group having 6 to 30 carbon atoms Or a polycyclic aryl group, a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, a monocyclic or polycyclic aliphatic group having 3 to 30 carbon atoms, and a monocyclic or polycyclic aromatic condensed hydrocarbon ring group having 6 to 30 carbon atoms, and combinations thereof It is substituted or unsubstituted with one or more selected from the group consisting of.
본 명세서의 일 실시상태에 따르면, 상기 R"는 메틸기; tert-부틸기; 페닐기; 바이페닐기; 터페닐기; 나프틸기; 플루오렌기; 트리페닐렌기; 디벤조퓨란기; 큐밀(cumyl)기; 아다만틸기; 테트라하이드로나프틸기; 또는 헥사하이드로디벤조퓨란기이고, 상기 치환기는 중수소, F, 시아노기, 메틸기, tert-부틸기, -CD3, -CF3, -OCF3, 시클로헥실기, 페닐기, 디페닐아민기, 피리딘기, 피리미딘기, 메톡시기, i-프로필기, 페녹시기, 트리페닐실릴기, 트리메틸실릴기, 테트라하이드로나프틸기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, R" is a methyl group; a tert-butyl group; a phenyl group; a biphenyl group; a terphenyl group; a naphthyl group; a fluorene group; a triphenylene group; a dibenzofuran group; a cumyl group; adamantyl group; tetrahydronaphthyl group; or hexahydrodibenzofuran group, wherein the substituents are deuterium, F, cyano group, methyl group, tert-butyl group, -CD 3 , -CF 3 , -OCF 3 , cyclohexyl group , a phenyl group, a diphenylamine group, a pyridine group, a pyrimidine group, a methoxy group, an i-propyl group, a phenoxy group, a triphenylsilyl group, a trimethylsilyl group, a tetrahydronaphthyl group, and combinations thereof. It is substituted or unsubstituted by one or more.
본 명세서의 일 실시상태에 따르면, 상기 Y1은 O이다.According to an exemplary embodiment of the present specification, Y1 is O.
본 명세서의 일 실시상태에 따르면, 상기 Y1은 S이다.According to an exemplary embodiment of the present specification, Y1 is S.
본 명세서의 일 실시상태에 따르면, 상기 Y2은 O이다.According to an exemplary embodiment of the present specification, Y2 is O.
본 명세서의 일 실시상태에 따르면, 상기 Y2은 S이다.According to an exemplary embodiment of the present specification, Y2 is S.
본 명세서의 일 실시상태에 따르면, 상기 Y3은 O이다.According to an exemplary embodiment of the present specification, Y3 is O.
본 명세서의 일 실시상태에 따르면, 상기 Y3은 S이다.According to an exemplary embodiment of the present specification, Y3 is S.
본 명세서의 일 실시상태에 따르면, 상기 Y4은 O이다.According to an exemplary embodiment of the present specification, Y4 is O.
본 명세서의 일 실시상태에 따르면, 상기 Y4은 S이다.According to an exemplary embodiment of the present specification, Y4 is S.
본 명세서의 일 실시상태에 따르면, 상기 Y5은 O이다.According to an exemplary embodiment of the present specification, Y5 is O.
본 명세서의 일 실시상태에 따르면, 상기 Y5은 S이다.According to an exemplary embodiment of the present specification, Y5 is S.
본 명세서의 일 실시상태에 따르면, 상기 Y101은 O이다.According to an exemplary embodiment of the present specification, Y101 is O.
본 명세서의 일 실시상태에 따르면, 상기 Y101은 S이다.According to an exemplary embodiment of the present specification, Y101 is S.
본 명세서의 일 실시상태에 따르면, 상기 Y101은 NR"'이다.According to an exemplary embodiment of the present specification, Y101 is NR"'.
본 명세서의 일 실시상태에 따르면, 상기 Y102은 O이다.According to an exemplary embodiment of the present specification, Y102 is O.
본 명세서의 일 실시상태에 따르면, 상기 Y102은 S이다.According to an exemplary embodiment of the present specification, Y102 is S.
본 명세서의 일 실시상태에 따르면, 상기 Y102은 NR"'이다.According to an exemplary embodiment of the present specification, Y102 is NR"'.
본 명세서의 일 실시상태에 따르면, 상기 Y103은 O이다.According to an exemplary embodiment of the present specification, Y103 is O.
본 명세서의 일 실시상태에 따르면, 상기 Y103은 S이다.According to an exemplary embodiment of the present specification, Y103 is S.
본 명세서의 일 실시상태에 따르면, 상기 Y103은 NR"'이다.According to an exemplary embodiment of the present specification, Y103 is NR"'.
본 명세서의 일 실시상태에 따르면, 상기 Y104은 O이다.According to an exemplary embodiment of the present specification, Y104 is O.
본 명세서의 일 실시상태에 따르면, 상기 Y104은 S이다.According to an exemplary embodiment of the present specification, Y104 is S.
본 명세서의 일 실시상태에 따르면, 상기 Y104은 NR"'이다.According to an exemplary embodiment of the present specification, Y104 is NR"'.
본 명세서의 일 실시상태에 따르면, 상기 Y105은 O이다.According to an exemplary embodiment of the present specification, Y105 is O.
본 명세서의 일 실시상태에 따르면, 상기 Y105은 S이다.According to an exemplary embodiment of the present specification, Y105 is S.
본 명세서의 일 실시상태에 따르면, 상기 Y105은 NR"'이다.According to an exemplary embodiment of the present specification, Y105 is NR"'.
본 명세서의 일 실시상태에 따르면, 상기 R1 및 G2는 서로 결합하여 치환 또는 비치환된 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, R1 and G2 are combined with each other to form a substituted or unsubstituted heterocycle.
본 명세서의 일 실시상태에 따르면, 상기 R1 및 G2는 서로 결합하여 치환 또는 비치환된 B 및 N을 포함하는 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, R1 and G2 are combined with each other to form a heterocycle including substituted or unsubstituted B and N.
본 명세서의 일 실시상태에 따르면, 상기 R1 및 G2는 서로 결합하여 치환 또는 비치환된 B 및 N을 포함하는 6원 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, R1 and G2 are combined with each other to form a 6-membered heterocycle including substituted or unsubstituted B and N.
본 명세서의 일 실시상태에 따르면, 상기 R1 및 G2는 서로 결합하여 아릴기로 치환된 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, R1 and G2 are combined with each other to form a heterocycle substituted with an aryl group.
본 명세서의 일 실시상태에 따르면, 상기 R1 및 G2는 서로 결합하여 아릴기로 치환된 B 및 N을 포함하는 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, R1 and G2 are combined with each other to form a heterocycle including B and N substituted with an aryl group.
본 명세서의 일 실시상태에 따르면, 상기 R1 및 G2는 서로 결합하여 페닐기로 치환된 B 및 Si을 포함하는 6원 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, R1 and G2 are combined with each other to form a 6-membered heterocycle including B and Si substituted with a phenyl group.
본 명세서의 일 실시상태에 따르면, 상기 R4 및 R'은 서로 결합하여, 하기 Group A로 표시되는 구조 중 어느 하나의 고리를 형성한다.According to an exemplary embodiment of the present specification, R4 and R' are bonded to each other to form a ring in any one of the structures represented by the following Group A.
<Group A><Group A>
Figure PCTKR2020017069-appb-I000078
Figure PCTKR2020017069-appb-I000078
상기 구조에 있어서, In the structure,
R10 내지 R14은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,R10 to R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
r10은 1 내지 10의 정수이며, r10 is an integer from 1 to 10,
r11은 1 내지 8의 정수이고,r11 is an integer from 1 to 8;
r12는 1 내지 6의 정수이며,r12 is an integer from 1 to 6,
상기 r10 내지 r12가 각각 2 이상인 경우, 2 이상의 괄호내의 구조는 서로 같거나 상이하며,When each of the r10 to r12 is 2 or more, the structures in the two or more parentheses are the same as or different from each other,
r1은 0 또는 1이고,r1 is 0 or 1,
r2는 0 또는 1이다.r2 is 0 or 1.
본 명세서의 일 실시상태에 따르면, 상기 R4 및 R'은 서로 결합하여, 하기 Group B로 표시되는 구조 중 어느 하나의 고리를 형성한다.According to an exemplary embodiment of the present specification, R4 and R' combine with each other to form a ring in any one of the structures represented by Group B below.
<Group B><Group B>
Figure PCTKR2020017069-appb-I000079
Figure PCTKR2020017069-appb-I000079
상기 구조에 있어서, In the structure,
R100 내지 R120는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고,R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
r100, r101, r108, r109 및 r116 내지 r118은 각각 1 내지 8의 정수이고,r100, r101, r108, r109 and r116 to r118 are each an integer of 1 to 8;
r102 및 r107는 각각1 내지 12의 정수이며,r102 and r107 are each an integer of 1 to 12,
r103 및 r104는 각각 1 내지 10의 정수이고,r103 and r104 are each an integer from 1 to 10,
r105는 1 내지 6의 정수이며,r105 is an integer from 1 to 6,
r106 및 r110 내지 r113는 각각 1 내지 4의 정수이며,r106 and r110 to r113 are each an integer of 1 to 4,
r114는 1 내지 14의 정수이고,r114 is an integer from 1 to 14;
r115는 1 내지 18의 정수이며,r115 is an integer from 1 to 18,
상기 r100 내지 r118이 각각 2 이상인 경우, 상기 2 이상의 괄호 내의 구조는 서로 같거나 상이하다.When each of r100 to r118 is two or more, the structures in the two or more parentheses are the same as or different from each other.
본 명세서의 일 실시상태에 따르면, 상기 Group B에서 상기 R100 내지 R120은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 실릴기; 또는 치환 또는 비치환된 아릴기이다.According to an exemplary embodiment of the present specification, in Group B, R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; or a substituted or unsubstituted aryl group.
본 명세서의 일 실시상태에 따르면, 상기 Group B에서 상기 R100 내지 R120은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기; 또는 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기이다.According to an exemplary embodiment of the present specification, in Group B, R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkylsilyl group; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 Group B에서 상기 R100 내지 R120은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 3 내지 20의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬실릴기; 또는 치환 또는 비치환된 탄소수 6 내지 20의 단환 또는 다환의 아릴기이다.According to an exemplary embodiment of the present specification, in Group B, R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C20 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted C1-C20 linear or branched alkylsilyl group; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 Group B에서 상기 R100 내지 R120은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 중수소로 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 중수소로 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 중수소로 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기; 또는 중수소로 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기이다.According to an exemplary embodiment of the present specification, in Group B, R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a linear or branched alkyl group having 1 to 30 carbon atoms substituted or unsubstituted with deuterium; a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms that is unsubstituted or substituted with deuterium; a linear or branched alkylsilyl group having 1 to 30 carbon atoms that is unsubstituted or substituted with deuterium; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms that is unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 따르면, 상기 Group B에서 상기 R100 내지 R120은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 중수소로 치환 또는 비치환된 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬기; 중수소로 치환 또는 비치환된 탄소수 3 내지 20의 단환 또는 다환의 시클로알킬기; 중수소로 치환 또는 비치환된 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬실릴기; 또는 중수소로 치환 또는 비치환된 탄소수 6 내지 20의 단환 또는 다환의 아릴기이다.According to an exemplary embodiment of the present specification, in Group B, R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a linear or branched alkyl group having 1 to 20 carbon atoms that is unsubstituted or substituted with deuterium; a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms that is unsubstituted or substituted with deuterium; a linear or branched alkylsilyl group having 1 to 20 carbon atoms that is unsubstituted or substituted with deuterium; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms that is unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 따르면, 상기 Group B에서 상기 R100 내지 R120은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 메틸기; -CD3; tert-부틸기; 시클로헥실기; 트리메틸 실릴기; 또는 중수소로 치환 또는 비치환된 페닐기이다.According to an exemplary embodiment of the present specification, in Group B, R100 to R120 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; methyl group; -CD 3 ; tert-butyl group; cyclohexyl group; trimethyl silyl group; Or a phenyl group unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 따르면, 상기 G1 내지 G28 및 G101 및 G128은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 시아노기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알킬기; 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기; 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴실릴기; 치환 또는 비치환된 탄소수 6 내지 30의 아릴알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 디아릴아민기; 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기이다.According to an exemplary embodiment of the present specification, the G1 to G28 and G101 and G128 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted C1-C30 linear or branched haloalkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkylsilyl group; a substituted or unsubstituted monocyclic or polycyclic arylsilyl group having 6 to 30 carbon atoms; a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic diarylamine group having 6 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 G1 내지 G28 및 G101 및 G128은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 시아노기; 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알킬기; 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기; 탄소수 6 내지 30의 단환 또는 다환의 아릴실릴기; 탄소수 6 내지 30의 아릴알킬기; 탄소수 6 내지 30의 단환 또는 다환의 디아릴아민기; 탄소수 6 내지 30의 단환 또는 다환의 아릴기; 또는 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기이고, 상기 치환기는 중수소, 할로겐기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, the G1 to G28 and G101 and G128 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a linear or branched alkyl group having 1 to 30 carbon atoms; a linear or branched haloalkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a linear or branched alkylsilyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic arylsilyl group having 6 to 30 carbon atoms; an arylalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic diarylamine group having 6 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, and the substituent is substituted with one or more selected from the group consisting of deuterium, a halogen group, a linear or branched alkyl group having 1 to 30 carbon atoms, and combinations thereof. is unsubstituted
본 명세서의 일 실시상태에 따르면, 상기 G1 내지 G28 및 G101 및 G128은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 시아노기; 메틸기; i-프로필기; tert-부틸기; -CF3; 아다만틸기; 트리메틸실릴기; 트리페닐실릴기; 디페닐아민기; 페닐기; 나프틸기; 큐밀(cumyl)기; 피리딜기; 또는 카바졸기이고, 상기 치환기는 중수소, F, 메틸기, tert-부틸기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, the G1 to G28 and G101 and G128 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; methyl group; i-propyl group; tert-butyl group; -CF 3 ; adamantyl group; trimethylsilyl group; triphenylsilyl group; diphenylamine group; phenyl group; naphthyl group; cumyl group; pyridyl group; or a carbazole group, and the substituent is unsubstituted or substituted with one or more selected from the group consisting of deuterium, F, a methyl group, a tert-butyl group, and combinations thereof.
본 명세서의 일 실시상태에 따르면, 상기 R"'는 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 지방족, 방향족, 또는 지방족과 방향족의 축합 탄화수소고리기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기이다.According to an exemplary embodiment of the present specification, R"' is a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms; substituted or unsubstituted monocyclic or polycyclic aliphatic, aromatic, or A condensed hydrocarbon ring group of an aliphatic and an aromatic, or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 R"'는 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 탄소수 6 내지 30의 단환 또는 다환의 지방족, 방향족, 또는 지방족과 방향족의 축합 탄화수소고리기; 또는 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기이고, 상기 치환기는 중수소, 할로겐기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알킬기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, R"' is a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic aliphatic, aromatic, or aliphatic and aromatic condensed hydrocarbon ring group having 6 to 30 carbon atoms; or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, and the substituents are deuterium, a halogen group, a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched chain haloalkyl group having 1 to 30 carbon atoms, and their It is substituted or unsubstituted with one or more selected from the group consisting of combinations.
본 명세서의 일 실시상태에 따르면, 상기 R"'는 tert-부틸기; 페닐기; 바이페닐기; 테트라하이드로벤조퓨란기; 피리딘기; 또는 트리아진기이고, 상기 치환기는 중수소, F, -CF3, 메틸기, tert-부틸기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, R"' is a tert-butyl group; a phenyl group; a biphenyl group; a tetrahydrobenzofuran group; a pyridine group; or a triazine group, and the substituents are deuterium, F, -CF 3 , a methyl group , tert- butyl group, and unsubstituted or substituted with one or more selected from the group consisting of combinations thereof.
본 명세서의 일 실시상태에 따르면, 상기 G1 내지 G28 및 G101 및 G128는 서로 같거나 상이하고, 각각 독립적으로 하기 Group C의 구조 중 어느 하나로 표시되는 기이다.According to an exemplary embodiment of the present specification, G1 to G28 and G101 and G128 are the same as or different from each other, and are each independently a group represented by any one of the structures of Group C below.
<Group C><Group C>
Figure PCTKR2020017069-appb-I000080
Figure PCTKR2020017069-appb-I000080
상기 구조에 있어서, In the structure,
R10 및 R11은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,R10 and R11 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
r10은 1 내지 10의 정수이며, r10 is an integer from 1 to 10,
r11은 1 내지 8의 정수이고,r11 is an integer from 1 to 8;
상기 r10 및 r11이 각각 2 이상인 경우, 2 이상의 괄호내의 구조는 서로 같거나 상이하며,When r10 and r11 are each 2 or more, the structures in parentheses of 2 or more are the same as or different from each other,
r1은 0 또는 1이고,r1 is 0 or 1,
r2는 0 또는 1이며,r2 is 0 or 1,
Figure PCTKR2020017069-appb-I000081
는 상기 화학식 1에 결합되는 부위이다.
Figure PCTKR2020017069-appb-I000081
is a site bound to Formula 1 above.
본 명세서의 일 실시상태에 따르면, 상기 G1 내지 G28 및 G101 및 G128는 서로 같거나 상이하고, 각각 독립적으로 하기 Group D의 구조 중 어느 하나로 표시되는 기이다.According to an exemplary embodiment of the present specification, G1 to G28 and G101 and G128 are the same as or different from each other, and are each independently a group represented by any one of the structures of Group D below.
<Group D><Group D>
Figure PCTKR2020017069-appb-I000082
Figure PCTKR2020017069-appb-I000082
상기 구조에 있어서, In the structure,
R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고,R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
r100, r101, r108 및 r109은 각각 1 내지 8의 정수이고,r100, r101, r108 and r109 are each an integer from 1 to 8;
r102 및 r107는 각각 1 내지 12의 정수이며,r102 and r107 are each an integer from 1 to 12,
r103 및 r104는 각각 1 내지 10의 정수이고,r103 and r104 are each an integer from 1 to 10,
r105는 1 내지 6의 정수이며,r105 is an integer from 1 to 6,
r106 및 r110 내지 r113는 각각 1 내지 4의 정수이며,r106 and r110 to r113 are each an integer of 1 to 4,
r114는 1 내지 14의 정수이고,r114 is an integer from 1 to 14;
r115는 1 내지 18의 정수이며,r115 is an integer from 1 to 18,
상기 r100 내지 r115가 각각 2 이상인 경우, 상기 2 이상의 괄호 내의 구조는 서로 같거나 상이하며,When each of the r100 to r115 is 2 or more, the structures in the two or more parentheses are the same as or different from each other,
Figure PCTKR2020017069-appb-I000083
는 상기 화학식 1에 결합되는 부위이다.
Figure PCTKR2020017069-appb-I000083
is a site bound to Formula 1 above.
본 명세서의 일 실시상태에 따르면, 상기 Group D에서 상기 R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 실릴기; 또는 치환 또는 비치환된 아릴기이다.According to an exemplary embodiment of the present specification, in Group D, R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; or a substituted or unsubstituted aryl group.
본 명세서의 일 실시상태에 따르면, 상기 Group D에서 상기 R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기; 또는 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기이다.According to an exemplary embodiment of the present specification, in Group D, R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkylsilyl group; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 Group D에서 상기 R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 3 내지 20의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬실릴기; 또는 치환 또는 비치환된 탄소수 6 내지 20의 단환 또는 다환의 아릴기이다.According to an exemplary embodiment of the present specification, in Group D, R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C20 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted C1-C20 linear or branched alkylsilyl group; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 Group D에서 상기 R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 중수소로 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 중수소로 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 중수소로 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기; 또는 중수소로 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기이다.According to an exemplary embodiment of the present specification, in Group D, R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a linear or branched alkyl group having 1 to 30 carbon atoms substituted or unsubstituted with deuterium; a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms that is unsubstituted or substituted with deuterium; a linear or branched alkylsilyl group having 1 to 30 carbon atoms that is unsubstituted or substituted with deuterium; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms that is unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 따르면, 상기 Group D에서 상기 R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 중수소로 치환 또는 비치환된 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬기; 중수소로 치환 또는 비치환된 탄소수 3 내지 20의 단환 또는 다환의 시클로알킬기; 중수소로 치환 또는 비치환된 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬실릴기; 또는 중수소로 치환 또는 비치환된 탄소수 6 내지 20의 단환 또는 다환의 아릴기이다.According to an exemplary embodiment of the present specification, in Group D, R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a linear or branched alkyl group having 1 to 20 carbon atoms that is unsubstituted or substituted with deuterium; a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms that is unsubstituted or substituted with deuterium; a linear or branched alkylsilyl group having 1 to 20 carbon atoms that is unsubstituted or substituted with deuterium; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms that is unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 따르면, 상기 Group D에서 상기 R100 내지 R115는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 메틸기; -CD3; tert-부틸기; 시클로헥실기; 트리메틸 실릴기; 또는 중수소로 치환 또는 비치환된 페닐기이다.According to an exemplary embodiment of the present specification, in Group D, R100 to R115 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; methyl group; -CD 3 ; tert-butyl group; cyclohexyl group; trimethyl silyl group; Or a phenyl group unsubstituted or substituted with deuterium.
본 명세서의 일 실시상태에 따르면, 상기 G1 내지 G28 및 G101 및 G128 중 인접한 기는 서로 결합하여 치환 또는 비치환된 탄화수소고리; 또는 치환 또는 비치환된 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, adjacent groups of G1 to G28 and G101 and G128 are bonded to each other to form a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted heterocycle is formed.
본 명세서의 일 실시상태에 따르면, 상기 G1 내지 G28 및 G101 및 G128 중 인접한 기는 서로 결합하여 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 탄화수소고리; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, adjacent groups of G1 to G28 and G101 and G128 are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocycle having 2 to 30 carbon atoms is formed.
본 명세서의 일 실시상태에 따르면, G1 내지 G28 및 G101 및 G128 중 인접한 기는 서로 결합하여 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 지방족, 방향족, 또는 지방족 및 방향족 축합 탄화수소고리; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 지방족 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, adjacent groups of G1 to G28 and G101 and G128 are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic aliphatic, aromatic, or aliphatic and aromatic condensed hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic aliphatic heterocycle having 2 to 30 carbon atoms is formed.
본 명세서의 일 실시상태에 따르면, 상기 G1 내지 G28 및 G101 및 G128 중 인접한 기는 서로 결합하여 탄소수 3 내지 30의 단환 또는 다환의 지방족, 방향족, 또는 지방족 및 방향족 축합 탄화수소고리; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 지방족 헤테로고리를 형성하고, 상기 고리는 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기로 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기, 및 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알킬기로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, adjacent groups of G1 to G28 and G101 and G128 are bonded to each other to form a monocyclic or polycyclic aliphatic, aromatic, or aliphatic and aromatic condensed hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic aliphatic heterocycle having 2 to 30 carbon atoms is formed, and the ring is monocyclic or polycyclic having 6 to 30 carbon atoms unsubstituted or substituted with a linear or branched alkyl group having 1 to 30 carbon atoms. It is substituted or unsubstituted with one or more selected from the group consisting of a ring aryl group, a linear or branched alkyl group having 1 to 30 carbon atoms, and a linear or branched haloalkyl group having 1 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 G1 내지 G28 및 G101 및 G128 중 인접한 기는 서로 결합하여 시클로펜탄고리; 시클로헥산고리; 시클로헵탄고리; 바이시클로[2.2.1]옥탄고리; 노보넨(norbornane)고리; 아다만탄고리; 인덴고리; 페난트렌고리; 테트라하이드로퓨란고리; 테트라하이드로티오펜고리; 테트라하이드로나프토퓨란고리; 테트라하이드라나프토티오펜고리; 피롤리딘고리; 옥타하이드로벤조퓨란고리; 옥타하이드로벤조티오펜고리; 옥타하이드로인덴고리; 벤젠고리; 페난트렌고리; 벤조퓨란고리; 플루오렌고리; 디하이드로안트라센고리; 크로멘(chroman)고리; 카바졸고리; 벤즈이미다졸; 테트라하이드로벤조인돌고리; 인돌고리; 또는 인돌로카바졸고리를 형성하고, 상기 고리는 tert-부틸기로 치환된 페닐기, 메틸기, tert-부틸기, 및 -CF3로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환된다.According to an exemplary embodiment of the present specification, adjacent groups of G1 to G28 and G101 and G128 are bonded to each other to form a cyclopentane ring; cyclohexane ring; cycloheptane ring; bicyclo[2.2.1]octane ring; norbornane ring; adamantane ring; indene ring; phenanthrene ring; tetrahydrofuran ring; tetrahydrothiophene ring; tetrahydronaphthofuran ring; tetrahydranaphthothiophene ring; pyrrolidine ring; octahydrobenzofuran ring; octahydrobenzothiophene ring; octahydroindene ring; benzene ring; phenanthrene ring; benzofuran ring; fluorene ring; dihydroanthracene ring; chroman ring; carbazole ring; benzimidazole; tetrahydrobenzoindole ring; indol ring; Or an indolocarbazole ring is formed, and the ring is unsubstituted or substituted with one or more selected from the group consisting of a phenyl group substituted with a tert-butyl group, a methyl group, a tert-butyl group, and -CF 3 .
본 명세서의 일 실시상태에 따르면, 상기 R"' 및 G102는 서로 결합하여 치환 또는 비치환된 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, R"' and G102 are combined with each other to form a substituted or unsubstituted heterocycle.
본 명세서의 일 실시상태에 따르면, 상기 R"' 및 G102는 서로 결합하여 치환 또는 비치환된 B 및 N을 포함하는 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, the R"' and G102 are combined with each other to form a heterocycle including substituted or unsubstituted B and N.
본 명세서의 일 실시상태에 따르면, 상기 R"' 및 G102는 서로 결합하여 치환 또는 비치환된 B 및 N을 포함하는 6원 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, the R"' and G102 are combined with each other to form a 6-membered heterocycle including substituted or unsubstituted B and N.
본 명세서의 일 실시상태에 따르면, 상기 R"' 및 G102는 서로 결합하여 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, the R"' and G102 are bonded to each other to form a heterocycle.
본 명세서의 일 실시상태에 따르면, 상기 R"' 및 G102는 서로 결합하여 B 및 N을 포함하는 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, the R"' and G102 are combined with each other to form a heterocycle including B and N.
본 명세서의 일 실시상태에 따르면, 상기 R"' 및 G102는 서로 결합하여 B 및 N을 포함하는 6원 헤테로고리를 형성한다.According to an exemplary embodiment of the present specification, the R"' and G102 are combined with each other to form a 6-membered heterocycle including B and N.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화합물 중에서 선택되는 어느 하나이다.According to an exemplary embodiment of the present specification, Formula 1 is any one selected from the following compounds.
Figure PCTKR2020017069-appb-I000084
Figure PCTKR2020017069-appb-I000084
Figure PCTKR2020017069-appb-I000085
Figure PCTKR2020017069-appb-I000085
Figure PCTKR2020017069-appb-I000086
Figure PCTKR2020017069-appb-I000086
Figure PCTKR2020017069-appb-I000087
Figure PCTKR2020017069-appb-I000087
Figure PCTKR2020017069-appb-I000088
Figure PCTKR2020017069-appb-I000088
Figure PCTKR2020017069-appb-I000089
Figure PCTKR2020017069-appb-I000089
Figure PCTKR2020017069-appb-I000090
Figure PCTKR2020017069-appb-I000090
Figure PCTKR2020017069-appb-I000091
Figure PCTKR2020017069-appb-I000091
Figure PCTKR2020017069-appb-I000092
Figure PCTKR2020017069-appb-I000092
Figure PCTKR2020017069-appb-I000093
Figure PCTKR2020017069-appb-I000093
Figure PCTKR2020017069-appb-I000094
Figure PCTKR2020017069-appb-I000094
Figure PCTKR2020017069-appb-I000095
Figure PCTKR2020017069-appb-I000095
Figure PCTKR2020017069-appb-I000096
Figure PCTKR2020017069-appb-I000096
Figure PCTKR2020017069-appb-I000097
Figure PCTKR2020017069-appb-I000097
Figure PCTKR2020017069-appb-I000098
Figure PCTKR2020017069-appb-I000098
Figure PCTKR2020017069-appb-I000099
Figure PCTKR2020017069-appb-I000099
Figure PCTKR2020017069-appb-I000100
Figure PCTKR2020017069-appb-I000100
Figure PCTKR2020017069-appb-I000101
Figure PCTKR2020017069-appb-I000101
Figure PCTKR2020017069-appb-I000102
Figure PCTKR2020017069-appb-I000102
Figure PCTKR2020017069-appb-I000103
Figure PCTKR2020017069-appb-I000103
Figure PCTKR2020017069-appb-I000104
Figure PCTKR2020017069-appb-I000104
Figure PCTKR2020017069-appb-I000105
Figure PCTKR2020017069-appb-I000105
Figure PCTKR2020017069-appb-I000106
Figure PCTKR2020017069-appb-I000106
Figure PCTKR2020017069-appb-I000107
Figure PCTKR2020017069-appb-I000107
상기 화합물에 있어서, Ph는 페닐기를 의미한다.In the above compound, Ph means a phenyl group.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1의 A1이 t-부틸기로 치환된 벤조퓨란 또는 t-부틸기로 치환된 벤조티오펜이며, R' 및 R"가 각각 독립적으로 t-부틸기 또는 이소프로필기로 치환된 페닐기, 또는 t-부틸기로 치환된 바이페닐기이며, R2 또는 R3가 t-부틸기, 또는 수소인 경우, R6이 터부틸기, 페닐기, 또는 아다만틸기인 화합물은 제외한다.According to an exemplary embodiment of the present specification, A1 of Formula 1 is benzofuran substituted with a t-butyl group or benzothiophene substituted with a t-butyl group, and R′ and R″ are each independently a t-butyl group or iso A compound in which a phenyl group substituted with a propyl group or a biphenyl group substituted with a t-butyl group and R2 or R3 is a t-butyl group or hydrogen, R6 is a terbutyl group, a phenyl group, or an adamantyl group is excluded.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1의 A1이 벤조퓨란 또는 디벤조퓨란인 경우, R2에서 t-부틸기로 치환 또는 비치환된 디페닐아민기인 화합물을 제외한다.According to an exemplary embodiment of the present specification, when A1 of Formula 1 is benzofuran or dibenzofuran, a compound that is a diphenylamine group unsubstituted or substituted with a t-butyl group in R2 is excluded.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1의 A1이 벤조퓨란 또는 디벤조퓨란이며, R' 및 R"가 각각 독립적으로 t-부틸기로 치환된 페닐기이며, R3가 t-부틸기인 경우, R6이 메틸기, 또는 시클로헥실기인 화합물을 제외한다.According to an exemplary embodiment of the present specification, when A1 of Formula 1 is benzofuran or dibenzofuran, R′ and R″ are each independently a phenyl group substituted with a t-butyl group, and R3 is a t-butyl group, R6 The compound which is this methyl group or a cyclohexyl group is excluded.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1의 A1이 벤조퓨란 또는 디벤조퓨란이며, R' 및 R"가 각각 독립적으로 t-부틸기로 치환된 바이페닐기이며, R3가 t-부틸기로 치환된 페닐기인 경우, R6이 메틸기인 화합물을 제외한다.According to an exemplary embodiment of the present specification, A1 of Formula 1 is benzofuran or dibenzofuran, R' and R" are each independently a biphenyl group substituted with a t-butyl group, and R3 is a substituted with a t-butyl group In the case of a phenyl group, the compound in which R6 is a methyl group is excluded.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1의 A1이 벤조퓨란 또는 디벤조퓨란이며, R' 및 R"가 각각 독립적으로 바이페닐기, 또는 디페닐아민기로 치환된 페닐기이며, R1 내지 R4가 수소인 경우, R6가 시클로헥실기인 화합물을 제외한다.According to an exemplary embodiment of the present specification, A1 of Formula 1 is benzofuran or dibenzofuran, R' and R" are each independently a biphenyl group or a phenyl group substituted with a diphenylamine group, and R1 to R4 are hydrogen In the case of , compounds in which R6 is a cyclohexyl group are excluded.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1의 A1이 5원 지방족 또는 방향족 헤테로고리를 포함하고, 상기 화학식 1의 A1이 5원 방향족 헤테로고리를 포함하는 경우, 상기 화학식 1은 지방족 탄화수소 축합고리를 적어도 하나 포함한다.According to an exemplary embodiment of the present specification, when A1 of Formula 1 includes a 5-membered aliphatic or aromatic heterocycle, and A1 of Formula 1 includes a 5-membered aromatic heterocycle, Formula 1 is an aliphatic hydrocarbon condensed ring includes at least one.
본 명세서는 상기 전술한 화합물을 포함하는 유기 발광 소자를 제공한다.The present specification provides an organic light emitting device including the above-described compound.
본 명세서에서 어떤 부재가 다른 부재 "상에" 위치하고 있다고 할 때, 이는 어떤 부재가 다른 부재에 접해 있는 경우뿐 아니라 두 부재 사이에 또 다른 부재가 존재하는 경우도 포함한다.In the present specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.
본 명세서에서 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다. In the present specification, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.
본 명세서에 있어서, 상기 '층'은 본 기술분야에 주로 사용되는 '필름'과 호환되는 의미이며, 목적하는 영역을 덮는 코팅을 의미한다. 상기 '층'의 크기는 한정되지 않으며, 각각의 '층'은 그 크기가 같거나 상이할 수 있다. 일 실시상태에 따르면, '층'의 크기는 전체 소자와 같을 수 있고, 특정 기능성 영역의 크기에 해당할 수 있으며, 단일 서브픽셀(sub-pixel)만큼 작을 수도 있다. In the present specification, the 'layer' means compatible with the 'film' mainly used in the present technical field, and refers to a coating covering a desired area. The size of the 'layers' is not limited, and each 'layer' may have the same size or different sizes. According to an exemplary embodiment, the size of the 'layer' may be the same as the entire device, may correspond to the size of a specific functional area, and may be as small as a single sub-pixel.
본 명세서에 있어서, 특정한 A 물질이 B층에 포함된다는 의미는 i) 1종 이상의 A 물질이 하나의 B층에 포함되는 것과 ii) B층이 1층 이상으로 구성되고, A 물질이 다층의 B층 중 1층 이상에 포함되는 것을 모두 포함한다.In this specification, the meaning that a specific material A is included in layer B means that i) one or more types of material A are included in one layer B, and ii) layer B is composed of one or more layers, and material A is multi-layered B. It includes everything included in one or more floors among the floors.
본 명세서에 있어서, 특정한 A 물질이 C층 또는 D층에 포함된다는 의미는 i) 1층 이상의 C층 중 1층 이상에 포함되거나, ii) 1층 이상의 D층 중 1층 이상에 포함되거나, iii) 1층 이상의 C층 및 1층 이상의 D층에 각각 포함되는 것을 모두 의미하는 것이다.In this specification, the meaning that a specific material A is included in the C layer or the D layer means i) is included in one or more of the one or more layers C, ii) is included in one or more of the one or more layers D, or iii) ) means all of which are included in one or more C-layers and one or more D-layers, respectively.
본 명세서는 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1 층 이상은 상기 화학식 1로 표시되는 화합물을 포함하는 것인 유기 발광 소자를 제공한다.The present specification includes a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound represented by Formula 1 above. do.
본 명세서의 유기 발광 소자의 유기물층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층, 전자 차단층, 정공 차단층 등을 포함하는 구조를 가질 수 있다. 그러나 유기 발광 소자의 구조는 이에 한정되지 않고 더 적은 수의 유기층을 포함할 수 있다.The organic material layer of the organic light emitting device of the present specification may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, and the like. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 화합물을 포함한다. In the exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by Formula 1 above.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 화합물을 발광층의 도펀트로서 포함한다.In the exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes the compound represented by Formula 1 as a dopant of the emission layer.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 화합물을 발광층의 청색 형광 도펀트로서 포함한다.In the exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes the compound represented by Formula 1 as a blue fluorescent dopant of the emission layer.
본 명세서의 일 실시상태에 있어서, 상기 유기 발광 소자는 정공 주입층, 정공 수송층. 발광층, 전자 수송층, 전자 주입층, 정공 차단층 및 전자 차단층으로 이루어진 군에서 선택되는 1층 또는 2층 이상을 더 포함한다.In an exemplary embodiment of the present specification, the organic light emitting device includes a hole injection layer and a hole transport layer. It further includes one or more layers selected from the group consisting of a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer.
본 명세서의 일 실시상태에 있어서, 상기 발광층은 호스트 화합물을 더 포함한다.In an exemplary embodiment of the present specification, the light emitting layer further includes a host compound.
본 명세서의 일 실시상태에 있어서, 상기 발광층은 호스트 화합물을 더 포함하고, 상기 호스트 화합물은 치환 가능한 위치의 적어도 하나의 수소가 중수소로 치환된 것이다.In an exemplary embodiment of the present specification, the light emitting layer further includes a host compound, wherein at least one hydrogen at a substitutable position is substituted with deuterium in the host compound.
본 명세서의 일 실시상태에 있어서, 상기 호스트 화합물이 중수소로 치환된 경우, 중수소로 30% 이상 치환된다. 또 다른 일 실시상태에 있어서, 상기 호스트 화합물은 중수소로 40% 이상 치환된다. 또 다른 일 실시상태에 있어서, 상기 호스트 화합물은 중수소로 60% 이상 치환된다. 또 다른 일 실시상태에 있어서, 상기 호스트 화합물은 중수소로 80% 이상 치환된다. 또 다른 일 실시상태에 있어서, 상기 호스트 화합물은 중수소로 100% 치환된다.In an exemplary embodiment of the present specification, when the host compound is substituted with deuterium, it is substituted with deuterium by 30% or more. In another exemplary embodiment, the host compound is substituted with deuterium by 40% or more. In another exemplary embodiment, the host compound is substituted with deuterium by 60% or more. In another exemplary embodiment, the host compound is substituted with deuterium by 80% or more. In another exemplary embodiment, the host compound is 100% substituted with deuterium.
본 명세서의 일 실시상태에 있어서, 상기 발광층은 하기 화학식 H로 표시되는 화합물을 더 포함한다.In an exemplary embodiment of the present specification, the light emitting layer further includes a compound represented by the following formula (H).
[화학식 H][Formula H]
Figure PCTKR2020017069-appb-I000108
Figure PCTKR2020017069-appb-I000108
상기 화학식 H에 있어서,In the formula (H),
L20 및 L21은 서로 동일하거나 상이하고, 각각 독립적으로 직접결합; 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 헤테로고리기이고,L20 and L21 are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heterocyclic group,
Ar20 및 Ar21은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고,Ar20 and Ar21 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R20은 수소; 중수소; 할로겐기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.R20 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 L20 및 L21은 서로 같거나 상이하고, 각각 독립적으로 직접결합; 탄소수 6 내지 30의 단환 또는 다환의 아릴렌기; 또는 탄소수 2 내지 30의 단환 또는 다환의 헤테로아릴렌기이다.In an exemplary embodiment of the present specification, L20 and L21 are the same as or different from each other, and each independently a direct bond; a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms; or a monocyclic or polycyclic heteroarylene group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 L20 및 L21은 서로 같거나 상이하고, 각각 독립적으로 직접결합; 탄소수 6 내지 20의 단환 또는 다환의 아릴렌기; 또는 탄소수 2 내지 20의 단환 또는 다환의 헤테로아릴렌기이다.In an exemplary embodiment of the present specification, L20 and L21 are the same as or different from each other, and each independently a direct bond; a monocyclic or polycyclic arylene group having 6 to 20 carbon atoms; or a monocyclic or polycyclic heteroarylene group having 2 to 20 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 L20 및 L21은 서로 같거나 상이하고, 각각 독립적으로 직접결합; 페닐렌기; 바이페닐릴렌기; 나프틸렌기; 2가의 디벤조퓨란기; 또는 2가의 디벤조티오펜기이다.In an exemplary embodiment of the present specification, L20 and L21 are the same as or different from each other, and each independently a direct bond; phenylene group; biphenylrylene group; naphthylene group; a divalent dibenzofuran group; or a divalent dibenzothiophene group.
본 명세서의 일 실시상태에 있어서, 상기 Ar20 및 Ar21은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기이다.In an exemplary embodiment of the present specification, Ar20 and Ar21 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 Ar20 및 Ar21은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 단환 또는 다환의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 20의 단환 또는 다환의 헤테로고리기이다.In an exemplary embodiment of the present specification, Ar20 and Ar21 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 20 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 Ar20 및 Ar21은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 단환 내지 4환의 아릴기; 또는 치환 또는 비치환된 탄소수 6 내지 20의 단환 내지 4환의 헤테로고리기이다.In an exemplary embodiment of the present specification, Ar20 and Ar21 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic to 4cyclic aryl group having 6 to 20 carbon atoms; or a substituted or unsubstituted monocyclic to 4cyclic heterocyclic group having 6 to 20 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 Ar20 및 Ar21은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 페닐기; 치환 또는 비치환된 바이페닐기; 치환 또는 비치환된 터페닐기; 치환 또는 비치환된 나프틸기; 치환 또는 비치환된 안트라센기; 치환 또는 비치환된 페난트렌기; 치환 또는 비치환된 페날렌기; 치환 또는 비치환된 플루오렌기; 치환 또는 비치환된 벤조플루오렌기; 치환 또는 비치환된 퓨란기; 치환 또는 비치환된 티오펜기; 치환 또는 비치환된 디벤조퓨란기; 치환 또는 비치환된 나프토벤조퓨란기; 치환 또는 비치환된 디벤조티오펜기; 또는 치환 또는 비치환된 나프토벤조티오펜기이다.In an exemplary embodiment of the present specification, Ar20 and Ar21 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted anthracene group; a substituted or unsubstituted phenanthrene group; a substituted or unsubstituted phenalene group; a substituted or unsubstituted fluorene group; a substituted or unsubstituted benzofluorene group; a substituted or unsubstituted furan group; a substituted or unsubstituted thiophene group; A substituted or unsubstituted dibenzofuran group; a substituted or unsubstituted naphthobenzofuran group; a substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted naphthobenzothiophene group.
본 명세서의 일 실시상태에 있어서, 상기 Ar20 및 Ar21은 서로 같거나 상이하고, 각각 독립적으로 중수소, 또는 탄소수 6 내지 20의 단환 또는 다환의 아릴기로 치환 또는 비치환된 페닐기; 탄소수 6 내지 20의 단환 또는 다환의 아릴기로 치환 또는 비치환된 바이페닐기; 중수소, 또는 탄소수 6 내지 20의 단환 또는 다환의 아릴기로 치환 또는 비치환된 나프틸기; 탄소수 6 내지 20의 단환 또는 다환의 아릴기로 치환 또는 비치환된 디벤조퓨란기; 탄소수 6 내지 20의 단환 또는 다환의 아릴기로 치환 또는 비치환된 나프토벤조퓨란기; 탄소수 6 내지 20의 단환 또는 다환의 아릴기로 치환 또는 비치환된 디벤조티오펜기; 또는 탄소수 6 내지 20의 단환 또는 다환의 아릴기로 치환 또는 비치환된 나프토벤조티오펜기이다.In an exemplary embodiment of the present specification, Ar20 and Ar21 are the same as or different from each other, and each independently represent a phenyl group unsubstituted or substituted with deuterium or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; a biphenyl group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; a naphthyl group unsubstituted or substituted with deuterium or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; a dibenzofuran group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; a naphthobenzofuran group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; a dibenzothiophene group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; or a naphthobenzothiophene group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 Ar20 및 Ar21은 서로 같거나 상이하고, 각각 독립적으로 중수소로 치환 또는 비치환된 페닐기; 바이페닐기; 중수소로 치환 또는 비치환된 나프틸기; 디벤조퓨란기; 나프토벤조퓨란기; 디벤조티오펜기; 또는 나프토벤조티오펜기이다.In an exemplary embodiment of the present specification, Ar20 and Ar21 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with deuterium; biphenyl group; a naphthyl group unsubstituted or substituted with deuterium; dibenzofuran group; naphthobenzofuran group; dibenzothiophene group; or a naphthobenzothiophene group.
본 명세서의 일 실시상태에 있어서, 상기 Ar20은 치환 또는 비치환된 헤테로고리기이고, 상기 Ar21은 치환 또는 비치환된 아릴기이다.In an exemplary embodiment of the present specification, Ar20 is a substituted or unsubstituted heterocyclic group, and Ar21 is a substituted or unsubstituted aryl group.
본 명세서의 일 실시상태에 있어서, 상기 R20은 수소; 중수소; 할로겐기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기이다.In an exemplary embodiment of the present specification, R 20 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 R20은 수소; 중수소; 불소; 치환 또는 비치환된 탄소수 1 내지 10의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 3 내지 10의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기이다.In an exemplary embodiment of the present specification, R 20 is hydrogen; heavy hydrogen; fluorine; a substituted or unsubstituted C1-C10 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 10 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 R20은 수소; 중수소; 중수소, 페닐기, 또는 나프틸기로 치환 또는 비치환된 페닐기; 중수소, 또는 페닐기로 치환 또는 비치환된 나프틸기; 바이페닐기; 디벤조퓨란기; 또는 디벤조티오펜기이다.In an exemplary embodiment of the present specification, R 20 is hydrogen; heavy hydrogen; a phenyl group unsubstituted or substituted with deuterium, a phenyl group, or a naphthyl group; a naphthyl group unsubstituted or substituted with deuterium or a phenyl group; biphenyl group; dibenzofuran group; or a dibenzothiophene group.
본 명세서의 일 실시상태에 있어서, 상기 화학식 H로 표시되는 화합물이 중수소로 치환된 경우, 치환 가능한 위치의 수소가 중수소로 30% 이상 치환된다. 또 다른 일 실시상태에 있어서, 상기 화학식 H의 구조는 치환 가능한 위치의 수소가 중수소로 40% 이상 치환된다. 또 다른 일 실시상태에 있어서, 상기 화학식 H의 구조는 치환 가능한 위치의 수소가 중수소로 60% 이상 치환된다. In an exemplary embodiment of the present specification, when the compound represented by Formula H is substituted with deuterium, 30% or more of hydrogen at a substitutable position is substituted with deuterium. In another exemplary embodiment, in the structure of Formula H, 40% or more of hydrogen at a substitutable position is substituted with deuterium. In another exemplary embodiment, in the structure of Formula H, 60% or more of hydrogen at a substitutable position is substituted with deuterium.
또 다른 일 실시상태에 있어서, 상기 화학식 H의 구조는 치환 가능한 위치의 수소가 중수소로 80% 이상 치환된다. 또 다른 일 실시상태에 있어서, 상기 화학식 H의 구조는 치환 가능한 위치의 수소가 중수소로 100% 치환된다.In another exemplary embodiment, in the structure of Formula H, 80% or more of hydrogen at a substitutable position is substituted with deuterium. In another exemplary embodiment, in the structure of Formula H, hydrogen at a substitutable position is 100% substituted with deuterium.
본 명세서의 일 실시상태에 있어서, 상기 화학식 H로 표시되는 화합물은 하기 화합물 중에서 선택되는 어느 하나이다. In an exemplary embodiment of the present specification, the compound represented by Formula H is any one selected from the following compounds.
Figure PCTKR2020017069-appb-I000109
Figure PCTKR2020017069-appb-I000109
Figure PCTKR2020017069-appb-I000110
Figure PCTKR2020017069-appb-I000110
Figure PCTKR2020017069-appb-I000111
Figure PCTKR2020017069-appb-I000111
본 명세서의 일 실시상태에 있어서, 상기 발광층에서 화학식 1로 표시되는 화합물은 도펀트로, 상기 화학식 H로 표시되는 화합물은 호스트로 사용된다. In an exemplary embodiment of the present specification, the compound represented by Formula 1 is used as a dopant in the emission layer, and the compound represented by Formula H is used as a host.
본 명세서의 일 실시상태에 있어서, 상기 발광층이 호스트 및 도펀트를 포함할 경우, 도펀트의 함량은 발광층의 100 중량부를 기준으로 0.01 내지 10 중량부의 범위에서 선택될 수 있으며, 이에 한정되지 않는다.In the exemplary embodiment of the present specification, when the light emitting layer includes a host and a dopant, the content of the dopant may be selected from 0.01 to 10 parts by weight based on 100 parts by weight of the light emitting layer, but is not limited thereto.
본 명세서의 일 실시상태에 있어서, 상기 발광층이 호스트 및 도펀트를 포함하고, 상기 호스트 및 도펀트는 99: 1 내지 1:99 중량비, 바람직하게는 99: 1 내지 70: 30 중량비, 더욱더 바람직하게는 99:1 내지 90: 10의 중량비로 포함한다.In an exemplary embodiment of the present specification, the light emitting layer includes a host and a dopant, and the host and the dopant are 99:1 to 1:99 by weight, preferably 99:1 to 70:30 by weight, even more preferably 99 It is included in a weight ratio of :1 to 90:10.
상기 발광층은 호스트 재료를 더 포함할 수 있고, 상기 호스트는 축합 방향족환 유도체 또는 헤테로환 함유 화합물 등이 있다. 구체적으로 축합 방향족환 유도체로는 안트라센 유도체, 피렌 유도체, 나프탈렌 유도체, 펜타센 유도체, 페난트렌 화합물, 플루오란텐 화합물 등이 있고, 헤테로환 함유 화합물로는 카바졸 유도체, 디벤조퓨란 유도체, 래더형 퓨란 화합물, 피리미딘 유도체 또는 트리아진 유도체 등이 있으며, 이들의 2 종 이상의 혼합물일 수 있으나, 이에 한정되지 않는다. The light emitting layer may further include a host material, and the host may include a condensed aromatic ring derivative or a heterocyclic compound containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type and a furan compound, a pyrimidine derivative, or a triazine derivative, and may be a mixture of two or more thereof, but is not limited thereto.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 1 종 이상의 도펀트, 및 호스트를 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes one or more dopants and a host.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 2종 이상의 혼합 도펀트 및 호스트를 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes two or more mixed dopants and a host.
본 명세서의 일 실시상태에 따르면, 상기 2종 이상의 혼합 도펀트 중 1 이상은 상기 화학식 1을 포함하고, 상기 호스트는 상기 화학식 H로 표시되는 화합물을 포함한다. 상기 2종 이상의 혼합 도펀트 중 1 이상은 상기 화학식 1을 포함하고, 나머지는 종래에 알려진 도펀트 물질을 사용할 수 있으나, 이에만 한정되는 것은 아니다.According to an exemplary embodiment of the present specification, at least one of the two or more mixed dopants includes Formula 1, and the host includes a compound represented by Formula H. At least one of the two or more mixed dopants may include Chemical Formula 1, and for the rest, a dopant material known in the art may be used, but the present invention is not limited thereto.
본 명세서의 일 실시상태에 따르면, 상기 2종 이상의 혼합 도펀트 중 1 이상은 상기 화학식 1을 포함하고, 나머지는 상기 화학식 1과 상이한 보론계 화합물, 파이렌계 화합물 및 지연형광계 화합물 중 1 이상을 사용할 수 있으나, 이에만 한정되는 것은 아니다.According to an exemplary embodiment of the present specification, at least one of the two or more mixed dopants includes Formula 1, and the remainder uses at least one of a boron-based compound, a pyrene-based compound, and a delayed fluorescence-based compound different from Formula 1 However, the present invention is not limited thereto.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 1 종 이상의 호스트를 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes at least one host.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 2종 이상의 혼합 호스트를 포함한다. According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes two or more types of mixed hosts.
본 명세서의 일 실시상태에 따르면, 상기 2 종 이상의 혼합 호스트 중 1 이상은 상기 화학식 H로 표시되는 화합물이다.According to an exemplary embodiment of the present specification, at least one of the two or more types of mixed hosts is a compound represented by Formula H.
본 명세서의 일 실시상태에 따르면, 상기 2 종 이상의 혼합 호스트는 서로 상이하고, 각각 독립적으로 상기 화학식 H로 표시되는 화합물이다.According to an exemplary embodiment of the present specification, the two or more types of mixed hosts are different from each other, and each independently represent a compound represented by Formula H.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 2종의 혼합 호스트를 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes two types of mixed hosts.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층 2 종의 혼합 호스트를 포함하고, 상기 2 종의 혼합 호스트는 서로 상이하며, 상기 2 종의 호스트는 상기 화학식 H로 표시되는 화합물이다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, the light emitting layer includes two types of mixed hosts, the two types of mixed hosts are different from each other, and the two types of hosts are represented by Formula H is a compound that becomes
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 화학식 H로 표시되는 제1 호스트; 및 상기 화학식 H로 표시되는 제2 호스트를 포함하고, 상기 제1 호스트 및 제2 호스트는 서로 상이하다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, the first host represented by the formula (H); and a second host represented by Formula H, wherein the first host and the second host are different from each other.
본 명세서의 일 실시상태에 따르면, 상기 제1 호스트: 제2 호스트는 95:5 내지 5:95의 중량비로 포함되고, 바람직하게는 70: 30 내지 30: 70의 중량비로 포합된다.According to an exemplary embodiment of the present specification, the first host: the second host is included in a weight ratio of 95:5 to 5:95, preferably 70:30 to 30:70 by weight.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 1 종 이상의 호스트, 및 도펀트를 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes at least one host and a dopant.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 1 종 이상의 호스트, 및 도펀트를 포함하고, 상기 호스트는 상기 화학식 H로 표시되는 화합물을 포함하고, 상기 도펀트는 상기 화학식 1로 표시되는 화합물을 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, the light emitting layer includes at least one host and a dopant, the host includes a compound represented by Formula H, and the dopant includes the above formula The compound represented by 1 is included.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 2 종 이상의 혼합 호스트, 및 도펀트를 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes two or more mixed hosts, and a dopant.
본 명세서의 일 실시상태에 따르면, 상기 2종 이상의 혼합 호스트 중 1 이상은 상기 화학식 H로 표시되는 화합물을 포함하고, 도펀트는 상기 화학식 1로 표시되는 화합물을 포함한다.According to an exemplary embodiment of the present specification, at least one of the two or more mixed hosts includes the compound represented by Formula H, and the dopant includes the compound represented by Formula 1 above.
본 명세서에서 상기 2종 이상의 혼합 호스트는 서로 상이하다.In the present specification, the two or more types of mixed hosts are different from each other.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 2 종의 혼합 호스트, 및 도펀트를 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes two types of mixed hosts, and a dopant.
본 명세서의 일 실시상태에 따르면, 상기 2 종의 혼합 호스트는 서로 상이하고, 각각 독립적으로 상기 화학식 H로 표시되는 화합물을 포함하고, 상기 도펀트는 상기 화학식 1로 표시되는 화합물을 포함한다.According to an exemplary embodiment of the present specification, the two types of mixed hosts are different from each other, and each independently include a compound represented by Formula H, and the dopant includes a compound represented by Formula 1 above.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 화학식 H로 표시되는 제1 호스트; 상기 화학식 H로 표시되는 제2 호스트; 및 상기 화학식 1로 표시되는 도펀트를 포함하고, 상기 제1 호스트 및 제2 호스트는 서로 상이하다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, the first host represented by the formula (H); a second host represented by the formula (H); and a dopant represented by Formula 1, wherein the first host and the second host are different from each other.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 1 종 이상의 호스트, 및 1 종 이상의 도펀트를 사용하고, 상기 1 종 이상의 호스트는 상기 화학식 H로 표시되는 화합물을 포함하고, 상기 1 종 이상의 도펀트는 상기 화학식 1로 표시되는 화합물을 포함한다.According to an exemplary embodiment of the present specification, the organic material layer uses at least one host and at least one dopant, and the at least one host includes a compound represented by Formula H, and the at least one dopant is and a compound represented by the formula (1).
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 2 종 이상의 혼합 호스트, 및 2 종 이상의 혼합 도펀트를 사용하고, 상기 2 종 이상의 혼합 호스트는 전술한 바와 동일한 재료를 사용할 수 있으며, 상기 2 종 이상의 혼합 도펀트는 전술한 바와 동일한 재료를 사용할 수 있다.According to an exemplary embodiment of the present specification, the organic material layer uses two or more types of mixed hosts, and two or more types of mixed dopants, and the two or more types of mixed hosts may use the same material as described above, and a mixture of the two or more types The dopant may use the same material as described above.
본 명세서의 일 실시상태에 있어서, 상기 유기 발광 소자는 제1 전극; 제2 전극; 상기 제1 전극과 상기 제2 전극 사이에 구비된 발광층; 및 상기 발광층과 상기 제1 전극 사이, 또는 상기 발광층과 상기 제2 전극 사이에 구비된 2층 이상의 유기물층을 포함하고, 상기 2층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함한다. In an exemplary embodiment of the present specification, the organic light emitting device includes a first electrode; a second electrode; a light emitting layer provided between the first electrode and the second electrode; and two or more organic material layers provided between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, wherein at least one of the two or more organic material layers includes a compound represented by Formula 1 above.
본 명세서의 일 실시상태에 있어서, 상기 2층 이상의 유기물층은 발광층, 정공 수송층, 정공 주입층, 정공 수송과 정공 주입을 동시에 하는 층 및 전자 차단층으로 이루어진 군에서 2 이상이 선택될 수 있다.In one embodiment of the present specification, the two or more organic material layers may be selected from the group consisting of a light emitting layer, a hole transport layer, a hole injection layer, a layer for simultaneously transporting and injecting holes, and an electron blocking layer.
본 명세서의 일 실시상태에 있어서, 상기 유기 발광 소자는 2층 이상의 전자 수송층을 포함할 수 있으나, 이에만 한정되는 것은 아니다.In the exemplary embodiment of the present specification, the organic light emitting device may include two or more electron transport layers, but is not limited thereto.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 2층 이상의 전자 수 송층을 포함하고, 상기 2층 이상의 전자 수송층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함한다. 구체적으로 본 명세서의 일 실시상태에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 2층 이상의 전자 수송층 중 1층에 포함될 수도 있으며, 각각의 2층 이상의 전자 수송층에 포함될 수 있다. In the exemplary embodiment of the present specification, the organic material layer includes two or more electron transport layers, and at least one of the two or more electron transport layers includes the compound represented by Formula 1 above. Specifically, in an exemplary embodiment of the present specification, the compound represented by Formula 1 may be included in one of the two or more electron transport layers, and may be included in each of the two or more electron transport layers.
또한, 본 명세서의 일 실시상태에 있어서, 상기 화합물이 상기 각각의 2층 이상의 전자 수송층에 포함되는 경우, 상기 화학식 1로 표시되는 화합물을 제외한 다른 재료들은 서로 동일하거나 상이할 수 있다.In addition, in the exemplary embodiment of the present specification, when the compound is included in each of the two or more electron transport layers, materials other than the compound represented by Formula 1 may be the same or different from each other.
상기 화학식 1로 표시되는 화합물을 포함하는 유기물층이 전자 수송층인 경우, 상기 전자 수송층은 n형 도펀트를 더 포함할 수 있다. 상기 n형 도펀트는 당 기술분야에 알려져 있는 것들을 사용할 수 있으며, 예컨대 금속 또는 금속착체를 사용할 수 있다. 예를 들어, 상기 화학식 1로 표시되는 화합물을 포함하는 전자 수송층은 LiQ(Lithium Quinolate)를 더 포함할 수 있다.When the organic material layer including the compound represented by Formula 1 is an electron transport layer, the electron transport layer may further include an n-type dopant. As the n-type dopant, those known in the art may be used, for example, a metal or a metal complex may be used. For example, the electron transport layer including the compound represented by Formula 1 may further include lithium quinolate (LiQ).
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 2층 이상의 정공수송층을 포함하고, 상기 2층 이상의 정공 수송층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함한다. 구체적으로, 본 명세서의 일 실시상태에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 2층 이상의 정공 수송층 중 1층에 포함될 수도 있으며, 각각의 2층 이상의 정공 수송층에 포함될 수 있다. In an exemplary embodiment of the present specification, the organic material layer includes two or more hole transport layers, and at least one of the two or more hole transport layers includes the compound represented by Formula 1 above. Specifically, in an exemplary embodiment of the present specification, the compound represented by Formula 1 may be included in one of the two or more hole transport layers, and may be included in each of the two or more hole transport layers.
또한, 본 명세서의 일 실시상태에 있어서, 상기 화학식 1로 표시되는 화합물이 상기 각각의 2층 이상의 정공 수송층에 포함되는 경우, 상기 화학식 1로 표시되는 화합물을 제외한 다른 재료들은 서로 동일하거나 상이할 수 있다.In addition, in an exemplary embodiment of the present specification, when the compound represented by Formula 1 is included in each of the two or more hole transport layers, materials other than the compound represented by Formula 1 may be the same or different from each other. have.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층 이외에 아릴아민기, 카바졸릴기 또는 벤조카바졸릴기를 포함하는 화합물을 포함하는 정공 주입층 또는 정공 수송층을 더 포함할 수 있다.In an exemplary embodiment of the present specification, the organic material layer includes a hole injection layer or a hole transport layer containing a compound including an arylamine group, a carbazolyl group or a benzocarbazolyl group in addition to the organic material layer including the compound represented by Formula 1 above. may include
본 명세서의 일 실시상태에 있어서, 상기 제1 전극은 애노드 또는 캐소드이다.In one embodiment of the present specification, the first electrode is an anode or a cathode.
본 명세서의 일 실시상태에 있어서, 상기 제2 전극은 캐소드 또는 애노드이다. In one embodiment of the present specification, the second electrode is a cathode or an anode.
본 명세서의 일 실시상태에 있어서, 상기 유기 발광 소자는 기판 상에 애노드, 1층 이상의 유기물층 및 캐소드가 순차적으로 적층된 구조(normal type)의 유기 발광 소자일 수 있다. In the exemplary embodiment of the present specification, the organic light emitting device may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.
본 명세서의 일 실시상태에 있어서, 상기 유기 발광 소자는 기판 상에 캐소드, 1층 이상의 유기물층 및 애노드가 순차적으로 적층된 역방향 구조(inverted type)의 유기 발광 소자일 수 있다.In the exemplary embodiment of the present specification, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.
예컨대, 본 명세서의 일 실시상태에 따른 유기 발광 소자의 구조가 도 1 내지 3에 예시되어 있다. 상기 도 1 내지 3은 유기 발광 소자를 예시한 것이며 이에 한정되는 것은 아니다. For example, the structure of an organic light emitting device according to an exemplary embodiment of the present specification is illustrated in FIGS. 1 to 3 . 1 to 3 illustrate an organic light emitting device, but is not limited thereto.
도 1은 기판(1), 제1 전극(2), 발광층(3) 및 제2 전극(4)이 순차적으로 적층된 유기 발광 소자의 구조가 예시되어 있다. 이와 같은 구조에 있어서, 상기 화합물은 상기 발광층(3)에 포함될 수 있다. 1 illustrates a structure of an organic light emitting device in which a substrate 1, a first electrode 2, a light emitting layer 3, and a second electrode 4 are sequentially stacked. In such a structure, the compound may be included in the light emitting layer 3 .
도 2는 기판 (1), 제1 전극 (2), 정공주입층(5), 정공수송층(8), 전자차단층(9), 발광층(3), 정공차단층(6), 전자주입 및 수송층(7), 및 제2 전극(4)이 순차적으로 적층된 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서 상기 화합물은 상기 발광층(3), 정공차단층(6), 전자주입 및 수송층(7) 및 정공주입층(8) 중 1층 이상에 포함될 수 있다.2 is a substrate (1), a first electrode (2), a hole injection layer (5), a hole transport layer (8), an electron blocking layer (9), a light emitting layer (3), a hole blocking layer (6), electron injection and An example of an organic light emitting device in which the transport layer 7 and the second electrode 4 are sequentially stacked is shown. In such a structure, the compound may be included in one or more of the light emitting layer 3 , the hole blocking layer 6 , the electron injection and transport layer 7 , and the hole injection layer 8 .
도 3은 기판 (1), 제1 전극 (2), 정공주입층(5), 정공수송층(8), 전자차단층(9), 발광층(3), 제1 전자수송층(10), 제2 전자수송층 (11), 전자주입층(12) 및 제2 전극(4)이 순차적으로 적층된 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서 상기 화합물은 상기 발광층(3)에 포함될 수 있다.3 is a substrate (1), a first electrode (2), a hole injection layer (5), a hole transport layer (8), an electron blocking layer (9), a light emitting layer (3), a first electron transport layer (10), the second An example of an organic light emitting device in which the electron transport layer 11 , the electron injection layer 12 , and the second electrode 4 are sequentially stacked is shown. In such a structure, the compound may be included in the light emitting layer 3 .
본 명세서의 유기 발광 소자는 유기물층 중 1층 이상이 상기 화합물, 즉 상기 화학식 1로 표시되는 화합물을 포함하는 것을 제외하고는 당 기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다. The organic light emitting device of the present specification may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound, that is, the compound represented by Formula 1 above.
상기 유기 발광 소자가 복수개의 유기물층을 포함하는 경우, 상기 유기물층은 동일한 물질 또는 다른 물질로 형성될 수 있다. When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
예컨대, 본 명세서의 유기 발광 소자는 기판 상에 제1 전극, 유기물층 및 제2 전극을 순차적으로 적층시킴으로써 제조할 수 있다. 이 때, 스퍼터링법(sputtering)이나 전자빔 증발법(e-beam evaporation)과 같은 PVD(physical Vapor Deposition)방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공 주입층, 정공 수송층, 발광층 및 전자 수송층을 포함하는 유기물층을 형성한 후, 그 위에 캐소드로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 캐소드 물질, 유기물층 및 애노드 물질을 차례로 증착시켜 유기 발광 소자를 제조할 수 있다. For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. It may be prepared by forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
또한, 상기 화학식 1로 표시되는 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하나, 이에 한정되는 것은 아니다. In addition, the compound represented by Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, 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 만들 수도 있다 (국제 특허 출원 공개 제 2003/012890호). 다만, 제조 방법이 이에 한정되는 것은 아니다. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (International Patent Application Laid-Open No. 2003/012890). However, the manufacturing method is not limited thereto.
상기 제1 전극 물질로는 통상 유기물층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 예를 들어, 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2 : Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이에 한정되는 것은 아니다. As the material for the first electrode, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. For example, metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO:Al or SnO 2 : a combination of a metal such as Sb and an oxide; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
상기 제2 전극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 예를 들어, 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이에 한정되는 것은 아니다.The second electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. metals or alloys thereof such as, for example, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead; LiF/Al or a multi-layered material such as LiO 2 /Al, but is not limited thereto.
상기 발광층은 호스트 재료 및 도펀트 재료를 포함할 수 있다. 호스트 재료로는 축합 방향족환 유도체 또는 헤테로환 함유 화합물 등이 있다. 구체적으로, 축합 방향족환 유도체로는 안트라센 유도체, 피렌 유도체, 나프탈렌 유도체, 펜타센 유도체, 페난트렌 화합물, 플루오란텐 화합물 등이 있고, 헤테로환 함유 화합물로는 디벤조퓨란 유도체, 래더형 퓨란 화합물, 피리미딘 유도체 등이 있으나, 이에 한정되는 것은 아니다. The emission layer may include a host material and a dopant material. Examples of the host material include a condensed aromatic ring derivative or a heterocyclic compound containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include dibenzofuran derivatives, ladder-type furan compounds, and pyrimidine derivatives, but is not limited thereto.
상기 도펀트 재료로는 상기 화학식 1로 표시되는 화합물 이외에 방향족 아민 유도체, 스트릴아민 화합물, 붕소 착체, 플루오란텐 화합물, 금속 착체 등이 있다. 구체적으로, 방향족 아민 유도체로는 치환 또는 비치환된 아릴아민기를 갖는 축합 방향족환 유도체로서, 아릴아민기를 갖는 피렌, 안트라센, 크리센, 페리플란텐 등이 있다. 또한, 스티릴아민 화합물은 치환 또는 비치환된 아릴아민에 적어도 1개의 아릴비닐기가 치환되어 있는 화합물로, 아릴기, 실릴기, 알킬기, 시클로알킬기 및 아릴아민기로 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 한정되는 것은 아니다. Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex, in addition to the compound represented by Formula 1 above. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamine group, and includes pyrene, anthracene, chrysene, periplanthene, and the like, having an arylamine group. In addition, the styrylamine compound is a compound in which at least one arylvinyl group is substituted with a substituted or unsubstituted arylamine, and one or two or more selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamine group A substituent is substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.
본 명세서에서, 상기 화학식 1로 표시되는 화합물이 발광층 이외의 유기물층에 포함되거나, 추가의 발광층이 구비되는 경우, 상기 발광층의 발광 물질로는 정공 수송층과 전자 수송층으로부터 정공과 전자를 각각 수송 받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다. 예를 들어, 8-히드록시-퀴놀린 알루미늄 착물(Alq3); 카르바졸 계열 화합물; 이량체화 스티릴(dimerized styryl) 화합물; BAlq; 10-히드록시벤조 퀴놀린-금속 화합물; 벤족사졸, 벤즈티아졸 및 벤즈이미다졸 계열의 화합물; 폴리(p-페닐렌비닐렌)(PPV) 계열의 고분자; 스피로(spiro) 화합물; 폴리플루오렌; 및 루브렌 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, when the compound represented by Formula 1 is included in an organic material layer other than the light emitting layer or an additional light emitting layer is provided, the light emitting material of the light emitting layer receives and bonds holes and electrons from the hole transport layer and the electron transport layer, respectively. As a material capable of emitting light in the visible light region, a material having good quantum efficiency for fluorescence or phosphorescence is preferable. For example, 8-hydroxy-quinoline aluminum complex (Alq 3 ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene; and rubrene, but is not limited thereto.
상기 정공 주입층은 전극으로부터 정공을 주입하는 층이다. 정공 주입 물질은 정공을 수송하는 능력을 가져 제1 전극에서의 정공 주입 효과 및 발광층 또는 발광 재료에 대하여 우수한 정공 주입 효과를 갖는 것이 바람직하다. 또한, 발광층에서 생성된 여기자의 전자 주입층 또는 전자 주입 재료에의 이동을 방지할 수 있는 능력이 우수한 물질이 바람직하다. 또한, 박막 형성 능력이 우수한 물질이 바람직하다. 또한, 정공 주입 물질의 HOMO(highest ocupied molecular orbital)가 제1 전극 물질의 일함수와 주변 유기물층의 HOMO 사이인 것이 바람직하다. 정공 주입 물질의 구체적인 예로는, 금속 포피린(porphyrin), 올리고티오펜, 아릴아민 계열의 유기물; 카르바졸 계열의 유기물; 니트릴 계열의 유기물; 헥사니트릴헥사아자트리페닐렌 계열의 유기물; 퀴나크리돈(quinacridone)계열의 유기물; 페릴렌(perylene) 계열의 유기물; 안트라퀴논, 폴리아닐린과 같은 폴리티오펜 계열의 전도성 고분자 등 또는 상기 예 중 2 이상을 혼합물 등이 있으나, 이에 한정 되는 것은 아니다. The hole injection layer is a layer for injecting holes from the electrode. It is preferable that the hole injection material has the ability to transport holes and thus has a hole injection effect at the first electrode and an excellent hole injection effect on the light emitting layer or the light emitting material. Also, a material excellent in the ability to prevent movement of excitons generated in the light emitting layer to the electron injection layer or the electron injection material is preferable. In addition, a material excellent in the ability to form a thin film is preferable. In addition, it is preferable that the highest ocupied molecular orbital (HOMO) of the hole injection material is between the work function of the first electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material; carbazole-based organics; nitrile-based organics; hexanitrile hexaazatriphenylene-based organic substances; quinacridone-based organic substances; perylene-based organic materials; Polythiophene-based conductive polymers such as anthraquinone and polyaniline or mixtures of two or more of the above examples, but are not limited thereto.
상기 정공 수송층은 정공 주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층이다. 정공 수송 물질로는 제1 전극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 바람직하다. 구체적인 예로는, 아릴아민 계열의 유기물, 카르바졸 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이에 한정되는 것은 아니다.The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. The hole transport material is a material capable of transporting holes from the first electrode or the hole injection layer to the light emitting layer, and a material having high hole mobility is preferable. Specific examples include, but are not limited to, an arylamine-based organic material, a carbazole-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.
상기 전자 수송층은 전자 주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하는 층이다. 전자 수송 물질로는 제2 전극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 바람직하다. 구체적인 예로는, 8-히드록시퀴놀린의 Al착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물; 트리아진 유도체; LiQ 등이 있으나, 이에 한정되는 것은 아니다. 전자 수송층은 종래기술에 따라 사용된 바와 같이, 임의의 원하는 제1 전극 물질과 함께 사용할 수 있다. 특히, 적절한 제1 전극 물질은 낮은 일함수를 가지며, 알루미늄층 또는 실버층이 뒤따르는 통상적인 물질이다. 구체적으로, 세슘, 바륨, 칼슘, 이테르븀 및 사마륨 등이 있고, 각 경우 알루미늄층 또는 실버층이 뒤따른다.The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. The electron transport material is a material capable of well injecting electrons from the second electrode and transferring them to the light emitting layer, and a material having high electron mobility is preferable. Specific examples include an Al complex of 8-hydroxyquinoline; complexes containing Alq 3 ; organic radical compounds; hydroxyflavone-metal complexes; triazine derivatives; LiQ, etc., but is not limited thereto. The electron transport layer may be used with any desired first electrode material, as used in accordance with the prior art. In particular, suitable first electrode materials are conventional materials having a low work function, followed by a layer of aluminum or silver. Specifically, there are cesium, barium, calcium, ytterbium, samarium, and the like, followed by an aluminum layer or a silver layer in each case.
상기 전자 주입층은 전극으로부터 전자를 주입하는 층이다. 전자 주입물로는 전자를 수송하는 능력이 우수하고, 제2 전극으로부터의 전자 주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자주입 효과를 갖는 것이 바람직하다. 또한, 발광층에서 생성된 여기자가 정공 주입층으로 이동하는 것을 방지하고, 박막 형성 능력이 우수한 물질이 바람직하다. 구체적으로는, 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 트리아진, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 함질소 5원환 유도체, 상기 예 중 2 이상의 혼합물 등이 있으나, 이에 한정되는 것은 아니다. The electron injection layer is a layer that injects electrons from the electrode. It is preferable that the electron injection material has excellent electron transporting ability and has excellent electron injection effect from the second electrode and electron injection effect with respect to the light emitting layer or the light emitting material. In addition, a material that prevents excitons generated in the light emitting layer from moving to the hole injection layer and has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, triazine, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. derivatives thereof, metal complex compounds and nitrogen-containing 5-membered ring derivatives, and mixtures of two or more of the above examples, but are not limited thereto.
상기 금속 착체 화합물로는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되는 것은 아니다.Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, and bis(8-hydroxyquinolinato)manganese. , tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h ]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato) (o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. , but is not limited thereto.
상기 전자 차단층은 전자 주입층으로부터 주입된 전자가 발광층을 지나 정공 주입층으로 진입하는 것을 방지하여 소자의 수명과 효율을 향상시킬 수 있는 층이다. 공지된 재료는 제한 없이 사용 가능하며, 발광층과 정공 주입층 사이에, 또는 발광층과 정공 주입 및 정공 수송을 동시에 하는 층 사이에 형성될 수 있다. The electron blocking layer is a layer capable of improving the lifetime and efficiency of the device by preventing electrons injected from the electron injection layer from entering the hole injection layer through the emission layer. A known material can be used without limitation, and may be formed between the light emitting layer and the hole injection layer, or between the light emitting layer and the layer that simultaneously injects and transports holes.
상기 정공 차단층은 정공이 발광층을 지나 음극으로 도달을 저지하는 층으로, 일반적으로 전자 주입층과 동일한 조건으로 형성될 수 있다. 구체적으로, 옥사디아졸 유도체나 트리아졸 유도체, 페난트롤린 유도체, 알루미늄 착물 (aluminum complex), 피리딘, 피리미딘 또는 트리아진 유도체 등이 있으나, 이에 한정되는 것은 아니다.The hole blocking layer is a layer that blocks holes from reaching the cathode through the light emitting layer, and may be generally formed under the same conditions as the electron injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, aluminum complexes, pyridine, pyrimidine or triazine derivatives, but is not limited thereto.
본 명세서에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to the present specification may be a top emission type, a back emission type, or a double side emission type depending on the material used.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1로 표시되는 화합물은 유기 발광 소자 외에도 유기 태양 전지 또는 유기 트랜지스터에 포함될 수 있다.In an exemplary embodiment of the present specification, the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
본 명세서에 따른 화합물은 유기 인광 소자, 유기 태양 전지, 유기 감광체, 유기 트랜지스터 등을 비롯한 유기 발광 소자에서도 유기 발광 소자에 적용되는 것과 유사한 원리로 작용할 수 있다. 예컨대, 상기 유기 태양 전지는 음극, 양극 및 상기 음극과 양극 사이에 구비된 광활성층을 포함하는 구조일 수 있고, 상기 광활성층은 상기 화합물을 포함할 수 있다.The compound according to the present specification may act on a principle similar to that applied to an organic light emitting device in an organic light emitting device including an organic phosphorescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and the like. For example, the organic solar cell may have a structure including a negative electrode, a positive electrode, and a photoactive layer provided between the negative electrode and the positive electrode, and the photoactive layer may include the compound.
본 명세서의 유기 발광 소자는 전술한 화합물을 이용하여 한 층 이상의 유기물층을 형성하는 것을 제외하고는, 통상의 유기 발광 소자의 제조방법 및 재료에 의하여 제조될 수 있다.The organic light emitting device of the present specification may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except for forming one or more organic material layers using the above-described compound.
이하, 본 명세서를 구체적으로 설명하기 위해 실시예 및 비교예 등을 들어 상세하게 설명하기로 한다. 그러나, 본 명세서에 따른 실시예 및 비교예는 여러 가지 다른 형태로 변형될 수 있으며, 본 명세서의 범위가 아래에서 상술하는 실시예 및 비교예에 한정되는 것으로 해석되지 않는다. 본 명세서의 실시예 및 비교예는 당업계에서 평균적인 지식을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, in order to describe the present specification in detail, it will be described in detail with reference to Examples and Comparative Examples. However, the Examples and Comparative Examples according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the Examples and Comparative Examples described in detail below. Examples and comparative examples of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art.
[합성예][Synthesis Example]
합성예1 : 화합물 1의 합성Synthesis Example 1: Synthesis of compound 1
단계 1) 화합물 1-a의 합성Step 1) Synthesis of compound 1-a
Figure PCTKR2020017069-appb-I000112
Figure PCTKR2020017069-appb-I000112
3구 플라스크에 1-브로모-3-클로로-5-메틸벤젠 (146 mmol, 30 g)과 비스(4-(터부틸)페닐)아민 (146 mmol, 41.1g)을 톨루엔 (0.2 M, 730 ml)에 녹이고 소듐 터부톡사이드(219 mmol, 21 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.46 mmol, 0.75 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 1시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-a 49g을 수득하였다. (수율 83%, MS[M+H]+= 405)In a three-necked flask, 1-bromo-3-chloro-5-methylbenzene (146 mmol, 30 g) and bis(4-(terbutyl)phenyl)amine (146 mmol, 41.1 g) were mixed with toluene (0.2 M, 730). ml), sodium terbutoxide (219 mmol, 21 g), bis(tri-terbutylphosphine)palladium (0) (1.46 mmol, 0.75 g) were added, and the mixture was stirred for 1 hour under reflux conditions under argon atmosphere . Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 49 g of compound 1-a. (Yield 83%, MS[M+H]+= 405)
단계 2) 화합물 1-b의 합성Step 2) Synthesis of compound 1-b
Figure PCTKR2020017069-appb-I000113
Figure PCTKR2020017069-appb-I000113
3구 플라스크에 3-브로모벤조퓨란 (101.5 mmol, 20 g)과 아닐린 (101.5 mmol, 9.45g)을 톨루엔 (0.2 M, 508 ml)에 녹이고 소듐 터부톡사이드(152 mmol, 14.6 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.0 mmol, 0.51 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 3시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-b 14.8g을 수득하였다. (수율 70%, MS[M+H]+= 209)In a three-necked flask, 3-bromobenzofuran (101.5 mmol, 20 g) and aniline (101.5 mmol, 9.45 g) were dissolved in toluene (0.2 M, 508 ml), and sodium terbutoxide (152 mmol, 14.6 g), bis After (tri-terbutylphosphine)palladium(0) (1.0 mmol, 0.51 g) was added, the mixture was stirred for 3 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 14.8 g of compound 1-b. (Yield 70%, MS[M+H]+=209)
단계 3) 화합물 1-c의 합성Step 3) Synthesis of compound 1-c
Figure PCTKR2020017069-appb-I000114
Figure PCTKR2020017069-appb-I000114
3구 플라스크에 화합물 1-a (49.3 mmol, 20 g)와 화합물 1-b (49.3 mmol, 13.7g)을 톨루엔 (0.2 M, 246 ml)에 녹이고 소듐 터부톡사이드(73.4 mmol, 7.1 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.49 mmol, 0.25 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-c 18.4 g을 수득하였다. (수율 65%, MS[M+H]+= 579)In a three-necked flask, compound 1-a (49.3 mmol, 20 g) and compound 1-b (49.3 mmol, 13.7 g) were dissolved in toluene (0.2 M, 246 ml), sodium terbutoxide (73.4 mmol, 7.1 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.49 mmol, 0.25 g), the mixture was stirred for 4 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 18.4 g of compound 1-c. (Yield 65%, MS[M+H]+= 579)
단계 4) 화합물 1의 합성Step 4) Synthesis of compound 1
Figure PCTKR2020017069-appb-I000115
Figure PCTKR2020017069-appb-I000115
3구 플라스크에 화합물 1-c (31.8 mmol, 18.4 g)을 1,2-디클로로벤젠 (0.1 M, 320 ml)에 녹이고 보론트리아이오다이드 (50.9 mmol, 19.9 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소 프로필에틸아민 (286 mmol, 37 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 1, 3.1g을 수득하였다. (수율 17%, MS[M+H]+= 587)In a three-necked flask, compound 1-c (31.8 mmol, 18.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 320 ml), boron triiodide (50.9 mmol, 19.9 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (286 mmol, 37 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain Compound 1, 3.1g. (Yield 17%, MS[M+H]+= 587)
합성예2 : 화합물 2의 합성Synthesis Example 2: Synthesis of compound 2
단계 1) 화합물 2-a의 합성Step 1) Synthesis of compound 2-a
Figure PCTKR2020017069-appb-I000116
Figure PCTKR2020017069-appb-I000116
3구 플라스크에 1-아다만틸아민 (132.2 mmol, 20 g)과 6-터부틸-3-브로모벤조퓨란 (132.2 mmol, 33.5 g)을 톨루엔 (0.2 M, 661 ml)에 녹이고 소듐 터부톡사이드(198 mmol, 19 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.32 mmol, 0.68 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-a 31.2g을 수득하였다. (수율 73%, MS[M+H]+= 323)In a three-necked flask, 1-adamantylamine (132.2 mmol, 20 g) and 6-terbutyl-3-bromobenzofuran (132.2 mmol, 33.5 g) were dissolved in toluene (0.2 M, 661 ml) and sodium terbutok Side (198 mmol, 19 g) and bis(tri-terbutylphosphine)palladium(0) (1.32 mmol, 0.68 g) were added, and the mixture was stirred under reflux conditions in an argon atmosphere for 6 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 31.2 g of compound 2-a. (Yield 73%, MS[M+H]+= 323)
단계 2) 화합물 2-b의 합성Step 2) Synthesis of compound 2-b
Figure PCTKR2020017069-appb-I000117
Figure PCTKR2020017069-appb-I000117
3구 플라스크에 화합물 1-a (61.6 mmol, 25 g)와 화합물 2-a (61.6 mmol, 19.9g)을 톨루엔 (0.2 M, 307 ml)에 녹이고 소듐 터부톡사이드 (92.4 mmol, 8.9 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.62 mmol, 0.31 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-b 24.4 g을 수득하였다. (수율 57%, MS[M+H]+= 693)In a three-necked flask, compound 1-a (61.6 mmol, 25 g) and compound 2-a (61.6 mmol, 19.9 g) were dissolved in toluene (0.2 M, 307 ml), sodium terbutoxide (92.4 mmol, 8.9 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.62 mmol, 0.31 g), the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 24.4 g of compound 2-b. (Yield 57%, MS[M+H]+=693)
단계 3) 화합물 2의 합성Step 3) Synthesis of compound 2
Figure PCTKR2020017069-appb-I000118
Figure PCTKR2020017069-appb-I000118
3구 플라스크에 화합물 2-b (30.8 mmol, 22.4 g)을 1,2-디클로로벤젠 (0.1 M, 308 ml)에 녹이고 보론트리아이오다이드 (49.3 mmol, 19.3 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소 프로필에틸아민 (277 mmol, 36 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 2, 3.4g을 수득하였다. (수율 16%, MS[M+H]+= 701)In a three-necked flask, compound 2-b (30.8 mmol, 22.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 308 ml), boron triiodide (49.3 mmol, 19.3 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0° C., and N,N-diisopropylethylamine (277 mmol, 36 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain Compound 2, 3.4 g. (yield 16%, MS[M+H]+= 701)
합성예3 : 화합물 3의 합성Synthesis Example 3: Synthesis of compound 3
단계 1) 화합물 3-a의 합성Step 1) Synthesis of compound 3-a
Figure PCTKR2020017069-appb-I000119
Figure PCTKR2020017069-appb-I000119
3구 플라스크에 4-터부틸-2-(1-나프탈레닐)-아닐린 (56.5 mmol, 15.5 g)과 5-터부틸-3-브로모벤조퓨란 (56.5 mmol, 14.3 g)을 톨루엔 (0.2 M, 282 ml)에 녹이고 소듐 터부톡사이드(85 mmol, 8.2 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.56 mmol, 0.29 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 3-a 21.7g을 수득하였다. (수율 86%, MS[M+H]+= 448)In a three-necked flask, 4-terbutyl-2-(1-naphthalenyl)-aniline (56.5 mmol, 15.5 g) and 5-terbutyl-3-bromobenzofuran (56.5 mmol, 14.3 g) were mixed with toluene (0.2 M, 282 ml), sodium terbutoxide (85 mmol, 8.2 g), bis(tri-terbutylphosphine)palladium (0) (0.56 mmol, 0.29 g) were added, and then 12 hours under reflux conditions in an argon atmosphere. stirred for a while. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 21.7 g of compound 3-a. (Yield 86%, MS[M+H]+= 448)
단계 2) 화합물 3-b의 합성Step 2) Synthesis of compound 3-b
Figure PCTKR2020017069-appb-I000120
Figure PCTKR2020017069-appb-I000120
3구 플라스크에 화합물 1-a (46.8 mmol, 19 g)와 화합물 3-a (46.8 mmol, 20.9g)을 톨루엔 (0.2 M, 234 ml)에 녹이고 소듐 터부톡사이드 (70.2 mmol, 6.7 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.47 mmol, 0.24 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 3-b 24.7 g을 수득하였다. (수율 65%, MS[M+H]+= 817)In a three-necked flask, compound 1-a (46.8 mmol, 19 g) and compound 3-a (46.8 mmol, 20.9 g) were dissolved in toluene (0.2 M, 234 ml), sodium terbutoxide (70.2 mmol, 6.7 g), After bis(tri-terbutylphosphine)palladium(0) (0.47 mmol, 0.24 g) was added, the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 24.7 g of compound 3-b. (Yield 65%, MS[M+H]+= 817)
단계 3) 화합물 3의 합성Step 3) Synthesis of compound 3
Figure PCTKR2020017069-appb-I000121
Figure PCTKR2020017069-appb-I000121
3구 플라스크에 화합물 3-b (30.2 mmol, 24.7 g)을 1,2-디클로로벤젠 (0.1 M, 303 ml)에 녹이고 보론트리아이오다이드 (48.4 mmol, 19 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소 프로필에틸아민 (272 mmol, 35 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 3, 3.9 g을 수득하였다. (수율 16%, MS[M+H]+= 825)In a three-necked flask, compound 3-b (30.2 mmol, 24.7 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 303 ml), boron triiodide (48.4 mmol, 19 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (272 mmol, 35 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 3, 3.9 g. (yield 16%, MS[M+H]+= 825)
합성예4 : 화합물 4의 합성Synthesis Example 4: Synthesis of compound 4
단계 1) 화합물 4-a의 합성Step 1) Synthesis of compound 4-a
Figure PCTKR2020017069-appb-I000122
Figure PCTKR2020017069-appb-I000122
3구 플라스크에 1,3-디브로모-5-클로로벤젠 (111 mmol, 30 g)과 비스(4-터부틸페닐)아민 (111 mmol, 31.2 g)을 톨루엔 (0.2 M, 555 ml)에 녹이고 소듐 터부톡사이드(166.5 mmol, 16 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.1 mmol, 0.58 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 1시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 4-a 30.6 g을 수득하였다. (수율 59%, MS[M+H]+= 471)In a three-necked flask, 1,3-dibromo-5-chlorobenzene (111 mmol, 30 g) and bis(4-terbutylphenyl)amine (111 mmol, 31.2 g) were dissolved in toluene (0.2 M, 555 ml). After dissolving, sodium terbutoxide (166.5 mmol, 16 g) and bis(tri-terbutylphosphine)palladium (0) (1.1 mmol, 0.58 g) were added, followed by stirring for 1 hour under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 30.6 g of compound 4-a. (yield 59%, MS[M+H]+=471)
단계 2) 화합물 4-b의 합성Step 2) Synthesis of compound 4-b
Figure PCTKR2020017069-appb-I000123
Figure PCTKR2020017069-appb-I000123
3구 플라스크에 3,5,5,8,8-펜타메틸-,6,7,8-테트라하이드로나프탈렌-2-아민 (79.1 mmol, 21.7 g)과 5-터부틸-3-브로모벤조퓨란 (79.1 mmol, 20 g)을 톨루엔 (0.2 M, 395 ml)에 녹이고 소듐 터부톡사이드 (118.6 mmol, 11.4 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.79 mmol, 0.40 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 4-b 25.3g을 수득하였다. (수율 82%, MS[M+H]+= 390)3,5,5,8,8-pentamethyl-,6,7,8-tetrahydronaphthalen-2-amine (79.1 mmol, 21.7 g) and 5-tertbutyl-3-bromobenzofuran in a 3-neck flask (79.1 mmol, 20 g) was dissolved in toluene (0.2 M, 395 ml), sodium terbutoxide (118.6 mmol, 11.4 g), bis(tri-terbutylphosphine)palladium(0) (0.79 mmol, 0.40 g) After adding, the mixture was stirred for 6 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 25.3 g of compound 4-b. (Yield 82%, MS[M+H]+=390)
단계 3) 화합물 4-c의 합성Step 3) Synthesis of compound 4-c
Figure PCTKR2020017069-appb-I000124
Figure PCTKR2020017069-appb-I000124
3구 플라스크에 화합물 4-a (63.7 mmol, 39 g)와 화합물 4-b (63.7 mmol, 24.8 g)을 톨루엔 (0.2 M, 319 ml)에 녹이고 소듐 터부톡사이드 (95.6 mmol, 9.2 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.64 mmol, 0.33 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 3시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 4-c 27.7 g을 수득하였다. (수율 56%, MS[M+H]+= 780)In a three-necked flask, compound 4-a (63.7 mmol, 39 g) and compound 4-b (63.7 mmol, 24.8 g) were dissolved in toluene (0.2 M, 319 ml), sodium terbutoxide (95.6 mmol, 9.2 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.64 mmol, 0.33 g), the mixture was stirred for 3 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 27.7 g of compound 4-c. (Yield 56%, MS[M+H]+=780)
단계 4) 화합물 4-d의 합성Step 4) Synthesis of compound 4-d
Figure PCTKR2020017069-appb-I000125
Figure PCTKR2020017069-appb-I000125
3구 플라스크에 화합물 4-c (35.5 mmol, 27.7 g)을 1,2-디클로로벤젠 (0.1 M, 355 ml)에 녹이고 보론트리아이오다이드 (56.9 mmol, 22.3 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (320 mmol, 41 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 4-d 6.2 g을 수득하였다. (수율 22%, MS[M+H]+= 787)In a three-neck flask, compound 4-c (35.5 mmol, 27.7 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 355 ml), boron triiodide (56.9 mmol, 22.3 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, and N,N-diisopropylethylamine (320 mmol, 41 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 6.2 g of compound 4-d. (Yield 22%, MS[M+H]+=787)
단계 5) 화합물 4 의 합성Step 5) Synthesis of compound 4
Figure PCTKR2020017069-appb-I000126
Figure PCTKR2020017069-appb-I000126
3구 플라스크에 화합물 4-d (7.9 mmol, 6.2 g)와 9,9-디메틸-9,10-디하이드로아크리딘 (9.4 mmol, 2 g)을 톨루엔 (0.2 M, 47 ml)에 녹이고 소듐 터부톡사이드 (11.8 mmol, 1.1 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.08 mmol, 0.04 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 4, 24.7 g을 수득하였다. (수율 77%, MS[M+H]+= 960)In a three-neck flask, compound 4-d (7.9 mmol, 6.2 g) and 9,9-dimethyl-9,10-dihydroacridine (9.4 mmol, 2 g) were dissolved in toluene (0.2 M, 47 ml), and sodium After terbutoxide (11.8 mmol, 1.1 g) and bis(tri-terbutylphosphine)palladium(0) (0.08 mmol, 0.04 g) were added, the mixture was stirred for 18 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 4, 24.7 g. (yield 77%, MS[M+H]+=960)
합성예5 : 화합물 5의 합성Synthesis Example 5: Synthesis of compound 5
단계 1) 화합물 5-a의 합성Step 1) Synthesis of compound 5-a
Figure PCTKR2020017069-appb-I000127
Figure PCTKR2020017069-appb-I000127
3구 플라스크에 1-브로모-3-클로로-5-터부틸벤젠 (121 mmol, 30 g)과 4-터부틸-N-(4-터부틸페닐)-2,6-디메틸아닐린 (121 mmol, 37.5g)을 톨루엔 (0.2 M, 605 ml)에 녹이고 소듐 터부톡사이드(182 mmol, 17.5 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.2 mmol, 0.62 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 5-a 51.2g을 수득하였다. (수율 89%, MS[M+H]+= 476)In a 3-neck flask, 1-bromo-3-chloro-5-terbutylbenzene (121 mmol, 30 g) and 4-terbutyl- N- (4-terbutylphenyl)-2,6-dimethylaniline (121 mmol) , 37.5 g) was dissolved in toluene (0.2 M, 605 ml), sodium terbutoxide (182 mmol, 17.5 g), bis (tri-terbutylphosphine) palladium (0) (1.2 mmol, 0.62 g) was added. , and stirred for 4 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 51.2 g of compound 5-a. (yield 89%, MS[M+H]+=476)
단계 2) 화합물 5-b의 합성Step 2) Synthesis of compound 5-b
Figure PCTKR2020017069-appb-I000128
Figure PCTKR2020017069-appb-I000128
3구 플라스크에 3-브로모-5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프토[2,3-b]퓨란 (97.6 mmol, 30 g)과 4-터부틸아닐린 (97.6 mmol, 14.6g)을 톨루엔 (0.2 M, 488 ml)에 녹이고 소듐 터부톡사이드 (146.5 mmol, 14.1 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.98 mmol, 0.5 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 5-b 35.4 g을 수득하였다. (수율 97%, MS[M+H]+= 376)3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho [2,3- b ] furan (97.6 mmol, 30 g) and 4- Terbutylaniline (97.6 mmol, 14.6 g) was dissolved in toluene (0.2 M, 488 ml), sodium terbutoxide (146.5 mmol, 14.1 g), bis (tri-terbutylphosphine) palladium (0) (0.98 mmol, 0.5 g) was added, and the mixture was stirred for 6 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 35.4 g of compound 5-b. (yield 97%, MS[M+H]+=376)
단계 3) 화합물 5-c의 합성Step 3) Synthesis of compound 5-c
Figure PCTKR2020017069-appb-I000129
Figure PCTKR2020017069-appb-I000129
3구 플라스크에 화합물 5-a (44.1 mmol, 21 g)와 화합물 5-b (44.1 mmol, 16.6 g)을 톨루엔 (0.2 M, 220 ml)에 녹이고 소듐 터부톡사이드 (66.2 mmol, 6.4 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.44 mmol, 0.23 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 5-c 21.8 g을 수득하였다. (수율 61%, MS[M+H]+= 815)In a three-necked flask, compound 5-a (44.1 mmol, 21 g) and compound 5-b (44.1 mmol, 16.6 g) were dissolved in toluene (0.2 M, 220 ml), sodium terbutoxide (66.2 mmol, 6.4 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.44 mmol, 0.23 g), the mixture was stirred for 6 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 21.8 g of compound 5-c. (Yield 61%, MS[M+H]+= 815)
단계 4) 화합물 5의 합성Step 4) Synthesis of compound 5
Figure PCTKR2020017069-appb-I000130
Figure PCTKR2020017069-appb-I000130
3구 플라스크에 화합물 5-c (26.7 mmol, 21.8 g)을 1,2-디클로로벤젠 (0.1 M, 267 ml)에 녹이고 보론트리아이오다이드 (42.8 mmol, 16.8 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (241 mmol, 31 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 5, 3.4 g을 수득하였다. (수율 15%, MS[M+H]+= 823)In a three-neck flask, compound 5-c (26.7 mmol, 21.8 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 267 ml), boron triiodide (42.8 mmol, 16.8 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (241 mmol, 31 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 5, 3.4 g. (yield 15%, MS[M+H]+= 823)
합성예6 : 화합물 6의 합성Synthesis Example 6: Synthesis of compound 6
단계 1) 화합물 6-a의 합성Step 1) Synthesis of compound 6-a
Figure PCTKR2020017069-appb-I000131
Figure PCTKR2020017069-appb-I000131
3구 플라스크에 1,4,6-트리메틸아닐린 (74.0 mmol, 10 g)과 3-브로모-5,8-디메틸-5,6,7,8-테트라하이드로-5,8-에타노나프토[2,3-b]퓨란 (74.0 mmol, 22.6 g)을 톨루엔 (0.2 M, 370 ml)에 녹이고 소듐 터부톡사이드(111 mmol, 10.7 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.740 mmol, 0.378 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 6-a 21.9 g을 수득하였다. (수율 82%, MS[M+H]+= 360)1,4,6-trimethylaniline (74.0 mmol, 10 g) and 3-bromo-5,8-dimethyl-5,6,7,8-tetrahydro-5,8-ethanonaphtho [ 2,3- b ]furan (74.0 mmol, 22.6 g) was dissolved in toluene (0.2 M, 370 ml), sodium terbutoxide (111 mmol, 10.7 g), bis(tri-terbutylphosphine)palladium (0) (0.740 mmol, 0.378 g) was added, and the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 21.9 g of compound 6-a. (Yield 82%, MS[M+H]+=360)
단계 2) 화합물 6-b의 합성Step 2) Synthesis of compound 6-b
Figure PCTKR2020017069-appb-I000132
Figure PCTKR2020017069-appb-I000132
3구 플라스크에 화합물 1-a (36.9 mmol, 15.0 g)와 화합물 2-a (36.9 mmol, 13.3 g)을 톨루엔 (0.2 M, 185 ml)에 녹이고 소듐 터부톡사이드 (55.4 mmol, 5.33 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.369 mmol, 0.189 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 6-b 21.5 g을 수득하였다. (수율 80%, MS[M+H]+= 729)In a three-necked flask, compound 1-a (36.9 mmol, 15.0 g) and compound 2-a (36.9 mmol, 13.3 g) were dissolved in toluene (0.2 M, 185 ml), sodium terbutoxide (55.4 mmol, 5.33 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.369 mmol, 0.189 g), the mixture was stirred for 12 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 21.5 g of compound 6-b. (yield 80%, MS[M+H]+= 729)
단계 3) 화합물 6의 합성Step 3) Synthesis of compound 6
Figure PCTKR2020017069-appb-I000133
Figure PCTKR2020017069-appb-I000133
3구 플라스크에 화합물 6-b (29.5 mmol, 21.5 g)을 1,2-디클로로벤젠 (0.1 M, 295 ml)에 녹이고 보론트리아이오다이드 (47.2 mmol, 18.5 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (265 mmol, 34.3 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 6, 4.2 g을 수득하였다. (수율 19%, MS[M+H]+= 737)In a three-necked flask, compound 6-b (29.5 mmol, 21.5 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 295 ml), boron triiodide (47.2 mmol, 18.5 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (265 mmol, 34.3 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 6, 4.2 g. (yield 19%, MS[M+H]+=737)
합성예7 : 화합물 7의 합성Synthesis Example 7: Synthesis of compound 7
단계 1) 화합물 7-a의 합성Step 1) Synthesis of compound 7-a
Figure PCTKR2020017069-appb-I000134
Figure PCTKR2020017069-appb-I000134
3구 플라스크에 4-터부틸아닐린 (33.5 mmol, 5 g)과 9-(3-브로모벤조퓨란-6-일)-4a,9a-디메틸-2,3,4,4a,9,9a-헥사하이드로-1H-카바졸 (33.5 mmol, 13.3 g)을 톨루엔 (0.2 M, 168 ml)에 녹이고 소듐 터부톡사이드(50.3 mmol, 4.83 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.335 mmol, 0.171 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 3시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 7-a 13.2 g을 수득하였다. (수율 85%, MS[M+H]+= 465)In a 3-neck flask, 4-terbutylaniline (33.5 mmol, 5 g) and 9-(3-bromobenzofuran-6-yl)-4a,9a-dimethyl-2,3,4,4a,9,9a- Hexahydro- 1H -carbazole (33.5 mmol, 13.3 g) was dissolved in toluene (0.2 M, 168 ml), sodium terbutoxide (50.3 mmol, 4.83 g), bis(tri-terbutylphosphine)palladium (0 ) (0.335 mmol, 0.171 g) was added, followed by stirring for 3 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 13.2 g of compound 7-a. (yield 85%, MS[M+H]+= 465)
단계 2) 화합물 7-b의 합성Step 2) Synthesis of compound 7-b
Figure PCTKR2020017069-appb-I000135
Figure PCTKR2020017069-appb-I000135
3구 플라스크에 화합물 1-a (25.9 mmol, 10.5 g)와 화합물 7-a (25.9 mmol, 12.0 g)을 톨루엔 (0.2 M, 129 ml)에 녹이고 소듐 터부톡사이드 (38.8 mmol, 3.73 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.259 mmol, 0.132 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 7-b 19.4 g을 수득하였다. (수율 90%, MS[M+H]+= 834)In a three-necked flask, compound 1-a (25.9 mmol, 10.5 g) and compound 7-a (25.9 mmol, 12.0 g) were dissolved in toluene (0.2 M, 129 ml), sodium terbutoxide (38.8 mmol, 3.73 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.259 mmol, 0.132 g), the mixture was stirred for 6 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 19.4 g of compound 7-b. (Yield 90%, MS[M+H]+=834)
단계 3) 화합물 7의 합성Step 3) Synthesis of compound 7
Figure PCTKR2020017069-appb-I000136
Figure PCTKR2020017069-appb-I000136
3구 플라스크에 화합물 7-b (23.3 mmol, 19.4 g)을 1,2-디클로로벤젠 (0.1 M, 233 ml)에 녹이고 보론트리아이오다이드 (37.2 mmol, 14.6 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (209 mmol, 27.1 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 7, 3.7 g을 수득하였다. (수율 19%, MS[M+H]+= 842)In a three-necked flask, compound 7-b (23.3 mmol, 19.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 233 ml), boron triiodide (37.2 mmol, 14.6 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, and N,N-diisopropylethylamine (209 mmol, 27.1 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 7, 3.7 g. (yield 19%, MS[M+H]+=842)
합성예 8 : 화합물 8의 합성Synthesis Example 8: Synthesis of compound 8
단계 1) 화합물 8-a의 합성Step 1) Synthesis of compound 8-a
Figure PCTKR2020017069-appb-I000137
Figure PCTKR2020017069-appb-I000137
3구 플라스크에 비스(4-터부틸페닐)아민 (46.2 mmol, 13 g)과 3-브로모-4'-터부틸-5-클로로-1,1'-바이페닐 (46.2 mmol, 15g)을 톨루엔 (0.2 M, 231 ml)에 녹이고 소듐 터부톡사이드 (69.3 mmol, 6.66 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.462 mmol, 0.236 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 2시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 8-a 19.4g을 수득하였다. (수율 80%, MS[M+H]+= 524)Bis (4-terbutylphenyl) amine (46.2 mmol, 13 g) and 3-bromo-4'-terbutyl-5-chloro-1,1'-biphenyl (46.2 mmol, 15 g) were added to a three-necked flask. Dissolved in toluene (0.2 M, 231 ml), sodium terbutoxide (69.3 mmol, 6.66 g), bis (tri-terbutylphosphine) palladium (0) (0.462 mmol, 0.236 g) was added, and argon atmosphere reflux conditions under stirring for 2 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 19.4 g of compound 8-a. (yield 80%, MS[M+H]+= 524)
단계 2) 화합물 8-b의 합성Step 2) Synthesis of compound 8-b
Figure PCTKR2020017069-appb-I000138
Figure PCTKR2020017069-appb-I000138
3구 플라스크에 2-브로모-5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프토[2,3-b]퓨란 (78.1 mmol, 24 g)과 4-터부틸아닐린 (78.1 mmol, 11.7g)을 톨루엔 (0.2 M, 390 ml)에 녹이고 소듐 터부톡사이드 (117.2 mmol, 11.3 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.781 mmol, 0.4 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 8-b 20.6 g을 수득하였다. (수율 70%, MS[M+H]+= 376)2-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho [2,3- b ] furan (78.1 mmol, 24 g) and 4- Terbutylaniline (78.1 mmol, 11.7 g) was dissolved in toluene (0.2 M, 390 ml), sodium terbutoxide (117.2 mmol, 11.3 g), bis(tri-terbutylphosphine)palladium (0) (0.781 mmol, 0.4 g) was added, and the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 20.6 g of compound 8-b. (Yield 70%, MS[M+H]+=376)
단계 3) 화합물 8-c의 합성Step 3) Synthesis of compound 8-c
Figure PCTKR2020017069-appb-I000139
Figure PCTKR2020017069-appb-I000139
3구 플라스크에 화합물 8-a (37.0 mmol, 19.4 g)와 화합물 8-b (37.0 mmol, 13.9 g)을 톨루엔 (0.2 M, 185 ml)에 녹이고 소듐 터부톡사이드 (55.5 mmol, 5.33 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.37 mmol, 0.189 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 8-c 22.0 g을 수득하였다. (수율 69%, MS[M+H]+= 863)In a three-necked flask, compound 8-a (37.0 mmol, 19.4 g) and compound 8-b (37.0 mmol, 13.9 g) were dissolved in toluene (0.2 M, 185 ml), sodium terbutoxide (55.5 mmol, 5.33 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.37 mmol, 0.189 g), the mixture was stirred for 18 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 22.0 g of compound 8-c. (yield 69%, MS[M+H]+=863)
단계 4) 화합물 8의 합성Step 4) Synthesis of compound 8
Figure PCTKR2020017069-appb-I000140
Figure PCTKR2020017069-appb-I000140
3구 플라스크에 화합물 8-c (25.5 mmol, 22.0 g)을 1,2-디클로로벤젠 (0.1 M, 255 ml)에 녹이고 보론트리아이오다이드 (40.8 mmol, 16.0 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (229 mmol, 30 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 8, 2.9 g을 수득하였다. (수율 13%, MS[M+H]+= 871)In a three-necked flask, compound 8-c (25.5 mmol, 22.0 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 255 ml), boron triiodide (40.8 mmol, 16.0 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (229 mmol, 30 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 8, 2.9 g. (Yield 13%, MS[M+H]+=871)
합성예 9 : 화합물 9의 합성Synthesis Example 9: Synthesis of compound 9
단계 1) 화합물 9-a의 합성Step 1) Synthesis of compound 9-a
Figure PCTKR2020017069-appb-I000141
Figure PCTKR2020017069-appb-I000141
3구 플라스크에 5-터부틸-N-(3-(2-페닐프로판-2-일)페닐)-[1,1'-바이페닐]-2-아민 (71.5 mmol, 30 g)과 1-브로모-3-클로로-5-메틸벤젠 (71.5 mmol, 14.7g)을 톨루엔 (0.2 M, 357 ml)에 녹이고 소듐 터부톡사이드 (107 mmol, 10.3 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.715 mmol, 0.365 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 9-a 34.6g을 수득하였다. (수율 89%, MS[M+H]+= 544)In a 3-neck flask, 5-tertbutyl- N- (3-(2-phenylpropan-2-yl)phenyl)-[1,1'-biphenyl]-2-amine (71.5 mmol, 30 g) and 1- Bromo-3-chloro-5-methylbenzene (71.5 mmol, 14.7 g) was dissolved in toluene (0.2 M, 357 ml), sodium terbutoxide (107 mmol, 10.3 g), bis(tri-terbutylphosphine) After palladium (0) (0.715 mmol, 0.365 g) was added, the mixture was stirred for 6 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 34.6 g of compound 9-a. (Yield 89%, MS[M+H]+= 544)
단계 2) 화합물 9-b의 합성Step 2) Synthesis of compound 9-b
Figure PCTKR2020017069-appb-I000142
Figure PCTKR2020017069-appb-I000142
3구 플라스크에 2-브로모-4,4-디메틸-4H-인데노[2,3-b]퓨란 (144 mmol, 38 g)과 4-터부틸아닐린 (144 mmol, 21.6g)을 톨루엔 (0.2 M, 722 ml)에 녹이고 소듐 터부톡사이드 (217 mmol, 20.8 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.44 mmol, 0.738 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 9-b 35.8 g을 수득하였다. (수율 75%, MS[M+H]+= 376)In a three-necked flask, 2-bromo-4,4-dimethyl- 4H -indeno[2,3- b ]furan (144 mmol, 38 g) and 4-terbutylaniline (144 mmol, 21.6 g) were mixed with toluene (0.2 M, 722 ml), sodium terbutoxide (217 mmol, 20.8 g), bis (tri-terbutylphosphine) palladium (0) (1.44 mmol, 0.738 g) were added, and then under reflux conditions in an argon atmosphere. Stirred for 18 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 35.8 g of compound 9-b. (yield 75%, MS[M+H]+=376)
단계 3) 화합물 9-c의 합성Step 3) Synthesis of compound 9-c
Figure PCTKR2020017069-appb-I000143
Figure PCTKR2020017069-appb-I000143
3구 플라스크에 화합물 9-a (51.3 mmol, 27.9 g)와 화합물 9-b (51.3 mmol, 17 g)을 톨루엔 (0.2 M, 256 ml)에 녹이고 소듐 터부톡사이드 (76.9mmol, 7.39 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.513 mmol, 0.262 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 9-c 27.3 g을 수득하였다. (수율 63%, MS[M+H]+= 839)In a three-necked flask, compound 9-a (51.3 mmol, 27.9 g) and compound 9-b (51.3 mmol, 17 g) were dissolved in toluene (0.2 M, 256 ml) and sodium terbutoxide (76.9 mmol, 7.39 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.513 mmol, 0.262 g), the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 27.3 g of compound 9-c. (Yield 63%, MS[M+H]+= 839)
단계 4) 화합물 9의 합성Step 4) Synthesis of compound 9
Figure PCTKR2020017069-appb-I000144
Figure PCTKR2020017069-appb-I000144
구 플라스크에 화합물 9-c (32.5 mmol, 27.3 g)을 1,2-디클로로벤젠 (0.1 M, 325 ml)에 녹이고 보론트리아이오다이드 (52.1 mmol, 20.4 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (293 mmol, 37.8 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 9, 4.2 g을 수득하였다. (수율 15%, MS[M+H]+= 847)In a flask, compound 9-c (32.5 mmol, 27.3 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 325 ml), boron triiodide (52.1 mmol, 20.4 g) was added, and then argon atmosphere 140 ° C. was stirred for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (293 mmol, 37.8 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then compound 9, 4.2 g, was obtained through sublimation purification. (yield 15%, MS[M+H]+= 847)
합성예 10 : 화합물 10의 합성Synthesis Example 10: Synthesis of compound 10
단계 1) 화합물 10-a의 합성Step 1) Synthesis of compound 10-a
Figure PCTKR2020017069-appb-I000145
Figure PCTKR2020017069-appb-I000145
3구 플라스크에 5-트리메틸실릴-N-(4-트리메틸실릴페닐)-[1,1'-바이페닐]-2-아민 (51.3 mmol, 20 g)과 1-브로모-3-클로로-5-터부틸벤젠 (51.3 mmol, 12.7g)을 톨루엔 (0.2 M, 257 ml)에 녹이고 소듐 터부톡사이드 (77.0 mmol, 7.40 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.513 mmol, 0.262 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 10-a 26.7g을 수득하였다. (수율 94%, MS[M+H]+= 556)5-trimethylsilyl- N- (4-trimethylsilylphenyl)-[1,1'-biphenyl]-2-amine (51.3 mmol, 20 g) and 1-bromo-3-chloro-5 in a 3-neck flask -terbutylbenzene (51.3 mmol, 12.7 g) was dissolved in toluene (0.2 M, 257 ml), sodium terbutoxide (77.0 mmol, 7.40 g), bis (tri-tertbutylphosphine) palladium (0) (0.513 mmol) , 0.262 g), and stirred for 4 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 26.7 g of compound 10-a. (Yield 94%, MS[M+H]+= 556)
단계 2) 화합물 10-b의 합성Step 2) Synthesis of compound 10-b
Figure PCTKR2020017069-appb-I000146
Figure PCTKR2020017069-appb-I000146
3구 플라스크에 3-브로모-8,8-디메틸-8H-인데노[2,1-b]퓨란 (76.0 mmol, 20 g)과 4-터부틸아닐린 (76.0 mmol, 11.3g)을 톨루엔 (0.2 M, 380 ml)에 녹이고 소듐 터부톡사이드 (114 mmol, 11.0 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.760 mmol, 0.388 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 10-b 17.3 g을 수득하였다. (수율 69%, MS[M+H]+= 331)3 -8,8- dimethyl-3-bromo-necked flask -8 H-indeno [2,1- b] furan (76.0 mmol, 20 g) and 4-emitter-butylaniline (76.0 mmol, 11.3g) in toluene (0.2 M, 380 ml), sodium terbutoxide (114 mmol, 11.0 g), bis (tri-terbutylphosphine) palladium (0) (0.760 mmol, 0.388 g) was added, and then under reflux conditions under argon atmosphere. Stirred for 12 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 17.3 g of compound 10-b. (yield 69%, MS[M+H]+= 331)
단계 3) 화합물 10-c의 합성Step 3) Synthesis of compound 10-c
Figure PCTKR2020017069-appb-I000147
Figure PCTKR2020017069-appb-I000147
3구 플라스크에 화합물 10-a (41.3 mmol, 23 g)와 화합물 10-b (41.3 mmol, 13.7 g)을 톨루엔 (0.2 M, 207 ml)에 녹이고 소듐 터부톡사이드 (62.0 mmol, 6.00 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.413 mmol, 0.211 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 10-c 23.7 g을 수득하였다. (수율 67%, MS[M+H]+= 839)In a three-necked flask, compound 10-a (41.3 mmol, 23 g) and compound 10-b (41.3 mmol, 13.7 g) were dissolved in toluene (0.2 M, 207 ml), sodium terbutoxide (62.0 mmol, 6.00 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.413 mmol, 0.211 g), the mixture was stirred for 18 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 23.7 g of compound 10-c. (Yield 67%, MS[M+H]+= 839)
단계 4) 화합물 10의 합성Step 4) Synthesis of compound 10
Figure PCTKR2020017069-appb-I000148
Figure PCTKR2020017069-appb-I000148
3구 플라스크에 화합물 10-c (27.8 mmol, 23.7 g)을 1,2-디클로로벤젠 (0.1 M, 280 ml)에 녹이고 보론트리아이오다이드 (44.5 mmol, 17.4 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (251 mmol, 32.4 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 10, 3.5 g을 수득하였다. (수율 15%, MS[M+H]+= 859)In a three-neck flask, compound 10-c (27.8 mmol, 23.7 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 280 ml), boron triiodide (44.5 mmol, 17.4 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, and N,N-diisopropylethylamine (251 mmol, 32.4 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 10, 3.5 g. (yield 15%, MS[M+H]+=859)
합성예 11 : 화합물 11의 합성Synthesis Example 11: Synthesis of compound 11
단계 1) 화합물 11-a의 합성Step 1) Synthesis of compound 11-a
Figure PCTKR2020017069-appb-I000149
Figure PCTKR2020017069-appb-I000149
3구 플라스크에 N 1,N 1-비스(페닐-d 5)-N 3-(4-트리메틸실릴페닐)벤젠-1,3-디아민 (47.8 mmol, 20 g)과 1-브로모-3-클로로-5-메틸벤젠 (47.8 mmol, 9.82g)을 톨루엔 (0.2 M, 240 ml)에 녹이고 소듐 터부톡사이드 (71.7 mmol, 6.89 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.478 mmol, 0.244 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 2시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 11-a 24.5g을 수득하였다. (수율 94%, MS[M+H]+= 543)In a three-necked flask, N 1 , N 1 -bis(phenyl- d 5 ) -N 3 -(4-trimethylsilylphenyl)benzene-1,3-diamine (47.8 mmol, 20 g) and 1-bromo-3- Chloro-5-methylbenzene (47.8 mmol, 9.82 g) was dissolved in toluene (0.2 M, 240 ml), sodium terbutoxide (71.7 mmol, 6.89 g), bis (tri-terbutylphosphine) palladium (0) ( 0.478 mmol, 0.244 g) was added, and the mixture was stirred for 2 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 24.5 g of compound 11-a. (Yield 94%, MS[M+H]+= 543)
단계 2) 화합물 11-b의 합성Step 2) Synthesis of compound 11-b
Figure PCTKR2020017069-appb-I000150
Figure PCTKR2020017069-appb-I000150
3구 플라스크에 3-브로모-4,4,7,7-테트라메틸-4,5,6,7-테트라하이드로퓨란 (38.9 mmol, 10 g)과 4-터부틸아닐린 (38.9 mmol, 5.80g)을 톨루엔 (0.2 M, 195 ml)에 녹이고 소듐 터부톡사이드 (58.3 mmol, 5.60 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.389 mmol, 0.200 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 11-b 11.2 g을 수득하였다. (수율 88%, MS[M+H]+= 331)In a 3-neck flask, 3-bromo-4,4,7,7-tetramethyl-4,5,6,7-tetrahydrofuran (38.9 mmol, 10 g) and 4-tertbutylaniline (38.9 mmol, 5.80 g) ) was dissolved in toluene (0.2 M, 195 ml), sodium terbutoxide (58.3 mmol, 5.60 g), bis(tri-terbutylphosphine)palladium (0) (0.389 mmol, 0.200 g) were added, and then argon atmosphere The mixture was stirred under reflux conditions for 4 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 11.2 g of compound 11-b. (Yield 88%, MS[M+H]+= 331)
단계 3) 화합물 11-c의 합성Step 3) Synthesis of compound 11-c
Figure PCTKR2020017069-appb-I000151
Figure PCTKR2020017069-appb-I000151
3구 플라스크에 화합물 11-a (33.1 mmol, 18 g)와 화합물 11-b (33.1 mmol, 10.8 g)을 톨루엔 (0.2 M, 165 ml)에 녹이고 소듐 터부톡사이드 (49.7 mmol, 4.78 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.331 mmol, 0.169 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 11-c 21.2 g을 수득하였다. (수율 77%, MS[M+H]+= 832)In a three-necked flask, compound 11-a (33.1 mmol, 18 g) and compound 11-b (33.1 mmol, 10.8 g) were dissolved in toluene (0.2 M, 165 ml), sodium terbutoxide (49.7 mmol, 4.78 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.331 mmol, 0.169 g), the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 21.2 g of compound 11-c. (Yield 77%, MS[M+H]+= 832)
단계 4) 화합물 11의 합성Step 4) Synthesis of compound 11
Figure PCTKR2020017069-appb-I000152
Figure PCTKR2020017069-appb-I000152
3구 플라스크에 화합물 11-c (25.5 mmol, 21.2 g)을 1,2-디클로로벤젠 (0.1 M, 255 ml)에 녹이고 보론트리아이오다이드 (40.8 mmol, 16.0 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (229 mmol, 29.6 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 11, 2.9 g을 수득하였다. (수율 14%, MS[M+H]+= 859)In a three-necked flask, compound 11-c (25.5 mmol, 21.2 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 255 ml), boron triiodide (40.8 mmol, 16.0 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (229 mmol, 29.6 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 11, 2.9 g. (Yield 14%, MS[M+H]+=859)
합성예 12 : 화합물 12의 합성Synthesis Example 12: Synthesis of compound 12
단계 1) 화합물 12-a의 합성Step 1) Synthesis of compound 12-a
Figure PCTKR2020017069-appb-I000153
Figure PCTKR2020017069-appb-I000153
3구 플라스크에 5-터부틸-N-(3-터부틸페닐)-[1,1'-바이페닐]-2-아민 (55.9 mmol, 20 g)과 1-브로모-3-클로로-5-메틸벤젠 (55.9 mmol, 11.5g)을 톨루엔 (0.2 M, 280 ml)에 녹이고 소듐 터부톡사이드 (83.9 mmol, 8.06 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.559 mmol, 0.286 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 5시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 12-a 23.8g을 수득하였다. (수율 88%, MS[M+H]+= 482)5-tertbutyl- N- (3-terbutylphenyl)-[1,1'-biphenyl]-2-amine (55.9 mmol, 20 g) and 1-bromo-3-chloro-5 in a 3-neck flask -Methylbenzene (55.9 mmol, 11.5 g) was dissolved in toluene (0.2 M, 280 ml), sodium terbutoxide (83.9 mmol, 8.06 g), bis (tri-terbutylphosphine) palladium (0) (0.559 mmol, 0.286 g), followed by stirring for 5 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 23.8 g of compound 12-a. (Yield 88%, MS[M+H]+=482)
단계 2) 화합물 12-b의 합성Step 2) Synthesis of compound 12-b
Figure PCTKR2020017069-appb-I000154
Figure PCTKR2020017069-appb-I000154
3구 플라스크에 4-브로모-2-(4-터부틸페닐)퓨란 (53.7 mmol, 15 g)과 4-트리메틸실릴아닐린 (53.7 mmol, 8.88 g)을 톨루엔 (0.2 M, 270 ml)에 녹이고 소듐 터부톡사이드 (80.6 mmol, 7.75 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.537 mmol, 0.275 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 10시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 12-b 17.4 g을 수득하였다. (수율 89%, MS[M+H]+= 331)In a three-necked flask, 4-bromo-2-(4-terbutylphenyl)furan (53.7 mmol, 15 g) and 4-trimethylsilylaniline (53.7 mmol, 8.88 g) were dissolved in toluene (0.2 M, 270 ml). After adding sodium terbutoxide (80.6 mmol, 7.75 g) and bis(tri-terbutylphosphine)palladium(0) (0.537 mmol, 0.275 g), the mixture was stirred for 10 hours under refluxing conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 17.4 g of compound 12-b. (yield 89%, MS[M+H]+= 331)
단계 3) 화합물 12-c의 합성Step 3) Synthesis of compound 12-c
Figure PCTKR2020017069-appb-I000155
Figure PCTKR2020017069-appb-I000155
3구 플라스크에 화합물 12-a (41.5 mmol, 20 g)와 화합물 12-b (41.5 mmol, 19.1 g)을 톨루엔 (0.2 M, 305 ml)에 녹이고 소듐 터부톡사이드 (62.2 mmol, 6.00 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.415 mmol, 0.212 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 12-c 24.7 g을 수득하였다. (수율 74%, MS[M+H]+= 832)In a three-necked flask, compound 12-a (41.5 mmol, 20 g) and compound 12-b (41.5 mmol, 19.1 g) were dissolved in toluene (0.2 M, 305 ml), sodium terbutoxide (62.2 mmol, 6.00 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.415 mmol, 0.212 g), the mixture was stirred for 18 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 24.7 g of compound 12-c. (Yield 74%, MS[M+H]+= 832)
단계 4) 화합물 12의 합성Step 4) Synthesis of compound 12
Figure PCTKR2020017069-appb-I000156
Figure PCTKR2020017069-appb-I000156
3구 플라스크에 화합물 12-c (30.5 mmol, 24.7 g)을 1,2-디클로로벤젠 (0.1 M, 305 ml)에 녹이고 보론트리아이오다이드 (48.8 mmol, 19.1 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (275 mmol, 35.5 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 12, 4.3 g을 수득하였다. (수율 17%, MS[M+H]+= 817)In a three-necked flask, compound 12-c (30.5 mmol, 24.7 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 305 ml), boron triiodide (48.8 mmol, 19.1 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, and N,N-diisopropylethylamine (275 mmol, 35.5 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 12, 4.3 g. (Yield 17%, MS[M+H]+= 817)
합성예13: 화합물 13의 합성Synthesis Example 13: Synthesis of compound 13
단계 1) 화합물 13-a의 합성Step 1) Synthesis of compound 13-a
Figure PCTKR2020017069-appb-I000157
Figure PCTKR2020017069-appb-I000157
3구 플라스크에 N-(4-터부틸페닐)-5'-메틸-[1,1',3',1''-터페닐]-2'-아민 (76.6 mmol, 30 g)과 1-브로모-3-클로로-5-터부틸벤젠 (76.6 mmol, 19.0g)을 톨루엔 (0.2 M, 380 ml)에 녹이고 소듐 터부톡사이드 (115 mmol, 11.0 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.766 mmol, 0.392 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 13-a 26.4g을 수득하였다. (수율 62%, MS[M+H]+= 558)In a 3-neck flask, N -(4-terbutylphenyl)-5'-methyl-[1,1',3',1''-terphenyl]-2'-amine (76.6 mmol, 30 g) and 1- Bromo-3-chloro-5-terbutylbenzene (76.6 mmol, 19.0 g) was dissolved in toluene (0.2 M, 380 ml), sodium terbutoxide (115 mmol, 11.0 g), bis(tri-terbutylphosphine) ) After adding palladium (0) (0.766 mmol, 0.392 g), the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 26.4 g of compound 13-a. (Yield 62%, MS[M+H]+= 558)
단계 2) 화합물 13-b의 합성Step 2) Synthesis of compound 13-b
Figure PCTKR2020017069-appb-I000158
Figure PCTKR2020017069-appb-I000158
3구 플라스크에 3-브로모-5,5-디메틸-5,6-디하이드로-4H-시클로펜타[b]퓨란 (93.0 mmol, 20 g)과 아닐린-d 5 (93.0 mmol, 9.13 g)을 톨루엔 (0.2 M, 465 ml)에 녹이고 소듐 터부톡사이드 (139 mmol, 13.4 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.93 mmol, 0.475 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 3시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 13-b 19.3 g을 수득하였다. (수율 89%, MS[M+H]+= 232)In a three-necked flask, 3-bromo-5,5-dimethyl-5,6-dihydro- 4H -cyclopenta[ b ]furan (93.0 mmol, 20 g) and aniline- d 5 (93.0 mmol, 9.13 g) was dissolved in toluene (0.2 M, 465 ml), sodium terbutoxide (139 mmol, 13.4 g), bis(tri-terbutylphosphine)palladium (0) (0.93 mmol, 0.475 g) were added, and argon atmosphere was refluxed. The mixture was stirred for 3 hours under conditions. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 19.3 g of compound 13-b. (yield 89%, MS[M+H]+=232)
단계 3) 화합물 13-c의 합성Step 3) Synthesis of compound 13-c
Figure PCTKR2020017069-appb-I000159
Figure PCTKR2020017069-appb-I000159
3구 플라스크에 화합물 13-a (44.8 mmol, 25 g)와 화합물 13-b (44.8 mmol, 10.4 g)을 톨루엔 (0.2 M, 225 ml)에 녹이고 소듐 터부톡사이드 (67.2 mmol, 6.46 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.448 mmol, 0.229 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 13-c 24.3 g을 수득하였다. (수율 72%, MS[M+H]+= 754)In a three-necked flask, compound 13-a (44.8 mmol, 25 g) and compound 13-b (44.8 mmol, 10.4 g) were dissolved in toluene (0.2 M, 225 ml), sodium terbutoxide (67.2 mmol, 6.46 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.448 mmol, 0.229 g), the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 24.3 g of compound 13-c. (yield 72%, MS[M+H]+= 754)
단계 4) 화합물 13의 합성Step 4) Synthesis of compound 13
Figure PCTKR2020017069-appb-I000160
Figure PCTKR2020017069-appb-I000160
3구 플라스크에 화합물 13-c (32.2 mmol, 24.3 g)을 1,2-디클로로벤젠 (0.1 M, 322 ml)에 녹이고 보론트리아이오다이드 (51.6 mmol, 20.2 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (290 mmol, 37.5 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 13 4.5 g을 수득하였다. (수율 18%, MS[M+H]+= 762)In a three-necked flask, compound 13-c (32.2 mmol, 24.3 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 322 ml), boron triiodide (51.6 mmol, 20.2 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (290 mmol, 37.5 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 4.5 g of compound 13 through sublimation purification. (yield 18%, MS[M+H]+=762)
합성예 14 : 화합물 14의 합성Synthesis Example 14: Synthesis of compound 14
단계 1) 화합물 14-a의 합성Step 1) Synthesis of compound 14-a
Figure PCTKR2020017069-appb-I000161
Figure PCTKR2020017069-appb-I000161
3구 플라스크에 4-터부틸-N-(4-터부틸페닐)-2-(1,5,5,8,8-펜타메틸-5,6,7,8-테트라하이드로나프탈렌-2-일)아닐린 (31.1 mmol, 15 g)과 1-브로모-3-클로로-5-메틸벤젠 (31.1 mmol, 6.40 g)을 톨루엔 (0.2 M, 155 ml)에 녹이고 소듐 터부톡사이드 (46.7 mmol, 4.49 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.311 mmol, 0.159 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 14-a 16.4 g을 수득하였다. (수율 87%, MS[M+H]+= 606)4-tertbutyl- N- (4-terbutylphenyl)-2-(1,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl in a 3-neck flask ) Aniline (31.1 mmol, 15 g) and 1-bromo-3-chloro-5-methylbenzene (31.1 mmol, 6.40 g) were dissolved in toluene (0.2 M, 155 ml) and sodium terbutoxide (46.7 mmol, 4.49) g), bis(tri-terbutylphosphine)palladium(0) (0.311 mmol, 0.159 g) was added, and the mixture was stirred for 24 hours under refluxing conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 16.4 g of compound 14-a. (Yield 87%, MS[M+H]+=606)
단계 2) 화합물 14-b의 합성Step 2) Synthesis of compound 14-b
Figure PCTKR2020017069-appb-I000162
Figure PCTKR2020017069-appb-I000162
3구 플라스크에 3-브로모-4,4-디메틸-7-트리플루오르메틸-4H-인데노[1,2-b]퓨란 (75.5 mmol, 25 g)과 4-터부틸아닐린 (75.5 mmol, 11.3 g)을 톨루엔 (0.2 M, 380 ml)에 녹이고 소듐 터부톡사이드 (113 mmol, 10.9 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.755 mmol, 0.386 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 3시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 14-b 26.9 g을 수득하였다. (수율 89%, MS[M+H]+= 399)In a three-necked flask, 3-bromo-4,4-dimethyl-7-trifluoromethyl- 4H -indeno[1,2- b ]furan (75.5 mmol, 25 g) and 4-terbutylaniline (75.5 mmol) , 11.3 g) was dissolved in toluene (0.2 M, 380 ml), and sodium terbutoxide (113 mmol, 10.9 g), bis(tri-terbutylphosphine)palladium (0) (0.755 mmol, 0.386 g) was added. , and stirred for 3 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 26.9 g of compound 14-b. (yield 89%, MS[M+H]+=399)
단계 3) 화합물 14-c의 합성Step 3) Synthesis of compound 14-c
Figure PCTKR2020017069-appb-I000163
Figure PCTKR2020017069-appb-I000163
3구 플라스크에 화합물 14-a (26.4 mmol, 16 g)와 화합물 14-b (26.4 mmol, 10.5 g)을 톨루엔 (0.2 M, 130 ml)에 녹이고 소듐 터부톡사이드 (39.6 mmol, 3.80 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.264 mmol, 0.135 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 14-c 20.4 g을 수득하였다. (수율 80%, MS[M+H]+= 969)In a three-necked flask, compound 14-a (26.4 mmol, 16 g) and compound 14-b (26.4 mmol, 10.5 g) were dissolved in toluene (0.2 M, 130 ml), sodium terbutoxide (39.6 mmol, 3.80 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.264 mmol, 0.135 g), the mixture was stirred for 18 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 20.4 g of compound 14-c. (yield 80%, MS[M+H]+=969)
단계 4) 화합물 14의 합성Step 4) Synthesis of compound 14
Figure PCTKR2020017069-appb-I000164
Figure PCTKR2020017069-appb-I000164
3구 플라스크에 화합물 14-c (21.0 mmol, 20.4 g)을 1,2-디클로로벤젠 (0.1 M, 210 ml)에 녹이고 보론트리아이오다이드 (33.7 mmol, 13.2 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (189 mmol, 24.5 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 14, 3.2 g을 수득하였다. (수율 16%, MS[M+H]+= 977)In a three-necked flask, compound 14-c (21.0 mmol, 20.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 210 ml), boron triiodide (33.7 mmol, 13.2 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (189 mmol, 24.5 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 14, 3.2 g. (yield 16%, MS[M+H]+=977)
합성예 15: 화합물 15의 합성Synthesis Example 15: Synthesis of compound 15
단계 1) 화합물 15-a의 합성Step 1) Synthesis of compound 15-a
Figure PCTKR2020017069-appb-I000165
Figure PCTKR2020017069-appb-I000165
3구 플라스크에 N-(4-터페닐)-1,5,5,8,8-펜타메틸-5,6,7,8-테트라하이드로나프탈렌-2-아민 (114 mmol, 40 g)과 1-브로모-3-클로로-5-메틸벤젠 (114 mmol, 23.5 g)을 톨루엔 (0.2 M, 572 ml)에 녹이고 소듐 터부톡사이드 (172 mmol, 16.5 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.14 mmol, 0.585 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 15-a 42.3 g을 수득하였다. (수율 78%, MS[M+H]+= 474)In a three-necked flask, N- (4-terphenyl)-1,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-amine (114 mmol, 40 g) and 1 -Bromo-3-chloro-5-methylbenzene (114 mmol, 23.5 g) was dissolved in toluene (0.2 M, 572 ml), sodium terbutoxide (172 mmol, 16.5 g), bis(tri-terbutylphosphine) ) After adding palladium (0) (1.14 mmol, 0.585 g), the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 42.3 g of compound 15-a. (Yield 78%, MS[M+H]+=474)
단계 2) 화합물 15-b의 합성Step 2) Synthesis of compound 15-b
Figure PCTKR2020017069-appb-I000166
Figure PCTKR2020017069-appb-I000166
3구 플라스크에 4-브로모-2,2,3,3-테트라메틸-2,3-디하이드로퓨란 (73.1 mmol, 15 g)과 [1,1'-바이페닐]-4-아민 (73.1 mmol, 12.4 g)을 톨루엔 (0.2 M, 370 ml)에 녹이고 소듐 터부톡사이드 (110 mmol, 10.5 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.731 mmol, 0.374 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 15-b 13.6 g을 수득하였다. (수율 63%, MS[M+H]+= 293)In a 3-neck flask, 4-bromo-2,2,3,3-tetramethyl-2,3-dihydrofuran (73.1 mmol, 15 g) and [1,1'-biphenyl]-4-amine (73.1 mmol, 12.4 g) was dissolved in toluene (0.2 M, 370 ml), sodium terbutoxide (110 mmol, 10.5 g), bis (tri-terbutylphosphine) palladium (0) (0.731 mmol, 0.374 g) was added. Then, the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 13.6 g of compound 15-b. (Yield 63%, MS[M+H]+= 293)
단계 3) 화합물 15-c의 합성Step 3) Synthesis of compound 15-c
Figure PCTKR2020017069-appb-I000167
Figure PCTKR2020017069-appb-I000167
3구 플라스크에 화합물 15-a (42.2 mmol, 20 g)와 화합물 15-b (42.2 mmol, 12.4 g)을 톨루엔 (0.2 M, 210 ml)에 녹이고 소듐 터부톡사이드 (63.3 mmol, 3.80 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.422 mmol, 0.216 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 3시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 15-c 19.2 g을 수득하였다. (수율 62%, MS[M+H]+= 731)In a three-necked flask, compound 15-a (42.2 mmol, 20 g) and compound 15-b (42.2 mmol, 12.4 g) were dissolved in toluene (0.2 M, 210 ml), sodium terbutoxide (63.3 mmol, 3.80 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.422 mmol, 0.216 g), the mixture was stirred for 3 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 19.2 g of compound 15-c. (Yield 62%, MS[M+H]+=731)
단계 4) 화합물 15의 합성Step 4) Synthesis of compound 15
Figure PCTKR2020017069-appb-I000168
Figure PCTKR2020017069-appb-I000168
3구 플라스크에 화합물 15-c (26.3 mmol, 19.2 g)을 1,2-디클로로벤젠 (0.1 M, 263 ml)에 녹이고 보론트리아이오다이드 (42.0 mmol, 16.5 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (236 mmol, 30.5 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 15, 3.8 g을 수득하였다. (수율 20%, MS[M+H]+= 739)In a three-necked flask, compound 15-c (26.3 mmol, 19.2 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 263 ml), boron triiodide (42.0 mmol, 16.5 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (236 mmol, 30.5 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 15, 3.8 g. (Yield 20%, MS[M+H]+= 739)
합성예 16 : 화합물 16의 합성Synthesis Example 16: Synthesis of compound 16
단계 1) 화합물 16-a의 합성Step 1) Synthesis of compound 16-a
Figure PCTKR2020017069-appb-I000169
Figure PCTKR2020017069-appb-I000169
3구 플라스크에 4-터부틸아닐린 (134 mmol, 20 g)과 3-브로모-5-터부틸벤조[b]싸이오펜 (134 mmol, 36.1 g)을 톨루엔 (0.2 M, 670 ml)에 녹이고 소듐 터부톡사이드 (201 mmol, 19.3 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.34 mmol, 0.685 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 3시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 16-a 40.7 g을 수득하였다. (수율 90%, MS[M+H]+= 338)Dissolve 4-terbutylaniline (134 mmol, 20 g) and 3-bromo-5-terbutylbenzo[ b ]thiophene (134 mmol, 36.1 g) in toluene (0.2 M, 670 ml) in a three-necked flask. Sodium terbutoxide (201 mmol, 19.3 g) and bis(tri-terbutylphosphine)palladium(0) (1.34 mmol, 0.685 g) were added, and the mixture was stirred under reflux conditions under argon atmosphere for 3 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 40.7 g of compound 16-a. (Yield 90%, MS[M+H]+=338)
단계 2) 화합물 16-b의 합성Step 2) Synthesis of compound 16-b
Figure PCTKR2020017069-appb-I000170
Figure PCTKR2020017069-appb-I000170
3구 플라스크에 화합물 1-a (73.4 mmol, 30 g)와 화합물 16-a (73.4 mmol, 24.9 g)을 톨루엔 (0.2 M, 370 ml)에 녹이고 소듐 터부톡사이드 (111 mmol, 10.7 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.734 mmol, 0.378 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 16-b 38.7 g을 수득하였다. (수율 74%, MS[M+H]+= 707)In a three-necked flask, compound 1-a (73.4 mmol, 30 g) and compound 16-a (73.4 mmol, 24.9 g) were dissolved in toluene (0.2 M, 370 ml), sodium terbutoxide (111 mmol, 10.7 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.734 mmol, 0.378 g), the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 38.7 g of compound 16-b. (Yield 74%, MS[M+H]+=707)
단계 3) 화합물 16의 합성Step 3) Synthesis of compound 16
Figure PCTKR2020017069-appb-I000171
Figure PCTKR2020017069-appb-I000171
3구 플라스크에 화합물 16-b (54.7 mmol, 38.7 g)을 1,2-디클로로벤젠 (0.1 M, 550 ml)에 녹이고 보론트리아이오다이드 (87.6 mmol, 34.3 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (493 mmol, 63.7 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 16, 6.4 g을 수득하였다. (수율 16%, MS[M+H]+= 715)In a three-necked flask, compound 16-b (54.7 mmol, 38.7 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 550 ml), boron triiodide (87.6 mmol, 34.3 g) was added, and argon atmosphere 140 It was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N -diisopropylethylamine (493 mmol, 63.7 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 16, 6.4 g. (yield 16%, MS[M+H]+= 715)
합성예 17 : 화합물 17의 합성Synthesis Example 17: Synthesis of compound 17
단계 1) 화합물 17-a의 합성Step 1) Synthesis of compound 17-a
Figure PCTKR2020017069-appb-I000172
Figure PCTKR2020017069-appb-I000172
3구 플라스크에 4-터부틸-N-(4-터부틸페닐)-2-(5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프탈렌-1-일)아닐린 (42.8 mmol, 20 g)과 1-브로모-3-클로로-5-터부틸벤젠 (42.8 mmol, 10.6 g)을 톨루엔 (0.2 M, 215 ml)에 녹이고 소듐 터부톡사이드 (64.1 mmol, 6.16 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.428 mmol, 0.219 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 17-a 22.9 g을 수득하였다. (수율 84%, MS[M+H]+= 634)4-tertbutyl- N- (4-terbutylphenyl)-2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-1-yl)aniline in a 3-neck flask (42.8 mmol, 20 g) and 1-bromo-3-chloro-5-terbutylbenzene (42.8 mmol, 10.6 g) were dissolved in toluene (0.2 M, 215 ml) and sodium terbutoxide (64.1 mmol, 6.16 g) ), bis(tri-terbutylphosphine)palladium(0) (0.428 mmol, 0.219 g) was added, and the mixture was stirred for 6 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 22.9 g of compound 17-a. (Yield 84%, MS[M+H]+= 634)
단계 2) 화합물 17-b의 합성Step 2) Synthesis of compound 17-b
Figure PCTKR2020017069-appb-I000173
Figure PCTKR2020017069-appb-I000173
3구 플라스크에 3-브로모-5-터부틸벤조[b]싸이오펜 (149 mmol, 40 g)과 4-터부틸아닐린 (149 mmol, 22.2 g)을 톨루엔 (0.2 M, 745 ml)에 녹이고 소듐 터부톡사이드 (223 mmol, 21.4 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.49 mmol, 0.759 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 17-b 45.6 g을 수득하였다. (수율 91%, MS[M+H]+= 338)In a three-necked flask, 3-bromo-5-terbutylbenzo[ b ]thiophene (149 mmol, 40 g) and 4-terbutylaniline (149 mmol, 22.2 g) were dissolved in toluene (0.2 M, 745 ml). After adding sodium terbutoxide (223 mmol, 21.4 g) and bis(tri-terbutylphosphine)palladium(0) (1.49 mmol, 0.759 g), the mixture was stirred for 18 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 45.6 g of compound 17-b. (Yield 91%, MS[M+H]+=338)
단계 3) 화합물 17-c의 합성Step 3) Synthesis of compound 17-c
Figure PCTKR2020017069-appb-I000174
Figure PCTKR2020017069-appb-I000174
3구 플라스크에 화합물 17-a (26.8 mmol, 17 g)와 화합물 17-b (26.8 mmol, 9.05 g)을 톨루엔 (0.2 M, 135 ml)에 녹이고 소듐 터부톡사이드 (40.2 mmol, 3.87 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.268 mmol, 0.137 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 17-c 20.1 g을 수득하였다. (수율 80%, MS[M+H]+= 935)In a three-necked flask, compound 17-a (26.8 mmol, 17 g) and compound 17-b (26.8 mmol, 9.05 g) were dissolved in toluene (0.2 M, 135 ml), sodium terbutoxide (40.2 mmol, 3.87 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.268 mmol, 0.137 g), the mixture was stirred for 18 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 20.1 g of compound 17-c. (yield 80%, MS[M+H]+=935)
단계 4) 화합물 17의 합성Step 4) Synthesis of compound 17
Figure PCTKR2020017069-appb-I000175
Figure PCTKR2020017069-appb-I000175
3구 플라스크에 화합물 17-c (21.5 mmol, 20.1 g)을 1,2-디클로로벤젠 (0.1 M, 215 ml)에 녹이고 보론트리아이오다이드 (34.4 mmol, 13.5 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (193 mmol, 25 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 17 3.4 g을 수득하였다. (수율 17%, MS[M+H]+= 943)In a three-necked flask, compound 17-c (21.5 mmol, 20.1 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 215 ml), boron triiodide (34.4 mmol, 13.5 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (193 mmol, 25 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then 3.4 g of compound 17 was obtained through sublimation purification. (Yield 17%, MS[M+H]+=943)
합성예 18 : 화합물 18의 합성Synthesis Example 18: Synthesis of compound 18
단계 1) 화합물 18-a의 합성Step 1) Synthesis of compound 18-a
Figure PCTKR2020017069-appb-I000176
Figure PCTKR2020017069-appb-I000176
3구 플라스크에 5-터부틸-N-(4-터부틸페닐)-[1,1'-바이페닐]-2-아민 (140 mmol, 50 g)과 1-브로모-3-클로로-5-메틸벤젠 (140 mmol, 28.7 g)을 톨루엔 (0.2 M, 700 ml)에 녹이고 소듐 터부톡사이드 (210 mmol, 20.2 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.40 mmol, 0.715 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 18-a 57.1 g을 수득하였다. (수율 85%, MS[M+H]+= 482)5-tertbutyl- N- (4-terbutylphenyl)-[1,1'-biphenyl]-2-amine (140 mmol, 50 g) and 1-bromo-3-chloro-5 in a 3-neck flask -Methylbenzene (140 mmol, 28.7 g) was dissolved in toluene (0.2 M, 700 ml), sodium terbutoxide (210 mmol, 20.2 g), bis(tri-terbutylphosphine)palladium (0) (1.40 mmol, 0.715 g) was added, and the mixture was stirred for 4 hours under reflux conditions under argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 57.1 g of compound 18-a. (Yield 85%, MS[M+H]+=482)
단계 2) 화합물 18-b의 합성Step 2) Synthesis of compound 18-b
Figure PCTKR2020017069-appb-I000177
Figure PCTKR2020017069-appb-I000177
3구 플라스크에 3-브로모-5-트리메틸실릴벤조[b]싸이오펜 (70.1 mmol, 20 g)과 4-터부틸아닐린 (70.1 mmol, 10.5 g)을 톨루엔 (0.2 M, 350 ml)에 녹이고 소듐 터부톡사이드 (105 mmol, 10.1 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.701 mmol, 0.358 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 18-b 19.2 g을 수득하였다. (수율 77%, MS[M+H]+= 354)Dissolve 3-bromo-5-trimethylsilylbenzo[ b ]thiophene (70.1 mmol, 20 g) and 4-terbutylaniline (70.1 mmol, 10.5 g) in toluene (0.2 M, 350 ml) in a 3-neck flask Sodium terbutoxide (105 mmol, 10.1 g) and bis(tri-terbutylphosphine)palladium(0) (0.701 mmol, 0.358 g) were added, and the mixture was stirred under reflux conditions in an argon atmosphere for 18 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 19.2 g of compound 18-b. (Yield 77%, MS[M+H]+= 354)
단계 3) 화합물 18-c의 합성Step 3) Synthesis of compound 18-c
Figure PCTKR2020017069-appb-I000178
Figure PCTKR2020017069-appb-I000178
3구 플라스크에 화합물 18-a (51.9 mmol, 25 g)와 화합물 18-b (51.9 mmol, 18.3 g)을 톨루엔 (0.2 M, 260 ml)에 녹이고 소듐 터부톡사이드 (77.9 mmol, 7.47 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.519 mmol, 0.265 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 18-c 33.2 g을 수득하였다. (수율 80%, MS[M+H]+= 799)In a three-necked flask, compound 18-a (51.9 mmol, 25 g) and compound 18-b (51.9 mmol, 18.3 g) were dissolved in toluene (0.2 M, 260 ml), sodium terbutoxide (77.9 mmol, 7.47 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.519 mmol, 0.265 g), the mixture was stirred for 18 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 33.2 g of compound 18-c. (yield 80%, MS[M+H]+=799)
단계 4) 화합물 18의 합성Step 4) Synthesis of compound 18
Figure PCTKR2020017069-appb-I000179
Figure PCTKR2020017069-appb-I000179
3구 플라스크에 화합물 18-c (41.5 mmol, 33.2 g)을 1,2-디클로로벤젠 (0.1 M, 415 ml)에 녹이고 보론트리아이오다이드 (66.5 mmol, 26.0 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (374 mmol, 48.3 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 18, 6.1 g을 수득하였다. (수율 18%, MS[M+H]+= 807)In a three-necked flask, compound 18-c (41.5 mmol, 33.2 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 415 ml), boron triiodide (66.5 mmol, 26.0 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (374 mmol, 48.3 g) was added, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then compound 18, 6.1 g, was obtained through sublimation purification. (Yield 18%, MS[M+H]+= 807)
합성예 19 : 화합물 19의 합성Synthesis Example 19: Synthesis of compound 19
단계 1) 화합물 19-a의 합성Step 1) Synthesis of compound 19-a
Figure PCTKR2020017069-appb-I000180
Figure PCTKR2020017069-appb-I000180
3구 플라스크에 5-터부틸-[1,1'-바이페닐]-2-아민 (66.6 mmol, 15 g)과 3-브로모-5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프토[2,3-b]싸이오펜 (66.6 mmol, 21.5 g)을 톨루엔 (0.2 M, 335 ml)에 녹이고 소듐 터부톡사이드 (99.9 mmol, 9.60 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.666 mmol, 0.340 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 19-a 24.2 g을 수득하였다. (수율 78%, MS[M+H]+= 468)In a 3-neck flask, 5-tertbutyl-[1,1'-biphenyl]-2-amine (66.6 mmol, 15 g) and 3-bromo-5,5,8,8-tetramethyl-5,6, 7,8-tetrahydronaphtho [2,3- b ] thiophene (66.6 mmol, 21.5 g) was dissolved in toluene (0.2 M, 335 ml) and sodium terbutoxide (99.9 mmol, 9.60 g), bis (tri -terbutylphosphine)palladium(0) (0.666 mmol, 0.340 g) was added, and the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 24.2 g of compound 19-a. (Yield 78%, MS[M+H]+= 468)
단계 2) 화합물 19-b의 합성Step 2) Synthesis of compound 19-b
Figure PCTKR2020017069-appb-I000181
Figure PCTKR2020017069-appb-I000181
3구 플라스크에 화합물 1-a (49.3 mmol, 20 g)와 화합물 19-a (49.3 mmol, 23.0 g)을 톨루엔 (0.2 M, 250 ml)에 녹이고 소듐 터부톡사이드 (73.9 mmol, 7.10 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.493 mmol, 0.252 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 19-b 36.1 g을 수득하였다. (수율 88%, MS[M+H]+= 837)In a three-necked flask, compound 1-a (49.3 mmol, 20 g) and compound 19-a (49.3 mmol, 23.0 g) were dissolved in toluene (0.2 M, 250 ml), sodium terbutoxide (73.9 mmol, 7.10 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.493 mmol, 0.252 g), the mixture was stirred for 12 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 36.1 g of compound 19-b. (Yield 88%, MS[M+H]+= 837)
단계 3) 화합물 19의 합성Step 3) Synthesis of compound 19
Figure PCTKR2020017069-appb-I000182
Figure PCTKR2020017069-appb-I000182
3구 플라스크에 화합물 19-b (43.1 mmol, 36.1 g)을 1,2-디클로로벤젠 (0.1 M, 430 ml)에 녹이고 보론트리아이오다이드 (69.0 mmol, 27.0 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (388 mmol, 50.2 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 19, 7.1 g을 수득하였다. (수율 19%, MS[M+H]+= 603)In a three-necked flask, compound 19-b (43.1 mmol, 36.1 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 430 ml), boron triiodide (69.0 mmol, 27.0 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (388 mmol, 50.2 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then compound 19, 7.1 g, was obtained through sublimation purification. (yield 19%, MS[M+H]+= 603)
합성예 20 : 화합물 20의 합성Synthesis Example 20: Synthesis of compound 20
단계 1) 화합물 20-a의 합성Step 1) Synthesis of compound 20-a
Figure PCTKR2020017069-appb-I000183
Figure PCTKR2020017069-appb-I000183
3구 플라스크에 4-터부틸아민 (36.7 mmol, 5.48 g)과 3-브로모-N,N-디-o-톨릴벤조[b]싸이오펜-5-아민 (36.7 mmol, 15 g)을 톨루엔 (0.2 M, 185 ml)에 녹이고 소듐 터부톡사이드 (55.1 mmol, 5.29 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.367 mmol, 0.188 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 20-a 15.9 g을 수득하였다. (수율 91%, MS[M+H]+= 477)In a three-necked flask, 4-terbutylamine (36.7 mmol, 5.48 g) and 3-bromo- N,N -di- o -tolylbenzo[ b ]thiophen-5-amine (36.7 mmol, 15 g) were mixed with toluene. (0.2 M, 185 ml), sodium terbutoxide (55.1 mmol, 5.29 g), bis (tri-terbutylphosphine) palladium (0) (0.367 mmol, 0.188 g) was added, and then under reflux conditions under argon atmosphere. Stirred for 12 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 15.9 g of compound 20-a. (Yield 91%, MS[M+H]+= 477)
단계 2) 화합물 20-b의 합성Step 2) Synthesis of compound 20-b
Figure PCTKR2020017069-appb-I000184
Figure PCTKR2020017069-appb-I000184
3구 플라스크에 화합물 1-a (29.6 mmol, 12 g)와 화합물 20-a (29.6 mmol, 14.1 g)을 톨루엔 (0.2 M, 150 ml)에 녹이고 소듐 터부톡사이드 (44.3 mmol, 4.26 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.296 mmol, 0.151 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 20-b 19.1 g을 수득하였다. (수율 76%, MS[M+H]+= 846)In a three-necked flask, compound 1-a (29.6 mmol, 12 g) and compound 20-a (29.6 mmol, 14.1 g) were dissolved in toluene (0.2 M, 150 ml), sodium terbutoxide (44.3 mmol, 4.26 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.296 mmol, 0.151 g), the mixture was stirred for 18 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 19.1 g of compound 20-b. (yield 76%, MS[M+H]+= 846)
단계 3) 화합물 20의 합성Step 3) Synthesis of compound 20
Figure PCTKR2020017069-appb-I000185
Figure PCTKR2020017069-appb-I000185
3구 플라스크에 화합물 20-b (22.6 mmol, 19.1 g)을 1,2-디클로로벤젠 (0.1 M, 226 ml)에 녹이고 보론트리아이오다이드 (36.1 mmol, 14.1 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (203 mmol, 26.3 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 20, 3.2 g을 수득하였다. (수율 17%, MS[M+H]+= 854)In a three-necked flask, compound 20-b (22.6 mmol, 19.1 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 226 ml), boron triiodide (36.1 mmol, 14.1 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (203 mmol, 26.3 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 20, 3.2 g. (Yield 17%, MS[M+H]+= 854)
합성예 21 : 화합물 21의 합성Synthesis Example 21: Synthesis of compound 21
단계 1) 화합물 21-a의 합성Step 1) Synthesis of compound 21-a
Figure PCTKR2020017069-appb-I000186
Figure PCTKR2020017069-appb-I000186
3구 플라스크에 N,N-비스(2-플루오르페닐)-4a,9a-디메틸-2,3,4,4a,9,9a-헥사하이드로-1H-카바졸-5-아민 (34.1 mmol, 13.8 g)과 1-브로모-3-클로로-5-메틸벤젠 (34.1 mmol, 7 g)을 톨루엔 (0.2 M, 170 ml)에 녹이고 소듐 터부톡사이드 (51.1 mmol, 4.91 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.341 mmol, 0.174 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 21-a 15.3 g을 수득하였다. (수율 85%, MS[M+H]+= 15.3) N,N -bis(2-fluorophenyl)-4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro- 1H -carbazol-5-amine (34.1 mmol, 13.8 g) and 1-bromo-3-chloro-5-methylbenzene (34.1 mmol, 7 g) were dissolved in toluene (0.2 M, 170 ml), and sodium terbutoxide (51.1 mmol, 4.91 g), bis(tri -terbutylphosphine)palladium(0) (0.341 mmol, 0.174 g) was added, and the mixture was stirred under reflux conditions in an argon atmosphere for 4 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , and concentrated, and the sample was purified by silica gel column chromatography to obtain 15.3 g of compound 21-a. (yield 85%, MS[M+H]+= 15.3)
단계 2) 화합물 21-b의 합성Step 2) Synthesis of compound 21-b
Figure PCTKR2020017069-appb-I000187
Figure PCTKR2020017069-appb-I000187
3구 플라스크에 화합물 21-a (28.4 mmol, 15 g)와 화합물 17-b (28.4 mmol, 9.57 g)을 톨루엔 (0.2 M, 140 ml)에 녹이고 소듐 터부톡사이드 (42.5 mmol, 4.09 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.284 mmol, 0.145 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 21-b 18.4 g을 수득하였다. (수율 78%, MS[M+H]+= 830)In a three-necked flask, compound 21-a (28.4 mmol, 15 g) and compound 17-b (28.4 mmol, 9.57 g) were dissolved in toluene (0.2 M, 140 ml), sodium terbutoxide (42.5 mmol, 4.09 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.284 mmol, 0.145 g), the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 18.4 g of compound 21-b. (Yield 78%, MS[M+H]+= 830)
단계 3) 화합물 21의 합성Step 3) Synthesis of compound 21
Figure PCTKR2020017069-appb-I000188
Figure PCTKR2020017069-appb-I000188
3구 플라스크에 화합물 21-b (22.2 mmol, 18.4 g)을 1,2-디클로로벤젠 (0.1 M, 220 ml)에 녹이고 보론트리아이오다이드 (35.5 mmol, 13.9 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (199 mmol, 25.8 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 21, 3.8 g을 수득하였다. (수율 20%, MS[M+H]+= 838)In a three-necked flask, compound 21-b (22.2 mmol, 18.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 220 ml), boron triiodide (35.5 mmol, 13.9 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, and N,N-diisopropylethylamine (199 mmol, 25.8 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4, concentrated, and the sample was purified by silica gel column chromatography, and then, compound 21, 3.8 g, was obtained through sublimation purification. (Yield 20%, MS[M+H]+= 838)
합성예 22 : 화합물 22의 합성Synthesis Example 22: Synthesis of compound 22
단계 1) 화합물 22-a의 합성Step 1) Synthesis of compound 22-a
Figure PCTKR2020017069-appb-I000189
Figure PCTKR2020017069-appb-I000189
3구 플라스크에 4'-터부틸-5-트리메틸실릴-[1,1'-바이페닐]-2-아민 (43.6 mmol, 13 g)과 3-브로모-5,8-디메틸-5,6,7,8-테트라하이드로-5,8-에타노나프토[2,3-b]싸이오펜 (43.6 mmol, 14 g)을 톨루엔 (0.2 M, 220 ml)에 녹이고 소듐 터부톡사이드 (65.4 mmol, 6.28 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.436 mmol, 0.223 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 22-a 14.6 g을 수득하였다. (수율 62%, MS[M+H]+= 538)4'-terbutyl-5-trimethylsilyl-[1,1'-biphenyl]-2-amine (43.6 mmol, 13 g) and 3-bromo-5,8-dimethyl-5,6 in a 3-neck flask ,7,8-tetrahydro-5,8-ethanonaphtho[2,3- b ]thiophene (43.6 mmol, 14 g) was dissolved in toluene (0.2 M, 220 ml) and sodium terbutoxide (65.4 mmol, 6.28 g) and bis(tri-terbutylphosphine)palladium(0) (0.436 mmol, 0.223 g) were added, and the mixture was stirred for 24 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 14.6 g of compound 22-a. (Yield 62%, MS[M+H]+= 538)
단계 2) 화합물 22-b의 합성Step 2) Synthesis of compound 22-b
Figure PCTKR2020017069-appb-I000190
Figure PCTKR2020017069-appb-I000190
3구 플라스크에 화합물 1-a (24.6 mmol, 10 g)와 화합물 22-a (24.6 mmol, 13.2 g)을 톨루엔 (0.2 M, 125 ml)에 녹이고 소듐 터부톡사이드 (36.9 mmol, 3.55 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.246 mmol, 0.126 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 22-b 16.5 g을 수득하였다. (수율 74%, MS[M+H]+= 907)In a three-necked flask, compound 1-a (24.6 mmol, 10 g) and compound 22-a (24.6 mmol, 13.2 g) were dissolved in toluene (0.2 M, 125 ml), sodium terbutoxide (36.9 mmol, 3.55 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.246 mmol, 0.126 g), the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 16.5 g of compound 22-b. (Yield 74%, MS[M+H]+=907)
단계 3) 화합물 22의 합성Step 3) Synthesis of compound 22
Figure PCTKR2020017069-appb-I000191
Figure PCTKR2020017069-appb-I000191
3구 플라스크에 화합물 22-b (18.2 mmol, 16.5 g)을 1,2-디클로로벤젠 (0.1 M, 180 ml)에 녹이고 보론트리아이오다이드 (29.1 mmol, 11.4 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (164 mmol, 21.1 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 22, 2.8 g을 수득하였다. (수율 17%, MS[M+H]+= 915)In a three-neck flask, compound 22-b (18.2 mmol, 16.5 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 180 ml), boron triiodide (29.1 mmol, 11.4 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (164 mmol, 21.1 g) was added, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then compound 22, 2.8 g, was obtained through sublimation purification. (Yield 17%, MS[M+H]+= 915)
합성예 23 : 화합물 23의 합성Synthesis Example 23: Synthesis of compound 23
단계 1) 화합물 23-a의 합성Step 1) Synthesis of compound 23-a
Figure PCTKR2020017069-appb-I000192
Figure PCTKR2020017069-appb-I000192
3구 플라스크에 비스-(4-터부틸페닐)-아민 (107 mmol, 30 g)과 1-브로모-3-클로로-5-(메틸-d-3)벤젠 (107 mmol, 22.2 g)을 톨루엔 (0.2 M, 535 ml)에 녹이고 소듐 터부톡사이드 (160 mmol, 15.4 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.07 mmol, 0.545 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 23-a 36.2 g을 수득하였다. (수율 83%, MS[M+H]+= 409)Bis-(4-terbutylphenyl)-amine (107 mmol, 30 g) and 1-bromo-3-chloro-5-(methyl- d- 3)benzene (107 mmol, 22.2 g) were added to a three-necked flask. Dissolved in toluene (0.2 M, 535 ml), sodium terbutoxide (160 mmol, 15.4 g), bis(tri-terbutylphosphine)palladium (0) (1.07 mmol, 0.545 g) were added, and then refluxed under argon atmosphere. under stirring for 4 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 36.2 g of compound 23-a. (Yield 83%, MS[M+H]+=409)
단계 2) 화합물 23-b의 합성Step 2) Synthesis of compound 23-b
Figure PCTKR2020017069-appb-I000193
Figure PCTKR2020017069-appb-I000193
3구 플라스크에 7-브로모-3,3-디메틸-2,3-디하이드로싸이에노[2,3-f]벤조퓨란 (53.0 mmol, 15 g)과 4-터부틸아닐린 (53.0 mmol, 7.9 g)을 톨루엔 (0.2 M, 265 ml)에 녹이고 소듐 터부톡사이드 (79.5 mmol, 7.64 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.530 mmol, 0.271 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 23-b 12.7 g을 수득하였다. (수율 68%, MS[M+H]+= 352)7-bromo-3,3-dimethyl-2,3-dihydrothieno [2,3- f ] benzofuran (53.0 mmol, 15 g) and 4-tertbutylaniline (53.0 mmol, 7.9 g) was dissolved in toluene (0.2 M, 265 ml), sodium terbutoxide (79.5 mmol, 7.64 g), bis(tri-terbutylphosphine)palladium(0) (0.530 mmol, 0.271 g) were added, The mixture was stirred for 18 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 12.7 g of compound 23-b. (Yield 68%, MS[M+H]+= 352)
단계 3) 화합물 23-c의 합성Step 3) Synthesis of compound 23-c
Figure PCTKR2020017069-appb-I000194
Figure PCTKR2020017069-appb-I000194
3구 플라스크에 화합물 23-a (34.2 mmol, 14 g)와 화합물 23-b (34.2 mmol, 12 g)을 톨루엔 (0.2 M, 170 ml)에 녹이고 소듐 터부톡사이드 (51.3 mmol, 4.93 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.342 mmol, 0.175 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 23-c 20.3 g을 수득하였다. (수율 82%, MS[M+H]+= 724)In a three-necked flask, compound 23-a (34.2 mmol, 14 g) and compound 23-b (34.2 mmol, 12 g) were dissolved in toluene (0.2 M, 170 ml), sodium terbutoxide (51.3 mmol, 4.93 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.342 mmol, 0.175 g), the mixture was stirred for 24 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 20.3 g of compound 23-c. (Yield 82%, MS[M+H]+= 724)
단계 4) 화합물 23의 합성Step 4) Synthesis of compound 23
Figure PCTKR2020017069-appb-I000195
Figure PCTKR2020017069-appb-I000195
3구 플라스크에 화합물 23-c (28.0 mmol, 20.3 g)을 1,2-디클로로벤젠 (0.1 M, 280 ml)에 녹이고 보론트리아이오다이드 (44.9 mmol, 17.6 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (252 mmol, 32.6 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 23, 4.1 g을 수득하였다. (수율 20%, MS[M+H]+= 732)In a three-necked flask, compound 23-c (28.0 mmol, 20.3 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 280 ml), boron triiodide (44.9 mmol, 17.6 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (252 mmol, 32.6 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then, compound 23, 4.1 g, was obtained through sublimation purification. (yield 20%, MS[M+H]+=732)
합성예 24 : 화합물 24의 합성Synthesis Example 24: Synthesis of compound 24
단계 1) 화합물 24-a의 합성Step 1) Synthesis of compound 24-a
Figure PCTKR2020017069-appb-I000196
Figure PCTKR2020017069-appb-I000196
3구 플라스크에 5-터부틸-[1,1'-바이페닐]-2',3,3',4,4',5',6,6'-d8-2-아민 (40.2 mmol, 9.38 g)과 2-브로모-5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프토[2,3-b]싸이오펜 (40.2 mmol, 13 g)을 톨루엔 (0.2 M, 200 ml)에 녹이고 소듐 터부톡사이드 (60.3 mmol, 5.80 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.402 mmol, 0.206 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 24-a 18.2 g을 수득하였다. (수율 95%, MS[M+H]+= 476)5-tertbutyl-[1,1'-biphenyl]-2',3,3',4,4',5',6,6'- d 8-2-amine (40.2 mmol, 9.38 g) and 2-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3- b ]thiophene (40.2 mmol, 13 g) in toluene (0.2 M, 200 ml), sodium terbutoxide (60.3 mmol, 5.80 g), bis (tri-terbutylphosphine) palladium (0) (0.402 mmol, 0.206 g) were added, and then under reflux conditions under argon atmosphere. Stirred for 4 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 18.2 g of compound 24-a. (yield 95%, MS[M+H]+=476)
단계 2) 화합물 24-b의 합성Step 2) Synthesis of compound 24-b
Figure PCTKR2020017069-appb-I000197
Figure PCTKR2020017069-appb-I000197
3구 플라스크에 화합물 1-a (36.9 mmol, 15 g)와 화합물 24-a (36.9 mmol, 17.6 g)을 톨루엔 (0.2 M, 185 ml)에 녹이고 소듐 터부톡사이드 (55.4 mmol, 5.33 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.369 mmol, 0.189 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 24-b 18.4 g을 수득하였다. (수율 59%, MS[M+H]+= 845)In a three-necked flask, compound 1-a (36.9 mmol, 15 g) and compound 24-a (36.9 mmol, 17.6 g) were dissolved in toluene (0.2 M, 185 ml), and sodium terbutoxide (55.4 mmol, 5.33 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.369 mmol, 0.189 g), the mixture was stirred for 12 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 18.4 g of compound 24-b. (yield 59%, MS[M+H]+= 845)
단계 3) 화합물 24의 합성Step 3) Synthesis of compound 24
Figure PCTKR2020017069-appb-I000198
Figure PCTKR2020017069-appb-I000198
3구 플라스크에 화합물 24-b (21.8 mmol, 18.4 g)을 1,2-디클로로벤젠 (0.1 M, 220 ml)에 녹이고 보론트리아이오다이드 (34.8 mmol, 13.6 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (196 mmol, 25.3 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 24, 3.2 g을 수득하였다. (수율 17%, MS[M+H]+= 853)In a three-necked flask, compound 24-b (21.8 mmol, 18.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 220 ml), boron triiodide (34.8 mmol, 13.6 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (196 mmol, 25.3 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain Compound 24, 3.2 g. (Yield 17%, MS[M+H]+=853)
합성예 25 : 화합물 25의 합성Synthesis Example 25: Synthesis of compound 25
단계 1) 화합물 25-a의 합성Step 1) Synthesis of compound 25-a
Figure PCTKR2020017069-appb-I000199
Figure PCTKR2020017069-appb-I000199
3구 플라스크에 비스-(4-터부틸페닐)-아민 (142 mmol, 40 g)과 (3r,5r,7r)-1-(3-브로모-5-클로로페닐)아다만테인 (142 mmol, 46.3 g)을 톨루엔 (0.2 M, 710 ml)에 녹이고 소듐 터부톡사이드 (213 mmol, 20.5 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.42 mmol, 0.726 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 3시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 25-a 63.8 g을 수득하였다. (수율 85%, MS[M+H]+= 526)Bis-(4-terbutylphenyl)-amine (142 mmol, 40 g) and (3 r ,5 r ,7 r )-1-(3-bromo-5-chlorophenyl)adamantane in a 3-neck flask (142 mmol, 46.3 g) was dissolved in toluene (0.2 M, 710 ml), sodium terbutoxide (213 mmol, 20.5 g), bis(tri-terbutylphosphine)palladium(0) (1.42 mmol, 0.726 g) After adding, the mixture was stirred for 3 hours under reflux conditions under argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 63.8 g of compound 25-a. (Yield 85%, MS[M+H]+= 526)
단계 2) 화합물 25-b의 합성Step 2) Synthesis of compound 25-b
Figure PCTKR2020017069-appb-I000200
Figure PCTKR2020017069-appb-I000200
3구 플라스크에 3-브로모-4,4,7,7-테트라메틸-4,5,6,7-테트라하이드로벤조[b]싸이오펜 (54.9 mmol, 15 g)과 3,5-비스(트리플루오르메틸)아닐린 (54.9 mmol, 12.6 g)을 톨루엔 (0.2 M, 275 ml)에 녹이고 소듐 터부톡사이드 (82.3 mmol, 7.91 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.549 mmol, 0.281 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 25-b 16.7 g을 수득하였다. (수율 72%, MS[M+H]+= 421)3-bromo-4,4,7,7-tetramethyl-4,5,6,7-tetrahydrobenzo [ b ] thiophene (54.9 mmol, 15 g) and 3,5-bis ( Trifluoromethyl)aniline (54.9 mmol, 12.6 g) was dissolved in toluene (0.2 M, 275 ml), sodium terbutoxide (82.3 mmol, 7.91 g), bis(tri-terbutylphosphine)palladium (0) (0.549) mmol, 0.281 g) was added, and the mixture was stirred for 18 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 16.7 g of compound 25-b. (Yield 72%, MS[M+H]+=421)
단계 3) 화합물 25-c의 합성Step 3) Synthesis of compound 25-c
Figure PCTKR2020017069-appb-I000201
Figure PCTKR2020017069-appb-I000201
3구 플라스크에 화합물 25-a (38.0 mmol, 20 g)와 화합물 25-b (38.0 mmol, 16 g)을 톨루엔 (0.2 M, 190 ml)에 녹이고 소듐 터부톡사이드 (57.0 mmol, 5.48 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.380 mmol, 0.194 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 25-c 22.7 g을 수득하였다. (수율 66%, MS[M+H]+= 911)In a three-necked flask, compound 25-a (38.0 mmol, 20 g) and compound 25-b (38.0 mmol, 16 g) were dissolved in toluene (0.2 M, 190 ml), sodium terbutoxide (57.0 mmol, 5.48 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.380 mmol, 0.194 g), the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 22.7 g of compound 25-c. (Yield 66%, MS[M+H]+= 911)
단계 4) 화합물 25의 합성Step 4) Synthesis of compound 25
Figure PCTKR2020017069-appb-I000202
Figure PCTKR2020017069-appb-I000202
3구 플라스크에 화합물 25-c (24.9 mmol, 22.7 g)을 1,2-디클로로벤젠 (0.1 M, 250 ml)에 녹이고 보론트리아이오다이드 (39.9 mmol, 15.6 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (224 mmol, 29.0 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 25, 3.9 g을 수득하였다. (수율 17%, MS[M+H]+= 919)In a three-neck flask, compound 25-c (24.9 mmol, 22.7 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 250 ml), boron triiodide (39.9 mmol, 15.6 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (224 mmol, 29.0 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then the compound 25, 3.9 g, was obtained through sublimation purification. (Yield 17%, MS[M+H]+= 919)
합성예 26 : 화합물 26의 합성Synthesis Example 26: Synthesis of compound 26
단계 1) 화합물 26-a의 합성Step 1) Synthesis of compound 26-a
Figure PCTKR2020017069-appb-I000203
Figure PCTKR2020017069-appb-I000203
3구 플라스크에 비스-(5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프탈렌-2-일)아민 (77.0 mmol, 30 g)과 1-브로모-3-클로로-5-메틸벤젠 (77.0 mmol, 15.8 g)을 톨루엔 (0.2 M, 385 ml)에 녹이고 소듐 터부톡사이드 (115 mmol, 11.1 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.77 mmol, 0.393 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 26-a 36.6 g을 수득하였다. (수율 92%, MS[M+H]+= 514)Bis-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)amine (77.0 mmol, 30 g) and 1-bromo-3- Chloro-5-methylbenzene (77.0 mmol, 15.8 g) was dissolved in toluene (0.2 M, 385 ml), sodium terbutoxide (115 mmol, 11.1 g), bis (tri-terbutylphosphine) palladium (0) ( 0.77 mmol, 0.393 g) was added, and the mixture was stirred for 6 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 36.6 g of compound 26-a. (Yield 92%, MS[M+H]+= 514)
단계 2) 화합물 26-b의 합성Step 2) Synthesis of compound 26-b
Figure PCTKR2020017069-appb-I000204
Figure PCTKR2020017069-appb-I000204
3구 플라스크에 2-브로모-7-터부틸-4,4-디메틸-4H-인데노[1,2-b]싸이오펜 (35.8 mmol, 12 g)과 4-터부틸-2-메틸아닐린 (35.8 mmol, 5.84 g)을 톨루엔 (0.2 M, 180 ml)에 녹이고 소듐 터부톡사이드 (53.7 mmol, 5.16 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.358 mmol, 0.183 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 26-b 13.4 g을 수득하였다. (수율 90%, MS[M+H]+= 418)In a three-necked flask, 2-bromo-7-terbutyl-4,4-dimethyl- 4H -indeno[1,2- b ]thiophene (35.8 mmol, 12 g) and 4-tertbutyl-2-methyl Aniline (35.8 mmol, 5.84 g) was dissolved in toluene (0.2 M, 180 ml), sodium terbutoxide (53.7 mmol, 5.16 g), bis(tri-terbutylphosphine)palladium(0) (0.358 mmol, 0.183 g) ), and stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 13.4 g of compound 26-b. (Yield 90%, MS[M+H]+= 418)
단계 3) 화합물 26-c의 합성Step 3) Synthesis of compound 26-c
Figure PCTKR2020017069-appb-I000205
Figure PCTKR2020017069-appb-I000205
3구 플라스크에 화합물 26-a (29.2 mmol, 15 g)와 화합물 26-b (29.2 mmol, 12.2 g)을 톨루엔 (0.2 M, 145 ml)에 녹이고 소듐 터부톡사이드 (43.8 mmol, 4.21 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.292 mmol, 0.149 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 15시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 26-c 19.2 g을 수득하였다. (수율 74%, MS[M+H]+= 895)In a three-necked flask, compound 26-a (29.2 mmol, 15 g) and compound 26-b (29.2 mmol, 12.2 g) were dissolved in toluene (0.2 M, 145 ml), sodium terbutoxide (43.8 mmol, 4.21 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.292 mmol, 0.149 g), the mixture was stirred for 15 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 19.2 g of compound 26-c. (Yield 74%, MS[M+H]+= 895)
단계 4) 화합물 26의 합성Step 4) Synthesis of compound 26
Figure PCTKR2020017069-appb-I000206
Figure PCTKR2020017069-appb-I000206
3구 플라스크에 화합물 26-c (21.4 mmol, 19.2 g)을 1,2-디클로로벤젠 (0.1 M, 215 ml)에 녹이고 보론트리아이오다이드 (34.3 mmol, 13.4 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (193 mmol, 24.9 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 26, 4.5 g을 수득하였다. (수율 23%, MS[M+H]+= 903)In a three-necked flask, compound 26-c (21.4 mmol, 19.2 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 215 ml), boron triiodide (34.3 mmol, 13.4 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (193 mmol, 24.9 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 26, 4.5 g. (Yield 23%, MS[M+H]+= 903)
합성예 27 : 화합물 27의 합성Synthesis Example 27: Synthesis of compound 27
단계 1) 화합물 27-a의 합성Step 1) Synthesis of compound 27-a
Figure PCTKR2020017069-appb-I000207
Figure PCTKR2020017069-appb-I000207
3구 플라스크에 4-터부틸아닐린 (80.4 mmol, 12 g)과 4-브로모-2-터부틸싸이오펜 (80.4 mmol, 17.6 g)을 톨루엔 (0.2 M, 400 ml)에 녹이고 소듐 터부톡사이드 (121 mmol, 11.6 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.804 mmol, 0.411 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 27-a 19.2g을 수득하였다. (수율 83%, MS[M+H]+= 287)Dissolve 4-terbutylaniline (80.4 mmol, 12 g) and 4-bromo-2-terbutylthiophene (80.4 mmol, 17.6 g) in toluene (0.2 M, 400 ml) in a three-necked flask, and then sodium terbutoxide (121 mmol, 11.6 g) and bis(tri-terbutylphosphine)palladium(0) (0.804 mmol, 0.411 g) were added, and the mixture was stirred under reflux conditions in an argon atmosphere for 24 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 19.2 g of compound 27-a. (Yield 83%, MS[M+H]+= 287)
단계 2) 화합물 27-b의 합성Step 2) Synthesis of compound 27-b
Figure PCTKR2020017069-appb-I000208
Figure PCTKR2020017069-appb-I000208
3구 플라스크에 화합물 4-a (38.2 mmol, 18 g)와 화합물 27-a (38.2 mmol, 11 g)을 톨루엔 (0.2 M, 190 ml)에 녹이고 소듐 터부톡사이드 (57.3 mmol, 5.51 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.382 mmol, 0.195 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 27-b 21.4 g을 수득하였다. (수율 83%, MS[M+H]+= 677)In a three-necked flask, compound 4-a (38.2 mmol, 18 g) and compound 27-a (38.2 mmol, 11 g) were dissolved in toluene (0.2 M, 190 ml), sodium terbutoxide (57.3 mmol, 5.51 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.382 mmol, 0.195 g), the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 21.4 g of compound 27-b. (Yield 83%, MS[M+H]+= 677)
단계 3) 화합물 27-c의 합성Step 3) Synthesis of compound 27-c
Figure PCTKR2020017069-appb-I000209
Figure PCTKR2020017069-appb-I000209
3구 플라스크에 화합물 27-b (31.6 mmol, 21.4 g)을 1,2-디클로로벤젠 (0.1 M, 315 ml)에 녹이고 보론트리아이오다이드 (50.5 mmol, 19.8 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (284 mmol, 36.7 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 27-c 4.4 g을 수득하였다. (수율 20%, MS[M+H]+= 685)In a three-necked flask, compound 27-b (31.6 mmol, 21.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 315 ml), boron triiodide (50.5 mmol, 19.8 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (284 mmol, 36.7 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 4.4 g of compound 27-c. (Yield 20%, MS[M+H]+=685)
단계 4) 화합물 27 의 합성Step 4) Synthesis of compound 27
Figure PCTKR2020017069-appb-I000210
Figure PCTKR2020017069-appb-I000210
3구 플라스크에 화합물 27-c (6.42 mmol, 4.4 g)와 디페닐아민 (7.7 mmol, 1.30 g)을 톨루엔 (0.2 M, 40 ml)에 녹이고 소듐 터부톡사이드 (9.63 mmol, 0.926 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.06 mmol, 0.033 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 27, 4.1 g을 수득하였다. (수율 78%, MS[M+H]+= 818)In a three-necked flask, compound 27-c (6.42 mmol, 4.4 g) and diphenylamine (7.7 mmol, 1.30 g) were dissolved in toluene (0.2 M, 40 ml), and sodium terbutoxide (9.63 mmol, 0.926 g), bis After (tri-terbutylphosphine)palladium(0) (0.06 mmol, 0.033 g) was added, the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 27, 4.1 g. (Yield 78%, MS[M+H]+= 818)
합성예 28 : 화합물 28의 합성Synthesis Example 28: Synthesis of compound 28
단계 1) 화합물 28-a의 합성Step 1) Synthesis of compound 28-a
Figure PCTKR2020017069-appb-I000211
Figure PCTKR2020017069-appb-I000211
3구 플라스크에 4-터부틸-2-메틸아닐린 (30.6 mmol, 5 g)과 4-브로모-2,3-디-o-톨릴싸이오펜 (30.6 mmol, 10.5 g)을 톨루엔 (0.2 M, 155 ml)에 녹이고 소듐 터부톡사이드 (45.9 mmol, 4.41 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.306 mmol, 0.157 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 28-a 10.4g을 수득하였다. (수율 80%, MS[M+H]+= 426)In a three-necked flask, 4-terbutyl-2-methylaniline (30.6 mmol, 5 g) and 4-bromo-2,3-di- o -tolylthiophene (30.6 mmol, 10.5 g) were mixed with toluene (0.2 M, 155 ml), sodium terbutoxide (45.9 mmol, 4.41 g), bis(tri-terbutylphosphine)palladium (0) (0.306 mmol, 0.157 g) were added, and then stirred for 12 hours under reflux conditions in an argon atmosphere. did. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 10.4 g of compound 28-a. (yield 80%, MS[M+H]+= 426)
단계 2) 화합물 28-b의 합성Step 2) Synthesis of compound 28-b
Figure PCTKR2020017069-appb-I000212
Figure PCTKR2020017069-appb-I000212
3구 플라스크에 화합물 4-a (23.4 mmol, 11 g)와 화합물 28-a (23.4 mmol, 9.94 g)을 톨루엔 (0.2 M, 120 ml)에 녹이고 소듐 터부톡사이드 (35.0 mmol, 3.37 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.234 mmol, 0.119 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 28-b 11.8 g을 수득하였다. (수율 62%, MS[M+H]+= 816)In a three-necked flask, compound 4-a (23.4 mmol, 11 g) and compound 28-a (23.4 mmol, 9.94 g) were dissolved in toluene (0.2 M, 120 ml), sodium terbutoxide (35.0 mmol, 3.37 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.234 mmol, 0.119 g), the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 11.8 g of compound 28-b. (Yield 62%, MS[M+H]+= 816)
단계 3) 화합물 28-c의 합성Step 3) Synthesis of compound 28-c
Figure PCTKR2020017069-appb-I000213
Figure PCTKR2020017069-appb-I000213
3구 플라스크에 화합물 28-b (14.5 mmol, 11.8 g)을 1,2-디클로로벤젠 (0.1 M, 145 ml)에 녹이고 보론트리아이오다이드 (23.1 mmol, 9.06 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (130 mmol, 16.8 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 28-c 2.9 g을 수득하였다. (수율 24%, MS[M+H]+= 823)In a three-necked flask, compound 28-b (14.5 mmol, 11.8 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 145 ml), boron triiodide (23.1 mmol, 9.06 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, and N,N-diisopropylethylamine (130 mmol, 16.8 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 2.9 g of compound 28-c. (yield 24%, MS[M+H]+= 823)
단계 4) 화합물 28의 합성Step 4) Synthesis of compound 28
Figure PCTKR2020017069-appb-I000214
Figure PCTKR2020017069-appb-I000214
3구 플라스크에 화합물 28-c (3.52 mmol, 2.9 g)와 10H-페녹사진 (4.23 mmol, 0.774 g)을 톨루엔 (0.2 M, 21 ml)에 녹이고 소듐 터부톡사이드 (5.28 mmol, 0.508 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.035 mmol, 0.018 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 18시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 28, 2.9 g을 수득하였다. (수율 85%, MS[M+H]+= 970)In a three-necked flask, compound 28-c (3.52 mmol, 2.9 g) and 10 H -phenoxazine (4.23 mmol, 0.774 g) were dissolved in toluene (0.2 M, 21 ml) and sodium terbutoxide (5.28 mmol, 0.508 g) , bis(tri-terbutylphosphine)palladium(0) (0.035 mmol, 0.018 g) was added, and the mixture was stirred for 18 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then compound 28, 2.9 g, was obtained through sublimation purification. (Yield 85%, MS[M+H]+=970)
합성예29 : 화합물 29의 합성Synthesis Example 29: Synthesis of compound 29
단계 1) 화합물 29-a의 합성Step 1) Synthesis of compound 29-a
Figure PCTKR2020017069-appb-I000215
Figure PCTKR2020017069-appb-I000215
3구 플라스크에 5-터부틸-N-(4-트리페닐실릴페닐)-[1,1'-바이페닐]-2-아민 (53.6 mmol, 30 g)과 1-브로모-3-클로로-5-메틸벤젠 (53.6 mmol, 11.0 g)을 톨루엔 (0.2 M, 270 ml)에 녹이고 소듐 터부톡사이드 (80.4 mmol, 7.72 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.536 mmol, 0.274 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 29-a 27.1 g을 수득하였다. (수율 74%, MS[M+H]+= 684)5-tertbutyl- N- (4-triphenylsilylphenyl)-[1,1'-biphenyl]-2-amine (53.6 mmol, 30 g) and 1-bromo-3-chloro- Dissolve 5-methylbenzene (53.6 mmol, 11.0 g) in toluene (0.2 M, 270 ml), sodium terbutoxide (80.4 mmol, 7.72 g), bis(tri-terbutylphosphine)palladium(0) (0.536 mmol) , 0.274 g), and stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 27.1 g of compound 29-a. (Yield 74%, MS[M+H]+= 684)
단계 2) 화합물 29-b의 합성Step 2) Synthesis of compound 29-b
Figure PCTKR2020017069-appb-I000216
Figure PCTKR2020017069-appb-I000216
3구 플라스크에 3-브로모싸이에노[2,3-b]벤조퓨란 (39.5 mmol, 10 g)과 4-터부틸-2-메틸아닐린 (39.5 mmol, 6.45 g)을 톨루엔 (0.2 M, 200 ml)에 녹이고 소듐 터부톡사이드 (59.3 mmol, 5.70 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.358 mmol, 0.183 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 15시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 29-b 9.8 g을 수득하였다. (수율 74%, MS[M+H]+= 335)In a three-necked flask, 3-bromothieno[2,3- b ]benzofuran (39.5 mmol, 10 g) and 4-terbutyl-2-methylaniline (39.5 mmol, 6.45 g) were mixed with toluene (0.2 M, 200 ml), sodium terbutoxide (59.3 mmol, 5.70 g), bis(tri-terbutylphosphine)palladium(0) (0.358 mmol, 0.183 g) were added, and then stirred for 15 hours under reflux conditions in an argon atmosphere. did. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 9.8 g of compound 29-b. (Yield 74%, MS[M+H]+=335)
단계 3) 화합물 29-c의 합성Step 3) Synthesis of compound 29-c
Figure PCTKR2020017069-appb-I000217
Figure PCTKR2020017069-appb-I000217
3구 플라스크에 화합물 29-a (29.2 mmol, 20 g)와 화합물 29-b (29.2 mmol, 9.80 g)을 톨루엔 (0.2 M, 145 ml)에 녹이고 소듐 터부톡사이드 (43.8 mmol, 4.21 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.292 mmol, 0.149 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 29-c 23.1 g을 수득하였다. (수율 80%, MS[M+H]+= 983)In a three-necked flask, compound 29-a (29.2 mmol, 20 g) and compound 29-b (29.2 mmol, 9.80 g) were dissolved in toluene (0.2 M, 145 ml), sodium terbutoxide (43.8 mmol, 4.21 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.292 mmol, 0.149 g), the mixture was stirred for 24 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 23.1 g of compound 29-c. (yield 80%, MS[M+H]+=983)
단계 4) 화합물 29의 합성Step 4) Synthesis of compound 29
Figure PCTKR2020017069-appb-I000218
Figure PCTKR2020017069-appb-I000218
3구 플라스크에 화합물 29-c (23.5 mmol, 23.1 g)을 1,2-디클로로벤젠 (0.1 M, 235 ml)에 녹이고 보론트리아이오다이드 (37.6 mmol, 14.7 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (211 mmol, 27.3 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 29, 3.7 g을 수득하였다. (수율 16%, MS[M+H]+= 991)In a three-neck flask, compound 29-c (23.5 mmol, 23.1 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 235 ml), boron triiodide (37.6 mmol, 14.7 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (211 mmol, 27.3 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 29, 3.7 g. (yield 16%, MS[M+H]+= 991)
합성예 30 : 화합물 30의 합성Synthesis Example 30: Synthesis of compound 30
단계 1) 화합물 30-a의 합성Step 1) Synthesis of compound 30-a
Figure PCTKR2020017069-appb-I000219
Figure PCTKR2020017069-appb-I000219
3구 플라스크에 6-터부틸-4a,9a-디메틸-2,3,4,4a,9,9a-헥사하이드로-1H-카바졸 (194 mmol, 50 g)과 1-브로모-3-클로로-5-메틸벤젠 (194 mmol, 39.9 g)을 톨루엔 (0.2 M, 970 ml)에 녹이고 소듐 터부톡사이드 (291 mmol, 28.0 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.94 mmol, 0.993 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 8시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 30-a 67.2 g을 수득하였다. (수율 91%, MS[M+H]+= 382)6-terbutyl-4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro- 1H -carbazole (194 mmol, 50 g) and 1-bromo-3- in a 3-neck flask Chloro-5-methylbenzene (194 mmol, 39.9 g) was dissolved in toluene (0.2 M, 970 ml), sodium terbutoxide (291 mmol, 28.0 g), bis(tri-terbutylphosphine)palladium (0) ( 1.94 mmol, 0.993 g) was added, and the mixture was stirred for 8 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 67.2 g of compound 30-a. (Yield 91%, MS[M+H]+= 382)
단계 2) 화합물 30-b의 합성Step 2) Synthesis of compound 30-b
Figure PCTKR2020017069-appb-I000220
Figure PCTKR2020017069-appb-I000220
3구 플라스크에 3-브로모-3a,7a-디메틸-3a,4,5,6,7,7a-헥사하이드로[b]싸이오펜 (56.6 mmol, 14 g)과 [1,1':3',1''-터페닐]-5'-아민 (56.6 mmol, 13.9 g)을 톨루엔 (0.2 M, 280 ml)에 녹이고 소듐 터부톡사이드 (85.0 mmol, 8.16 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.566 mmol, 0.289 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 30-b 17.4 g을 수득하였다. (수율 75%, MS[M+H]+= 412)3-bromo-3a,7a-dimethyl-3a,4,5,6,7,7a-hexahydro[ b ]thiophene (56.6 mmol, 14 g) and [1,1':3' in a 3-neck flask ,1''-terphenyl]-5'-amine (56.6 mmol, 13.9 g) was dissolved in toluene (0.2 M, 280 ml), sodium terbutoxide (85.0 mmol, 8.16 g), bis(tri-terbutylphos Pin) palladium (0) (0.566 mmol, 0.289 g) was added, and the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 17.4 g of compound 30-b. (yield 75%, MS[M+H]+= 412)
단계 3) 화합물 30-c의 합성Step 3) Synthesis of compound 30-c
Figure PCTKR2020017069-appb-I000221
Figure PCTKR2020017069-appb-I000221
3구 플라스크에 화합물 30-a (39.3 mmol, 15 g)와 화합물 30-b (39.3 mmol, 16.2 g)을 톨루엔 (0.2 M, 200 ml)에 녹이고 소듐 터부톡사이드 (58.9 mmol, 5.66 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.393 mmol, 0.2 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 30-c 24.8 g을 수득하였다. (수율 83%, MS[M+H]+= 757)In a three-necked flask, compound 30-a (39.3 mmol, 15 g) and compound 30-b (39.3 mmol, 16.2 g) were dissolved in toluene (0.2 M, 200 ml), sodium terbutoxide (58.9 mmol, 5.66 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.393 mmol, 0.2 g), the mixture was stirred for 24 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 24.8 g of compound 30-c. (Yield 83%, MS[M+H]+= 757)
단계 4) 화합물 30의 합성Step 4) Synthesis of compound 30
Figure PCTKR2020017069-appb-I000222
Figure PCTKR2020017069-appb-I000222
3구 플라스크에 화합물 30-c (32.8 mmol, 24.8 g)을 1,2-디클로로벤젠 (0.1 M, 330 ml)에 녹이고 보론트리아이오다이드 (52.4 mmol, 20.5 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (295 mmol, 38.1 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 30, 4.1 g을 수득하였다. (수율 16%, MS[M+H]+= 765)In a three-necked flask, compound 30-c (32.8 mmol, 24.8 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 330 ml), boron triiodide (52.4 mmol, 20.5 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, and N,N-diisopropylethylamine (295 mmol, 38.1 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 30, 4.1 g. (yield 16%, MS[M+H]+=765)
합성예 31 : 화합물 31의 합성Synthesis Example 31: Synthesis of compound 31
단계 1) 화합물 31-a의 합성Step 1) Synthesis of compound 31-a
Figure PCTKR2020017069-appb-I000223
Figure PCTKR2020017069-appb-I000223
3구 플라스크에 3-브로모-4,4-디메틸-4H-인데노[1,2-b]싸이오펜 (36.1 mmol, 10 g)과 4-(2-페닐프로판-2-일)아닐린 (36.1 mmol, 8 g)을 톨루엔 (0.2 M, 180 ml)에 녹이고 소듐 터부톡사이드 (54.2 mmol, 5.21 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.361 mmol, 0.185 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 31-a 12.5 g을 수득하였다. (수율 84%, MS[M+H]+= 410)3-bromo-4,4-dimethyl- 4H -indeno[1,2- b ]thiophene (36.1 mmol, 10 g) and 4-(2-phenylpropan-2-yl)aniline in a 3-neck flask (36.1 mmol, 8 g) was dissolved in toluene (0.2 M, 180 ml), sodium terbutoxide (54.2 mmol, 5.21 g), bis(tri-terbutylphosphine)palladium(0) (0.361 mmol, 0.185 g) After adding, the mixture was stirred for 4 hours under reflux conditions under argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 12.5 g of compound 31-a. (Yield 84%, MS[M+H]+= 410)
단계 2) 화합물 31-b의 합성Step 2) Synthesis of compound 31-b
Figure PCTKR2020017069-appb-I000224
Figure PCTKR2020017069-appb-I000224
3구 플라스크에 화합물 1-a (29.6 mmol, 12 g)와 화합물 31-a (29.6 mmol, 12.1 g)을 톨루엔 (0.2 M, 150 ml)에 녹이고 소듐 터부톡사이드 (44.3 mmol, 4.26 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.296 mmol, 0.151 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 31-b 17.3 g을 수득하였다. (수율 75%, MS[M+H]+= 779)In a three-neck flask, compound 1-a (29.6 mmol, 12 g) and compound 31-a (29.6 mmol, 12.1 g) were dissolved in toluene (0.2 M, 150 ml), sodium terbutoxide (44.3 mmol, 4.26 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.296 mmol, 0.151 g), the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 17.3 g of compound 31-b. (yield 75%, MS[M+H]+=779)
단계 3) 화합물 31의 합성Step 3) Synthesis of compound 31
Figure PCTKR2020017069-appb-I000225
Figure PCTKR2020017069-appb-I000225
3구 플라스크에 화합물 31-b (22.2 mmol, 17.3 g)을 1,2-디클로로벤젠 (0.1 M, 220 ml)에 녹이고 보론트리아이오다이드 (35.5 mmol, 13.9 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (200 mmol, 25.8 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 31, 3.8 g을 수득하였다. (수율 22%, MS[M+H]+= 787)In a three-neck flask, compound 31-b (22.2 mmol, 17.3 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 220 ml), boron triiodide (35.5 mmol, 13.9 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (200 mmol, 25.8 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 31, 3.8 g. (Yield 22%, MS[M+H]+=787)
합성예 32 : 화합물 32의 합성Synthesis Example 32: Synthesis of compound 32
단계 1) 화합물 32-a의 합성Step 1) Synthesis of compound 32-a
Figure PCTKR2020017069-appb-I000226
Figure PCTKR2020017069-appb-I000226
3구 플라스크에 8-터부틸-10,10-디메틸-5,10-디하이드로인데노[1,2-b]인돌 (104 mmol, 30 g)과 1-브로모-3-클로로-5-메틸벤젠 (104 mmol, 21.3 g)을 톨루엔 (0.2 M, 520 ml)에 녹이고 소듐 터부톡사이드 (155 mmol, 14.9 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.04 mmol, 0.530 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 32-a 39.2 g을 수득하였다. (수율 91%, MS[M+H]+= 414)In a 3-neck flask, 8-terbutyl-10,10-dimethyl-5,10-dihydroindeno[1,2- b ]indole (104 mmol, 30 g) and 1-bromo-3-chloro-5- Methylbenzene (104 mmol, 21.3 g) was dissolved in toluene (0.2 M, 520 ml), sodium terbutoxide (155 mmol, 14.9 g), bis(tri-terbutylphosphine)palladium(0) (1.04 mmol, 0.530) g), and stirred for 4 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 39.2 g of compound 32-a. (Yield 91%, MS[M+H]+= 414)
단계 2) 화합물 32-b의 합성Step 2) Synthesis of compound 32-b
Figure PCTKR2020017069-appb-I000227
Figure PCTKR2020017069-appb-I000227
3구 플라스크에 4-브로모-2,3-디메틸-2,3-디페닐-2,3-디하이드로싸이오펜 (57.9 mmol, 20 g)과 4-터부틸아닐린 (57.9 mmol, 8.64 g)을 톨루엔 (0.2 M, 290 ml)에 녹이고 소듐 터부톡사이드 (86.9 mmol, 8.35 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.579 mmol, 0.296 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 32-b 12.3 g을 수득하였다. (수율 51%, MS[M+H]+= 414)In a 3-neck flask, 4-bromo-2,3-dimethyl-2,3-diphenyl-2,3-dihydrothiophene (57.9 mmol, 20 g) and 4-terbutylaniline (57.9 mmol, 8.64 g) was dissolved in toluene (0.2 M, 290 ml), sodium terbutoxide (86.9 mmol, 8.35 g), bis(tri-terbutylphosphine)palladium (0) (0.579 mmol, 0.296 g) were added, and argon atmosphere was refluxed. The mixture was stirred for 24 hours under conditions. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 12.3 g of compound 32-b. (Yield 51%, MS[M+H]+= 414)
단계 3) 화합물 32-c의 합성Step 3) Synthesis of compound 32-c
Figure PCTKR2020017069-appb-I000228
Figure PCTKR2020017069-appb-I000228
3구 플라스크에 화합물 32-a (29.0 mmol, 12 g)와 화합물 32-b (29.0 mmol, 12 g)을 톨루엔 (0.2 M, 145 ml)에 녹이고 소듐 터부톡사이드 (43.5 mmol, 4.18 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.290 mmol, 0.148 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 32-c 18.8 g을 수득하였다. (수율 82%, MS[M+H]+= 791)In a three-necked flask, compound 32-a (29.0 mmol, 12 g) and compound 32-b (29.0 mmol, 12 g) were dissolved in toluene (0.2 M, 145 ml), and sodium terbutoxide (43.5 mmol, 4.18 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.290 mmol, 0.148 g), the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 18.8 g of compound 32-c. (Yield 82%, MS[M+H]+=791)
단계 4) 화합물 32의 합성Step 4) Synthesis of compound 32
Figure PCTKR2020017069-appb-I000229
Figure PCTKR2020017069-appb-I000229
3구 플라스크에 화합물 32-c (23.8 mmol, 18.8 g)을 1,2-디클로로벤젠 (0.1 M, 240 ml)에 녹이고 보론트리아이오다이드 (38.0 mmol, 14.9 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (214 mmol, 27.6 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 32, 3.1 g을 수득하였다. (수율 16%, MS[M+H]+= 799)In a three-necked flask, compound 32-c (23.8 mmol, 18.8 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 240 ml), boron triiodide (38.0 mmol, 14.9 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (214 mmol, 27.6 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 32, 3.1 g. (yield 16%, MS[M+H]+=799)
합성예 33 : 화합물 33의 합성Synthesis Example 33: Synthesis of compound 33
단계 1) 화합물 33-a의 합성Step 1) Synthesis of compound 33-a
Figure PCTKR2020017069-appb-I000230
Figure PCTKR2020017069-appb-I000230
3구 플라스크에 4-터부틸아닐린 (67.0 mmol, 10 g)과 4'-브로모-3'H-스파이로[플루오렌-9,2'-싸이오펜] (67.0 mmol, 21.1 g)을 톨루엔 (0.2 M, 335 ml)에 녹이고 소듐 터부톡사이드 (101 mmol, 9.66 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.670 mmol, 0.342 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 15시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 33-a 16.8g을 수득하였다. (수율 65%, MS[M+H]+= 384)Three-necked flask was charged with 4-emitter-butylaniline (67.0 mmol, 10 g) and 4'-bromo -3 'H - spy [fluorene -9,2'- thiophene] (67.0 mmol, 21.1 g) in toluene (0.2 M, 335 ml), sodium terbutoxide (101 mmol, 9.66 g), bis (tri-terbutylphosphine) palladium (0) (0.670 mmol, 0.342 g) were added, and then under reflux conditions under argon atmosphere. Stirred for 15 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 16.8 g of compound 33-a. (Yield 65%, MS[M+H]+=384)
단계 2) 화합물 33-b의 합성Step 2) Synthesis of compound 33-b
Figure PCTKR2020017069-appb-I000231
Figure PCTKR2020017069-appb-I000231
3구 플라스크에 화합물 4-a (42.5 mmol, 20 g)와 화합물 33-a (42.5 mmol, 16.3 g)을 톨루엔 (0.2 M, 210 ml)에 녹이고 소듐 터부톡사이드 (63.7 mmol, 6.12 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.425 mmol, 0.217 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 33-b 23.0 g을 수득하였다. (수율 70%, MS[M+H]+= 774)In a three-necked flask, compound 4-a (42.5 mmol, 20 g) and compound 33-a (42.5 mmol, 16.3 g) were dissolved in toluene (0.2 M, 210 ml), sodium terbutoxide (63.7 mmol, 6.12 g), After bis(tri-terbutylphosphine)palladium(0) (0.425 mmol, 0.217 g) was added, the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 23.0 g of compound 33-b. (Yield 70%, MS[M+H]+=774)
단계 3) 화합물 33-c의 합성Step 3) Synthesis of compound 33-c
Figure PCTKR2020017069-appb-I000232
Figure PCTKR2020017069-appb-I000232
3구 플라스크에 화합물 33-b (29.7 mmol, 23 g)을 1,2-디클로로벤젠 (0.1 M, 300 ml)에 녹이고 보론트리아이오다이드 (47.5 mmol, 18.6 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (268 mmol, 34.6 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 33-c 3.9 g을 수득하였다. (수율 17%, MS[M+H]+= 781)In a three-neck flask, compound 33-b (29.7 mmol, 23 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 300 ml), boron triiodide (47.5 mmol, 18.6 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, and N,N-diisopropylethylamine (268 mmol, 34.6 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 3.9 g of compound 33-c. (Yield 17%, MS[M+H]+=781)
단계 4) 화합물 33 의 합성Step 4) Synthesis of compound 33
Figure PCTKR2020017069-appb-I000233
Figure PCTKR2020017069-appb-I000233
3구 플라스크에 화합물 33-c (4.99 mmol, 3.9 g)와 9H-카바졸 (5.99 mmol, 1.00 g)을 톨루엔 (0.2 M, 30 ml)에 녹이고 소듐 터부톡사이드 (7.49 mmol, 0.719 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.05 mmol, 0.026 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 33, 3.7 g을 수득하였다. (수율 81%, MS[M+H]+= 912)Three-necked flask, the compound 33-c (4.99 mmol, 3.9 g) and 9 H - carbazole (5.99 mmol, 1.00 g) in toluene sodium taboo ethoxide (7.49 mmol, 0.719 g) is dissolved in (0.2 M, 30 ml) , bis(tri-terbutylphosphine)palladium(0) (0.05 mmol, 0.026 g) was added, and the mixture was stirred for 24 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 33, 3.7 g. (Yield 81%, MS[M+H]+= 912)
합성예 34 : 화합물 34의 합성Synthesis Example 34: Synthesis of compound 34
단계 1) 화합물 34-a의 합성Step 1) Synthesis of compound 34-a
Figure PCTKR2020017069-appb-I000234
Figure PCTKR2020017069-appb-I000234
3구 플라스크에 3-브로모나프토[2,3-b]싸이오펜 (88.8 mmol, 23.4 g)과 5-터부틸-[1,1'-바이페닐]-2-아민 (88.8 mmol, 20 g)을 톨루엔 (0.2 M, 445 ml)에 녹이고 소듐 터부톡사이드 (133 mmol, 12.8 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.888 mmol, 0.454 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 34-a 21.9 g을 수득하였다. (수율 61%, MS[M+H]+= 408)In a 3-neck flask, 3-bromonaphtho [2,3- b ] thiophene (88.8 mmol, 23.4 g) and 5-tertbutyl- [1,1'-biphenyl] -2-amine (88.8 mmol, 20 g) ) was dissolved in toluene (0.2 M, 445 ml), sodium terbutoxide (133 mmol, 12.8 g), bis(tri-terbutylphosphine)palladium (0) (0.888 mmol, 0.454 g) were added, and then argon atmosphere The mixture was stirred under reflux conditions for 24 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 21.9 g of compound 34-a. (Yield 61%, MS[M+H]+= 408)
단계 2) 화합물 34-b의 합성Step 2) Synthesis of compound 34-b
Figure PCTKR2020017069-appb-I000235
Figure PCTKR2020017069-appb-I000235
3구 플라스크에 화합물 1-a (24.6 mmol, 10 g)와 화합물 34-a (24.6 mmol, 10 g)을 톨루엔 (0.2 M, 125 ml)에 녹이고 소듐 터부톡사이드 (36.9 mmol, 3.55 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.246 mmol, 0.126 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 34-b 16.3 g을 수득하였다. (수율 85%, MS[M+H]+= 777)In a three-necked flask, compound 1-a (24.6 mmol, 10 g) and compound 34-a (24.6 mmol, 10 g) were dissolved in toluene (0.2 M, 125 ml), sodium terbutoxide (36.9 mmol, 3.55 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.246 mmol, 0.126 g), the mixture was stirred for 24 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 16.3 g of compound 34-b. (yield 85%, MS[M+H]+=777)
단계 3) 화합물 34의 합성Step 3) Synthesis of compound 34
Figure PCTKR2020017069-appb-I000236
Figure PCTKR2020017069-appb-I000236
3구 플라스크에 화합물 34-b (21.0 mmol, 16.3 g)을 1,2-디클로로벤젠 (0.1 M, 210 ml)에 녹이고 보론트리아이오다이드 (33.6 mmol, 13.1 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (189 mmol, 24.4 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 34, 4.8 g을 수득하였다. (수율 29%, MS[M+H]+= 785)In a three-necked flask, compound 34-b (21.0 mmol, 16.3 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 210 ml), boron triiodide (33.6 mmol, 13.1 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (189 mmol, 24.4 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 34, 4.8 g. (Yield 29%, MS[M+H]+=785)
합성예 35 : 화합물 35의 합성Synthesis Example 35: Synthesis of compound 35
단계 1) 화합물 35-a의 합성Step 1) Synthesis of compound 35-a
Figure PCTKR2020017069-appb-I000237
Figure PCTKR2020017069-appb-I000237
3구 플라스크에 3-브로모-5-메틸페놀 (53.5 mmol, 10 g)과 N-(4-터부틸페닐)-3-클로로아닐린 (53.5 mmol, 13.9 g)을 톨루엔 (0.2 M, 270 ml)에 녹이고 소듐 터부톡사이드 (80.2 mmol, 7.71 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.535 mmol, 0.273 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 35-a 17.6 g을 수득하였다. (수율 90%, MS[M+H]+= 366)In a three-necked flask, 3-bromo-5-methylphenol (53.5 mmol, 10 g) and N- (4-terbutylphenyl)-3-chloroaniline (53.5 mmol, 13.9 g) were mixed with toluene (0.2 M, 270 ml). ), sodium terbutoxide (80.2 mmol, 7.71 g), bis(tri-terbutylphosphine)palladium(0) (0.535 mmol, 0.273 g) were added, and the mixture was stirred under reflux conditions in an argon atmosphere for 4 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 17.6 g of compound 35-a. (Yield 90%, MS[M+H]+=366)
단계 2) 화합물 35-b의 합성Step 2) Synthesis of compound 35-b
Figure PCTKR2020017069-appb-I000238
Figure PCTKR2020017069-appb-I000238
3구 플라스크에 화합물 35-a (48.1 mmol, 17.6 g)과 포타슘 카보네이트 (144 mmol, 20 g)을 테트라하이드로퓨란과 물 (0.1 M, 480 ml)에 녹이고 퍼플루오르-1-부테인설폰 플로라이드 (144 mmol, 43.6 g)을 넣은 후, 상온에서 5시간동안 교반하였다. 반응이 종료되면 톨루엔과 물을 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 35-b 30.2 g을 수득하였다. (수율 97%, MS[M+H]+= 648)In a three-necked flask, compound 35-a (48.1 mmol, 17.6 g) and potassium carbonate (144 mmol, 20 g) were dissolved in tetrahydrofuran and water (0.1 M, 480 ml), and perfluoro-1-butanesulfone fluoride (144 mmol, 43.6 g) was added and stirred at room temperature for 5 hours. When the reaction was completed, toluene and water were added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 30.2 g of compound 35-b. (yield 97%, MS[M+H]+= 648)
단계 3) 화합물 35-c의 합성Step 3) Synthesis of compound 35-c
Figure PCTKR2020017069-appb-I000239
Figure PCTKR2020017069-appb-I000239
3구 플라스크에 화합물 35-b (46.6 mmol, 30.2 g)와 N-(5-터부틸-[1,1'-바이페닐]-2-일)-5,5,8,8-테트라메틸-5,6,7,8-테트라나프토[2,3-b]싸이오펜-3-아민 (46.6 mmol, 21.8 g)을 톨루엔 (0.2 M, 233 ml)에 녹이고 소듐 터부톡사이드 (69.9 mmol, 6.72 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.466 mmol, 0.238 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 35-c 27.4 g을 수득하였다. (수율 72%, MS[M+H]+= 816)Compound 35-b (46.6 mmol, 30.2 g) and N- (5-terbutyl-[1,1'-biphenyl]-2-yl)-5,5,8,8-tetramethyl- in a 3- neck flask 5,6,7,8-tetranaphtho[2,3- b ]thiophen-3-amine (46.6 mmol, 21.8 g) was dissolved in toluene (0.2 M, 233 ml) and sodium terbutoxide (69.9 mmol, 6.72 g) and bis(tri-terbutylphosphine)palladium(0) (0.466 mmol, 0.238 g) were added, and the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 27.4 g of compound 35-c. (Yield 72%, MS[M+H]+= 816)
단계 4) 화합물 35-d의 합성Step 4) Synthesis of compound 35-d
Figure PCTKR2020017069-appb-I000240
Figure PCTKR2020017069-appb-I000240
3구 플라스크에 화합물 35-c (33.6 mmol, 27.4 g)을 1,2-디클로로벤젠 (0.1 M, 335 ml)에 녹이고 보론트리아이오다이드 (53.8 mmol, 21.0 g)를 넣은 후, 아르곤 분위기 140 ℃에서 8시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (302 mmol, 39.1 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 35-d 5.3 g을 수득하였다. (수율 19%, MS[M+H]+= 824)In a three-necked flask, compound 35-c (33.6 mmol, 27.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 335 ml), boron triiodide (53.8 mmol, 21.0 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 8 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (302 mmol, 39.1 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then 5.3 g of compound 35-d was obtained through sublimation purification. (yield 19%, MS[M+H]+= 824)
단계 5) 화합물 35의 합성Step 5) Synthesis of compound 35
Figure PCTKR2020017069-appb-I000241
Figure PCTKR2020017069-appb-I000241
3구 플라스크에 화합물 35-d (6.44 mmol, 5.3 g)와 비스(5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프탈렌-2-일)아민 (7.72 mmol, 3 g)을 톨루엔 (0.2 M, 39 ml)에 녹이고 소듐 터부톡사이드 (9.66 mmol, 0.928 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.064 mmol, 0.033 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하고 승화정제를 통해 화합물 35, 4.1 g을 수득하였다. (수율 54%, MS[M+H]+= 1177)Compound 35-d (6.44 mmol, 5.3 g) and bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)amine (7.72 mmol, 3 g) was dissolved in toluene (0.2 M, 39 ml), sodium terbutoxide (9.66 mmol, 0.928 g), bis(tri-terbutylphosphine)palladium (0) (0.064 mmol, 0.033 g) were added, The mixture was stirred for 6 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and compound 35, 4.1 g, was obtained through sublimation purification. (Yield 54%, MS[M+H]+= 1177)
합성예 36 : 화합물 36의 합성Synthesis Example 36: Synthesis of compound 36
단계 1) 화합물 36-a의 합성Step 1) Synthesis of compound 36-a
Figure PCTKR2020017069-appb-I000242
Figure PCTKR2020017069-appb-I000242
3구 플라스크에 3-브로모-5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프토[2,3-b]싸이오펜 (155 mmol, 50 g)과 5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프탈렌-2-아민 (155 mmol, 31.4 g)을 톨루엔 (0.2 M, 775 ml)에 녹이고 소듐 터부톡사이드 (232 mmol, 22.3 g), 비스(트리-터부틸포스핀)팔라듐(0) (1.55 mmol, 0.79 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 36-a 47.6 g을 수득하였다. (수율 69%, MS[M+H]+= 446)In a 3-neck flask, 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho [2,3- b ] thiophene (155 mmol, 50 g) and 5 ,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-amine (155 mmol, 31.4 g) was dissolved in toluene (0.2 M, 775 ml) and sodium terbutoxide (232 mmol) , 22.3 g), bis(tri-terbutylphosphine)palladium(0) (1.55 mmol, 0.79 g) were added, and the mixture was stirred for 4 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 47.6 g of compound 36-a. (yield 69%, MS[M+H]+= 446)
단계 2) 화합물 36-b의 합성Step 2) Synthesis of compound 36-b
Figure PCTKR2020017069-appb-I000243
Figure PCTKR2020017069-appb-I000243
3구 플라스크에 화합물 5-a (35.7 mmol, 17 g)와 화합물 36-a (35.7 mmol, 15.9 g)을 톨루엔 (0.2 M, 180 ml)에 녹이고 소듐 터부톡사이드 (53.6 mmol, 5.15 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.357 mmol, 0.182 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 13시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 36-b 22.1 g을 수득하였다. (수율 70%, MS[M+H]+= 886)In a three-necked flask, compound 5-a (35.7 mmol, 17 g) and compound 36-a (35.7 mmol, 15.9 g) were dissolved in toluene (0.2 M, 180 ml), sodium terbutoxide (53.6 mmol, 5.15 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.357 mmol, 0.182 g), the mixture was stirred for 13 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 22.1 g of compound 36-b. (Yield 70%, MS[M+H]+= 886)
단계 3) 화합물 36의 합성Step 3) Synthesis of compound 36
Figure PCTKR2020017069-appb-I000244
Figure PCTKR2020017069-appb-I000244
3구 플라스크에 화합물 36-b (25.0 mmol, 22.1 g)을 1,2-디클로로벤젠 (0.1 M, 250 ml)에 녹이고 보론트리아이오다이드 (39.9 mmol, 15.6 g)를 넣은 후, 아르곤 분위기 140 ℃에서 8시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (225 mmol, 29 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 36, 2.9 g을 수득하였다. (수율 13%, MS[M+H]+= 893)In a three-necked flask, compound 36-b (25.0 mmol, 22.1 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 250 ml), boron triiodide (39.9 mmol, 15.6 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 8 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (225 mmol, 29 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 36, 2.9 g. (Yield 13%, MS[M+H]+= 893)
합성예 37 : 화합물 37의 합성Synthesis Example 37: Synthesis of compound 37
단계 1) 화합물 37-a의 합성Step 1) Synthesis of compound 37-a
Figure PCTKR2020017069-appb-I000245
Figure PCTKR2020017069-appb-I000245
3구 플라스크에 3-브로모-5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프토[2,3-b]싸이오펜 (46.4 mmol, 15 g)과 디벤조[b,d]퓨란-1-아민 (46.4 mmol, 8.5 g)을 톨루엔 (0.2 M, 230 ml)에 녹이고 소듐 터부톡사이드 (69.6 mmol, 6.69 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.464 mmol, 0.237 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 10시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 37-a 17.4g을 수득하였다. (수율 88%, MS[M+H]+= 426)In a 3-neck flask, 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3- b ]thiophene (46.4 mmol, 15 g) and di Dissolve benzo[ b,d ]furan-1-amine (46.4 mmol, 8.5 g) in toluene (0.2 M, 230 ml), sodium terbutoxide (69.6 mmol, 6.69 g), bis(tri-terbutylphosphine) After adding palladium (0) (0.464 mmol, 0.237 g), the mixture was stirred for 10 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 17.4 g of compound 37-a. (Yield 88%, MS[M+H]+= 426)
단계 2) 화합물 37-b의 합성Step 2) Synthesis of compound 37-b
Figure PCTKR2020017069-appb-I000246
Figure PCTKR2020017069-appb-I000246
3구 플라스크에 화합물 4-a (36.1 mmol, 17 g)와 화합물 37-a (36.1 mmol, 15.4 g)을 톨루엔 (0.2 M, 180 ml)에 녹이고 소듐 터부톡사이드 (54.2 mmol, 5.2 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.361 mmol, 0.185 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 9시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 37-b 24.6 g을 수득하였다. (수율 84%, MS[M+H]+= 816)In a three-necked flask, compound 4-a (36.1 mmol, 17 g) and compound 37-a (36.1 mmol, 15.4 g) were dissolved in toluene (0.2 M, 180 ml), sodium terbutoxide (54.2 mmol, 5.2 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.361 mmol, 0.185 g), the mixture was stirred for 9 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 24.6 g of compound 37-b. (Yield 84%, MS[M+H]+= 816)
단계 3) 화합물 37-c의 합성Step 3) Synthesis of compound 37-c
Figure PCTKR2020017069-appb-I000247
Figure PCTKR2020017069-appb-I000247
3구 플라스크에 화합물 37-b (30.2 mmol, 24.6 g)을 1,2-디클로로벤젠 (0.1 M, 300 ml)에 녹이고 보론트리아이오다이드 (48.3 mmol, 18.9 g)를 넣은 후, 아르곤 분위기 140 ℃에서 6시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (271 mmol, 35 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 37-c 5.2 g을 수득하였다. (수율 21%, MS[M+H]+= 823)In a three-necked flask, compound 37-b (30.2 mmol, 24.6 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 300 ml), boron triiodide (48.3 mmol, 18.9 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 6 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (271 mmol, 35 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 5.2 g of compound 37-c. (Yield 21%, MS[M+H]+= 823)
단계 4) 화합물 37 의 합성Step 4) Synthesis of compound 37
Figure PCTKR2020017069-appb-I000248
Figure PCTKR2020017069-appb-I000248
3구 플라스크에 화합물 37-c (6.32 mmol, 5.2 g)와 디페닐아민 (7.58 mmol, 1.3 g)을 톨루엔 (0.2 M, 38 ml)에 녹이고 소듐 터부톡사이드 (9.47 mmol, 0.91 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.06 mmol, 0.032 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 12시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 37, 3.3 g을 수득하였다. (수율 55%, MS[M+H]+= 956)In a three-necked flask, compound 37-c (6.32 mmol, 5.2 g) and diphenylamine (7.58 mmol, 1.3 g) were dissolved in toluene (0.2 M, 38 ml), and sodium terbutoxide (9.47 mmol, 0.91 g), bis After (tri-terbutylphosphine)palladium(0) (0.06 mmol, 0.032 g) was added, the mixture was stirred for 12 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then compound 37, 3.3 g, was obtained through sublimation purification. (Yield 55%, MS[M+H]+=956)
합성예 38 : 화합물 38의 합성Synthesis Example 38: Synthesis of compound 38
단계 1) 화합물 38-a의 합성Step 1) Synthesis of compound 38-a
Figure PCTKR2020017069-appb-I000249
Figure PCTKR2020017069-appb-I000249
3구 플라스크에 9,9-디메틸-9H-플루오렌-4-아민 (92.8 mmol, 30 g)과 3-브로모-5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프토[2,3-b]싸이오펜 (92.8 mmol, 19.4 g)을 톨루엔 (0.2 M, 465 ml)에 녹이고 소듐 터부톡사이드 (139 mmol, 13.4 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.928 mmol, 0.474 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 38-a 37.4g을 수득하였다. (수율 89%, MS[M+H]+= 452)Three-necked flask was charged with 9,9-dimethyl -9 H - fluoren-4-amine (92.8 mmol, 30 g) and 3-bromo--5,5,8,8- tetramethyl -5,6,7,8 -Tetrahydronaphtho[2,3- b ]thiophene (92.8 mmol, 19.4 g) was dissolved in toluene (0.2 M, 465 ml) and sodium terbutoxide (139 mmol, 13.4 g), bis(tri-terbutyl) Phosphine) palladium (0) (0.928 mmol, 0.474 g) was added, and the mixture was stirred for 4 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 37.4 g of compound 38-a. (yield 89%, MS[M+H]+=452)
단계 2) 화합물 38-b의 합성Step 2) Synthesis of compound 38-b
Figure PCTKR2020017069-appb-I000250
Figure PCTKR2020017069-appb-I000250
3구 플라스크에 1-브로모-3-클로로-5-메틸벤젠 (29.2 mmol, 6 g)과 5,5,8,8-테트라메틸-3-페닐-N-(5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프탈렌-2-일)-5,6,7,8-테트라하이드로나프탈렌-2-아민 (29.2 mmol, 13.6 g)을 톨루엔 (0.2 M, 150 ml)에 녹이고 소듐 터부톡사이드 (30.5 mmol, 2.93 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.292 mmol, 0.15 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 38-b 12.3g을 수득하였다. (수율 71%, MS[M+H]+= 590)In a 3-neck flask, 1-bromo-3-chloro-5-methylbenzene (29.2 mmol, 6 g) and 5,5,8,8-tetramethyl-3-phenyl- N- (5,5,8,8 -Tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-5,6,7,8-tetrahydronaphthalen-2-amine (29.2 mmol, 13.6 g) was mixed with toluene (0.2 M, 150 ml), sodium terbutoxide (30.5 mmol, 2.93 g), and bis(tri-terbutylphosphine)palladium (0) (0.292 mmol, 0.15 g) were added, followed by stirring under reflux conditions under argon atmosphere for 24 hours. . Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 12.3 g of compound 38-b. (Yield 71%, MS[M+H]+=590)
단계 3) 화합물 38-c의 합성Step 3) Synthesis of compound 38-c
Figure PCTKR2020017069-appb-I000251
Figure PCTKR2020017069-appb-I000251
3구 플라스크에 화합물 38-a (20.3 mmol, 9.18 g)와 화합물 38-b (20.3 mmol, 12 g)을 톨루엔 (0.2 M, 100 ml)에 녹이고 소듐 터부톡사이드 (30.5 mmol, 2.93 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.2 mmol, 0.1 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 38-c 14.2 g을 수득하였다. (수율 69%, MS[M+H]+= 1006)In a three-necked flask, compound 38-a (20.3 mmol, 9.18 g) and compound 38-b (20.3 mmol, 12 g) were dissolved in toluene (0.2 M, 100 ml), sodium terbutoxide (30.5 mmol, 2.93 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.2 mmol, 0.1 g), the mixture was stirred for 24 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 14.2 g of compound 38-c. (yield 69%, MS[M+H]+= 1006)
단계 4) 화합물 38의 합성Step 4) Synthesis of compound 38
Figure PCTKR2020017069-appb-I000252
Figure PCTKR2020017069-appb-I000252
3구 플라스크에 화합물 38-c (14.1 mmol, 14.2 g)을 1,2-디클로로벤젠 (0.1 M, 140 ml)에 녹이고 보론트리아이오다이드 (22.6 mmol, 8.85 g)를 넣은 후, 아르곤 분위기 140 ℃에서 10시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (127 mmol, 16.5 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제하여 화합물 38, 2.6 g을 수득하였다. (수율 18%, MS[M+H]+= 1013)In a three-neck flask, compound 38-c (14.1 mmol, 14.2 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 140 ml), boron triiodide (22.6 mmol, 8.85 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 10 hours. The reaction mass was cooled to 0 °C, and N,N-diisopropylethylamine (127 mmol, 16.5 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 38, 2.6 g. (Yield 18%, MS[M+H]+= 1013)
합성예 39 : 화합물 39의 합성Synthesis Example 39: Synthesis of compound 39
단계 1) 화합물 39-a의 합성Step 1) Synthesis of compound 39-a
Figure PCTKR2020017069-appb-I000253
Figure PCTKR2020017069-appb-I000253
3구 플라스크에 N-(4-터부틸페닐)-7,7,10,10-테트라메틸-7,8,9,10-테트라하이드로나프토[2,3-b]벤조퓨란 (35.2 mmol, 15 g)과 1-브로모-3-클로로-5-터부틸벤젠 (35.2 mmol, 8.7 g)을 톨루엔 (0.2 M, 175 ml)에 녹이고 소듐 터부톡사이드 (52.9 mmol, 5.08 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.352 mmol, 0.18 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 39-a 18.2 g을 수득하였다. (수율 87%, MS[M+H]+= 592) N -(4-terbutylphenyl)-7,7,10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3- b ]benzofuran (35.2 mmol, 15 g) and 1-bromo-3-chloro-5-terbutylbenzene (35.2 mmol, 8.7 g) were dissolved in toluene (0.2 M, 175 ml), and sodium terbutoxide (52.9 mmol, 5.08 g), bis( After tri-tertbutylphosphine)palladium(0) (0.352 mmol, 0.18 g) was added, the mixture was stirred for 6 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 18.2 g of compound 39-a. (Yield 87%, MS[M+H]+=592)
단계 2) 화합물 39-b의 합성Step 2) Synthesis of compound 39-b
Figure PCTKR2020017069-appb-I000254
Figure PCTKR2020017069-appb-I000254
3구 플라스크에 화합물 39-a (30.7 mmol, 18.2 g)와 N-(4-터부틸페닐)-5-(2-페닐프로판-2-일)벤조[b]싸이오펜-3-아민 (41.6 mmol, 19.6 g)을 톨루엔 (0.2 M, 155 ml)에 녹이고 소듐 터부톡사이드 (46.1 mmol, 4.43 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.307 mmol, 0.157 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 39-b 21.5 g을 수득하였다. (수율 73%, MS[M+H]+= 955)Compound 39-a (30.7 mmol, 18.2 g) and N- (4-terbutylphenyl)-5-(2-phenylpropan-2-yl)benzo[ b ]thiophen-3-amine (41.6) in a three-necked flask mmol, 19.6 g) was dissolved in toluene (0.2 M, 155 ml), sodium terbutoxide (46.1 mmol, 4.43 g), bis (tri-terbutylphosphine) palladium (0) (0.307 mmol, 0.157 g) was added. Then, the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 21.5 g of compound 39-b. (Yield 73%, MS[M+H]+=955)
단계 3) 화합물 39의 합성Step 3) Synthesis of compound 39
Figure PCTKR2020017069-appb-I000255
Figure PCTKR2020017069-appb-I000255
3구 플라스크에 화합물 39-b (22.5 mmol, 21.5 g)을 1,2-디클로로벤젠 (0.1 M, 225 ml)에 녹이고 보론트리아이오다이드 (36 mmol, 14.1 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (203 mmol, 26.2 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 39, 3.8 g을 수득하였다. (수율 18%, MS[M+H]+= 963)In a three-necked flask, compound 39-b (22.5 mmol, 21.5 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 225 ml), boron triiodide (36 mmol, 14.1 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (203 mmol, 26.2 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4, concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 39, 3.8 g. (Yield 18%, MS[M+H]+=963)
합성예 40 : 화합물 40의 합성Synthesis Example 40: Synthesis of compound 40
단계 1) 화합물 40-a의 합성Step 1) Synthesis of compound 40-a
Figure PCTKR2020017069-appb-I000256
Figure PCTKR2020017069-appb-I000256
3구 플라스크에 2-(퍼플루오로페닐)-N-페닐벤조퓨란-6-아민 (53.3 mmol, 20 g)과 1-브로모-3-클로로-5-아이오도벤젠 (79.9 mmol, 7.68 g)을 톨루엔 (0.2 M, 270 ml)에 녹이고 소듐 터부톡사이드 (80 mmol, 7.68 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.532 mmol, 0.272 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 3시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 40-a 20.7g을 수득하였다. (수율 69%, MS[M+H]+= 565) 2-(perfluorophenyl)-N -phenylbenzofuran-6-amine (53.3 mmol, 20 g) and 1-bromo-3-chloro-5-iodobenzene (79.9 mmol, 7.68 g) in a 3-neck flask ) was dissolved in toluene (0.2 M, 270 ml), sodium terbutoxide (80 mmol, 7.68 g), bis(tri-terbutylphosphine)palladium (0) (0.532 mmol, 0.272 g) were added, and then argon atmosphere Stirred under reflux conditions for 3 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 20.7 g of compound 40-a. (yield 69%, MS[M+H]+= 565)
단계 2) 화합물 40-b의 합성Step 2) Synthesis of compound 40-b
Figure PCTKR2020017069-appb-I000257
Figure PCTKR2020017069-appb-I000257
3구 플라스크에 화합물 40-a (35.6 mmol, 20.1 g)와 화합물 17-b (35.6 mmol, 12 g)을 톨루엔 (0.2 M, 180 ml)에 녹이고 소듐 터부톡사이드 (53.3 mmol, 5.12 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.356 mmol, 0.182 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 40-b 26.1 g을 수득하였다. (수율 89%, MS[M+H]+= 821)In a three-necked flask, compound 40-a (35.6 mmol, 20.1 g) and compound 17-b (35.6 mmol, 12 g) were dissolved in toluene (0.2 M, 180 ml), sodium terbutoxide (53.3 mmol, 5.12 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.356 mmol, 0.182 g), the mixture was stirred for 6 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 26.1 g of compound 40-b. (yield 89%, MS[M+H]+=821)
단계 3) 화합물 40-c의 합성Step 3) Synthesis of compound 40-c
Figure PCTKR2020017069-appb-I000258
Figure PCTKR2020017069-appb-I000258
3구 플라스크에 화합물 40-b (31.8 mmol, 26.1 g)을 1,2-디클로로벤젠 (0.1 M, 320 ml)에 녹이고 보론트리아이오다이드 (50.8 mmol, 20 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (286 mmol, 37 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 40-c 4.6 g을 수득하였다. (수율 17%, MS[M+H]+= 829)In a three-necked flask, compound 40-b (31.8 mmol, 26.1 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 320 ml), boron triiodide (50.8 mmol, 20 g) was added, and argon atmosphere 140 It was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (286 mmol, 37 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 4.6 g of compound 40-c. (Yield 17%, MS[M+H]+= 829)
단계 4) 화합물 40의 합성Step 4) Synthesis of compound 40
Figure PCTKR2020017069-appb-I000259
Figure PCTKR2020017069-appb-I000259
3구 플라스크에 화합물 40-c (5.55 mmol, 4.6 g)와 4a,9a-디메틸-2,3,4,4a,9,9a-헥사하이드로-1H-카바졸 (6.66 mmol, 1.34 g)을 톨루엔 (0.2 M, 33 ml)에 녹이고 소듐 터부톡사이드 (8.32 mmol, 0.8 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.055 mmol, 0.028 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 40, 3.8 g을 수득하였다. (수율 69%, MS[M+H]+= 994)Compound 40-c (5.55 mmol, 4.6 g) and 4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro-1 H -carbazole (6.66 mmol, 1.34 g) were added to a three-necked flask. Dissolved in toluene (0.2 M, 33 ml), sodium terbutoxide (8.32 mmol, 0.8 g), bis (tri-terbutylphosphine) palladium (0) (0.055 mmol, 0.028 g) was added, and then refluxed under argon atmosphere. under stirring for 24 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 40, 3.8 g. (yield 69%, MS[M+H]+=994)
합성예 41 : 화합물 41의 합성Synthesis Example 41: Synthesis of compound 41
단계 1) 화합물 41-a의 합성Step 1) Synthesis of compound 41-a
Figure PCTKR2020017069-appb-I000260
Figure PCTKR2020017069-appb-I000260
3구 플라스크에 N-(4-터부틸페닐)-5a,9a-디메틸-5a,6,7,8,9,9a-헥사하이드로디벤조[b,d]퓨란-2-아민 (51.5 mmol, 18 g)과 1-브로모-3-클로로-5-메틸벤젠 (51.5 mmol, 10.6 g)을 톨루엔 (0.2 M, 260 ml)에 녹이고 소듐 터부톡사이드 (77.2 mmol, 7.42 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.515 mmol, 0.263 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 2시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 41-a 20.5 g을 수득하였다. (수율 84%, MS[M+H]+= 474) N -(4-terbutylphenyl)-5a,9a-dimethyl-5a,6,7,8,9,9a-hexahydrodibenzo[ b , d ]furan-2-amine (51.5 mmol, 18 g) and 1-bromo-3-chloro-5-methylbenzene (51.5 mmol, 10.6 g) were dissolved in toluene (0.2 M, 260 ml), and sodium terbutoxide (77.2 mmol, 7.42 g), bis(tri -terbutylphosphine)palladium(0) (0.515 mmol, 0.263 g) was added, and the mixture was stirred for 2 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 20.5 g of compound 41-a. (Yield 84%, MS[M+H]+=474)
단계 2) 화합물 41-b의 합성Step 2) Synthesis of compound 41-b
Figure PCTKR2020017069-appb-I000261
Figure PCTKR2020017069-appb-I000261
3구 플라스크에 화합물 41-a (43.2 mmol, 20.5 g)와 N-(4-터부틸페닐)-3'H-스파이로[플루오렌-9,2'-싸이오펜]-4'-아민 (43.2 mmol, 16.6 g)을 톨루엔 (0.2 M, 220 ml)에 녹이고 소듐 터부톡사이드 (64.9 mmol, 6.23 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.432 mmol, 0.221 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 41-b 22.9 g을 수득하였다. (수율 64%, MS[M+H]+= 821)Three-necked flask was charged with compound 41-a (43.2 mmol, 20.5 g) and N - (4- emitter-butylphenyl) -3 'H - -4'- amine spy [fluorene -9,2'- thiophene ( 43.2 mmol, 16.6 g) was dissolved in toluene (0.2 M, 220 ml) and sodium terbutoxide (64.9 mmol, 6.23 g), bis(tri-terbutylphosphine)palladium(0) (0.432 mmol, 0.221 g) was added. After addition, the mixture was stirred for 24 hours under reflux conditions under argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 22.9 g of compound 41-b. (Yield 64%, MS[M+H]+= 821)
단계 3) 화합물 41의 합성Step 3) Synthesis of compound 41
Figure PCTKR2020017069-appb-I000262
Figure PCTKR2020017069-appb-I000262
3구 플라스크에 화합물 41-b (27.9 mmol, 22.9 g)을 1,2-디클로로벤젠 (0.1 M, 280 ml)에 녹이고 보론트리아이오다이드 (44.6 mmol, 17.5 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (251 mmol, 32.4 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 41, 4.1 g을 수득하였다. (수율 18%, MS[M+H]+= 829)In a three-necked flask, compound 41-b (27.9 mmol, 22.9 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 280 ml), boron triiodide (44.6 mmol, 17.5 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, and N,N-diisopropylethylamine (251 mmol, 32.4 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then the compound 41, 4.1 g, was obtained through sublimation purification. (Yield 18%, MS[M+H]+= 829)
합성예 42 : 화합물 42의 합성Synthesis Example 42: Synthesis of compound 42
단계 1) 화합물 42-a의 합성Step 1) Synthesis of compound 42-a
Figure PCTKR2020017069-appb-I000263
Figure PCTKR2020017069-appb-I000263
3구 플라스크에 5a,9a-디메틸-N-페닐-5a,6,7,8,9,9a-헥사하이드로벤조[b,d]싸이오펜-2-아민 (48.5 mmol, 15 g)과 1-브로모-3-클로로-5-아이오도벤젠 (48.5 mmol, 15.4 g)을 톨루엔 (0.2 M, 240 ml)에 녹이고 소듐 터부톡사이드 (72.7 mmol, 7 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.485 mmol, 0.248 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 3시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 42-a 15.6g을 수득하였다. (수율 65%, MS[M+H]+= 499)5a, 9a-dimethyl-N -phenyl-5a,6,7,8,9,9a-hexahydrobenzo[ b,d ]thiophen-2-amine (48.5 mmol, 15 g) and 1- Bromo-3-chloro-5-iodobenzene (48.5 mmol, 15.4 g) was dissolved in toluene (0.2 M, 240 ml), sodium terbutoxide (72.7 mmol, 7 g), bis(tri-terbutylphosphine) ) Palladium (0) (0.485 mmol, 0.248 g) was added, and the mixture was stirred for 3 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 15.6 g of compound 42-a. (Yield 65%, MS[M+H]+= 499)
단계 2) 화합물 42-b의 합성Step 2) Synthesis of compound 42-b
Figure PCTKR2020017069-appb-I000264
Figure PCTKR2020017069-appb-I000264
3구 플라스크에 화합물 42-a (31.3 mmol, 15.6 g)와 N-([1,1'-바이페닐]-2-일)-6,6,9,9-테트라메틸-6,7,8,9-테트라하이드로나프토[1,2-b]싸이오펜-2-아민 (31.3 mmol, 12.9 g)을 톨루엔 (0.2 M, 160 ml)에 녹이고 소듐 터부톡사이드 (46.9 mmol, 4.51 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.313 mmol, 0.16 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 42-b 19.2 g을 수득하였다. (수율 74%, MS[M+H]+= 830)Compound 42-a (31.3 mmol, 15.6 g) and N -([1,1'-biphenyl]-2-yl)-6,6,9,9-tetramethyl-6,7,8 in a 3-neck flask ,9-tetrahydronaphtho[1,2- b ]thiophen-2-amine (31.3 mmol, 12.9 g) was dissolved in toluene (0.2 M, 160 ml) and sodium terbutoxide (46.9 mmol, 4.51 g), After adding bis(tri-terbutylphosphine)palladium(0) (0.313 mmol, 0.16 g), the mixture was stirred for 4 hours under reflux condition in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 19.2 g of compound 42-b. (Yield 74%, MS[M+H]+= 830)
단계 3) 화합물 42-c의 합성Step 3) Synthesis of compound 42-c
Figure PCTKR2020017069-appb-I000265
Figure PCTKR2020017069-appb-I000265
3구 플라스크에 화합물 42-b (23.1 mmol, 19.2 g)을 1,2-디클로로벤젠 (0.1 M, 230 ml)에 녹이고 보론트리아이오다이드 (37.0 mmol, 14.5 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (208 mmol, 27 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 42-c 2.7 g을 수득하였다. (수율 14%, MS[M+H]+= 837)In a three-neck flask, compound 42-b (23.1 mmol, 19.2 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 230 ml), boron triiodide (37.0 mmol, 14.5 g) was added, and argon atmosphere 140 It was stirred at ℃ for 3 hours. The reaction mass was cooled to 0° C., and N,N-diisopropylethylamine (208 mmol, 27 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 2.7 g of compound 42-c. (Yield 14%, MS[M+H]+= 837)
단계 4) 화합물 42의 합성Step 4) Synthesis of compound 42
Figure PCTKR2020017069-appb-I000266
Figure PCTKR2020017069-appb-I000266
3구 플라스크에 화합물 42-c (3.22 mmol, 2.7 g)와 3-터부틸-10H-벤조[4,5]싸이에노[3,2-b]인돌 (3.87 mmol, 1.08 g)을 톨루엔 (0.2 M, 19 ml)에 녹이고 소듐 터부톡사이드 (4.84 mmol, 0.46 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.032 mmol, 0.016 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 42, 2.5 g을 수득하였다. (수율 72%, MS[M+H]+= 1080)Compound 42-c (3.22 mmol, 2.7 g) and 3-tertbutyl- 10H -benzo [4,5] thieno [3,2- b ] indole (3.87 mmol, 1.08 g) in toluene in a three-necked flask (0.2 M, 19 ml), sodium terbutoxide (4.84 mmol, 0.46 g), bis(tri-terbutylphosphine)palladium (0) (0.032 mmol, 0.016 g) were added, and then under reflux conditions under argon atmosphere. Stirred for 24 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 42, 2.5 g. (Yield 72%, MS[M+H]+= 1080)
합성예 43 : 화합물 43의 합성Synthesis Example 43: Synthesis of compound 43
단계 1) 화합물 43-a의 합성Step 1) Synthesis of compound 43-a
Figure PCTKR2020017069-appb-I000267
Figure PCTKR2020017069-appb-I000267
3구 플라스크에 N,2,3-트리페닐벤조[b]싸이오펜-6-아민 (53.0 mmol, 20 g)과 1-브로모-3-클로로-5-메틸벤젠 (53.0 mmol, 10.9 g)을 톨루엔 (0.2 M, 265 ml)에 녹이고 소듐 터부톡사이드 (79.5 mmol, 7.64 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.53 mmol, 0.271 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 6시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 43-a 19.7 g을 수득하였다. (수율 74%, MS[M+H]+= 502) N ,2,3-triphenylbenzo[ b ]thiophen-6-amine (53.0 mmol, 20 g) and 1-bromo-3-chloro-5-methylbenzene (53.0 mmol, 10.9 g) in a 3-neck flask was dissolved in toluene (0.2 M, 265 ml), sodium terbutoxide (79.5 mmol, 7.64 g), bis(tri-terbutylphosphine)palladium (0) (0.53 mmol, 0.271 g) were added, and argon atmosphere was refluxed. The mixture was stirred for 6 hours under conditions. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 19.7 g of compound 43-a. (Yield 74%, MS[M+H]+=502)
단계 2) 화합물 43-b의 합성Step 2) Synthesis of compound 43-b
Figure PCTKR2020017069-appb-I000268
Figure PCTKR2020017069-appb-I000268
3구 플라스크에 화합물 43-a (39.2 mmol, 19.7 g)와 16-a (39.2 mmol, 8.84 g)을 톨루엔 (0.2 M, 200 ml)에 녹이고 소듐 터부톡사이드 (58.9 mmol, 5.66 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.392 mmol, 0.2 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 43-b 23.4 g을 수득하였다. (수율 86%, MS[M+H]+= 691)In a three-necked flask, compounds 43-a (39.2 mmol, 19.7 g) and 16-a (39.2 mmol, 8.84 g) were dissolved in toluene (0.2 M, 200 ml), and sodium terbutoxide (58.9 mmol, 5.66 g), bis After (tri-tertbutylphosphine)palladium(0) (0.392 mmol, 0.2 g) was added, the mixture was stirred under reflux conditions in an argon atmosphere for 24 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 23.4 g of compound 43-b. (Yield 86%, MS[M+H]+=691)
단계 3) 화합물 43의 합성Step 3) Synthesis of compound 43
Figure PCTKR2020017069-appb-I000269
Figure PCTKR2020017069-appb-I000269
3구 플라스크에 화합물 43-b (33.9 mmol, 23.4 g)을 1,2-디클로로벤젠 (0.1 M, 340 ml)에 녹이고 보론트리아이오다이드 (54.2 mmol, 21.2 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (305 mmol, 39.4 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 43, 5.2 g을 수득하였다. (수율 22%, MS[M+H]+= 699)In a three-neck flask, compound 43-b (33.9 mmol, 23.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 340 ml), boron triiodide (54.2 mmol, 21.2 g) was added, and argon atmosphere 140 It was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N-diisopropylethylamine (305 mmol, 39.4 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 43, 5.2 g. (Yield 22%, MS[M+H]+= 699)
합성예 44 : 화합물 44의 합성Synthesis Example 44: Synthesis of compound 44
단계 1) 화합물 44-a의 합성Step 1) Synthesis of compound 44-a
Figure PCTKR2020017069-appb-I000270
Figure PCTKR2020017069-appb-I000270
3구 플라스크에 8-터부틸-N-(4-터부틸페닐)디벤조[b,d]싸이오펜-4-아민 (38.7 mmol, 15 g)과 1-브로모-3-클로로-5-메틸벤젠 (38.7 mmol, 8 g)을 톨루엔 (0.2 M, 195 ml)에 녹이고 소듐 터부톡사이드 (58.1 mmol, 5.58 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.387 mmol, 0.198 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 2시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 44-a 18.8 g을 수득하였다. (수율 95%, MS[M+H]+= 512)In a three-necked flask, 8-terbutyl- N- (4-terbutylphenyl)dibenzo[ b,d ]thiophen-4-amine (38.7 mmol, 15 g) and 1-bromo-3-chloro-5- Methylbenzene (38.7 mmol, 8 g) was dissolved in toluene (0.2 M, 195 ml), sodium terbutoxide (58.1 mmol, 5.58 g), bis(tri-terbutylphosphine)palladium(0) (0.387 mmol, 0.198) g), followed by stirring for 2 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 18.8 g of compound 44-a. (yield 95%, MS[M+H]+=512)
단계 2) 화합물 44-b의 합성Step 2) Synthesis of compound 44-b
Figure PCTKR2020017069-appb-I000271
Figure PCTKR2020017069-appb-I000271
3구 플라스크에 화합물 44-a (36.7 mmol, 18.8 g)와 5-터부틸-N-(4-터부틸페닐)벤조[b]싸이오펜-2-아민 (36.7 mmol, 12.4 g)을 톨루엔 (0.2 M, 180 ml)에 녹이고 소듐 터부톡사이드 (55.1 mmol, 5.29 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.367 mmol, 0.187 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 44-b 27.4 g을 수득하였다. (수율 92%, MS[M+H]+= 813)In a three-neck flask, compound 44-a (36.7 mmol, 18.8 g) and 5-terbutyl- N- (4-terbutylphenyl)benzo[ b ]thiophen-2-amine (36.7 mmol, 12.4 g) were mixed with toluene ( 0.2 M, 180 ml), sodium terbutoxide (55.1 mmol, 5.29 g), bis(tri-terbutylphosphine)palladium (0) (0.367 mmol, 0.187 g) were added, and then 24 under reflux conditions in an argon atmosphere. stirred for an hour. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 27.4 g of compound 44-b. (yield 92%, MS[M+H]+= 813)
단계 3) 화합물 44의 합성Step 3) Synthesis of compound 44
Figure PCTKR2020017069-appb-I000272
Figure PCTKR2020017069-appb-I000272
3구 플라스크에 화합물 44-b (33.7 mmol, 27.4 g)을 1,2-디클로로벤젠 (0.1 M, 340 ml)에 녹이고 보론트리아이오다이드 (53.9 mmol, 21.1 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (303 mmol, 39.2 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 44, 4.6 g을 수득하였다. (수율 17%, MS[M+H]+= 821)In a three-necked flask, compound 44-b (33.7 mmol, 27.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 340 ml), boron triiodide (53.9 mmol, 21.1 g) was added, and argon atmosphere 140 It was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N -diisopropylethylamine (303 mmol, 39.2 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 44, 4.6 g. (Yield 17%, MS[M+H]+= 821)
합성예 45 : 화합물 45의 합성Synthesis Example 45: Synthesis of compound 45
단계 1) 화합물 45-a의 합성Step 1) Synthesis of compound 45-a
Figure PCTKR2020017069-appb-I000273
Figure PCTKR2020017069-appb-I000273
3구 플라스크에 N-메시틸-5a,10a-디메틸-5-페닐-5,5a,6,7,8,9,10,10a-옥타하이드로시클로펜타[b]인돌-2-아민 (47.1 mmol, 20 g)과 1-브로모-3-클로로-5-메틸벤젠 (47.1 mmol, 9.68 g)을 톨루엔 (0.2 M, 235 ml)에 녹이고 소듐 터부톡사이드 (70.6 mmol, 6.79 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.471 mmol, 0.241 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 8시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 45-a 21.5 g을 수득하였다. (수율 83%, MS[M+H]+= 549)In a 3-neck flask, N -mesityl-5a,10a-dimethyl-5-phenyl-5,5a,6,7,8,9,10,10a-octahydrocyclopenta[ b ]indol-2-amine (47.1 mmol , 20 g) and 1-bromo-3-chloro-5-methylbenzene (47.1 mmol, 9.68 g) were dissolved in toluene (0.2 M, 235 ml) and sodium terbutoxide (70.6 mmol, 6.79 g), bis ( After tri-tertbutylphosphine)palladium(0) (0.471 mmol, 0.241 g) was added, the mixture was stirred for 8 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 21.5 g of compound 45-a. (Yield 83%, MS[M+H]+= 549)
단계 2) 화합물 45-b의 합성Step 2) Synthesis of compound 45-b
Figure PCTKR2020017069-appb-I000274
Figure PCTKR2020017069-appb-I000274
3구 플라스크에 화합물 45-a (39.1 mmol, 21.5 g)와 N-(4-터부틸페닐)-4,4,6,6-테트라메틸-5,6-디하이드로-4H-시클로펜타[b]싸이오펜-3-아민 (39.1 mmol, 12.8 g)을 톨루엔 (0.2 M, 195 ml)에 녹이고 소듐 터부톡사이드 (58.7 mmol, 5.64 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.391 mmol, 0.2 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 45-b 21.9 g을 수득하였다. (수율 67%, MS[M+H]+= 840)In a three-necked flask, compound 45-a (39.1 mmol, 21.5 g) and N- (4-terbutylphenyl)-4,4,6,6-tetramethyl-5,6-dihydro- 4H -cyclopenta[ b ] Thiophen-3-amine (39.1 mmol, 12.8 g) was dissolved in toluene (0.2 M, 195 ml), sodium terbutoxide (58.7 mmol, 5.64 g), bis(tri-terbutylphosphine)palladium (0 ) (0.391 mmol, 0.2 g) was added, and the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 21.9 g of compound 45-b. (Yield 67%, MS[M+H]+=840)
단계 3) 화합물 45의 합성Step 3) Synthesis of compound 45
Figure PCTKR2020017069-appb-I000275
Figure PCTKR2020017069-appb-I000275
3구 플라스크에 화합물 45-b (26.1 mmol, 21.9 g)을 1,2-디클로로벤젠 (0.1 M, 260 ml)에 녹이고 보론트리아이오다이드 (41.7 mmol, 16.3 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (235 mmol, 30.3 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 45, 3.5 g을 수득하였다. (수율 16%, MS[M+H]+= 848)In a three-necked flask, compound 45-b (26.1 mmol, 21.9 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 260 ml), boron triiodide (41.7 mmol, 16.3 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N -diisopropylethylamine (235 mmol, 30.3 g) was added, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 45, 3.5 g. (yield 16%, MS[M+H]+= 848)
합성예 46 : 화합물 46의 합성Synthesis Example 46: Synthesis of compound 46
단계 1) 화합물 46-a의 합성Step 1) Synthesis of compound 46-a
Figure PCTKR2020017069-appb-I000276
Figure PCTKR2020017069-appb-I000276
3구 플라스크에 6-터부틸-9-페닐-N-(5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프탈렌-2-일-9H-카바졸-3-아민 (39.9 mmol, 20 g)과 1-브로모-3-클로로-5-메틸벤젠 (39.9 mmol, 8.21 g)을 톨루엔 (0.2 M, 200 ml)에 녹이고 소듐 터부톡사이드 (60 mmol, 5.76 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.4 mmol, 0.204 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 5시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 46-a 20.9 g을 수득하였다. (수율 84%, MS[M+H]+= 625)Three-necked flask was charged with 6-butyl-9-phenyl-emitter - N - (5,5,8,8- tetramethyl-5,6,7,8-tetrahydronaphthalene-2-yl -9 H - carbazol -3 -Amine (39.9 mmol, 20 g) and 1-bromo-3-chloro-5-methylbenzene (39.9 mmol, 8.21 g) were dissolved in toluene (0.2 M, 200 ml) and sodium terbutoxide (60 mmol, 5.76) g), bis(tri-terbutylphosphine)palladium(0) (0.4 mmol, 0.204 g) was added, and then stirred for 5 hours under reflux condition under argon atmosphere.After completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 20.9 g of compound 46-a (yield 84%, MS[M]. +H]+= 625)
단계 2) 화합물 46-b의 합성Step 2) Synthesis of compound 46-b
Figure PCTKR2020017069-appb-I000277
Figure PCTKR2020017069-appb-I000277
3구 플라스크에 화합물 46-a (33.4 mmol, 20.9 g)와 6-터부틸-N-(5,5,8,8-테트라메틸-5,6,7,8-테트라하이드로나프탈렌-2-일)벤조[b]싸이오펜-2-아민 (33.4 mmol, 13.1 g)을 톨루엔 (0.2 M, 170 ml)에 녹이고 소듐 터부톡사이드 (50.1 mmol, 4.82 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.334 mmol, 0.171 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 46-b 25.2 g을 수득하였다. (수율 77%, MS[M+H]+= 980)Compound 46-a (33.4 mmol, 20.9 g) and 6-tertbutyl- N- (5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl in a three-necked flask ) Benzo[ b ]thiophen-2-amine (33.4 mmol, 13.1 g) was dissolved in toluene (0.2 M, 170 ml), sodium terbutoxide (50.1 mmol, 4.82 g), bis(tri-terbutylphosphine) After adding palladium (0) (0.334 mmol, 0.171 g), the mixture was stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 25.2 g of compound 46-b. (Yield 77%, MS[M+H]+=980)
단계 3) 화합물 46의 합성Step 3) Synthesis of compound 46
Figure PCTKR2020017069-appb-I000278
Figure PCTKR2020017069-appb-I000278
3구 플라스크에 화합물 46-b (25.7 mmol, 25.2 g)을 1,2-디클로로벤젠 (0.1 M, 260 ml)에 녹이고 보론트리아이오다이드 (41.1 mmol, 16.1 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (231 mmol, 30 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 46, 4.1 g을 수득하였다. (수율 16%, MS[M+H]+= 988)In a three-necked flask, compound 46-b (25.7 mmol, 25.2 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 260 ml), boron triiodide (41.1 mmol, 16.1 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N -diisopropylethylamine (231 mmol, 30 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 46, 4.1 g. (Yield 16%, MS[M+H]+=988)
합성예 47 : 화합물 47의 합성Synthesis Example 47: Synthesis of compound 47
단계 1) 화합물 47-a의 합성Step 1) Synthesis of compound 47-a
Figure PCTKR2020017069-appb-I000279
Figure PCTKR2020017069-appb-I000279
3구 플라스크에 9-(2,6,-디플루오로페닐)-1,1,4,4-테트라메틸-N-(3,5,5,8,8-펜타메틸-5,6,7,8-테트라하이드로나프탈렌-2-일)-2,3,4,9-테트라하이드로-1H-카바졸-7-아민 (36.1 mmol, 20 g)과 1-브로모-3-클로로-5-메틸벤젠 (36.1 mmol, 7.41 g)을 톨루엔 (0.2 M, 180 ml)에 녹이고 소듐 터부톡사이드 (54.1 mmol, 5.20 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.36 mmol, 0.184 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 8시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 47-a 21.7 g을 수득하였다. (수율 89%, MS[M+H]+= 679)9-(2,6,-difluorophenyl)-1,1,4,4-tetramethyl- N- (3,5,5,8,8-pentamethyl-5,6,7 in a 3-neck flask ,8-tetrahydronaphthalen-2-yl)-2,3,4,9-tetrahydro-1 H -carbazol-7-amine (36.1 mmol, 20 g) and 1-bromo-3-chloro-5 -Methylbenzene (36.1 mmol, 7.41 g) was dissolved in toluene (0.2 M, 180 ml), sodium terbutoxide (54.1 mmol, 5.20 g), bis(tri-terbutylphosphine)palladium (0) (0.36 mmol, 0.184 g), followed by stirring for 8 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 21.7 g of compound 47-a. (yield 89%, MS[M+H]+= 679)
단계 2) 화합물 47-b의 합성Step 2) Synthesis of compound 47-b
Figure PCTKR2020017069-appb-I000280
Figure PCTKR2020017069-appb-I000280
3구 플라스크에 화합물 47-a (31.9 mmol, 21.7 g)와 5-플루오로-N-(페닐-d5)벤조[b]싸이오펜-3-아민 (31.9 mmol, 7.93 g)을 톨루엔 (0.2 M, 160 ml)에 녹이고 소듐 터부톡사이드 (47.9 mmol, 4.6 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.319 mmol, 0.163 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 47-b 20.1 g을 수득하였다. (수율 71%, MS[M+H]+= 891)In a three-necked flask, compound 47-a (31.9 mmol, 21.7 g) and 5-fluoro- N- (phenyl- d 5)benzo[ b ]thiophen-3-amine (31.9 mmol, 7.93 g) were mixed with toluene (0.2 M, 160 ml), sodium terbutoxide (47.9 mmol, 4.6 g), bis(tri-terbutylphosphine)palladium (0) (0.319 mmol, 0.163 g) were added, and then under reflux conditions under argon atmosphere for 24 hours. stirred for a while. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 20.1 g of compound 47-b. (Yield 71%, MS[M+H]+= 891)
단계 3) 화합물 47의 합성Step 3) Synthesis of compound 47
Figure PCTKR2020017069-appb-I000281
Figure PCTKR2020017069-appb-I000281
3구 플라스크에 화합물 47-b (22.6 mmol, 20.1 g)을 1,2-디클로로벤젠 (0.1 M, 225 ml)에 녹이고 보론트리아이오다이드 (36.1 mmol, 14.1 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (203 mmol, 36.2 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 47, 2.5 g을 수득하였다. (수율 12%, MS[M+H]+= 899)In a three-necked flask, compound 47-b (22.6 mmol, 20.1 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 225 ml), boron triiodide (36.1 mmol, 14.1 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, and N,N -diisopropylethylamine (203 mmol, 36.2 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then compound 47, 2.5 g, was obtained through sublimation purification. (Yield 12%, MS[M+H]+= 899)
합성예 48 : 화합물 48의 합성Synthesis Example 48: Synthesis of compound 48
단계 1) 화합물 48-a의 합성Step 1) Synthesis of compound 48-a
Figure PCTKR2020017069-appb-I000282
Figure PCTKR2020017069-appb-I000282
3구 플라스크에 9-(2,6,-디플루오로페닐)-1,1,4,4-테트라메틸-N-(3,5,5,8,8-펜타메틸-5,6,7,8-테트라하이드로나프탈렌-2-일)-2,3,4,9-테트라하이드로-1H-카바졸-7-아민 (53.1 mmol, 20 g)과 1-브로모-3-클로로-5-메틸벤젠 (53.1 mmol, 10.9 g)을 톨루엔 (0.2 M, 265 ml)에 녹이고 소듐 터부톡사이드 (79.7 mmol, 10.9 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.531 mmol, 0.271 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 2시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 48-a 22.8 g을 수득하였다. (수율 86%, MS[M+H]+= 501)9-(2,6,-difluorophenyl)-1,1,4,4-tetramethyl- N- (3,5,5,8,8-pentamethyl-5,6,7 in a 3-neck flask ,8-tetrahydronaphthalen-2-yl)-2,3,4,9-tetrahydro-1 H -carbazol-7-amine (53.1 mmol, 20 g) and 1-bromo-3-chloro-5 -Methylbenzene (53.1 mmol, 10.9 g) was dissolved in toluene (0.2 M, 265 ml), sodium terbutoxide (79.7 mmol, 10.9 g), bis (tri-terbutylphosphine) palladium (0) (0.531 mmol, 0.271 g) was added, and the mixture was stirred for 2 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 22.8 g of compound 48-a. (Yield 86%, MS[M+H]+= 501)
단계 2) 화합물 48-b의 합성Step 2) Synthesis of compound 48-b
Figure PCTKR2020017069-appb-I000283
Figure PCTKR2020017069-appb-I000283
3구 플라스크에 화합물 48-a (45.5 mmol, 22.8 g)와 4,4,6,6-테트라메틸-N-페닐-5,6-디하이드로-4H-시클로펜타[b]퓨란-3-아민 (45.5 mmol, 11.6 g)을 톨루엔 (0.2 M, 230 ml)에 녹이고 소듐 터부톡사이드 (68.3 mmol, 6.56 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.455 mmol, 0.233 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 48-b 23.1 g을 수득하였다. (수율 71%, MS[M+H]+= 720)In a 3-neck flask, compound 48-a (45.5 mmol, 22.8 g) and 4,4,6,6-tetramethyl- N -phenyl-5,6-dihydro- 4H -cyclopenta[ b ]furan-3- An amine (45.5 mmol, 11.6 g) was dissolved in toluene (0.2 M, 230 ml), sodium terbutoxide (68.3 mmol, 6.56 g), bis(tri-terbutylphosphine)palladium(0) (0.455 mmol, 0.233 g) ), and stirred for 24 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 23.1 g of compound 48-b. (Yield 71%, MS[M+H]+=720)
단계 3) 화합물 48의 합성Step 3) Synthesis of compound 48
Figure PCTKR2020017069-appb-I000284
Figure PCTKR2020017069-appb-I000284
3구 플라스크에 화합물 48-b (32.1 mmol, 23.1 g)을 1,2-디클로로벤젠 (0.1 M, 320 ml)에 녹이고 보론트리아이오다이드 (51.3 mmol, 20.1 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (289 mmol, 37.3 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 48, 3.6 g을 수득하였다. (수율 15%, MS[M+H]+= 728)In a three-necked flask, compound 48-b (32.1 mmol, 23.1 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 320 ml), boron triiodide (51.3 mmol, 20.1 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, and N , N -diisopropylethylamine (289 mmol, 37.3 g) was added thereto, followed by stirring for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 48, 3.6 g. (yield 15%, MS[M+H]+= 728)
합성예 49 : 화합물 49의 합성Synthesis Example 49: Synthesis of compound 49
단계 1) 화합물 49-a의 합성Step 1) Synthesis of compound 49-a
Figure PCTKR2020017069-appb-I000285
Figure PCTKR2020017069-appb-I000285
3구 플라스크에 N-(4-터부틸-2-메틸페닐)디벤조[b,d]싸이오펜-3-아민 (43.4 mmol, 15 g)과 3-브로모-5-클로로-1,1'-바이페닐 (43.4 mmol, 11.6 g)을 톨루엔 (0.2 M, 220 ml)에 녹이고 소듐 터부톡사이드 (65.1 mmol, 6.26 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.434 mmol, 0.222 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 2시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 49-a 20.1 g을 수득하였다. (수율 87%, MS[M+H]+= 532)In a three-necked flask, N- (4-terbutyl-2-methylphenyl)dibenzo[ b,d ]thiophen-3-amine (43.4 mmol, 15 g) and 3-bromo-5-chloro-1,1' -Biphenyl (43.4 mmol, 11.6 g) was dissolved in toluene (0.2 M, 220 ml), sodium terbutoxide (65.1 mmol, 6.26 g), bis (tri-terbutylphosphine) palladium (0) (0.434 mmol, 0.222 g) was added, and the mixture was stirred for 2 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 20.1 g of compound 49-a. (Yield 87%, MS[M+H]+=532)
단계 2) 화합물 49-b의 합성Step 2) Synthesis of compound 49-b
Figure PCTKR2020017069-appb-I000286
Figure PCTKR2020017069-appb-I000286
3구 플라스크에 화합물 49-a (37.8 mmol, 20.1 g)와 6-터부틸-N-(4-터부틸-2-메틸페닐)벤조퓨란-2-아민 (37.8 mmol, 12.7 g)을 톨루엔 (0.2 M, 190 ml)에 녹이고 소듐 터부톡사이드 (56.7 mmol, 5.4 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.378 mmol, 0.193 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 24시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 49-b 21.7 g을 수득하였다. (수율 69%, MS[M+H]+= 831)In a three-necked flask, compound 49-a (37.8 mmol, 20.1 g) and 6-terbutyl- N- (4-terbutyl-2-methylphenyl)benzofuran-2-amine (37.8 mmol, 12.7 g) were mixed with toluene (0.2 M, 190 ml), sodium terbutoxide (56.7 mmol, 5.4 g), bis(tri-terbutylphosphine)palladium (0) (0.378 mmol, 0.193 g) was added, and then under reflux conditions under argon atmosphere for 24 hours. stirred for a while. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 21.7 g of compound 49-b. (yield 69%, MS[M+H]+= 831)
단계 3) 화합물 49의 합성Step 3) Synthesis of compound 49
Figure PCTKR2020017069-appb-I000287
Figure PCTKR2020017069-appb-I000287
3구 플라스크에 화합물 49-b (26.1 mmol, 21.7 g)을 1,2-디클로로벤젠 (0.1 M, 260 ml)에 녹이고 보론트리아이오다이드 (41.8 mmol, 16.4 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (235 mmol, 30.4 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 49, 3.3 g을 수득하였다. (수율 15%, MS[M+H]+= 839)In a three-necked flask, compound 49-b (26.1 mmol, 21.7 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 260 ml), boron triiodide (41.8 mmol, 16.4 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N -diisopropylethylamine (235 mmol, 30.4 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, followed by sublimation purification to obtain compound 49, 3.3 g. (yield 15%, MS[M+H]+= 839)
합성예 50 : 화합물 50의 합성Synthesis Example 50: Synthesis of compound 50
단계 1) 화합물 50-a의 합성Step 1) Synthesis of compound 50-a
Figure PCTKR2020017069-appb-I000288
Figure PCTKR2020017069-appb-I000288
3구 플라스크에 N-(4-터부틸페닐)-6,6,9,9-테트라메틸-6,7,8,9-테트라하이드로디벤조[b,d]퓨란-2-아민 (39.9 mmol, 15 g)과 1-브로모-3-클로로-5-메틸벤젠 (39.9 mmol, 8.21 g)을 톨루엔 (0.2 M, 200 ml)에 녹이고 소듐 터부톡사이드 (59.9 mmol, 5.76 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.399 mmol, 0.204 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 4시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 50-a 18.5 g을 수득하였다. (수율 93%, MS[M+H]+= 500)In a three-necked flask, N -(4-terbutylphenyl)-6,6,9,9-tetramethyl-6,7,8,9-tetrahydrodibenzo[ b,d ]furan-2-amine (39.9 mmol , 15 g) and 1-bromo-3-chloro-5-methylbenzene (39.9 mmol, 8.21 g) were dissolved in toluene (0.2 M, 200 ml) and sodium terbutoxide (59.9 mmol, 5.76 g), bis ( After tri-tertbutylphosphine)palladium(0) (0.399 mmol, 0.204 g) was added, the mixture was stirred under reflux conditions under argon atmosphere for 4 hours. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 18.5 g of compound 50-a. (Yield 93%, MS[M+H]+= 500)
단계 2) 화합물 50-b의 합성Step 2) Synthesis of compound 50-b
Figure PCTKR2020017069-appb-I000289
Figure PCTKR2020017069-appb-I000289
3구 플라스크에 화합물 50-a (37.0 mmol, 18.5 g)와 N-(4-터부틸페닐)-4,4,7,7-테트라메틸-4,5,6,7-테트라하이드로벤조퓨란-2-아민 (37.0 mmol, 12.0 g)을 톨루엔 (0.2 M, 185 ml)에 녹이고 소듐 터부톡사이드 (55.5 mmol, 5.33 g), 비스(트리-터부틸포스핀)팔라듐(0) (0.370 mmol, 0.189 g)을 넣은 후, 아르곤 분위기 환류 조건하에서 15시간동안 교반하였다. 반응이 종료되면 상온으로 냉각한 후, H2O를 넣고 반응액을 분액 깔대기에 옮겨 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 50-b 22.8 g을 수득하였다. (수율 78%, MS[M+H]+= 789)Compound 50-a (37.0 mmol, 18.5 g) and N- (4-terbutylphenyl)-4,4,7,7-tetramethyl-4,5,6,7-tetrahydrobenzofuran- Dissolve 2-amine (37.0 mmol, 12.0 g) in toluene (0.2 M, 185 ml), sodium terbutoxide (55.5 mmol, 5.33 g), bis(tri-terbutylphosphine)palladium(0) (0.370 mmol, 0.189 g) was added, and the mixture was stirred for 15 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography to obtain 22.8 g of compound 50-b. (Yield 78%, MS[M+H]+= 789)
단계 3) 화합물 50의 합성Step 3) Synthesis of compound 50
Figure PCTKR2020017069-appb-I000290
Figure PCTKR2020017069-appb-I000290
3구 플라스크에 화합물 50-b (28.9 mmol, 22.8 g)을 1,2-디클로로벤젠 (0.1 M, 290 ml)에 녹이고 보론트리아이오다이드 (46.2 mmol, 18.1 g)를 넣은 후, 아르곤 분위기 140 ℃에서 3시간동안 교반하였다. 반응물을 0 ℃까지 냉각하고 N,N-디이소프로필에틸아민 (260 mmol, 33.6 g)을 첨가한 후 1시간 교반하였다. 톨루엔과 H2O을 이용해 분액 깔대기에서 추출하였다. 추출액을 MgSO4로 건조, 농축하고 시료를 실리카 겔 컬럼 크로마토그래피로 정제한 후 승화정제를 통해 화합물 50, 4.1 g을 수득하였다. (수율 18%, MS[M+H]+= 797)In a three-neck flask, compound 50-b (28.9 mmol, 22.8 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 290 ml), boron triiodide (46.2 mmol, 18.1 g) was added, and argon atmosphere 140 The mixture was stirred at ℃ for 3 hours. The reaction mass was cooled to 0 °C, N,N -diisopropylethylamine (260 mmol, 33.6 g) was added thereto, and the mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H 2 O. The extract was dried over MgSO 4 , concentrated, and the sample was purified by silica gel column chromatography, and then the compound 50, 4.1 g, was obtained through sublimation purification. (Yield 18%, MS[M+H]+= 797)
실험예 1: 광발광 분석 실험Experimental Example 1: Photoluminescence analysis experiment
한국 등록 특허 공보 10-2030309에 의하면 산소 또는 황을 포함하는 방향족 5원환을 보론 화합물에 대칭구조로 치환시켰을 때 6원 방향족환 3개 치환된 보론화합물보다 평평(flat)한 구조의 보론화합물을 만들 수 있으며, 이를 이용하여 고색순도, 고효율, 장수명의 소자를 얻을 수 있음을 알 수 있었다.According to Korean Patent Publication No. 10-2030309, when an aromatic 5-membered ring containing oxygen or sulfur is symmetrically substituted with a boron compound, a boron compound having a flatter structure than a boron compound substituted with 3 6-membered aromatic rings is produced. It was found that a device with high color purity, high efficiency, and long life can be obtained using this.
본 명세서의 일 실시상태에 따른 화학식 1의 화합물 즉, 1개의 방향족 5원환을 포함하는 비대칭 보론 화합물을 함유하는 층을 유기 발광 소자의 유기물층에 포함하여 상기 한국 등록 특허 공보 10-2030309 보다 우수한 효과의 유기 발광 소자를 얻을 수 있음을 확인하였다.The compound of Formula 1 according to an exemplary embodiment of the present specification, that is, a layer containing an asymmetric boron compound including one aromatic 5-membered ring, is included in the organic material layer of the organic light emitting device, which is superior to that of Korean Patent Publication No. 10-2030309. It was confirmed that an organic light emitting device could be obtained.
하기 광발광 분석실험을 통해 종래의 대칭형 화합물과 본 명세서의 일 실시상태에 따른 화학식 1의 화합물 즉, 비대칭형 화합물의 형광 스펙트럼을 확인하였다. 광발광 분석실험에는 보론에 3개의 벤젠고리가 치환되어 있는 BD-A를 대칭형 화합물인 2개의 벤조싸이오펜과 1개의 벤젠고리가 치환되어 있는 BD-C, 본 명세서의 일 실시상태에 따른 화학식 1인 합성예 16으로부터 합성된 화합물 16을 사용하였다.The fluorescence spectrum of the conventional symmetric compound and the compound of Formula 1 according to an exemplary embodiment of the present specification, that is, the asymmetric compound, was confirmed through the following photoluminescence analysis experiment. In the photoluminescence analysis experiment, BD-A in which three benzene rings are substituted in boron, BD-C in which two benzothiophene and one benzene ring are substituted, which are symmetric compounds, Chemical Formula 1 according to an exemplary embodiment of the present specification Compound 16 synthesized in Synthesis Example 16 was used.
Figure PCTKR2020017069-appb-I000291
Figure PCTKR2020017069-appb-I000291
광발광 분석실험은 JASCO FP-8600 형광분광광도계를 이용하였으며, 하기의 방법으로 최대 발광 파장을 측정하였다.For the photoluminescence analysis experiment, a JASCO FP-8600 fluorescence spectrophotometer was used, and the maximum emission wavelength was measured by the following method.
톨루엔을 용매로 하여 측정할 화합물인 상기 BD-A, BD-C 및 화합물 16을 각각 1Х 10-5M 농도로 용해하여 측정용 시료를 준비하였다. 시료용액을 석영셀에 넣고 질소 기체 (N2)를 이용하여 탈기(degassing)해주어 용액내 산소를 제거한 다음, 측정 장비를 이용하여 실온(300K)에서 형광 스펙트럼을 측정하였다. 이때 최대발광피크의 파장값(nm)을 얻고, 최대 발광 피크에서의 2분의 1 높이에서의 그래프의 퍼진폭(반치폭, FWHM, Full width at half maximum, nm)을 구하여 하기 표 1에 나타내었으며, 측정 그래프를 도 4에 도시하였다.Using toluene as a solvent, BD-A, BD-C, and compound 16, which are compounds to be measured, were each dissolved at a concentration of 1Х 10 -5 M to prepare a measurement sample. The sample solution was placed in a quartz cell and degassed using nitrogen gas (N 2 ) to remove oxygen in the solution, and then the fluorescence spectrum was measured at room temperature (300K) using a measuring device. At this time, the wavelength value (nm) of the maximum emission peak was obtained, and the spread width (full width at half maximum, FWHM, full width at half maximum, nm) of the graph at a height of 1/2 at the maximum emission peak was obtained and shown in Table 1 below. , a measurement graph is shown in FIG. 4 .
화합물compound 최대 발광 파장(nm)Maximum emission wavelength (nm) 반치폭(nm)Full width at half maximum (nm) CIEyCIEy
BD-ABD-A 456.1456.1 23.423.4 0.08590.0859
BD-CBD-C 463.0 463.0 20.920.9 0.17770.1777
화합물16compound 16 456.1456.1 21.921.9 0.10430.1043
상기 표 1 및 도 4에서, BD-A, BD-C 및 화합물 16의 각각의 화합물에 있어서 헤테로고리기가 1개씩 늘어날 때 마다, 메인피크 (main peak)보다 장파장영역대에서 형성되는 두번째 피크가 세지는 것을 확인할 수 있다. 두번 째 피크가 커질수록 유기 발광 소자에서의 색순도가 나빠지는 단점이 있는데, 비 대칭형인 본 명세서의 상기 화학식 1의 화합물 16은 대칭형인 화합물 BD-C 보다 두번째 피크가 약하다. 따라서, 상기 발광특성으로 인해 대칭형 화합물보다 비대칭형 화합물인 본 명세서의 일 실시상태에 따른 화학식 1의 화합물에서 고색순도와 고효율의 소자를 구성할 수 있음을 알 수 있다.In Table 1 and FIG. 4, whenever the heterocyclic group increases by one in each compound of BD-A, BD-C and compound 16, the second peak formed in a longer wavelength band than the main peak is stronger can be confirmed that As the second peak increases, there is a disadvantage in that the color purity in the organic light emitting device is deteriorated. Compound 16 of Formula 1 of the present specification, which is asymmetric, has a weaker second peak than compound BD-C, which is a symmetrical type. Therefore, it can be seen that a device having high color purity and high efficiency can be constructed from the compound of Formula 1 according to an exemplary embodiment of the present specification, which is an asymmetric compound rather than a symmetric compound due to the light emission characteristics.
실험예 2: 양자화학 계산 실험Experimental Example 2: Quantum Chemistry Calculation Experiment
실험예 1의 광발광 분석실험 결과의 원인을 파악 위해 대칭형 싸이오펜-보론 화합물(하기 DABNA 및 BD-F)과 본 명세서의 일 실시상태에 따른 화학식 1의 화합물 즉, 비대칭형 싸이오펜-보론 화합물(하기 BD-E)에 대해 양자 계산을 진행하였다. 양자 계산은 Schrodinger Material Science Suite 프로그램의 밀도범함수 이론(DFT, Density functional theory) 계산과 시간의존 밀도범함수 이론 (Time-dependent density functional theory) 계산으로 진행하였고 이 때 범함수는 B3LYP를, 기저함수는 6-31G*를 사용하였다. 발광 파장의 프랑크-콘돈 분석법 (Franck-Condon analysis)은 선행문헌을 참고하여 Schrodinger Material Science Suite 프로그램으로 진행하였으며, 그 결과를 표 2 내지 4에 나타내었다 (예를 들면, 문헌 「Santoro, F., Lami, A., Improta, R., Bloino, J., Barone, V. J. Chem. Phys. 128, 224311 (2008). 」 및 문헌 「Kondo, Y., Yoshiura, K., Kitera, S. et al. Nat. Photonics 13, 678 (2019).」를 참조).In order to determine the cause of the photoluminescence assay result of Experimental Example 1, a symmetric thiophene-boron compound (DABNA and BD-F below) and a compound of Formula 1 according to an exemplary embodiment of the present specification, that is, an asymmetric thiophene-boron compound Quantum calculation was performed for (BD-E below). Quantum calculations were carried out by density functional theory (DFT) and time-dependent density functional theory calculations of the Schrodinger Material Science Suite program. In this case, the functional function was B3LYP, and the basis function was used 6-31G*. The Frank-Condon analysis of the emission wavelength was carried out with the Schrodinger Material Science Suite program with reference to the prior literature, and the results are shown in Tables 2 to 4 (for example, in Santoro, F., Lami, A., Improta, R., Bloino, J., Barone, VJ Chem. Phys. 128, 224311 (2008). and Kondo, Y., Yoshiura, K., Kitera, S. et al. Nat. Photonics 13, 678 (2019).”).
Figure PCTKR2020017069-appb-I000292
Figure PCTKR2020017069-appb-I000292
Figure PCTKR2020017069-appb-T000001
Figure PCTKR2020017069-appb-T000001
Figure PCTKR2020017069-appb-T000002
Figure PCTKR2020017069-appb-T000002
Figure PCTKR2020017069-appb-T000003
Figure PCTKR2020017069-appb-T000003
상기 표 2 내지 4에 있어서, 헤테로고리기를 포함하는 상기 BD-E 및 BD-F의 화합물은 방향족탄화수소고리(벤젠)을 포함하는 상기 DABNA 보다 장파장 영역에서 더 강한 세기의 두번째 피크가 형성되는 것을 확인하였다. 그러나, 비대칭형인 본 명세서의 일 실시상태에 따른 화합물인 상기 BD-E의 두번 째 피크가 상기 BD-F에 비해 더 적은 세기로 나타날 것이 예상되었으며, 이 결과는 실험예 1에서 화합물 16과 BD-C 간의 색순도 차이를 원인을 나타낸다. 상기 실험예 1 및 2의 결과들로부터 대칭형 보론 화합물에 비해 비대칭형 보론 화합물인 본 명세서의 일 실시상태에 따른 화학식 1을 유기 발광 소자의 유기물층에 사용하였을때 더 우수한 발광특성을 갖는 소자를 구현할 수 있다는 것을 확인하였다.In Tables 2 to 4, it was confirmed that the compounds of BD-E and BD-F containing a heterocyclic group form a second peak with a stronger intensity in a longer wavelength region than the DABNA containing an aromatic hydrocarbon ring (benzene). did. However, it was expected that the second peak of the BD-E, which is an asymmetric compound according to an exemplary embodiment of the present specification, would appear with a lower intensity than that of the BD-F, and this result shows that in Experimental Example 1, compound 16 and BD- C indicates the cause of the difference in color purity. From the results of Experimental Examples 1 and 2, when Chemical Formula 1 according to an exemplary embodiment of the present specification, which is an asymmetric boron compound compared to a symmetric boron compound, is used in the organic material layer of the organic light emitting device, a device having better light emitting characteristics can be realized. confirmed that there is.
실험예 3: 열중량분석 실험Experimental Example 3: Thermogravimetric analysis experiment
TGA(thermos gravimetric analyzer, 열중량분석기)는 시료에 온도를 가하여 시료의 질량변화를 시간이나 온도의 함수로써 측정하는 장비이다. 재료의 질량손실은 증발이나 가스상 산물을 생성하는 화학반응에 의해 발생된다. Q-500를 이용하여 Pt pan위에 승화정제를 완료한 3mg 이상 5mg미만의 하기 표 5의 화합물을 각각 덜어 10 ℃/min의 속도로 상온에서부터 700℃까지 가열하였다. 이때, 화합물의 전체 중량 대비 5%의 질량이 감소되는 온도(=Td-5% loss)와 700℃까지 가열한 이후 pan에 남아있는 잔류물의 양(퍼센트)를 측정하였다. 합성예 19로 제조된 화합물 19의 열중량분석 그래프는 도 5에 도시하였으며, BD-A와 BD-C의 열중량분석 그래프를 각각 도 6 및 7에 도시하였다.TGA (thermos gravimetric analyzer, thermogravimetric analyzer) is a device that measures the change in mass of a sample as a function of time or temperature by applying temperature to the sample. Mass loss of a material is caused by evaporation or chemical reactions that produce gaseous products. Using Q-500, 3 mg or more and less than 5 mg of each of the compounds in Table 5, which had completed sublimation purification, were added onto a Pt pan and heated from room temperature to 700° C. at a rate of 10° C./min. At this time, the temperature at which the mass of the compound is reduced by 5% relative to the total weight (=Td-5% loss) and the amount (percent) of the residue remaining in the pan after heating to 700°C were measured. A thermogravimetric analysis graph of compound 19 prepared in Synthesis Example 19 is shown in FIG. 5, and thermogravimetric analysis graphs of BD-A and BD-C are shown in FIGS. 6 and 7, respectively.
화합물compound 분자량Molecular Weight Td (5% loss)Td (5% loss) 잔류 (%)Residual (%)
BD-ABD-A 658.78658.78 368368 0.30.3
BD-CBD-C 770.95770.95 459459 30.130.1
화합물 19compound 19 845.05845.05 375375 4.24.2
상기 표 5 및 도 5 내지 7에 있어서, 본 명세서의 일 실시상태에 따른 화합물 1 즉, O 또는 S를 포함하는 5원 고리를 포함하는 비대칭 보론 화합물인 화합물 19는 O 또는 S를 포함하는 5원 고리를 포함하지만 대칭 구조의 보론 화합물인 BD-C에 비해 더 높은 분자량에도 불구하고 더 낮은 Td-5% loss 값을 갖는 것을 확인하였다. 또한, 분석 후 pan에 잔류하는 화합물의 비율도 헤테로아릴기를 갖지 않는 보론 화합물인 BD-A와 유사하게 5% 이내의 비율로 얻어졌다.이 실험을 통해 본 명세서의 일 실시상태에 따른 화학식 1, 즉 O 또는 S를 포함하는 5원 고리를 포함하는 비대칭 보론 화합물은 유사한 분자량 대비 낮은 Td-5% loss 값을 가지므로 낮은 승화온도를 가질 수 있어 열안정성 측명에서 우수하고, 증착 소자에도 적합한 유기 재료라는 것을 확인하였다.In Table 5 and Figures 5 to 7, Compound 1 according to an exemplary embodiment of the present specification, that is, Compound 19, which is an asymmetric boron compound including a 5-membered ring containing O or S, is a 5-membered compound containing O or S. It was confirmed that it has a lower Td-5% loss value despite a higher molecular weight than BD-C, a boron compound having a ring but having a symmetric structure. In addition, the ratio of the compound remaining in the pan after the analysis was obtained in a ratio within 5% similar to BD-A, which is a boron compound having no heteroaryl group. Through this experiment, Formula 1 according to an exemplary embodiment of the present specification, That is, an asymmetric boron compound containing a 5-membered ring containing O or S has a low Td-5% loss value compared to a similar molecular weight, so it can have a low sublimation temperature, so it is excellent in thermal stability and an organic material suitable for a deposition device It was confirmed that
실험예 4. 유기 발광 소자의 제작Experimental Example 4. Fabrication of an organic light emitting device
실시예 1Example 1
ITO(indium tin oxide)가 1,400Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척 하였다. 이 때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀리포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후, 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후, 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다. A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,400 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and 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.
상기와 같이 준비된 ITO 투명 전극 위에 하기 HI-A와 LG-101을 각각 650 Å, 50 Å*의 두께로 열 진공증착하여 정공주입층을 형성하였다. 상기 정공 주입층 위에 하기 HT-A를 600 Å의 두께로 진공 증착하여 정공수송층을 형성하였다. 상기 정공수송층 위에 하기 HT-B를 50 Å의 두께로 진공 증착하여 전자차단층을 형성하였다. 이어서, 상기 전자차단층 위에 청색 발광 도펀트로 상기 합성예 1의 화합물 1을 발광층 100중량부 기준으로 4중량부로 사용하고, 호스트로 하기 BH-A를 200Å의 두께로 진공 증착하여 발광층을 형성하였다. 그 다음에 상기 발광층 위에 제1 전자수송층으로 하기 화합물 ET-A 50Å을 진공 증착하고, 연이어 하기 ET-B 및 LiQ 를 1:1 중량비로 진공증착하여 360Å의 두께로 제2 전자수송층을 형성하였다. 상기 제2 전자수송층 위에 LiQ를 진공 증착하여 5Å의 두께로 진공증착하여 전자주입층을 형성하였다. 상기 전자주입층 위에 220Å두께로 알루미늄과 은을 10:1의 중량비로 증착하고 그 위에 알루미늄을 1000Å두께로 증착하여 음극을 형성하였다. On the ITO transparent electrode prepared as described above, the following HI-A and LG-101 were thermally vacuum-deposited to a thickness of 650 Å and 50 Å*, respectively, to form a hole injection layer. On the hole injection layer, the following HT-A was vacuum deposited to a thickness of 600 Å to form a hole transport layer. On the hole transport layer, the following HT-B was vacuum deposited to a thickness of 50 Å to form an electron blocking layer. Next, 4 parts by weight of Compound 1 of Synthesis Example 1 as a blue light emitting dopant on the electron blocking layer was used based on 100 parts by weight of the light emitting layer, and the following BH-A as a host was vacuum deposited to a thickness of 200 Å to form a light emitting layer. Then, 50 Å of the following compound ET-A was vacuum-deposited as a first electron transport layer on the light emitting layer, followed by vacuum deposition of ET-B and LiQ in a 1:1 weight ratio to form a second electron transport layer to a thickness of 360 Å. On the second electron transport layer, LiQ was vacuum-deposited to a thickness of 5 Å to form an electron injection layer. On the electron injection layer, aluminum and silver were deposited to a thickness of 220 Å in a weight ratio of 10:1, and aluminum was deposited thereon to a thickness of 1000 Å to form a cathode.
상기의 과정에서 유기물의 증착속도는 0.4 ~ 0.9 Å/sec를 유지하였고, 음극의 알루미늄은 2 Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 1 × 10-7~ 5 × 10-8 torr를 유지하여, 유기 발광 소자를 제작하였다.In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.9 Å/sec, the deposition rate of the aluminum of the cathode was maintained at 2 Å/sec, and the vacuum degree during deposition was 1 × 10 -7 ~ 5 × 10 -8 torr to manufacture an organic light emitting device.
Figure PCTKR2020017069-appb-I000293
Figure PCTKR2020017069-appb-I000293
실시예 2 내지 50 및 비교예 1 내지 3Examples 2 to 50 and Comparative Examples 1 to 3
상기 실시예 1에서 발광층의 도펀트로 상기 화합물 1 대신 하기 표 6에 기재한 화합물을 각각 사용한 것을 제외하고는 실시예 1과 동일한 방법을 이용하여 실시예 2 내지 실시예 50 및 비교예 1 내지 비교예 3의 유기 발광 소자를 각각 제작하였다.Examples 2 to 50 and Comparative Examples 1 to Comparative Examples using the same method as in Example 1, except that the compounds shown in Table 6 below were used instead of Compound 1 as the dopant of the light emitting layer in Example 1, respectively. Each of the organic light emitting devices of 3 was fabricated.
Figure PCTKR2020017069-appb-I000294
Figure PCTKR2020017069-appb-I000294
상기 실시예 1 내지 50 및 비교예 1 내지 3의 유기 발광 소자에 10 mA/cm2의 전류 밀도를 인가할 때의 전압, 효율 및 20 mA/cm2의 전류 밀도를 인가할 때의 수명(T95)을 측정하고, 그 결과를 하기 표 6에 나타내었다. 이 때, T95는 전류 밀도 20 mA/cm2에서의 초기 휘도를 100%로 하였을 때 휘도가 95%로 감소되는데 소요되는 시간을 의미하며, 비교예 1을 기준(100%)으로 비율을 나타내었다.Voltage when applying a current density of 10 mA/cm 2 to the organic light emitting devices of Examples 1 to 50 and Comparative Examples 1 to 3, efficiency, and lifetime when applying a current density of 20 mA/cm 2 (T95 ) was measured, and the results are shown in Table 6 below. At this time, T95 denotes the time it takes for the luminance to decrease to 95% when the initial luminance at a current density of 20 mA/cm 2 is 100%, and the ratio is expressed based on Comparative Example 1 (100%). .
Figure PCTKR2020017069-appb-T000004
Figure PCTKR2020017069-appb-T000004
Figure PCTKR2020017069-appb-I000295
Figure PCTKR2020017069-appb-I000295
Figure PCTKR2020017069-appb-I000296
Figure PCTKR2020017069-appb-I000296
실시예 51 내지 54 및 비교예 4Examples 51 to 54 and Comparative Example 4
상기 실시예 1에서 발광층의 도펀트로 상기 화합물 1 대신 하기 표 7에 기재된 화합물을 사용하고, 호스트 물질로 BH-A 대신 하기로 하기 표 7에 기재된 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법을 이용하여 실시예 51 내지 54, 비교예 4의 유기 발광 소자를 각각 제작하였다.The same method as in Example 1, except that in Example 1, the compound shown in Table 7 was used instead of Compound 1 as the dopant of the light emitting layer, and the compound shown in Table 7 was used instead of BH-A as the host material. The organic light emitting devices of Examples 51 to 54 and Comparative Example 4 were manufactured using the .
발광층의 제 1 호스트와 제 2 호스트의 중량비는 50 : 50 이다. The weight ratio of the first host to the second host in the emission layer is 50:50.
상기 실시예 51 내지 54 및 비교예 4의 유기 발광 소자에 10 mA/cm2의 전류 밀도를 인가할 때의 전압, 효율 및 20 mA/cm2의 전류 밀도를 인가할 때의 수명(T95)을 측정하고, 그 결과를 하기 표 7에 나타내었다. 이 때, T95는 전류 밀도 20 mA/cm2에서의 초기 휘도를 100%로 하였을 때 휘도가 95%로 감소되는데 소요되는 시간을 의미하며 상기 표 6의 비교예 1을 기준(100%)으로 비율로 나타내었다.Voltage when applying a current density of 10 mA/cm 2 to the organic light emitting devices of Examples 51 to 54 and Comparative Example 4, efficiency, and lifetime (T95) when applying a current density of 20 mA/cm 2 was measured, and the results are shown in Table 7 below. At this time, T95 denotes the time it takes for the luminance to decrease to 95% when the initial luminance at a current density of 20 mA/cm 2 is 100%, and the ratio is based on Comparative Example 1 in Table 6 (100%). indicated as
Figure PCTKR2020017069-appb-I000297
Figure PCTKR2020017069-appb-I000297
　 제1 호스트first host 제2 호스트 second host 도펀트dopant 10 mA/cm2 10 mA/cm 2 20mA/cm2 20mA / cm 2
전압(V)Voltage (V) 양자효율(QE)Quantum Efficiency (QE) LT95LT95
실시예 51Example 51 BH-ABH-A BH-BBH-B 화합물 5compound 5 3.82 3.82 8.13 8.13 130130
실시예 52Example 52 BH-ABH-A BH-BBH-B 화합물 19compound 19 3.79 3.79 8.53 8.53 142142
실시예 53Example 53 BH-ABH-A BH-CBH-C 화합물 26compound 26 3.72 3.72 8.22 8.22 128128
실시예 54Example 54 BH-BBH-B BH-CBH-C 화합물 48compound 48 3.68 3.68 8.57 8.57 116116
비교예 4Comparative Example 4 BH-ABH-A BH-BBH-B BD-DBD-D 3.943.94 7.527.52 9393
실시예 55 내지 57 및 비교예 5Examples 55 to 57 and Comparative Example 5
상기 실시예 1에서 발광층의 도펀트로 상기 화합물 1 대신 하기 표 8에 기재된 화합물을 사용하고, 호스트 물질로 BH-A 대신 하기로 하기 표 8에 기재된 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법을 이용하여 실시예 55 내지 57 및 비교예 5의 유기 발광 소자를 각각 제작하였다.In Example 1, the same method as in Example 1, except that the compound shown in Table 8 was used instead of Compound 1 as the dopant of the light emitting layer, and the compound shown in Table 8 below was used instead of BH-A as the host material. The organic light emitting devices of Examples 55 to 57 and Comparative Example 5 were manufactured using the .
발광층의 제 1 도펀트와 제 2 도펀트의 중량비는 50 : 50 이다.A weight ratio of the first dopant and the second dopant in the emission layer is 50:50.
Figure PCTKR2020017069-appb-I000298
Figure PCTKR2020017069-appb-I000298
상기 실시예 55 내지 57 및 비교예 5의 유기 발광 소자에 10 mA/cm2의 전류 밀도를 인가할 때의 전압, 효율 및 20 mA/cm2의 전류 밀도를 인가할 때의 수명(T95)을 측정하고, 그 결과를 하기 표 8에 나타내었다. 이 때, T95는 전류 밀도 20 mA/cm2에서의 초기 휘도를 100%로 하였을 때 휘도가 95%로 감소되는데 소요되는 시간을 의미하며 상기 표 6의 비교예 1을 기준(100%)으로 비율로 나타내었다.Voltage when applying a current density of 10 mA/cm 2 to the organic light emitting devices of Examples 55 to 57 and Comparative Example 5, efficiency, and lifetime (T95) when applying a current density of 20 mA/cm 2 measured, and the results are shown in Table 8 below. At this time, T95 denotes the time it takes for the luminance to decrease to 95% when the initial luminance at a current density of 20 mA/cm 2 is 100%, and the ratio is based on Comparative Example 1 in Table 6 (100%). indicated as
호스트host 제1 도펀트first dopant 제2 도펀트 second dopant 10 mA/cm2 10 mA/cm 2 20mA/cm2 20mA/cm 2
전압(V)Voltage (V) 양자효율(QE)Quantum Efficiency (QE) LT95LT95
실시예 55Example 55 BH-ABH-A 화합물 17compound 17 BD-ABD-A 3.87 3.87 8.47 8.47 121121
실시예 56Example 56 BH-ABH-A 화합물 37compound 37 화합물 50compound 50 3.75 3.75 8.36 8.36 119119
실시예 57Example 57 BH-CBH-C 화합물 14compound 14 화합물 39compound 39 3.81 3.81 8.28 8.28 124124
비교예 5Comparative Example 5 BH-ABH-A BD-ABD-A BD-BBD-B 3.90 3.90 7.087.08 109109
상기 표 6 내지 8에 있어서, 본 명세서의 일 실시상태에 따른 화학식 1, 즉 O 또는 S를 포함하는 5원 고리를 포함하는 비대칭 보론 화합물을 유기 발광 소자에 포함하는 실시예 1 내지 57는 대칭구조의 보론 화합물을 포함하는 비교예 1 내지 5 보다 구동 전압이 낮고, 효율이 우수하며, 색순도가 좋고, 장수명의 효과를 나타냄을 알 수 있었다.In Tables 6 to 8, Chemical Formula 1 according to an exemplary embodiment of the present specification, that is, Examples 1 to 57 including an asymmetric boron compound including a 5-membered ring including O or S in an organic light emitting device is a symmetric structure It was found that the driving voltage was lower than that of Comparative Examples 1 to 5 containing the boron compound, the efficiency was excellent, the color purity was good, and the effect of long life was exhibited.

Claims (20)

  1. 하기 화학식 1로 표시되는 화합물:A compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2020017069-appb-I000299
    Figure PCTKR2020017069-appb-I000299
    상기 화학식 1에 있어서,In Formula 1,
    A1은 치환 또는 비치환되고, O 또는 S를 포함하는 5원 고리를 포함하는 단환 또는 다환의 헤테로고리이고,A1 is a substituted or unsubstituted monocyclic or polycyclic heterocycle including a 5-membered ring including O or S,
    R1 내지 R7, R' 및 R"은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성한다.R1 to R7, R′ and R″ are the same as or different from each other, and each independently represents hydrogen; deuterium; halogen group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted haloalkyl group; substituted or unsubstituted cyclo Alkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted haloalkoxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted hydrocarbon ring group; or a substituted or unsubstituted a heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group.
  2. 청구항 1에 있어서, 상기 A1은 하기 화학식 A1-1 또는 A1-2로 표시되는 구조인 것인 화합물:The compound according to claim 1, wherein A1 is a structure represented by the following formula A1-1 or A1-2:
    [화학식 A1-1][Formula A1-1]
    Figure PCTKR2020017069-appb-I000300
    Figure PCTKR2020017069-appb-I000300
    [화학식 A1-2][Formula A1-2]
    Figure PCTKR2020017069-appb-I000301
    Figure PCTKR2020017069-appb-I000301
    상기 화학식 A1-1 및 A1-2에 있어서,In Formulas A1-1 and A1-2,
    Y1 및 Y3는 서로 같거나 상이하고, 각각 독립적으로 O; 또는 S이며,Y1 and Y3 are the same as or different from each other, and each independently O; or S;
    G1, G2 및 G7 내지 G10은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,G1, G2 and G7 to G10 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted silyl group; A substituted or unsubstituted hydrocarbon ring group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
    Figure PCTKR2020017069-appb-I000302
    는 상기 화학식 1에 결합되는 부위를 의미한다.
    Figure PCTKR2020017069-appb-I000302
    denotes a site bound to Formula 1 above.
  3. 청구항 1에 있어서, 상기 A1은 하기 화학식 A1-3 내지 Al-5 중 어느 하나로 표시되는 구조인 것인 화합물:The compound of claim 1, wherein A1 is a structure represented by any one of the following Chemical Formulas A1-3 to Al-5:
    [화학식 A1-3][Formula A1-3]
    Figure PCTKR2020017069-appb-I000303
    Figure PCTKR2020017069-appb-I000303
    [화학식 A1-4][Formula A1-4]
    Figure PCTKR2020017069-appb-I000304
    Figure PCTKR2020017069-appb-I000304
    [화학식 A1-5][Formula A1-5]
    Figure PCTKR2020017069-appb-I000305
    Figure PCTKR2020017069-appb-I000305
    상기 화학식 A1-3 내지 A1-5에 있어서,In Formulas A1-3 to A1-5,
    Y2, Y4 및 Y5는 서로 같거나 상이하고, 각각 독립적으로 O; 또는 S이며,Y2, Y4 and Y5 are the same as or different from each other, and each independently O; or S;
    G3 내지 G6 및 G11 내지 G28은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,G3 to G6 and G11 to G28 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted silyl group; A substituted or unsubstituted hydrocarbon ring group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
    n11 및 n12는 각각 0 내지 2의 정수이며,n11 and n12 are each an integer of 0 to 2,
    상기 n11 및 n12가 2인 경우, 상기 두 개의 괄호 내의 구조는 서로 같거나 상이하고,When n11 and n12 are 2, the structures in the two parentheses are the same as or different from each other,
    Figure PCTKR2020017069-appb-I000306
    는 상기 화학식 1에 결합되는 부위를 의미한다.
    Figure PCTKR2020017069-appb-I000306
    denotes a site bound to Formula 1 above.
  4. 청구항 1에 있어서, 상기 화학식 1은 하기 화학식 1-1 내지 1-5 중 어느 하나로 표시되는 것인 화합물:The method according to claim 1, wherein Formula 1 is a compound represented by any one of the following Formulas 1-1 to 1-5:
    [화학식 1-1][Formula 1-1]
    Figure PCTKR2020017069-appb-I000307
    Figure PCTKR2020017069-appb-I000307
    [화학식 1-2][Formula 1-2]
    Figure PCTKR2020017069-appb-I000308
    Figure PCTKR2020017069-appb-I000308
    [화학식 1-3][Formula 1-3]
    Figure PCTKR2020017069-appb-I000309
    Figure PCTKR2020017069-appb-I000309
    [화학식 1-4][Formula 1-4]
    Figure PCTKR2020017069-appb-I000310
    Figure PCTKR2020017069-appb-I000310
    [화학식 1-5][Formula 1-5]
    Figure PCTKR2020017069-appb-I000311
    Figure PCTKR2020017069-appb-I000311
    상기 화학식 1-1 내지 1-5에 있어서,In Formulas 1-1 to 1-5,
    R', R" 및 R1 내지 R7의 정의는 상기 화학식 1에서 정의한 바와 동일하고,The definitions of R', R" and R1 to R7 are the same as those defined in Formula 1 above,
    Y1 내지 Y5는 서로 같거나 상이하고, 각각 독립적으로 O; 또는 S이며,Y1 to Y5 are the same as or different from each other, and each independently O; or S;
    G1 내지 G28은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,G1 to G28 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted haloalkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylalkyl group; a substituted or unsubstituted silyl group; A substituted or unsubstituted hydrocarbon ring group; Or a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
    n11 및 n12는 각각 0 내지 2의 정수이며,n11 and n12 are each an integer of 0 to 2,
    상기 n11 및 n12가 2인 경우, 상기 두 개의 괄호 내의 구조는 서로 같거나 상이하다.When n11 and n12 are 2, structures within the two parentheses are the same as or different from each other.
  5. 청구항 1에 있어서, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여, 하기 화학식 B1-1 또는 B1-2로 표시되는 고리를 형성하는 것인 화합물:The compound according to claim 1, wherein adjacent groups of R1 to R4 combine with each other to form a ring represented by the following formula B1-1 or B1-2:
    [화학식 B1-1][Formula B1-1]
    Figure PCTKR2020017069-appb-I000312
    Figure PCTKR2020017069-appb-I000312
    [화학식 B1-2][Formula B1-2]
    Figure PCTKR2020017069-appb-I000313
    Figure PCTKR2020017069-appb-I000313
    상기 화학식 B1-1 및 B1-2에 있어서,In the formulas B1-1 and B1-2,
    Y101 및 Y103는 서로 같거나 상이하고, 각각 독립적으로 O; S; 또는 NR"'이며,Y101 and Y103 are the same as or different from each other, and each independently O; S; or NR"';
    R"', G101, G102 및 G107 내지 G110은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,R"', G101, G102, and G107 to G110 are the same as or different from each other, and each independently represents hydrogen; deuterium; halogen group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted haloalkyl group; substituted or unsubstituted a cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkylthioxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; substituted or unsubstituted boron group; substituted or unsubstituted amine group; substituted or unsubstituted arylalkyl group; substituted or unsubstituted silyl group; substituted or unsubstituted hydrocarbon ring group; or substituted or or an unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
    Figure PCTKR2020017069-appb-I000314
    는 상기 화학식 1에 결합되는 부위를 의미한다.
    Figure PCTKR2020017069-appb-I000314
    denotes a site bound to Formula 1 above.
  6. 청구항 1에 있어서, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여, 하기 화학식 B1-3 내지 Bl-5 중 어느 하나로 표시되는 고리를 형성하는 것인 화합물:The compound according to claim 1, wherein adjacent groups of R1 to R4 combine with each other to form a ring represented by any one of Formulas B1-3 to Bl-5:
    [화학식 B1-3][Formula B1-3]
    Figure PCTKR2020017069-appb-I000315
    Figure PCTKR2020017069-appb-I000315
    [화학식 B1-4][Formula B1-4]
    Figure PCTKR2020017069-appb-I000316
    Figure PCTKR2020017069-appb-I000316
    [화학식 B1-5][Formula B1-5]
    Figure PCTKR2020017069-appb-I000317
    Figure PCTKR2020017069-appb-I000317
    상기 화학식 B1-3 내지 B1-5에 있어서,In the formulas B1-3 to B1-5,
    Y102, Y104 및 Y105는 서로 같거나 상이하고, 각각 독립적으로 O; S; 또는 NR"'이며,Y102, Y104 and Y105 are the same as or different from each other, and each independently O; S; or NR"';
    R"', G103 내지 G106 및 G111 내지 G128은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 할로알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 할로알콕시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 탄화수소고리기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접하는 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하고,R"', G103 to G106 and G111 to G128 are the same as or different from each other, and each independently represents hydrogen; deuterium; halogen group; cyano group; substituted or unsubstituted alkyl group; substituted or unsubstituted haloalkyl group; substituted or unsubstituted a cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted haloalkoxy group; a substituted or unsubstituted alkylthioxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkenyl group; substituted or unsubstituted boron group; substituted or unsubstituted amine group; substituted or unsubstituted arylalkyl group; substituted or unsubstituted silyl group; substituted or unsubstituted hydrocarbon ring group; or substituted or or an unsubstituted heterocyclic group, or a substituted or unsubstituted ring by combining with an adjacent group,
    n111 및 n112는 각각 0 내지 2의 정수이며,n111 and n112 are each an integer from 0 to 2,
    상기 n111 및 n112가 2인 경우, 상기 두 개의 괄호 내의 구조는 서로 같거나 상이하고,When n111 and n112 are 2, the structures in the two parentheses are the same as or different from each other,
    Figure PCTKR2020017069-appb-I000318
    는 상기 화학식 1에 결합되는 부위를 의미한다.
    Figure PCTKR2020017069-appb-I000318
    denotes a site bound to Formula 1 above.
  7. 청구항 1에 있어서, 상기 R1 내지 R7은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 시아노기; 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기; 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알킬기; 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알콕시기; 탄소수 6 내지 30의 아릴알킬기; 탄소수 6 내지 30의 단환 또는 다환의 디아릴아민기; 탄소수 6 내지 30의 단환 또는 다환의 아릴기; 또는 탄소수 2 내지 30의 단화 또는 다환의 헤테로고리기이고, 상기 치환기는 중수소, 할로겐기, 시아노기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기, 탄소수 6 내지 30의 단환 또는 다환의 아릴기 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환되는 것인 화합물.The method according to claim 1, wherein R1 to R7 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a linear or branched alkylsilyl group having 1 to 30 carbon atoms; a linear or branched haloalkyl group having 1 to 30 carbon atoms; a linear or branched haloalkoxy group having 1 to 30 carbon atoms; an arylalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic diarylamine group having 6 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, and the substituents are deuterium, a halogen group, a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, or a straight or branched chain alkylsilyl having 1 to 30 carbon atoms. A compound that is substituted or unsubstituted with one or more selected from the group consisting of a group, a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, and combinations thereof.
  8. 청구항 1에 있어서, 상기 R1 내지 R4 중 인접한 기는 서로 결합하여 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 탄화수소고리; 또는 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리를 형성하는 것인 화합물.The method according to claim 1, wherein adjacent groups of R1 to R4 are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic hydrocarbon ring having 3 to 30 carbon atoms; Or a substituted or unsubstituted compound to form a monocyclic or polycyclic heterocycle having 2 to 30 carbon atoms.
  9. 청구항 1에 있어서, 상기 R' 및 R"는 서로 같거나 상이하고, 각각 독립적으로 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 탄소수 6 내지 30의 아릴알킬기; 탄소수 3 내지 30의 단환 또는 다환의 탄화수소고리기; 또는 탄소수 2 내지 30의 단환 또는 다환의 헤테로고리기이며, 상기 치환기는 중수소, 할로겐기, 시아노기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기, 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬실릴기, 탄소수 3 내지 30의 아릴실릴기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알콕시기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알킬기, 탄소수 1 내지 30의 직쇄 또는 분지쇄의 할로알콕시기, 탄소수 6 내지 30의 아릴옥시기, 탄소수 6 내지 30의 단환 또는 다환의 아릴알킬기, 탄소수 6 내지 30의 단환 또는 다환의 디아릴아민기, 탄소수 6 내지 30의 단환 또는 다환의 아릴기, 및 탄소수 2 내지 30의 단화 또는 다환의 헤테로고리기, 및 이들의 조합으로 이루어진 군으로부터 선택되는 1 이상으로 치환 또는 비치환되는 것인 화합물.The method according to claim 1, wherein R' and R" are the same as or different from each other, and each independently a linear or branched alkyl group having 1 to 30 carbon atoms; an arylalkyl group having 6 to 30 carbon atoms; monocyclic or polycyclic having 3 to 30 carbon atoms. A hydrocarbon ring group, or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, wherein the substituents are deuterium, a halogen group, a cyano group, a linear or branched alkyl group having 1 to 30 carbon atoms, a monocyclic or polycyclic group having 3 to 30 carbon atoms A cyclic cycloalkyl group, a linear or branched alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 3 to 30 carbon atoms, a linear or branched alkoxy group having 1 to 30 carbon atoms, a straight or branched chain having 1 to 30 carbon atoms Haloalkyl group, linear or branched haloalkoxy group having 1 to 30 carbon atoms, aryloxy group having 6 to 30 carbon atoms, monocyclic or polycyclic arylalkyl group having 6 to 30 carbon atoms, monocyclic or polycyclic diarylamine having 6 to 30 carbon atoms A compound that is unsubstituted or substituted with one or more selected from the group consisting of a group, a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, and a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms, and combinations thereof.
  10. 청구항 1에 있어서, 상기 화학식 1은 하기 화합물 중에서 선택되는 어느 하나인 것인 화합물:The compound according to claim 1, wherein Formula 1 is any one selected from the following compounds:
    Figure PCTKR2020017069-appb-I000319
    Figure PCTKR2020017069-appb-I000319
    Figure PCTKR2020017069-appb-I000320
    Figure PCTKR2020017069-appb-I000320
    Figure PCTKR2020017069-appb-I000321
    Figure PCTKR2020017069-appb-I000321
    Figure PCTKR2020017069-appb-I000322
    Figure PCTKR2020017069-appb-I000322
    Figure PCTKR2020017069-appb-I000323
    Figure PCTKR2020017069-appb-I000323
    Figure PCTKR2020017069-appb-I000324
    Figure PCTKR2020017069-appb-I000324
    Figure PCTKR2020017069-appb-I000325
    Figure PCTKR2020017069-appb-I000325
    Figure PCTKR2020017069-appb-I000326
    Figure PCTKR2020017069-appb-I000326
    Figure PCTKR2020017069-appb-I000327
    Figure PCTKR2020017069-appb-I000327
    Figure PCTKR2020017069-appb-I000328
    Figure PCTKR2020017069-appb-I000328
    Figure PCTKR2020017069-appb-I000329
    Figure PCTKR2020017069-appb-I000329
    Figure PCTKR2020017069-appb-I000330
    Figure PCTKR2020017069-appb-I000330
    Figure PCTKR2020017069-appb-I000331
    Figure PCTKR2020017069-appb-I000331
    Figure PCTKR2020017069-appb-I000332
    Figure PCTKR2020017069-appb-I000332
    Figure PCTKR2020017069-appb-I000333
    Figure PCTKR2020017069-appb-I000333
    Figure PCTKR2020017069-appb-I000334
    Figure PCTKR2020017069-appb-I000334
    Figure PCTKR2020017069-appb-I000335
    Figure PCTKR2020017069-appb-I000335
    Figure PCTKR2020017069-appb-I000336
    Figure PCTKR2020017069-appb-I000336
    Figure PCTKR2020017069-appb-I000337
    Figure PCTKR2020017069-appb-I000337
    Figure PCTKR2020017069-appb-I000338
    Figure PCTKR2020017069-appb-I000338
    Figure PCTKR2020017069-appb-I000339
    Figure PCTKR2020017069-appb-I000339
    Figure PCTKR2020017069-appb-I000340
    Figure PCTKR2020017069-appb-I000340
    Figure PCTKR2020017069-appb-I000341
    Figure PCTKR2020017069-appb-I000341
    Figure PCTKR2020017069-appb-I000342
    Figure PCTKR2020017069-appb-I000342
    상기 화합물에 있어서, Ph는 페닐기를 의미한다.In the above compound, Ph means a phenyl group.
  11. 제1 전극; 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 청구항 1 내지 10 중 어느 한 항에 따른 화합물을 포함하는 것인 유기 발광 소자.a first electrode; a second electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one organic material layer comprises the compound according to any one of claims 1 to 10. light emitting element.
  12. 청구항 11에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화합물을 포함하는 것인 유기 발광 소자.The organic light-emitting device of claim 11 , wherein the organic material layer includes an emission layer, and the emission layer includes the compound.
  13. 청구항 11에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 도펀트 물질을 포함하며, 상기 도펀트 물질은 상기 화합물을 포함하는 것인 유기 발광 소자.The organic light emitting device of claim 11 , wherein the organic material layer includes an emission layer, the emission layer includes a dopant material, and the dopant material includes the compound.
  14. 청구항 11에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 하기 화학식 H로 표시되는 화합물을 더 포함하는 것인 유기 발광 소자:The organic light emitting device of claim 11 , wherein the organic material layer includes a light emitting layer, and the light emitting layer further comprises a compound represented by the following Chemical Formula H:
    [화학식 H][Formula H]
    Figure PCTKR2020017069-appb-I000343
    Figure PCTKR2020017069-appb-I000343
    상기 화학식 H에 있어서,In the formula (H),
    L20 및 L21은 서로 같거나 상이하고, 각각 독립적으로 직접결합; 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 헤테로아릴렌기이고,L20 and L21 are the same as or different from each other, and are each independently a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
    Ar20 및 Ar21은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고,Ar20 and Ar21 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
    R20은 수소; 중수소; 할로겐기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.R20 is hydrogen; heavy hydrogen; halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  15. 청구항 14에 있어서, 상기 Ar20은 치환 또는 비치환된 헤테로고리기이고, 상기 Ar21은 치환 또는 비치환된 아릴기인 것인 유기 발광 소자.The organic light-emitting device of claim 14 , wherein Ar20 is a substituted or unsubstituted heterocyclic group, and Ar21 is a substituted or unsubstituted aryl group.
  16. 청구항 11에 있어서, 상기 유기물층은 발광층을 포함하며, 상기 발광층은 호스트 화합물을 더 포함하고, 상기 호스트 화합물은 치환 가능한 위치의 적어도 하나의 수소가 중수소로 치환된 것인 유기 발광 소자.The organic light emitting device of claim 11 , wherein the organic material layer comprises a light emitting layer, the light emitting layer further comprises a host compound, and in the host compound, at least one hydrogen at a substitutable position is substituted with deuterium.
  17. 청구항 11에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 1종 이상의 도펀트 및 호스트를 포함하는 것인 유기 발광 소자.The organic light-emitting device of claim 11 , wherein the organic material layer includes an emission layer, and the emission layer includes one or more dopants and a host.
  18. 청구항 11에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 2종 이상의 혼합 도펀트 및 호스트를 포함하는 것인 유기 발광 소자.The organic light emitting device of claim 11 , wherein the organic material layer includes an emission layer, and the emission layer includes two or more mixed dopants and a host.
  19. 청구항 11에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 1 종 이상의 호스트, 및 도펀트를 포함하는 것인 유기 발광 소자.The organic light emitting device of claim 11 , wherein the organic material layer includes an emission layer, and the emission layer includes at least one host and a dopant.
  20. 청구항 11에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 2종 이상의 혼합 호스트, 및 도펀트를 포함하는 것인 유기 발광 소자.The organic light emitting device of claim 11 , wherein the organic material layer includes an emission layer, and the emission layer includes two or more mixed hosts and a dopant.
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