WO2020080872A1 - Heterocyclic compound and organic light-emitting device comprising same - Google Patents

Heterocyclic compound and organic light-emitting device comprising same Download PDF

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WO2020080872A1
WO2020080872A1 PCT/KR2019/013722 KR2019013722W WO2020080872A1 WO 2020080872 A1 WO2020080872 A1 WO 2020080872A1 KR 2019013722 W KR2019013722 W KR 2019013722W WO 2020080872 A1 WO2020080872 A1 WO 2020080872A1
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group
substituted
unsubstituted
formula
light emitting
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French (fr)
Korean (ko)
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윤정민
김공겸
구기동
오중석
오상민
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주식회사 엘지화학
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Priority to CN201980012175.5A priority Critical patent/CN111699191B/en
Publication of WO2020080872A1 publication Critical patent/WO2020080872A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/658—Organoboranes
    • 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 Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • 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 Table
    • C07F5/02—Boron compounds
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present specification relates to a heterocyclic compound and an organic light emitting device including the same.
  • the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material.
  • An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween.
  • the organic material layer is often composed of a multi-layered structure composed of different materials, 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 heterocyclic compound and an organic light emitting device including the same.
  • the present invention provides a heterocyclic compound represented by Formula 1 below.
  • R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , R 51 to R 55 , And R 61 to R 64 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted Or an unsubstituted silyl group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted amine group, a substituted or unsubstituted boron group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or adjacent Combines with a substituent to form a substituted or unsubstituted ring,
  • the present specification is a first electrode; A second electrode provided opposite to the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the above-described heterocyclic compound. to provide.
  • the heterocyclic compound according to an exemplary embodiment of the present specification may be used as a material of an organic material layer of an organic light emitting device, and by using this, it is possible to improve efficiency, improve low driving voltage and / or lifespan characteristics in the organic light emitting device.
  • the heterocyclic compound of the present specification has a small half width in structure, it can exhibit high efficiency characteristics in a device.
  • FIG. 1 shows an organic light emitting diode according to an exemplary embodiment of the present specification.
  • FIG. 2 shows an organic light emitting diode according to an exemplary embodiment of the present specification.
  • FIG 3 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.
  • the present specification provides a heterocyclic compound represented by Chemical Formula 1 above.
  • the existing spiro structure has a right-angled structure based on the carbon atom in the center, or limits the characteristics of enhancing luminous efficiency by suppressing the interaction between molecules and controlling the wavelength using simple cyclization compounds such as dimethylfluorene. It is possible to improve the efficiency and lifetime of the OLED device by controlling the electrical and luminescence properties using new materials including adamantane.
  • the core including boron and nitrogen has a small half width, and thus exhibits high efficiency characteristics in the device.
  • substitution means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more are substituted , 2 or more substituents may be the same or different from each other.
  • substituted or unsubstituted refers to deuterium; Nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group, substituted with 1 or 2 or more substituents selected from the group, or substituted with 2 or more substituents among the exemplified substituents, or having no substituents.
  • the "substituent in which two or more substituents are connected" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, or the like.
  • the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 30. Specifically, it is preferable to have 1 to 20 carbon atoms. More specifically, it is preferable to have 1 to 10 carbon atoms.
  • Specific examples include methyl groups; Ethyl group; Propyl group; n-propyl group; Isopropyl group; Butyl group; n-butyl group; Isobutyl group; tert-butyl group; sec-butyl group; 1-methylbutyl group; 1-ethyl butyl group; Pentyl group; n-pentyl group; Isopentyl group; Neopentyl group; tert-pentyl group; Hexyl group; n-hexyl group; 1-methylpentyl group; 2-methylpentyl group; 4-methyl-2-pentyl group; 3,3-dimethylbutyl group; 2-ethylbutyl group; Heptyl group; n-heptyl group; 1-methylhexyl group; Cyclopentyl methyl group; Cyclohexylmethyl group; Octyl group; n-octyl group; tert-oct
  • the cycloalkyl group is not particularly limited, but is preferably 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.
  • the alkoxy group may be a straight chain, branched chain or cyclic chain.
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it is preferable to have 1 to 20 carbon atoms. More specifically, it is preferable to have 1 to 10 carbon atoms.
  • the amine group may be represented by the formula of -NRdRe, wherein Rd and Re are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; It may be a substituted or unsubstituted heterocyclic group, but is not limited thereto. Further, the number of carbon atoms of the amine group is not limited, but is preferably 1 to 30.
  • amine groups include methylamine groups; Dimethylamine group; Ethylamine group; Diethylamine group; Phenylamine group; Naphthylamine group; Biphenylamine group; Anthracenylamine group; 9-methyl anthracenylamine group; Diphenylamine group; N-phenyl naphthylamine group; Ditolylamine group; N-phenyltolylamine group; Triphenylamine group; N-phenylbiphenylamine group; N-phenyl naphthylamine group; N-biphenyl naphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenylfluorenylamine group; N-phenyl terphenylamine group; N-phenanthrenylfluorenylamine group; N-biphenyl fluoren
  • the silyl group may be represented by the formula of —SiRaRbRc, wherein Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; It may be a substituted or unsubstituted aryl group.
  • the silyl group is specifically a trimethylsilyl group; Triethylsilyl group; tert-butyldimethylsilyl group; Vinyl dimethyl silyl group; Propyl dimethyl silyl group; Triphenylsilyl group; Diphenylsilyl group; Phenylsilyl group, and the like, but is not limited thereto.
  • the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms.
  • the aryl group may be monocyclic or polycyclic.
  • the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. More specifically, it is preferable that it has 6 to 20 carbon atoms.
  • a phenyl group; Biphenyl group; It may be a terphenyl group, but is not limited thereto.
  • the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited.
  • a polycyclic aryl group is a naphthyl group; Anthracenyl group; Phenanthryl group; Triphenyl group; Pyrenyl group; Phenenyl group; Perylenyl group; Chrysenyl group; It may be a fluorenyl group, and the like, but is not limited thereto.
  • two substituents of carbon number 9 of the fluorenyl group may be bonded to each other to form a spiro structure such as 9,9-dimethylfluorenyl group or 9,9-diphenylfluorenyl group.
  • a spiro structure such as 9,9-dimethylfluorenyl group or 9,9-diphenylfluorenyl group.
  • the “adjacent” group refers to a substituent substituted on an atom directly connected to an atom in which the substituent is substituted, a substituent positioned closest to the substituent and the other substituent substituted on the atom in which the substituent is substituted. You can. For example, two substituents substituted in the ortho position on the benzene ring and two substituents substituted on the same carbon in the aliphatic ring may be interpreted as "adjacent" groups to each other.
  • ring is a hydrocarbon ring; Or a hetero ring.
  • the hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the cycloalkyl group or aryl group, except for the divalent group.
  • heterocyclic groups can be applied to the heterocycle except that it is divalent.
  • examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group.
  • the aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group.
  • the arylamine group containing two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.
  • the aryl group in the arylamine group can be selected from the examples of the aryl group described above.
  • the heterocyclic group includes one or more non-carbon atoms, that is, heteroatoms, and specifically, the heteroatoms include one or more atoms selected from the group consisting of O, N, Se, SO, SO 2 and S, etc. It can contain.
  • the number of carbon atoms is not particularly limited, preferably 2 to 60 carbon atoms, more preferably 2 to 30 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic.
  • heteroaryl group examples include a thiophene group; Furanyl group; Pyrrol group; Imidazolyl group; Thiazolyl group; Oxazolyl group; Oxadiazolyl group; Pyridyl group; Bipyridyl group; Pyrimidyl group; Triazinyl group; Triazolyl group; Acridil group; Pyridazinyl group; Pyrazinyl group; Quinolinyl group; Quinazolinyl group; Quinoxalinyl group; Phthalazinyl group; Pyridopyrimidyl group; Pyrido pyrazinyl group; Pyrazino pyrazinyl group; Isoquinolinyl group; Indole group; Carbazolyl group; Benzoxazolyl group; Benzimidazole group; Benzothiazolyl group; Benzocarbazolyl group; Benzothiophene group; Dibenzothiophene group; Benzofuranyl group; Ph
  • R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , R 51 to R 55 and R 61 to R 64 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Alkoxy group, substituted or unsubstituted silyl group, substituted or unsubstituted phosphine oxide group, substituted or unsubstituted amine group, substituted or unsubstituted boron group, substituted or unsubstituted aryl group, substituted or unsubstituted hetero A ring group, or combine with an adjacent substituent to form a substituted or unsubstituted ring, and R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 ,
  • R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And R 51 to R 55 , a substituent that does not bind to Formula 2; And R 61 to R 64 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cyclo group having 3 to 30 carbon atoms.
  • Alkyl group substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted silyl group having 1 to 60 carbon atoms, substituted or unsubstituted amine group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 60 carbon atoms
  • the 'substituted or unsubstituted' is deuterium, nitrile group, halogen group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, silyl group having 1 to 30 carbon atoms, carbon number 1 It means that one or more selected from the group consisting of an amine group having 30 to 30, an aryl group having 6 to 30 carbon atoms and a heterocyclic group having 2 to 30 carbon atoms is substituted or unsubstituted with a connected substituent.
  • R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And R 51 to R 55 , a substituent that does not bind to Formula 2; And R 61 to R 64 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted Or an unsubstituted butyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted methoxy group , Substituted or unsubsti
  • the 'substituted or unsubstituted' is deuterium, nitrile group, halogen group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted butyl group, substituted or unsubstituted Substituted cyclopropyl group, substituted or unsubstituted cyclobutyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted methoxy group, substituted or unsubstituted ethoxy group, substituted Or an unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamine group, a substituted or unsub
  • Chemical Formula 1 is represented by one of the following Chemical Formulas 1-1 to 1-7.
  • R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43, R 51 to R 55 , and R 61 to R 64 are as defined in Formulas 1 and 2,
  • R 71 to R 74 , R 81 to R 84 , R 91 to R 94 , And Ra to Re are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted A substituted silyl group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or in combination with an adjacent substituent, substituted or unsubstituted Form a ring,
  • a and c are each an integer from 0 to 3
  • b and f are each 0 or 1
  • d and e are each an integer from 0 to 2
  • the R 71 To R 74 , R 81 to R 84 , R 91 to R 94 , And Ra to Re are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted Or an unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted silyl group having 1 to 60 carbon atoms, a substituted or unsubstituted amine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms , Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or by combining with an adjacent substituent, a substituted or
  • the 'substituted or unsubstituted' is deuterium, nitrile group, halogen group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, silyl group having 1 to 30 carbon atoms, carbon number 1 It means that one or more selected from the group consisting of an amine group having 30 to 30, an aryl group having 6 to 30 carbon atoms and a heterocyclic group having 2 to 30 carbon atoms is substituted or unsubstituted with a connected substituent.
  • R 71 To R 74 , R 81 To R 84 , R 91 To R 94 , And Ra to Re are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted Substituted butyl group, substituted or unsubstituted cyclopropyl group, substituted or unsubstituted cyclobutyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted methoxy group, substituted Or an unsubstituted ethoxy group, a substituted or unsubstituted trimethylsilyl group, a substituted or unsub
  • the 'substituted or unsubstituted' is deuterium, nitrile group, halogen group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted butyl group, substituted or unsubstituted Substituted cyclopropyl group, substituted or unsubstituted cyclobutyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted methoxy group, substituted or unsubstituted ethoxy group, substituted Or an unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamine group, a substituted or unsub
  • Chemical Formula 1 is represented by one of the following Chemical Formulas 2-1 to 2-5.
  • R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , and R 51 to R 55 are as defined in Chemical Formulas 1 and 2,
  • X 1 and X 2 are the same as or different from each other, and each independently O, S or NR,
  • R, R 101 to R 111 , and R 201 to R 228 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted Or an unsubstituted alkoxy group, a substituted or unsubstituted silyl group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted amine group, a substituted or unsubstituted boron group, a substituted or unsubstituted aryl group, a substituted or Unsubstituted heterocyclic group,
  • n1 to n9 are each an integer of 0 to 2
  • n10 and n11 are each an integer from 0 to 4,
  • n1 to n11 are each 2 or more, the substituents in parentheses are the same as or different from each other.
  • the R, R 101 to R 111 and R 201 to R 228 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted carbon number 1 To 20 alkyl groups, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted silyl groups having 1 to 60 carbon atoms, substituted or unsubstituted carbon atoms It is an amine group of 1 to 30, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or bonded to each other with adjacent substituents to have 3 or more unsubstituted or substituted carbon atoms.
  • the 'substituted or unsubstituted' is deuterium, nitrile group, halogen group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, silyl group having 1 to 30 carbon atoms, carbon number 1 It means that one or more selected from the group consisting of an amine group having 30 to 30, an aryl group having 6 to 30 carbon atoms and a heterocyclic group having 2 to 30 carbon atoms is substituted or unsubstituted with a connected substituent.
  • R, R 101 to R 111 and R 201 to R 228 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted methyl group , Substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted butyl group, substituted or unsubstituted cyclopropyl group, substituted or unsubstituted cyclobutyl group, substituted or unsubstituted cyclopentyl group , Substituted or unsubstituted cyclohexyl group, substituted or unsubstituted methoxy group, substituted or unsubstituted ethoxy group, substituted or unsubstituted trimethylsilyl group, substituted or unsubstituted triphenylsilyl group, substituted or unsubstituted triphen
  • the 'substituted or unsubstituted' is deuterium, nitrile group, halogen group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted butyl group, substituted or unsubstituted Substituted cyclopropyl group, substituted or unsubstituted cyclobutyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted methoxy group, substituted or unsubstituted ethoxy group, substituted Or an unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamine group, a substituted or unsub
  • Chemical Formula 1 is any one selected from the following compounds.
  • D deuterium Me is a methyl group
  • Ph means a phenyl group.
  • the organic light emitting device of the present invention comprises a first electrode; A second electrode provided opposite to the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer may include the aforementioned heterocyclic compound.
  • the structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 to 3, but is not limited thereto.
  • FIG. 1 a structure of an organic light emitting device in which the first electrode 2, the organic material layer 3, and the second electrode 4 are sequentially stacked on the substrate 1 is illustrated.
  • FIG 1 illustrates an organic light emitting device and is not limited thereto.
  • FIG. 2 illustrates a structure of an organic light emitting device in which a first electrode 2, a light emitting layer 5, and a second electrode 4 are sequentially stacked on a substrate 1.
  • FIG. 2 illustrates an organic light emitting device, and is not limited thereto, and may further include an additional organic material layer between the first electrode 2 and the light emitting layer 5 and the light emitting layer 5 and the second electrode 4. have.
  • FIG. 3 a first electrode 2, a hole injection layer 6, a hole transport layer-1 (7), a hole transport layer-2 (8), a light emitting layer 5, an electron transport layer 9 and a first electrode on the substrate 1 are shown in FIG.
  • the structure of the organic light emitting device in which the two electrodes 4 are sequentially stacked is illustrated.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by Chemical Formula 1 above.
  • the organic light emitting device of the present invention includes a light emitting layer, and the light emitting layer may include a host and a dopant in a mass ratio of 99.9: 0.1 to 90:10.
  • the organic light emitting device of the present invention includes a light emitting layer, and the light emitting layer may include a host and a dopant in a mass ratio of 99.5: 0.5 to 95: 5.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound represented by Chemical Formula 1 as a dopant.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound represented by Chemical Formula 1 as a dopant in the light emitting layer.
  • the organic material layer includes at least one layer of a hole injection layer, a hole transport layer, and a hole injection and transport layer, and at least one layer of the hole injection layer, a hole transport layer, and a hole injection and transport layer is It may include a heterocyclic compound of the formula (1).
  • the organic material layer includes at least one layer of an electron injection layer, an electron transport layer, and an electron injection and transport layer, and at least one layer of the electron injection layer, the electron transport layer, and the electron injection and transport layer is It may include a heterocyclic compound of the formula (1).
  • the organic material layer includes one or more of the electron blocking layer and the hole blocking layer, and the electron blocking layer and / or the hole blocking layer may include the heterocyclic compound of Formula 1 .
  • 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 materials and methods known in the art, except that at least one layer of the organic material layer is formed using the heterocyclic compound.
  • the present specification also provides a method for manufacturing an organic light emitting device formed using the heterocyclic compound.
  • the organic light emitting device uses a metal vapor deposition (PVD) method, such as sputtering or e-beam evaporation, to have a metal or conductive metal oxide on the substrate or alloys thereof To form an anode, and then form an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an organic material layer containing the compound of Formula 1, and then use a material that can be used as a cathode thereon. It can be produced by vapor deposition.
  • an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
  • the positive electrode material is usually a material having a large work function to facilitate hole injection into the organic material layer.
  • Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO 2 : Combination of metal and oxide such as Sb; 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 cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof;
  • There is a multilayer structure material such as LiF / Al or LiO 2 / Al, but is not limited thereto.
  • a hole injection material can be well injected from the anode at a low voltage, and it is preferable that the hole injection material has a high occupied molecular orbital (HOMO) between the work function of the cathode material and the HOMO of the surrounding organic material layer.
  • HOMO occupied molecular orbital
  • Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances.
  • a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is suitable as a material having high mobility for holes.
  • Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.
  • a material capable of emitting light in the visible light region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively is preferably a material having good quantum efficiency for fluorescence or phosphorescence.
  • Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly (p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.
  • the dopant material examples include an aromatic compound, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex.
  • the aromatic compound is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a styrylamine compound.
  • a compound in which at least one arylvinyl group is substituted with an arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted.
  • aryl group a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group
  • styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like but are not limited thereto.
  • examples of the metal complex include an iridium complex and a platinum complex, but are not limited thereto.
  • the electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer.
  • the electron transport material a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. Do. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these.
  • the electron transport layer can be used with any desired cathode material as used according to the prior art.
  • suitable cathode materials are those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, each case followed by an aluminum layer or a silver layer.
  • the electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred.
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
  • Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.
  • the hole blocking layer is a layer that prevents the cathode from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but are not limited thereto.
  • the organic light emitting device may be a front emission type, a back emission type, or a double-sided emission type, depending on the material used.
  • a glass substrate coated with a thin film of indium tin oxide (ITO) at a thickness of 1300 ⁇ was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves.
  • ITO indium tin oxide
  • Fischer Co. was used as a detergent
  • distilled water filtered secondarily by a filter of Millipore Co. was used as distilled water.
  • ultrasonic cleaning was repeated twice for 10 minutes with distilled water.
  • ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and transporting to a plasma cleaner.
  • the substrate was transferred to a vacuum evaporator.
  • the following compound HAT was thermally vacuum-deposited to a thickness of 50 Pa to form a hole injection layer. Thereafter, the following compound HT-A 1000A was vacuum-deposited as a first hole transport layer, and subsequently the following compound HT-B 100 ⁇ was deposited as a second hole transport layer.
  • the host BH-A and the dopant Compound 1 were vacuum deposited at a weight ratio of 95: 5 to form a 200 mm thick light emitting layer.
  • the deposition rate of the organic material in the above process, 0.4 to 1.0 was maintained ⁇ / sec, the lithium fluoride of the cathode was maintained at the deposition speed of 0.3 ⁇ / sec of aluminum is 2 ⁇ / sec, the deposition upon the degree of vacuum is 1 ⁇ 10 - By maintaining 7 to 5 ⁇ 10 -8 torr, an organic light emitting device was manufactured.
  • An organic light-emitting device was manufactured in the same manner as in Example 1, except that the host and dopant compounds described in Table 1 below were used as the light-emitting layer material in Example 1.
  • An organic light-emitting device was manufactured in the same manner as in Example 1, except that the host and dopant compounds described in Table 1 below were used as the light-emitting layer material in Example 1.
  • An organic light-emitting device was manufactured in the same manner as in Example 1, except that the host and dopant compounds described in Table 1 below were used as the light-emitting layer material in Example 1. Specifically, the host used the first host and the second host in a 1: 1 weight ratio instead of the BH-A of Example 1.

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Abstract

The present specification provides an organic light-emitting device comprising a first electrode, a second electrode provided facing the first electrode, one or at least two organic layers provided between the first electrode and the second electrode, wherein at least one of the organic layers comprises a heterocyclic compound represented by chemical formula 1.

Description

헤테로고리 화합물 및 이를 포함하는 유기 발광 소자Heterocyclic compound and organic light emitting device including same
본 명세서는 2018년 10월 18일 한국 특허청에 제출된 한국 특허 출원 제10-2018-0124532호의 출원일 이익을 주장하며, 그 내용 전부는 본 명세서에 포함된다.This specification claims the filing date benefit of Korean Patent Application No. 10-2018-0124532 filed with the Korean Intellectual Property Office on October 18, 2018, all of which is included in this specification.
본 명세서는 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다.The present specification relates to a heterocyclic 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 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어질 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, 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 at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it will shine.
상기와 같은 유기 발광 소자를 위한 새로운 재료의 개발이 계속 요구되고 있다.The development of new materials for such organic light-emitting devices continues to be required.
미국 특허 출원 공개 제2004-0251816호US Patent Application Publication No. 2004-0251816
본 명세서는 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자를 제공한다.The present specification provides a heterocyclic compound and an organic light emitting device including the same.
본 발명은 하기 화학식 1로 표시되는 헤테로고리 화합물을 제공한다.The present invention provides a heterocyclic compound represented by Formula 1 below.
[화학식 1][Formula 1]
Figure PCTKR2019013722-appb-I000001
Figure PCTKR2019013722-appb-I000001
[화학식 2][Formula 2]
Figure PCTKR2019013722-appb-I000002
Figure PCTKR2019013722-appb-I000002
상기 화학식 1 및 화학식 2에 있어서,In Formula 1 and Formula 2,
R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, R51 내지 R55, 및 R61 내지 R64는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기, 치환 또는 비치환된 알콕시기, 치환 또는 비치환된 실릴기, 치환 또는 비치환된 포스핀옥사이드기, 치환 또는 비치환된 아민기, 치환 또는 비치환된 붕소기, 치환 또는 비치환의 아릴기, 치환 또는 비치환의 헤테로고리기이거나, 인접한 치환기와 결합하여 치환 또는 비치환된 고리를 형성하고,R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , R 51 to R 55 , And R 61 to R 64 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted Or an unsubstituted silyl group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted amine group, a substituted or unsubstituted boron group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or adjacent Combines with a substituent to form a substituted or unsubstituted ring,
상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 2개의 치환기 그룹; 및 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 치환기가 결합하여 형성된 치환 또는 비치환된 고리의 인접한 2개의 치환기 그룹 중 1 이상의 그룹이 상기 화학식 2의 점선과 결합된다.R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And two adjacent substituent groups among R 51 to R 55 ; And R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And one or more groups of two adjacent substituent groups of a substituted or unsubstituted ring formed by combining adjacent substituents among R 51 to R 55 are bonded to the dotted line of Formula 2.
또한, 본 명세서는 제1 전극; 상기 제1 전극에 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 또는 2층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 전술한 헤테로고리 화합물을 포함하는 것인 유기 발광 소자를 제공한다.In addition, the present specification is a first electrode; A second electrode provided opposite to the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the above-described heterocyclic compound. to provide.
본 명세서의 일 실시상태에 따른 헤테로고리 화합물은 유기 발광 소자의 유기물층의 재료로서 사용될 수 있고, 이를 사용함으로써 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성의 향상이 가능하다. The heterocyclic compound according to an exemplary embodiment of the present specification may be used as a material of an organic material layer of an organic light emitting device, and by using this, it is possible to improve efficiency, improve low driving voltage and / or lifespan characteristics in the organic light emitting device.
본 명세서의 헤테로고리 화합물은 구조상 작은 반치폭을 가짐으로써, 소자에서 높은 효율 특성을 나타낼 수 있다.Since the heterocyclic compound of the present specification has a small half width in structure, it can exhibit high efficiency characteristics in a device.
도 1은 본 명세서의 일 실시상태에 따르는 유기 발광 소자를 도시한 것이다.1 shows an organic light emitting diode according to an exemplary embodiment of the present specification.
도 2는 본 명세서의 일 실시상태에 따르는 유기 발광 소자를 도시한 것이다.2 shows an organic light emitting diode according to an exemplary embodiment of the present specification.
도 3은 본 명세서의 일 실시상태에 따르는 유기 발광 소자를 도시한 것이다.3 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.
1: 기판1: Substrate
2: 제1 전극2: first electrode
3: 유기물층3: organic layer
4: 제2 전극4: Second electrode
5: 발광층5: light emitting layer
6: 정공주입층6: hole injection layer
7: 정공수송층-17: hole transport layer-1
8: 정공수송층-28: hole transport layer-2
9: 전자수송층9: electron transport layer
이하, 본 명세서에 대하여 더욱 상세하게 설명한다.Hereinafter, the present specification will be described in more detail.
본 명세서는 상기 화학식 1로 표시되는 헤테로고리 화합물을 제공한다.The present specification provides a heterocyclic compound represented by Chemical Formula 1 above.
기존의 스피로 구조는 중앙에 있는 탄소 원자를 기준으로 직각의 구조를 이루고 있거나, 디메틸플루오렌과 같이 단순한 고리화 화합물을 활용한 파장 조절과 분자간의 상호작용을 억제하여 발광 효율을 높이는 특성의 한계를 아다만탄(adamantane)을 포함한 신물질을 이용하여 전기적 특성과 발광특성을 제어하여 OLED 소자의 효율과 수명을 개선할 수 있다. The existing spiro structure has a right-angled structure based on the carbon atom in the center, or limits the characteristics of enhancing luminous efficiency by suppressing the interaction between molecules and controlling the wavelength using simple cyclization compounds such as dimethylfluorene. It is possible to improve the efficiency and lifetime of the OLED device by controlling the electrical and luminescence properties using new materials including adamantane.
또한, 붕소와 질소를 포함한 코어의 경우, 작은 반치폭을 가지므로써, 소자에서 높은 효율 특성을 나타낸다. In addition, the core including boron and nitrogen has a small half width, and thus exhibits high efficiency characteristics in the device.
본 명세서에 있어서 치환기의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다.Examples of substituents in the present specification are described below, but are not limited thereto.
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 동일하거나 상이할 수 있다.The term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more are substituted , 2 or more substituents may be the same or different from each other.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 니트릴기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴기; 및 치환 또는 비치환된 헤테로고리기로 이루어진 군에서 선택된 1 또는 2 이상의 치환기로 치환되었거나 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환기로 치환되거나, 또는 어떠한 치환기도 갖지 않는 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 아릴기로 치환된 아릴기, 헤테로아릴기로 치환된 아릴기, 아릴기로 치환된 헤테로고리기, 알킬기로 치환된 아릴기 등일 수 있다. The term "substituted or unsubstituted" as used herein refers to deuterium; Nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group, substituted with 1 or 2 or more substituents selected from the group, or substituted with 2 or more substituents among the exemplified substituents, or having no substituents. For example, the "substituent in which two or more substituents are connected" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, or the like.
본 명세서에 있어서, 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 30인 것이 바람직하다. 구체적으로 탄소수 1 내지 20인 것이 바람직하다. 더 구체적으로는 탄소수 1 내지 10인 것이 바람직하다. 구체적인 예로는 메틸기; 에틸기; 프로필기; n-프로필기; 이소프로필기; 부틸기; n-부틸기; 이소부틸기; tert-부틸기; sec-부틸기; 1-메틸부틸기; 1-에틸부틸기; 펜틸기; n-펜틸기; 이소펜틸기; 네오펜틸기; tert-펜틸기; 헥실기; n-헥실기; 1-메틸펜틸기; 2-메틸펜틸기; 4-메틸-2-펜틸기; 3,3-디메틸부틸기; 2-에틸부틸기; 헵틸기; n-헵틸기; 1-메틸헥실기; 시클로펜틸메틸기; 시클로헥실메틸기; 옥틸기; n-옥틸기; tert-옥틸기; 1-메틸헵틸기; 2-에틸헥실기; 2-프로필펜틸기; n-노닐기; 2,2-디메틸헵틸기; 1-에틸프로필기; 1,1-디메틸프로필기; 이소헥실기; 2-메틸펜틸기; 4-메틸헥실기; 5-메틸헥실기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 30. Specifically, it is preferable to have 1 to 20 carbon atoms. More specifically, it is preferable to have 1 to 10 carbon atoms. Specific examples include methyl groups; Ethyl group; Propyl group; n-propyl group; Isopropyl group; Butyl group; n-butyl group; Isobutyl group; tert-butyl group; sec-butyl group; 1-methylbutyl group; 1-ethyl butyl group; Pentyl group; n-pentyl group; Isopentyl group; Neopentyl group; tert-pentyl group; Hexyl group; n-hexyl group; 1-methylpentyl group; 2-methylpentyl group; 4-methyl-2-pentyl group; 3,3-dimethylbutyl group; 2-ethylbutyl group; Heptyl group; n-heptyl group; 1-methylhexyl group; Cyclopentyl methyl group; Cyclohexylmethyl group; Octyl group; n-octyl group; tert-octyl group; 1-methylheptyl group; 2-ethylhexyl group; 2-propylpentyl group; n-nonyl group; 2,2-dimethylheptyl group; 1-ethylpropyl group; 1,1-dimethylpropyl group; Isohexyl group; 2-methylpentyl group; 4-methylhexyl group; 5-methylhexyl group, and the like, but is not limited thereto.
본 명세서에 있어서, 시클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 30인 것이 바람직하며, 탄소수 3 내지 20인 것이 더 바람직하다. 구체적으로 시클로프로필기; 시클로부틸기; 시클로펜틸기; 3-메틸시클로펜틸기; 2,3-디메틸시클로펜틸기; 시클로헥실기; 3-메틸시클로헥실기; 4-메틸시클로헥실기; 2,3-디메틸시클로헥실기; 3,4,5-트리메틸시클로헥실기; 4-tert-부틸시클로헥실기; 시클로헵틸기; 시클로옥틸기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the cycloalkyl group is not particularly limited, but is preferably 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms. Specifically, a cyclopropyl group; Cyclobutyl group; Cyclopentyl group; 3-methylcyclopentyl group; 2,3-dimethylcyclopentyl group; Cyclohexyl group; 3-methylcyclohexyl group; 4-methylcyclohexyl group; 2,3-dimethylcyclohexyl group; 3,4,5-trimethylcyclohexyl group; 4-tert-butylcyclohexyl group; Cycloheptyl group; Cyclooctyl group, and the like, but is not limited thereto.
본 명세서에 있어서, 알콕시기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 알콕시기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 30인 것이 바람직하다. 구체적으로 탄소수 1 내지 20인 것이 바람직하다. 더 구체적으로 탄소수 1 내지 10인 것이 바람직하다. 구체적으로, 메톡시기; 에톡시기; n-프로폭시기; i-프로필옥시기; n-부톡시기; 이소부톡시기; tert-부톡시기; sec-부톡시기; n-펜틸옥시기; 네오펜틸옥시기; 이소펜틸옥시기; n-헥실옥시기; 3,3-디메틸부틸옥시기; 2-에틸부틸옥시기; n-옥틸옥시기; n-노닐옥시기; n-데실옥시기; 벤질옥시기; p-메틸벤질옥시기 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. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it is preferable to have 1 to 20 carbon atoms. More specifically, it is preferable to have 1 to 10 carbon atoms. Specifically, a methoxy group; Ethoxy group; n-propoxy group; i-propyloxy group; n-butoxy group; Isobutoxy group; tert-butoxy group; sec-butoxy group; n-pentyloxy group; Neopentyloxy group; Isopentyloxy group; n-hexyloxy group; 3,3-dimethylbutyloxy group; 2-ethylbutyloxy group; n-octyloxy group; n-nonyloxy group; n-decyloxy group; Benzyloxy group; p-methylbenzyloxy group, and the like, but is not limited thereto.
본 명세서에 있어서, 아민기는 -NRdRe의 화학식으로 표시될 수 있으며, 상기 Rd 및 Re는 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 헤테로고리기 등일 수 있으나, 이에 한정되는 것은 아니다. 또한, 상기 아민기의 탄소수는 한정되지 않으나, 1 내지 30인 것이 바람직하다. 아민기의 구체적인 예로는 메틸아민기; 디메틸아민기; 에틸아민기; 디에틸아민기; 페닐아민기; 나프틸아민기; 바이페닐아민기; 안트라세닐아민기; 9-메틸안트라세닐아민기; 디페닐아민기; N-페닐나프틸아민기; 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 may be represented by the formula of -NRdRe, wherein Rd and Re are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; It may be a substituted or unsubstituted heterocyclic group, but is not limited thereto. Further, the number of carbon atoms of the amine group is not limited, but is preferably 1 to 30. Specific examples of amine groups include methylamine groups; Dimethylamine group; Ethylamine group; Diethylamine group; Phenylamine group; Naphthylamine group; Biphenylamine group; Anthracenylamine group; 9-methyl anthracenylamine group; Diphenylamine group; N-phenyl naphthylamine group; Ditolylamine group; N-phenyltolylamine group; Triphenylamine group; N-phenylbiphenylamine group; N-phenyl naphthylamine group; N-biphenyl naphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenylfluorenylamine group; N-phenyl terphenylamine group; N-phenanthrenylfluorenylamine group; N-biphenyl fluorenylamine group and the like, but is not limited thereto.
본 명세서에 있어서, 실릴기는 ―SiRaRbRc의 화학식으로 표시될 수 있고, 상기 Ra, Rb 및 Rc는 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 아릴기 등일 수 있다. 상기 실릴기는 구체적으로 트리메틸실릴기; 트리에틸실릴기; tert-부틸디메틸실릴기; 비닐디메틸실릴기; 프로필디메틸실릴기; 트리페닐실릴기; 디페닐실릴기; 페닐실릴기 등이 있으나, 이에 한정되는 것은 아니다. In the present specification, the silyl group may be represented by the formula of —SiRaRbRc, wherein Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; It may be a substituted or unsubstituted aryl group. The silyl group is specifically a trimethylsilyl group; Triethylsilyl group; tert-butyldimethylsilyl group; Vinyl dimethyl silyl group; Propyl dimethyl silyl group; Triphenylsilyl group; Diphenylsilyl group; Phenylsilyl group, and the like, but is not limited thereto.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나, 탄소수 6 내지 60인 것이 바람직하며, 탄소수 6 내지 30인 것이 더 바람직하다. 상기 아릴기는 단환식 또는 다환식일 수 있다. 상기 아릴기가 단환식 아릴기인 경우 탄소수는 특별히 한정되지 않으나, 탄소수 6 내지 30인 것이 바람직하다. 더 구체적으로는 탄소수 6 내지 20인 것이 바람직하다. 구체적으로 단환식 아릴기로는 페닐기; 바이페닐기; 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 아릴기가 다환식 아릴기인 경우 탄소수는 특별히 한정되지 않으나. 탄소수 10 내지 30인 것이 바람직하고 더 구체적으로 탄소수 10 내지 20인 것이 바람직하다. 구체적으로 다환식 아릴기로는 나프틸기; 안트라세닐기; 페난트릴기; 트리페닐기; 파이레닐기; 페날레닐기; 페릴레닐기; 크라이세닐기; 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms. The aryl group may be monocyclic or polycyclic. When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. More specifically, it is preferable that it has 6 to 20 carbon atoms. Specifically, as the monocyclic aryl group, a phenyl group; Biphenyl group; It may be a terphenyl group, but is not limited thereto. When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferably 10 to 30 carbon atoms, and more preferably 10 to 20 carbon atoms. Specifically, a polycyclic aryl group is a naphthyl group; Anthracenyl group; Phenanthryl group; Triphenyl group; Pyrenyl group; Phenenyl group; Perylenyl group; Chrysenyl group; It may be a fluorenyl group, and the like, but is not limited thereto.
상기 플루오레닐기는 치환되는 경우, 플루오레닐기의 9번 탄소원자의 2개의 치환기가 서로 결합하여 9,9-디메틸플루오레닐기, 9,9-디페닐플루오레닐기 등의 스피로 구조를 형성할 수 있으나, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted, two substituents of carbon number 9 of the fluorenyl group may be bonded to each other to form a spiro structure such as 9,9-dimethylfluorenyl group or 9,9-diphenylfluorenyl group. However, it 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.In the present specification, the “adjacent” group refers to a substituent substituted on an atom directly connected to an atom in which the substituent is substituted, a substituent positioned closest to the substituent and the other substituent substituted on the atom in which the substituent is substituted. You can. For example, two substituents substituted in the ortho position on the benzene ring and two substituents substituted on the same carbon in the aliphatic ring may be interpreted as "adjacent" groups to each other.
본 명세서에 있어서, 서로 결합하여 형성되는 치환 또는 비치환된 고리에서, "고리"는 탄화수소 고리; 또는 헤테로 고리를 의미한다.In the present specification, in the substituted or unsubstituted ring formed by bonding to each other, "ring" is a hydrocarbon ring; Or a hetero ring.
상기 탄화수소 고리는 방향족, 지방족 또는 방향족과 지방족의 축합고리일 수 있으며, 상기 2가기인 것을 제외하고 상기 시클로알킬기 또는 아릴기의 예시 중에서 선택될 수 있다.The hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the cycloalkyl group or aryl group, except for the divalent group.
본 명세서에 있어서, 방향족 탄화수소고리는 2가인 것을 제외하고는 상기 아릴기에 관한 설명이 적용될 수 있다.In this specification, the description of the aryl group can be applied, except that the aromatic hydrocarbon ring is divalent.
상기 헤테로고리는 2가인 것을 제외하고는 하기 헤테로고리기에 대한 설명이 적용될 수 있다.The description of the following heterocyclic groups can be applied to the heterocycle except that it is divalent.
본 명세서에 있어서, 아릴아민기의 예로는 치환 또는 비치환된 모노아릴아민기, 치환 또는 비치환된 디아릴아민기, 또는 치환 또는 비치환된 트리아릴아민기가 있다. 상기 아릴아민기 중의 아릴기는 단환식 아릴기일 수 있고, 다환식 아릴기일 수 있다. 상기 아릴기가 2 이상을 포함하는 아릴아민기는 단환식 아릴기, 다환식 아릴기, 또는 단환식 아릴기와 다환식 아릴기를 동시에 포함할 수 있다. 예컨대, 상기 아릴아민기 중의 아릴기는 전술한 아릴기의 예시 중에서 선택될 수 있다.In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group can be selected from the examples of the aryl group described above.
본 명세서에 있어서, 헤테로고리기는 탄소가 아닌 원자, 즉 이종원자를 1 이상 포함하는 것으로서, 구체적으로 상기 이종원자는 O, N, Se, SO, SO2 및 S 등으로 이루어진 군에서 선택되는 원자를 1 이상 포함할 수 있다. 탄소수는 특별히 한정되지 않으나, 탄소수 2 내지 60인 것이 바람직하며, 탄소수 2 내지 30인 것이 더 바람직하고, 상기 헤테로고리기는 단환식 또는 다환식일 수 있다. 상기 헤테로아릴기의 예로는 티오펜기; 퓨라닐기; 피롤기; 이미다졸릴기; 티아졸릴기; 옥사졸릴기; 옥사디아졸릴기; 피리딜기; 바이피리딜기; 피리미딜기; 트리아지닐기; 트리아졸릴기; 아크리딜기; 피리다지닐기; 피라지닐기; 퀴놀리닐기; 퀴나졸리닐기; 퀴녹살리닐기; 프탈라지닐기; 피리도 피리미딜기; 피리도 피라지닐기; 피라지노 피라지닐기; 이소퀴놀리닐기; 인돌릴기; 카바졸릴기; 벤즈옥사졸릴기; 벤즈이미다졸릴기; 벤조티아졸릴기; 벤조카바졸릴기; 벤조티오펜기; 디벤조티오펜기; 벤조퓨라닐기; 페난쓰롤리닐기(phenanthroline); 이소옥사졸릴기; 티아디아졸릴기; 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the heterocyclic group includes one or more non-carbon atoms, that is, heteroatoms, and specifically, the heteroatoms include one or more atoms selected from the group consisting of O, N, Se, SO, SO 2 and S, etc. It can contain. The number of carbon atoms is not particularly limited, preferably 2 to 60 carbon atoms, more preferably 2 to 30 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic. Examples of the heteroaryl group include a thiophene group; Furanyl group; Pyrrol group; Imidazolyl group; Thiazolyl group; Oxazolyl group; Oxadiazolyl group; Pyridyl group; Bipyridyl group; Pyrimidyl group; Triazinyl group; Triazolyl group; Acridil group; Pyridazinyl group; Pyrazinyl group; Quinolinyl group; Quinazolinyl group; Quinoxalinyl group; Phthalazinyl group; Pyridopyrimidyl group; Pyrido pyrazinyl group; Pyrazino pyrazinyl group; Isoquinolinyl group; Indole group; Carbazolyl group; Benzoxazolyl group; Benzimidazole group; Benzothiazolyl group; Benzocarbazolyl group; Benzothiophene group; Dibenzothiophene group; Benzofuranyl group; Phenanthroline group (phenanthroline); Isooxazolyl group; Thiadiazolyl group; Phenothiazinyl group and dibenzofuranyl group, and the like, but is not limited thereto.
본 명세서의 일 실시상태에 따르면, 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, R51 내지 R55 및 R61 내지 R64는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기, 치환 또는 비치환된 알콕시기, 치환 또는 비치환된 실릴기, 치환 또는 비치환된 포스핀옥사이드기, 치환 또는 비치환된 아민기, 치환 또는 비치환된 붕소기, 치환 또는 비치환의 아릴기, 치환 또는 비치환의 헤테로고리기이거나, 인접한 치환기와 결합하여 치환 또는 비치환된 고리를 형성하고, 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 2개의 치환기 그룹; 및 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 치환기가 결합하여 형성된 치환 또는 비치환된 고리의 인접한 2개의 치환기 그룹 중 1 이상의 그룹이 상기 화학식 2의 점선과 결합된다. According to one embodiment of the present specification, R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , R 51 to R 55 and R 61 to R 64 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Alkoxy group, substituted or unsubstituted silyl group, substituted or unsubstituted phosphine oxide group, substituted or unsubstituted amine group, substituted or unsubstituted boron group, substituted or unsubstituted aryl group, substituted or unsubstituted hetero A ring group, or combine with an adjacent substituent to form a substituted or unsubstituted ring, and R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And two adjacent substituent groups among R 51 to R 55 ; And R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And one or more groups of two adjacent substituent groups of a substituted or unsubstituted ring formed by combining adjacent substituents among R 51 to R 55 are bonded to the dotted line of Formula 2.
상기 'R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 2개의 치환기 그룹'이란, 상기 화학식 1에서 오르토(ortho)위치로 치환된 2개의 치환기를 의미한다. 구체적으로, 상기 화학식 1에서 R11과 R12; R12와 R13; R13과 R14; R21과 R22; R22와 R23; R23과 R24; R31과 R32; R32와 R33; R33과 R34; R34와 R35; R41과 R42; R42와 R43; R51과 R52; R52와 R53; R53과 R54; 및 R54와 R55는 각각 인접한 2개의 치환기로 하나의 그룹에 해당한다. 또한, 상기 'R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 치환기가 결합하여 형성된 치환 또는 비치환된 고리의 인접한 2개의 치환기 그룹'이란, 하기와 같이 화학식 1의 R23 및 R24가 서로 결합하여 벤젠고리를 형성한 경우, 하기 R25와 R26; R26과 R27; 및 R27과 R28는 각각 인접한 2개의 치환기로 하나의 그룹에 해당한다.The 'R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And two adjacent groups of substituents among R 51 to R 55 'means two substituents substituted with the ortho position in the formula (1). Specifically, R 11 and R 12 in Formula 1; R 12 and R 13 ; R 13 and R 14 ; R 21 and R 22 ; R 22 and R 23 ; R 23 and R 24 ; R 31 and R 32 ; R 32 and R 33 ; R 33 and R 34 ; R 34 and R 35 ; R 41 and R 42 ; R 42 and R 43 ; R 51 and R 52 ; R 52 and R 53 ; R 53 and R 54 ; And R 54 and R 55 each belong to one group with two adjacent substituents. In addition, the 'R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And a group of two adjacent substituents of a substituted or unsubstituted ring formed by combining adjacent substituents among R 51 to R 55 , when R 23 and R 24 of Formula 1 are combined with each other to form a benzene ring, R 25 and R 26 below ; R 26 and R 27 ; And R 27 and R 28 each belong to one group with two adjacent substituents.
Figure PCTKR2019013722-appb-I000003
Figure PCTKR2019013722-appb-I000003
본 명세서의 일 실시상태에 따르면, 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 2개의 치환기 그룹; 및 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 치환기가 결합하여 형성된 치환 또는 비치환된 고리의 인접한 2개의 치환기 그룹 중 1개 내지 4개의 그룹이 상기 화학식 2의 점선과 결합된다.According to one embodiment of the present specification, R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And two adjacent substituent groups among R 51 to R 55 ; And R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And 1 to 4 groups of 2 adjacent groups of substituted or unsubstituted rings formed by combining adjacent substituents of R 51 to R 55 with the dotted line of Formula 2.
본 명세서의 일 실시상태에 따르면, 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 2개의 치환기 그룹; 및 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 치환기가 결합하여 형성된 치환 또는 비치환된 고리의 인접한 2개의 치환기 그룹 중 1 이상의 그룹이 상기 화학식 2의 점선과 결합되고, 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 화학식 2와 결합하지 않는 치환기; 및 R61 내지 R64는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기, 치환 또는 비치환된 알콕시기, 치환 또는 비치환된 실릴기, 치환 또는 비치환된 포스핀옥사이드기, 치환 또는 비치환된 아민기, 치환 또는 비치환된 붕소기, 치환 또는 비치환의 아릴기, 치환 또는 비치환의 헤테로고리기이거나, 인접한 치환기와 결합하여 치환 또는 비치환된 고리를 형성한다.According to one embodiment of the present specification, R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And two adjacent substituent groups among R 51 to R 55 ; And R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And one or more groups of two adjacent substituent groups of a substituted or unsubstituted ring formed by combining adjacent substituents among R 51 to R 55 are combined with a dotted line of Formula 2, and R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And R 51 to R 55 , a substituent that does not bind to Formula 2; And R 61 to R 64 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted Or an unsubstituted silyl group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted amine group, a substituted or unsubstituted boron group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or adjacent It combines with a substituent to form a substituted or unsubstituted ring.
본 명세서의 일 실시상태에 있어서, 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 화학식 2와 결합하지 않는 치환기; 및 R61 내지 R64는 서로 같거나 상이하고, 각각 독립적으로, 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬기, 치환 또는 비치환된 탄소수 3 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 1 내지 20의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 60의 실릴기, 치환 또는 비치환된 탄소수 1 내지 30의 아민기, 치환 또는 비치환된 탄소수 6 내지 60의 아릴기, 또는 치환 또는 비치환된 탄소수 2 내지 60의 헤테로고리기이거나, 인접한 치환기와 서로 결합하여 치환 또는 비치환된 탄소수 3 내지 60의 탄화수소고리, 또는 치환 또는 비치환된 탄소수 2 내지 60의 헤테로고리를 형성한다. 상기 '치환 또는 비치환된'은 중수소, 니트릴기, 할로겐기, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 30의 시클로알킬기, 탄소수 1 내지 20의 알콕시기, 탄소수 1 내지 30의 실릴기, 탄소수 1 내지 30의 아민기, 탄소수 6 내지 30의 아릴기 및 탄소수 2 내지 30의 헤테로고리기로 이루어진 군으로부터 선택된 1 이상이 연결된 치환기로 치환 또는 비치환됨을 의미한다. In one embodiment of the present specification, R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And R 51 to R 55 , a substituent that does not bind to Formula 2; And R 61 to R 64 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cyclo group having 3 to 30 carbon atoms. Alkyl group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted silyl group having 1 to 60 carbon atoms, substituted or unsubstituted amine group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 60 carbon atoms An aryl group, or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or a substituted or unsubstituted hydrocarbon ring having 3 to 60 carbon atoms, or a substituted or unsubstituted carbon atom having 2 to 60 carbon atoms in combination with an adjacent substituent group To form a heterocycle. The 'substituted or unsubstituted' is deuterium, nitrile group, halogen group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, silyl group having 1 to 30 carbon atoms, carbon number 1 It means that one or more selected from the group consisting of an amine group having 30 to 30, an aryl group having 6 to 30 carbon atoms and a heterocyclic group having 2 to 30 carbon atoms is substituted or unsubstituted with a connected substituent.
본 명세서의 일 실시상태에 있어서, 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 화학식 2와 결합하지 않는 치환기; 및 R61 내지 R64는 서로 같거나 상이하고, 각각 독립적으로, 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 메틸기, 치환 또는 비치환된 에틸기, 치환 또는 비치환된 프로필기, 치환 또는 비치환된 부틸기, 치환 또는 비치환된 시클로프로필기, 치환 또는 비치환된 시클로부틸기, 치환 또는 비치환된 시클로펜틸기, 치환 또는 비치환된 시클로헥실기, 치환 또는 비치환된 메톡시기, 치환 또는 비치환된 에톡시기, 치환 또는 비치환된 트리메틸실릴기, 치환 또는 비치환된 트리페닐실릴기, 치환 또는 비치환된 디페닐아민기, 치환 또는 비치환된 디벤조퓨란페닐아민기, 치환 또는 비치환된 페닐기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 카바졸기, 치환 또는 비치환된 디벤조퓨란기, 치환 또는 비치환된 디벤조티오펜기 또는 치환 또는 비치환된 피리딜기이거나, 인접한 치환기와 서로 결합하여 치환 또는 비치환된 탄소수 3 내지 30의 방향족 또는 지방족 탄화수소고리, 또는 치환 또는 비치환된 탄소수 2 내지 30의 이종원소로 N, O 및 S 중 1 이상을 포함하는 헤테로고리를 형성한다. 상기 '치환 또는 비치환된'은 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 메틸기, 치환 또는 비치환된 에틸기, 치환 또는 비치환된 프로필기, 치환 또는 비치환된 부틸기, 치환 또는 비치환된 시클로프로필기, 치환 또는 비치환된 시클로부틸기, 치환 또는 비치환된 시클로펜틸기, 치환 또는 비치환된 시클로헥실기, 치환 또는 비치환된 메톡시기, 치환 또는 비치환된 에톡시기, 치환 또는 비치환된 트리메틸실릴기, 치환 또는 비치환된 트리페닐실릴기, 치환 또는 비치환된 디페닐아민기, 치환 또는 비치환된 디벤조퓨란페닐아민기, 치환 또는 비치환된 페닐기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 카바졸기, 치환 또는 비치환된 디벤조퓨란기, 치환 또는 비치환된 디벤조티오펜기 및 치환 또는 비치환된 피리딜기로 이루어진 군으로부터 선택된 1 이상이 연결된 치환기로 치환 또는 비치환됨을 의미한다.In one embodiment of the present specification, R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And R 51 to R 55 , a substituent that does not bind to Formula 2; And R 61 to R 64 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted Or an unsubstituted butyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted methoxy group , Substituted or unsubstituted ethoxy group, substituted or unsubstituted trimethylsilyl group, substituted or unsubstituted triphenylsilyl group, substituted or unsubstituted diphenylamine group, substituted or unsubstituted dibenzofuranphenylamine group, Substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted carbazole group, substituted or unsubstituted dibene A furan group, a substituted or unsubstituted dibenzothiophene group, a substituted or unsubstituted pyridyl group, or an aromatic or aliphatic hydrocarbon ring having 3 to 30 carbon atoms, which is substituted or unsubstituted by bonding to adjacent substituents, or a substituted or unsubstituted Heterocycle containing 1 or more of N, O, and S as hetero atoms having 2 to 30 carbon atoms. The 'substituted or unsubstituted' is deuterium, nitrile group, halogen group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted butyl group, substituted or unsubstituted Substituted cyclopropyl group, substituted or unsubstituted cyclobutyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted methoxy group, substituted or unsubstituted ethoxy group, substituted Or an unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamine group, a substituted or unsubstituted dibenzofuranphenylamine group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted Substituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted carbazole group, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted dibenzo It means that one or more selected from the group consisting of a thiophene group and a substituted or unsubstituted pyridyl group is substituted or unsubstituted with a linked substituent.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1은 하기 화학식 1-1 내지 1-7 중 하나로 표시된다.In one embodiment of the present specification, Chemical Formula 1 is represented by one of the following Chemical Formulas 1-1 to 1-7.
[화학식 1-1][Formula 1-1]
Figure PCTKR2019013722-appb-I000004
Figure PCTKR2019013722-appb-I000004
[화학식 1-2][Formula 1-2]
Figure PCTKR2019013722-appb-I000005
Figure PCTKR2019013722-appb-I000005
[화학식 1-3][Formula 1-3]
Figure PCTKR2019013722-appb-I000006
Figure PCTKR2019013722-appb-I000006
[화학식 1-4][Formula 1-4]
Figure PCTKR2019013722-appb-I000007
Figure PCTKR2019013722-appb-I000007
[화학식 1-5][Formula 1-5]
Figure PCTKR2019013722-appb-I000008
Figure PCTKR2019013722-appb-I000008
[화학식 1-6][Formula 1-6]
Figure PCTKR2019013722-appb-I000009
Figure PCTKR2019013722-appb-I000009
[화학식 1-7][Formula 1-7]
Figure PCTKR2019013722-appb-I000010
Figure PCTKR2019013722-appb-I000010
상기 화학식 1-1 내지 1-7에 있어서, In Chemical Formulas 1-1 to 1-7,
R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, R51 내지 R55, 및 R61 내지 R64는 화학식 1 및 2에서 정의한 바와 같고,R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43, R 51 to R 55 , and R 61 to R 64 are as defined in Formulas 1 and 2,
R71 내지 R74, R81 내지 R84, R91 내지 R94, 및 Ra 내지 Re는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기, 치환 또는 비치환된 알콕시기, 치환 또는 비치환된 실릴기, 치환 또는 비치환된 포스핀옥사이드기, 치환 또는 비치환된 아민기, 치환 또는 비치환의 아릴기, 또는 치환 또는 비치환의 헤테로고리기이거나, 인접한 치환기와 결합하여 치환 또는 비치환된 고리를 형성하고,R 71 to R 74 , R 81 to R 84 , R 91 to R 94 , And Ra to Re are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted A substituted silyl group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or in combination with an adjacent substituent, substituted or unsubstituted Form a ring,
a 및 c는 각각 0 내지 3의 정수이고,a and c are each an integer from 0 to 3,
b 및 f는 각각 0 또는 1이고,b and f are each 0 or 1,
d 및 e는 각각 0 내지 2의 정수이고, d and e are each an integer from 0 to 2,
a, 및 c 내지 e가 각각 2 이상인 경우, 괄호 안의 치환기는 서로 같거나 상이하다.When a and c to e are each 2 or more, the substituents in parentheses are the same or different from each other.
본 명세서의 일 실시상태에 따르면, 상기 R71 내지 R74, R81 내지 R84, R91 내지 R94, 및 Ra 내지 Re는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬기, 치환 또는 비치환된 탄소수 3 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 1 내지 20의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 60의 실릴기, 치환 또는 비치환된 탄소수 1 내지 30의 아민기, 치환 또는 비치환된 탄소수 6 내지 60의 아릴기, 또는 치환 또는 비치환된 탄소수 2 내지 60의 헤테로고리기이거나, 인접한 치환기와 서로 결합하여 치환 또는 비치환된 탄소수 3 내지 60의 탄화수소 고리, 또는 치환 또는 비치환된 탄소수 2 내지 60의 헤테로 고리를 형성한다. 상기 '치환 또는 비치환된'은 중수소, 니트릴기, 할로겐기, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 30의 시클로알킬기, 탄소수 1 내지 20의 알콕시기, 탄소수 1 내지 30의 실릴기, 탄소수 1 내지 30의 아민기, 탄소수 6 내지 30의 아릴기 및 탄소수 2 내지 30의 헤테로고리기로 이루어진 군으로부터 선택된 1 이상이 연결된 치환기로 치환 또는 비치환됨을 의미한다.According to an exemplary embodiment of the present specification, the R 71 To R 74 , R 81 to R 84 , R 91 to R 94 , And Ra to Re are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted Or an unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted silyl group having 1 to 60 carbon atoms, a substituted or unsubstituted amine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms , Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or by combining with an adjacent substituent, a substituted or unsubstituted hydrocarbon ring having 3 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms. To form. The 'substituted or unsubstituted' is deuterium, nitrile group, halogen group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, silyl group having 1 to 30 carbon atoms, carbon number 1 It means that one or more selected from the group consisting of an amine group having 30 to 30, an aryl group having 6 to 30 carbon atoms and a heterocyclic group having 2 to 30 carbon atoms is substituted or unsubstituted with a connected substituent.
본 명세서의 일 실시상태에 있어서, 상기 R71 내지 R74, R81 내지 R84, R91 내지 R94, 및 Ra 내지 Re는 서로 같거나 상이하고, 각각 독립적으로, 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 메틸기, 치환 또는 비치환된 에틸기, 치환 또는 비치환된 프로필기, 치환 또는 비치환된 부틸기, 치환 또는 비치환된 시클로프로필기, 치환 또는 비치환된 시클로부틸기, 치환 또는 비치환된 시클로펜틸기, 치환 또는 비치환된 시클로헥실기, 치환 또는 비치환된 메톡시기, 치환 또는 비치환된 에톡시기, 치환 또는 비치환된 트리메틸실릴기, 치환 또는 비치환된 트리페닐실릴기, 치환 또는 비치환된 디페닐아민기, 치환 또는 비치환된 디벤조퓨란페닐아민기, 치환 또는 비치환된 페닐기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 카바졸기, 치환 또는 비치환된 디벤조퓨란기, 치환 또는 비치환된 디벤조티오펜기 또는 치환 또는 비치환된 피리딜기이거나, 인접한 치환기와 서로 결합하여 치환 또는 비치환된 탄소수 3 내지 30의 방향족 또는 지방족 탄화수소고리, 또는 치환 또는 비치환된 탄소수 2 내지 30의 이종원소로 N, O 및 S 중 1 이상을 포함하는 헤테로고리를 형성한다. 상기 '치환 또는 비치환된'은 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 메틸기, 치환 또는 비치환된 에틸기, 치환 또는 비치환된 프로필기, 치환 또는 비치환된 부틸기, 치환 또는 비치환된 시클로프로필기, 치환 또는 비치환된 시클로부틸기, 치환 또는 비치환된 시클로펜틸기, 치환 또는 비치환된 시클로헥실기, 치환 또는 비치환된 메톡시기, 치환 또는 비치환된 에톡시기, 치환 또는 비치환된 트리메틸실릴기, 치환 또는 비치환된 트리페닐실릴기, 치환 또는 비치환된 디페닐아민기, 치환 또는 비치환된 디벤조퓨란페닐아민기, 치환 또는 비치환된 페닐기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 카바졸기, 치환 또는 비치환된 디벤조퓨란기, 치환 또는 비치환된 디벤조티오펜기 및 치환 또는 비치환된 피리딜기로 이루어진 군으로부터 선택된 1 이상이 연결된 치환기로 치환 또는 비치환됨을 의미한다.In one embodiment of the present specification, R71 To R74, R81 To R84, R91 To R94, And Ra to Re are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted Substituted butyl group, substituted or unsubstituted cyclopropyl group, substituted or unsubstituted cyclobutyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted methoxy group, substituted Or an unsubstituted ethoxy group, a substituted or unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamine group, a substituted or unsubstituted dibenzofuranphenylamine group, substituted or Unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted carbazole group, substituted or unsubstituted dibenzofu A lan group, a substituted or unsubstituted dibenzothiophene group, a substituted or unsubstituted pyridyl group, or a substituted or unsubstituted aromatic or aliphatic hydrocarbon ring having 3 to 30 carbon atoms in combination with each other, or a substituted or unsubstituted It is a hetero atom having 2 to 30 carbon atoms to form a heterocycle containing one or more of N, O and S. The 'substituted or unsubstituted' is deuterium, nitrile group, halogen group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted butyl group, substituted or unsubstituted Substituted cyclopropyl group, substituted or unsubstituted cyclobutyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted methoxy group, substituted or unsubstituted ethoxy group, substituted Or an unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamine group, a substituted or unsubstituted dibenzofuranphenylamine group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted Substituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted carbazole group, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted dibenzo It means that one or more selected from the group consisting of a thiophene group and a substituted or unsubstituted pyridyl group is substituted or unsubstituted with a linked substituent.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1은 하기 화학식 2-1 내지 2-5 중 하나로 표시된다.In one embodiment of the present specification, Chemical Formula 1 is represented by one of the following Chemical Formulas 2-1 to 2-5.
[화학식 2-1][Formula 2-1]
Figure PCTKR2019013722-appb-I000011
Figure PCTKR2019013722-appb-I000011
[화학식 2-2][Formula 2-2]
Figure PCTKR2019013722-appb-I000012
Figure PCTKR2019013722-appb-I000012
[화학식 2-3][Formula 2-3]
Figure PCTKR2019013722-appb-I000013
Figure PCTKR2019013722-appb-I000013
[화학식 2-4][Formula 2-4]
Figure PCTKR2019013722-appb-I000014
Figure PCTKR2019013722-appb-I000014
[화학식 2-5][Formula 2-5]
Figure PCTKR2019013722-appb-I000015
Figure PCTKR2019013722-appb-I000015
상기 화학식 2-1 내지 2-5에 있어서, In Chemical Formulas 2-1 to 2-5,
R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55는 화학식 1 및 2에서 정의한 바와 같고,R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , and R 51 to R 55 are as defined in Chemical Formulas 1 and 2,
X1 및 X2는 서로 같거나 상이하고, 각각 독립적으로 O, S 또는 NR이며,X 1 and X 2 are the same as or different from each other, and each independently O, S or NR,
R, R101 내지 R111, 및 R201 내지 R228는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기, 치환 또는 비치환된 알콕시기, 치환 또는 비치환된 실릴기, 치환 또는 비치환된 포스핀옥사이드기, 치환 또는 비치환된 아민기, 치환 또는 비치환된 붕소기, 치환 또는 비치환의 아릴기, 치환 또는 비치환의 헤테로고리기이고,R, R 101 to R 111 , and R 201 to R 228 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted Or an unsubstituted alkoxy group, a substituted or unsubstituted silyl group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted amine group, a substituted or unsubstituted boron group, a substituted or unsubstituted aryl group, a substituted or Unsubstituted heterocyclic group,
n1 내지 n9는 각각 0 내지 2의 정수이며,n1 to n9 are each an integer of 0 to 2,
n10 및 n11은 각각 0 내지 4의 정수이고,n10 and n11 are each an integer from 0 to 4,
n1 내지 n11이 각각 2 이상인 경우, 괄호 내의 치환기는 서로 같거나 상이하다.When n1 to n11 are each 2 or more, the substituents in parentheses are the same as or different from each other.
본 명세서의 일 실시상태에 따르면, 상기 R, R101 내지 R111 및 R201 내지 R228는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬기, 치환 또는 비치환된 탄소수 3 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 1 내지 20의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 60의 실릴기, 치환 또는 비치환된 탄소수 1 내지 30의 아민기, 치환 또는 비치환된 탄소수 6 내지 60의 아릴기, 또는 치환 또는 비치환된 탄소수 2 내지 60의 헤테로고리기이거나, 인접한 치환기와 서로 결합하여 치환 또는 비치환된 탄소수 3 내지 60의 탄화수소 고리, 또는 치환 또는 비치환된 탄소수 2 내지 60의 헤테로 고리를 형성한다. 상기 '치환 또는 비치환된'은 중수소, 니트릴기, 할로겐기, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 30의 시클로알킬기, 탄소수 1 내지 20의 알콕시기, 탄소수 1 내지 30의 실릴기, 탄소수 1 내지 30의 아민기, 탄소수 6 내지 30의 아릴기 및 탄소수 2 내지 30의 헤테로고리기로 이루어진 군으로부터 선택된 1 이상이 연결된 치환기로 치환 또는 비치환됨을 의미한다.According to an exemplary embodiment of the present specification, the R, R 101 to R 111 and R 201 to R 228 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted carbon number 1 To 20 alkyl groups, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted silyl groups having 1 to 60 carbon atoms, substituted or unsubstituted carbon atoms It is an amine group of 1 to 30, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or bonded to each other with adjacent substituents to have 3 or more unsubstituted or substituted carbon atoms. 60 hydrocarbon rings, or substituted or unsubstituted heterocycles having 2 to 60 carbon atoms. The 'substituted or unsubstituted' is deuterium, nitrile group, halogen group, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, silyl group having 1 to 30 carbon atoms, carbon number 1 It means that one or more selected from the group consisting of an amine group having 30 to 30, an aryl group having 6 to 30 carbon atoms and a heterocyclic group having 2 to 30 carbon atoms is substituted or unsubstituted with a connected substituent.
본 명세서의 일 실시상태에 있어서, 상기 R, R101 내지 R111 및 R201 내지 R228는 서로 같거나 상이하고, 각각 독립적으로, 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 메틸기, 치환 또는 비치환된 에틸기, 치환 또는 비치환된 프로필기, 치환 또는 비치환된 부틸기, 치환 또는 비치환된 시클로프로필기, 치환 또는 비치환된 시클로부틸기, 치환 또는 비치환된 시클로펜틸기, 치환 또는 비치환된 시클로헥실기, 치환 또는 비치환된 메톡시기, 치환 또는 비치환된 에톡시기, 치환 또는 비치환된 트리메틸실릴기, 치환 또는 비치환된 트리페닐실릴기, 치환 또는 비치환된 디페닐아민기, 치환 또는 비치환된 디벤조퓨란페닐아민기, 치환 또는 비치환된 페닐기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 카바졸기, 치환 또는 비치환된 디벤조퓨란기, 치환 또는 비치환된 디벤조티오펜기 또는 치환 또는 비치환된 피리딜기이거나, 인접한 치환기와 서로 결합하여 치환 또는 비치환된 탄소수 3 내지 30의 방향족 또는 지방족 탄화수소고리, 또는 치환 또는 비치환된 탄소수 2 내지 30의 이종원소로 N, O 및 S 중 1 이상을 포함하는 헤테로고리를 형성한다. 상기 '치환 또는 비치환된'은 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 메틸기, 치환 또는 비치환된 에틸기, 치환 또는 비치환된 프로필기, 치환 또는 비치환된 부틸기, 치환 또는 비치환된 시클로프로필기, 치환 또는 비치환된 시클로부틸기, 치환 또는 비치환된 시클로펜틸기, 치환 또는 비치환된 시클로헥실기, 치환 또는 비치환된 메톡시기, 치환 또는 비치환된 에톡시기, 치환 또는 비치환된 트리메틸실릴기, 치환 또는 비치환된 트리페닐실릴기, 치환 또는 비치환된 디페닐아민기, 치환 또는 비치환된 디벤조퓨란페닐아민기, 치환 또는 비치환된 페닐기, 치환 또는 비치환된 바이페닐기, 치환 또는 비치환된 터페닐기, 치환 또는 비치환된 나프틸기, 치환 또는 비치환된 카바졸기, 치환 또는 비치환된 디벤조퓨란기, 치환 또는 비치환된 디벤조티오펜기 및 치환 또는 비치환된 피리딜기로 이루어진 군으로부터 선택된 1 이상이 연결된 치환기로 치환 또는 비치환됨을 의미한다.In one embodiment of the present specification, R, R 101 to R 111 and R 201 to R 228 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted methyl group , Substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted butyl group, substituted or unsubstituted cyclopropyl group, substituted or unsubstituted cyclobutyl group, substituted or unsubstituted cyclopentyl group , Substituted or unsubstituted cyclohexyl group, substituted or unsubstituted methoxy group, substituted or unsubstituted ethoxy group, substituted or unsubstituted trimethylsilyl group, substituted or unsubstituted triphenylsilyl group, substituted or unsubstituted Diphenylamine group, substituted or unsubstituted dibenzofuranphenylamine group, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted naphthyl , A substituted or unsubstituted carbazole group, a substituted or unsubstituted dibenzofuran group, a substituted or unsubstituted dibenzothiophene group, or a substituted or unsubstituted pyridyl group, or substituted or unsubstituted by combining with adjacent substituents An aromatic or aliphatic hydrocarbon ring having 3 to 30 carbon atoms, or a substituted or unsubstituted hetero atom having 2 to 30 carbon atoms to form a heterocycle containing one or more of N, O and S. The 'substituted or unsubstituted' is deuterium, nitrile group, halogen group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted butyl group, substituted or unsubstituted Substituted cyclopropyl group, substituted or unsubstituted cyclobutyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted methoxy group, substituted or unsubstituted ethoxy group, substituted Or an unsubstituted trimethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted diphenylamine group, a substituted or unsubstituted dibenzofuranphenylamine group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted Substituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted carbazole group, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted dibenzo It means that one or more selected from the group consisting of a thiophene group and a substituted or unsubstituted pyridyl group is substituted or unsubstituted with a linked substituent.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1은 하기 화합물 중에서 선택되는 어느 하나이다.In one embodiment of the present specification, Chemical Formula 1 is any one selected from the following compounds.
Figure PCTKR2019013722-appb-I000016
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상기 구체예들에 있어서, D는 중수소, Me는 메틸기, Ph는 페닐기를 의미한다.In the above embodiments, D deuterium, Me is a methyl group, Ph means a phenyl group.
본 명세서에 있어서, 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, it means that the component may further include other components, not to exclude other components, unless otherwise stated.
본 명세서에 있어서, 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 positioned “on” another member, this includes not only the case where one member is in contact with the other member but also another member between the two members.
본 발명의 유기 발광 소자는 제1 전극; 상기 제1 전극에 대향하여 구비된 제2 전극; 및 상기 제1 전극과 제2 전극 사이에 구비된 1층 또는 2층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1 층 이상은 전술한 헤테로고리 화합물을 포함할 수 있다.The organic light emitting device of the present invention comprises a first electrode; A second electrode provided opposite to the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer may include the aforementioned heterocyclic compound.
예컨대, 본 발명의 유기 발광 소자의 구조는 도 1 내지 3에 나타낸 것과 같은 구조를 가질 수 있으나, 이에만 한정되는 것은 아니다.For example, the structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 to 3, but is not limited thereto.
도 1에는 기판(1) 위에 제1 전극(2), 유기물층(3), 및 제2 전극(4)이 순차적으로 적층된 유기 발광 소자의 구조가 예시되어 있다.In FIG. 1, a structure of an organic light emitting device in which the first electrode 2, the organic material layer 3, and the second electrode 4 are sequentially stacked on the substrate 1 is illustrated.
상기 도 1은 유기 발광 소자를 예시한 것이며 이에 한정되지 않는다. 1 illustrates an organic light emitting device and is not limited thereto.
도 2에는 기판(1) 위에 제1 전극(2), 발광층(5) 및 제2 전극(4)이 순차적으로 적층된 유기 발광 소자의 구조가 예시되어 있다. 2 illustrates a structure of an organic light emitting device in which a first electrode 2, a light emitting layer 5, and a second electrode 4 are sequentially stacked on a substrate 1.
상기 도 2는 유기 발광 소자를 예시한 것이며, 이에 한정되지 않고, 제1 전극(2)과 발광층(5) 및 발광층(5)과 제2 전극(4)사이에 추가의 유기물층을 더 포함할 수 있다.2 illustrates an organic light emitting device, and is not limited thereto, and may further include an additional organic material layer between the first electrode 2 and the light emitting layer 5 and the light emitting layer 5 and the second electrode 4. have.
도 3에는 기판(1) 위에 제1 전극(2), 정공주입층(6), 정공수송층-1(7), 정공수송층-2(8), 발광층(5), 전자수송층(9) 및 제2 전극(4)이 순차적으로 적층된 유기 발광 소자의 구조가 예시되어 있다.3, a first electrode 2, a hole injection layer 6, a hole transport layer-1 (7), a hole transport layer-2 (8), a light emitting layer 5, an electron transport layer 9 and a first electrode on the substrate 1 are shown in FIG. The structure of the organic light emitting device in which the two electrodes 4 are sequentially stacked is illustrated.
본 발명의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1의 헤테로고리 화합물을 포함한다.In an exemplary embodiment of the present invention, the organic material layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by Chemical Formula 1 above.
본 발명의 유기 발광 소자는 발광층을 포함하고, 상기 발광층은 호스트와 도펀트를 99.9:0.1 내지 90:10의 질량비로 포함할 수 있다.The organic light emitting device of the present invention includes a light emitting layer, and the light emitting layer may include a host and a dopant in a mass ratio of 99.9: 0.1 to 90:10.
본 발명의 유기 발광 소자는 발광층을 포함하고, 상기 발광층은 호스트와 도펀트를 99.5:0.5 내지 95:5의 질량비로 포함할 수 있다.The organic light emitting device of the present invention includes a light emitting layer, and the light emitting layer may include a host and a dopant in a mass ratio of 99.5: 0.5 to 95: 5.
본 발명의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1의 헤테로고리 화합물을 도펀트로 포함한다.In one embodiment of the present invention, the organic material layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound represented by Chemical Formula 1 as a dopant.
본 발명의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1의 헤테로고리 화합물을 상기 발광층의 도펀트로 포함한다.In one embodiment of the present invention, the organic material layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound represented by Chemical Formula 1 as a dopant in the light emitting layer.
본 발명의 일 실시상태에 있어서, 상기 유기물층은 정공주입층, 정공수송층, 및 정공 주입 및 수송층 중 1층 이상을 포함하고, 상기 정공주입층, 정공수송층, 및 정공 주입 및 수송층 중 1층 이상은 상기 화학식 1의 헤테로고리 화합물을 포함할 수 있다.In an exemplary embodiment of the present invention, the organic material layer includes at least one layer of a hole injection layer, a hole transport layer, and a hole injection and transport layer, and at least one layer of the hole injection layer, a hole transport layer, and a hole injection and transport layer is It may include a heterocyclic compound of the formula (1).
본 발명의 일 실시상태에 있어서, 상기 유기물층은 전자주입층, 전자수송층, 및 전자 주입 및 수송층 중 1층 이상을 포함하고, 상기 전자주입층, 전자수송층, 및 전자 주입 및 수송층 중 1층 이상은 상기 화학식 1의 헤테로고리 화합물을 포함할 수 있다.In an exemplary embodiment of the present invention, the organic material layer includes at least one layer of an electron injection layer, an electron transport layer, and an electron injection and transport layer, and at least one layer of the electron injection layer, the electron transport layer, and the electron injection and transport layer is It may include a heterocyclic compound of the formula (1).
본 발명의 일 실시상태에 있어서, 상기 유기물층은 전자저지층 및 정공저지층 중 1층 이상을 포함하고, 상기 전자저지층 및/또는 정공저지층은 상기 화학식 1의 헤테로고리 화합물을 포함할 수 있다.In one embodiment of the present invention, the organic material layer includes one or more of the electron blocking layer and the hole blocking layer, and the electron blocking layer and / or the hole blocking layer may include the heterocyclic compound of Formula 1 .
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.
본 명세서의 유기 발광 소자는 유기물층 중 1층 이상이 상기 헤테로고리 화합물을 이용하여 형성되는 것을 제외하고는 당 기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다.The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer is formed using the heterocyclic compound.
본 명세서는 또한, 상기 헤테로고리 화합물을 이용하여 형성된 유기 발광 소자의 제조 방법을 제공한다.The present specification also provides a method for manufacturing an organic light emitting device formed using the heterocyclic compound.
예컨대, 본 발명에 따른 유기 발광 소자는 스퍼터링(sputtering)이나 전자빔 증발(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 정공주입층, 정공수송층, 발광층, 전자수송층 등을 포함하는 유기물층 및 상기 화학식 1의 화합물을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수도 있다.For example, the organic light emitting device according to the present invention uses a metal vapor deposition (PVD) method, such as sputtering or e-beam evaporation, to have a metal or conductive metal oxide on the substrate or alloys thereof To form an anode, and then form an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an organic material layer containing the compound of Formula 1, and then use a material that can be used as a cathode thereon. It can be produced by vapor deposition. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
상기 양극 물질로는 통상 유기물층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 본 발명에서 사용될 수 있는 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2 : Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.The positive electrode material is usually a material having a large work function to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO 2 : Combination of metal and oxide such as Sb; 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 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다.The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; There is a multilayer structure material such as LiF / Al or LiO 2 / Al, but is not limited thereto.
상기 정공주입물질로는 낮은 전압에서 양극으로부터 정공을 잘 주입 받을 수 있는 물질로서, 정공주입물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물층의 HOMO 사이인 것이 바람직하다. 정공 주입 물질의 구체적인 예로는 금속 포피린(porphyrine), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone) 계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.As the hole injection material, a hole injection material can be well injected from the anode at a low voltage, and it is preferable that the hole injection material has a high occupied molecular orbital (HOMO) between the work function of the cathode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances. Organic materials, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.
상기 정공수송물질로는 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다.As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is suitable as a material having high mobility for holes. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.
상기 발광 물질로는 정공 수송층과 전자 수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다. 구체적인 예로는 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, 루브렌등이 있으나, 이들에만 한정되는 것은 아니다.As the light-emitting material, a material capable of emitting light in the visible light region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly (p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.
도펀트 재료로는 방향족 화합물, 스트릴아민 화합물, 붕소 착체, 플루오란텐 화합물, 금속 착체 등이 있다. 구체적으로 방향족 화합물로는 치환 또는 비치환된 아릴아미노기를 갖는 축합 방향족환 유도체로서, 아릴아미노기를 갖는 피렌, 안트라센, 크리센, 페리플란텐 등이 있으며, 스티릴아민 화합물로는 치환 또는 비치환된 아릴아민에 적어도 1개의 아릴비닐기가 치환되어 있는 화합물로, 아릴기, 실릴기, 알킬기, 시클로알킬기 및 아릴아미노기로 이루어진 군에서 1 또는 2이상 선택되는 치환기가 치환 또는 비치환된다. 구체적으로 스티릴아민, 스티릴디아민, 스티릴트리아민, 스티릴테트라아민 등이 있으나, 이에 한정되지 않는다. 또한, 금속 착체로는 이리듐 착체, 백금 착체 등이 있으나, 이에 한정되지 않는다.Examples of the dopant material include an aromatic compound, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic compound is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a styrylamine compound. A compound in which at least one arylvinyl group is substituted with an arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, examples of the metal complex include an iridium complex and a platinum complex, but are not limited thereto.
상기 전자수송층은 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하는 층으로 전자 수송 물질로는 캐소드로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 8-히드록시퀴놀린의 Al착물; Alq3을 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자 수송층은 종래기술에 따라 사용된 바와 같이 임의의 원하는 캐소드 물질과 함께 사용할 수 있다. 특히, 적절한 캐소드 물질의 예는 낮은 일함수를 가지고 알루미늄층 또는 실버층이 뒤따르는 통상적인 물질이다. 구체적으로 세슘, 바륨, 칼슘, 이테르븀 및 사마륨이고, 각 경우 알루미늄 층 또는 실버층이 뒤따른다.The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. Do. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, each case followed by an aluminum layer or a silver layer.
상기 전자주입층은 전극으로부터 전자를 주입하는 층으로, 전자를 수송하는 능력을 갖고, 캐소드로부터의 전자주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자 주입 효과를 가지며, 발광층에서 생성된 여기자의 정공 주입층에의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물이 바람직하다. 구체적으로는 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 함질소 5원환 유도체 등이 있으나, 이에 한정되지 않는다.The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.
상기 정공저지층은 정공의 캐소드 도달을 저지하는 층으로, 일반적으로 정공주입층과 동일한 조건으로 형성될 수 있다. 구체적으로 옥사디아졸 유도체나 트리아졸 유도체, 페난트롤린 유도체, BCP, 알루미늄 착물 (aluminum complex) 등이 있으나, 이에 한정되지 않는다.The hole blocking layer is a layer that prevents the cathode from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but are 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 front emission type, a back emission type, or a double-sided emission type, depending on the material used.
이하, 본 명세서를 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 명세서에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 명세서의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되지 않는다. 본 명세서의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.
<< 제조예Manufacturing example >>
제조예Manufacturing example 1. One.
1)One)
Figure PCTKR2019013722-appb-I000092
Figure PCTKR2019013722-appb-I000092
1-브로모-2,3-디클로로벤젠 (22.6 g), 중간체 A-1 (16.9 g), Pd(PtBu3)2 (0.51 g), NaOtBu (19.2 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 A-2(25.5g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=315에서 피크가 확인되었다.1-bromo-2,3-dichlorobenzene (22.6 g), intermediate A-1 (16.9 g), Pd (P t Bu 3 ) 2 (0.51 g), NaOtBu (19.2 g) and toluene (400 ml) The entered flask was heated at 110 ° C. and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate A-2 (25.5 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M + H +] = 315.
2)2)
Figure PCTKR2019013722-appb-I000093
Figure PCTKR2019013722-appb-I000093
중간체 A-2 (20.0 g), 중간체 A-3 (24.0 g), Pd(PtBu3)2 (0.33g), NaOtBu (12.23g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 실리카겔 컬럼 크로마토그래피 (전개액: 헥산/에틸아세테이트 = 50%/50%(부피비))로 정제하여, 중간체 A-4(13.35 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=378에서 피크가 확인되었다.The flask containing intermediate A-2 (20.0 g), intermediate A-3 (24.0 g), Pd (P t Bu 3 ) 2 (0.33 g), NaOtBu (12.23 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developer: hexane / ethyl acetate = 50% / 50% (volume ratio)) gave Intermediate A-4 (13.35 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 378.
3)3)
Figure PCTKR2019013722-appb-I000094
Figure PCTKR2019013722-appb-I000094
중간체 A-4 (9.76 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 화합물 1 (3.2 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=629에서 피크가 확인되었다.To a flask containing intermediate A-4 (9.76 g) and tert-butyl benzene (160 ml), a 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give compound 1 (3.2 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 629.
제조예Manufacturing example 2. 2.
1)One)
Figure PCTKR2019013722-appb-I000095
Figure PCTKR2019013722-appb-I000095
1-브로모-2,3-디클로로벤젠 (22.6 g), 중간체 B-1 (19.7 g), Pd(PtBu3)2 (0.51 g), NaOtBu (19.2 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 B-2(24.0 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=343에서 피크가 확인되었다.1-bromo-2,3-dichlorobenzene (22.6 g), intermediate B-1 (19.7 g), Pd (P t Bu 3 ) 2 (0.51 g), NaOtBu (19.2 g) and toluene (400 ml) The entered flask was heated at 110 ° C. and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate B-2 (24.0 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 343.
2)2)
Figure PCTKR2019013722-appb-I000096
Figure PCTKR2019013722-appb-I000096
중간체 B-2 (15.0 g), 중간체 B-3 (20.7 g), Pd(PtBu3)2 (0.22 g), NaOtBu (8.42 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 실리카겔 컬럼 크로마토그래피 (전개액: 헥산/에틸아세테이트 = 50%/50%(부피비))로 정제하여, 중간체 B-4(17.1 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=780에서 피크가 확인되었다.The flask with intermediate B-2 (15.0 g), intermediate B-3 (20.7 g), Pd (P t Bu 3 ) 2 (0.22 g), NaOtBu (8.42 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developer: hexane / ethyl acetate = 50% / 50% (volume ratio)) gave intermediate B-4 (17.1 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 780.
3)3)
Figure PCTKR2019013722-appb-I000097
Figure PCTKR2019013722-appb-I000097
중간체 B-4 (11.6 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 화합물 2 (3.8 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=753에서 피크가 확인되었다.To a flask containing intermediate B-4 (11.6 g) and tert-butyl benzene (160 ml), 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C. under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give compound 2 (3.8 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 753.
제조예Manufacturing example 3. 3.
1)One)
Figure PCTKR2019013722-appb-I000098
Figure PCTKR2019013722-appb-I000098
1-브로모-2,3-디클로로벤젠 (22.6 g), 중간체 C-1 (19.7 g), Pd(PtBu3)2 (0.51 g), NaOtBu (19.2 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 C-2(24.0 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=343에서 피크가 확인되었다.1-bromo-2,3-dichlorobenzene (22.6 g), intermediate C-1 (19.7 g), Pd (P t Bu 3 ) 2 (0.51 g), NaOtBu (19.2 g) and toluene (400 ml) The entered flask was heated at 110 ° C. and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate C-2 (24.0 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 343.
2)2)
Figure PCTKR2019013722-appb-I000099
Figure PCTKR2019013722-appb-I000099
중간체 C-2 (15.0 g), 중간체 C-3 (17.2 g), Pd(PtBu3)2 (0.22 g), NaOtBu (8.42 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 실리카겔 컬럼 크로마토그래피 (전개액: 헥산/에틸아세테이트 = 50%/50%(부피비))로 정제하여, 중간체 C-4(14.2 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=698에서 피크가 확인되었다.The flask with intermediate C-2 (15.0 g), intermediate C-3 (17.2 g), Pd (P t Bu 3 ) 2 (0.22 g), NaOtBu (8.42 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developer: hexane / ethyl acetate = 50% / 50% (volume ratio)) gave Intermediate C-4 (14.2 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 698.
3)3)
Figure PCTKR2019013722-appb-I000100
Figure PCTKR2019013722-appb-I000100
중간체 C-4 (10.4 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 화합물 3 (3.5 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=671에서 피크가 확인되었다.To a flask containing intermediate C-4 (10.4 g) and tert-butyl benzene (160 ml), a 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give compound 3 (3.5 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 671.
제조예Manufacturing example 4. 4.
1)One)
Figure PCTKR2019013722-appb-I000101
Figure PCTKR2019013722-appb-I000101
1-브로모-2,3-디클로로벤젠 (22.6 g), 중간체 D-1 (45.5 g), Pd(PtBu3)2 (0.51 g), NaOtBu (19.2 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 D-2(28.5 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=600에서 피크가 확인되었다.1-bromo-2,3-dichlorobenzene (22.6 g), intermediate D-1 (45.5 g), Pd (P t Bu 3 ) 2 (0.51 g), NaOtBu (19.2 g) and toluene (400 ml) The entered flask was heated at 110 ° C. and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate D-2 (28.5 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 600.
2)2)
Figure PCTKR2019013722-appb-I000102
Figure PCTKR2019013722-appb-I000102
중간체 D-2 (26.3 g), 중간체 D-3 (19.9 g), Pd(PtBu3)2 (0.22 g), NaOtBu (8.42 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 실리카겔 컬럼 크로마토그래피 (전개액: 헥산/에틸아세테이트 = 50%/50%(부피비))로 정제하여, 중간체 D-4(18.1 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=1018에서 피크가 확인되었다.The flask containing intermediate D-2 (26.3 g), intermediate D-3 (19.9 g), Pd (P t Bu 3 ) 2 (0.22 g), NaOtBu (8.42 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developer: hexane / ethyl acetate = 50% / 50% (volume ratio)) gave intermediate D-4 (18.1 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 1018.
3)3)
Figure PCTKR2019013722-appb-I000103
Figure PCTKR2019013722-appb-I000103
중간체 D-4 (15.2 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 화합물 4 (5.0 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=992에서 피크가 확인되었다.To a flask containing intermediate D-4 (15.2 g) and tert-butyl benzene (160 ml), 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give compound 4 (5.0 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 992.
제조예Manufacturing example 5. 5.
1)One)
Figure PCTKR2019013722-appb-I000104
Figure PCTKR2019013722-appb-I000104
1-브로모-2,3-디클로로벤젠 (22.6 g), 중간체 E-1 (48.3 g), Pd(PtBu3)2 (0.51 g), NaOtBu (19.2 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 E-2(28.0 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=628에서 피크가 확인되었다.1-bromo-2,3-dichlorobenzene (22.6 g), intermediate E-1 (48.3 g), Pd (P t Bu 3 ) 2 (0.51 g), NaOtBu (19.2 g) and toluene (400 ml) The entered flask was heated at 110 ° C. and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate E-2 (28.0 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 628.
2)2)
Figure PCTKR2019013722-appb-I000105
Figure PCTKR2019013722-appb-I000105
중간체 E-2 (27.5 g), 중간체 E-3 (20.1 g), Pd(PtBu3)2 (0.22 g), NaOtBu (8.42 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 실리카겔 컬럼 크로마토그래피 (전개액: 헥산/에틸아세테이트 = 50%/50%(부피비))로 정제하여, 중간체 E-4(23.0 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=1051에서 피크가 확인되었다.The flask with intermediate E-2 (27.5 g), intermediate E-3 (20.1 g), Pd (P t Bu 3 ) 2 (0.22 g), NaOtBu (8.42 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developer: hexane / ethyl acetate = 50% / 50% (volume ratio)) gave intermediate E-4 (23.0 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 1051.
3)3)
Figure PCTKR2019013722-appb-I000106
Figure PCTKR2019013722-appb-I000106
중간체 E-4 (15.7 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 화합물 5 (8.8 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=1025에서 피크가 확인되었다.To a flask containing intermediate E-4 (15.7 g) and tert-butyl benzene (160 ml), a 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give compound 5 (8.8 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 1025.
제조예Manufacturing example 6. 6.
1)One)
Figure PCTKR2019013722-appb-I000107
Figure PCTKR2019013722-appb-I000107
1-브로모-2,3-디클로로벤젠 (22.6 g), 중간체 F-1 (120.0 g), Pd(PtBu3)2 (1.02 g), NaOtBu (38.4 g) 및 톨루엔 (800 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 F-2(50.1 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=1309에서 피크가 확인되었다.1-bromo-2,3-dichlorobenzene (22.6 g), intermediate F-1 (120.0 g), Pd (P t Bu 3 ) 2 (1.02 g), NaOtBu (38.4 g) and toluene (800 ml) The entered flask was heated at 110 ° C. and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate F-2 (50.1 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 1309.
2)2)
Figure PCTKR2019013722-appb-I000108
Figure PCTKR2019013722-appb-I000108
중간체 F-2 (19.5 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 화합물 6 (9.8 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=1282에서 피크가 확인되었다.To a flask containing intermediate F-2 (19.5 g) and tert-butyl benzene (160 ml), a 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C. under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give compound 6 (9.8 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 1282.
제조예Manufacturing example 7. 7.
1)One)
Figure PCTKR2019013722-appb-I000109
Figure PCTKR2019013722-appb-I000109
1-브로모-2,3-디클로로벤젠 (22.6 g), 중간체 G-1 (16.9 g), Pd(PtBu3)2 (0.51 g), NaOtBu (19.2 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 G-2(25.5g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=315에서 피크가 확인되었다.1-bromo-2,3-dichlorobenzene (22.6 g), intermediate G-1 (16.9 g), Pd (P t Bu 3 ) 2 (0.51 g), NaOtBu (19.2 g) and toluene (400 ml) The entered flask was heated at 110 ° C. and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate G-2 (25.5 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M + H +] = 315.
2)2)
Figure PCTKR2019013722-appb-I000110
Figure PCTKR2019013722-appb-I000110
중간체 G-2 (13.8 g), 중간체 G-3 (40.0 g), Pd(PtBu3)2 (0.22 g), NaOtBu (8.42 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 실리카겔 컬럼 크로마토그래피 (전개액: 헥산/에틸아세테이트 = 50%/50%(부피비))로 정제하여, 중간체 G-4(26.6 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=1191에서 피크가 확인되었다.The flask with intermediate G-2 (13.8 g), intermediate G-3 (40.0 g), Pd (P t Bu 3 ) 2 (0.22 g), NaOtBu (8.42 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developer: hexane / ethyl acetate = 50% / 50% (volume ratio)) gave intermediate G-4 (26.6 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 1191.
3)3)
Figure PCTKR2019013722-appb-I000111
Figure PCTKR2019013722-appb-I000111
중간체 G-4 (17.7 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 화합물 7 (6.6 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=1164에서 피크가 확인되었다.To a flask containing intermediate G-4 (17.7 g) and tert-butyl benzene (160 ml), 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give compound 7 (6.6 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 1164.
제조예Manufacturing example 8. 8.
1) One)
Figure PCTKR2019013722-appb-I000112
Figure PCTKR2019013722-appb-I000112
3-브로모-4,5-디클로로-1,1'-바이페닐 (30.2 g), 중간체 H-1 (47.0 g), Pd(PtBu3)2 (0.51 g), NaOtBu (19.2 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 H-2(55.9 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=691에서 피크가 확인되었다.3-Bromo-4,5-dichloro-1,1'-biphenyl (30.2 g), intermediate H-1 (47.0 g), Pd (P t Bu 3 ) 2 (0.51 g), NaOtBu (19.2 g) And the flask containing toluene (400 ml) was heated at 110 ° C. and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate H-2 (55.9 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 691.
2)2)
Figure PCTKR2019013722-appb-I000113
Figure PCTKR2019013722-appb-I000113
중간체 H-2 (30.3 g), 중간체 H-3 (9.6 g), Pd(PtBu3)2 (0.22 g), NaOtBu (8.42 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 실리카겔 컬럼 크로마토그래피 (전개액: 헥산/에틸아세테이트 = 50%/50%(부피비))로 정제하여, 중간체 H-4(23.7 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=874에서 피크가 확인되었다.The flask with intermediate H-2 (30.3 g), intermediate H-3 (9.6 g), Pd (P t Bu 3 ) 2 (0.22 g), NaOtBu (8.42 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developer: hexane / ethyl acetate = 50% / 50% (volume ratio)) gave intermediate H-4 (23.7 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M + H +] = 874.
3)3)
Figure PCTKR2019013722-appb-I000114
Figure PCTKR2019013722-appb-I000114
중간체 H-4 (13.0 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 화합물 8 (8.7 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=847에서 피크가 확인되었다.To a flask containing intermediate H-4 (13.0 g) and tert-butyl benzene (160 ml), a 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give compound 8 (8.7 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 847.
제조예 9.Preparation Example 9.
1)One)
Figure PCTKR2019013722-appb-I000115
Figure PCTKR2019013722-appb-I000115
1-브로모-2,3-디클로로-5-메틸벤젠 (24.0 g), 중간체 I-1 (37.8 g), Pd(PtBu3)2 (0.51 g), NaOtBu (19.2 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 I-2(40.2 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=537에서 피크가 확인되었다.1-bromo-2,3-dichloro-5-methylbenzene (24.0 g), intermediate I-1 (37.8 g), Pd (P t Bu 3 ) 2 (0.51 g), NaOtBu (19.2 g) and toluene ( The flask containing 400 ml) was heated at 110 ° C. and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate I-2 (40.2 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 537.
2)2)
Figure PCTKR2019013722-appb-I000116
Figure PCTKR2019013722-appb-I000116
중간체 I-2 (23.5 g), 중간체 I-3 (16.5 g), Pd(PtBu3)2 (0.22 g), NaOtBu (8.42 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 실리카겔 컬럼 크로마토그래피 (전개액: 헥산/에틸아세테이트 = 50%/50%(부피비))로 정제하여, 중간체 I-4(19.3 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=878에서 피크가 확인되었다.The flask containing intermediate I-2 (23.5 g), intermediate I-3 (16.5 g), Pd (P t Bu 3 ) 2 (0.22 g), NaOtBu (8.42 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developer: hexane / ethyl acetate = 50% / 50% (volume ratio)) gave Intermediate I-4 (19.3 g). As a result of mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 878.
3)3)
Figure PCTKR2019013722-appb-I000117
Figure PCTKR2019013722-appb-I000117
중간체 I-4 (13.1 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 화합물 9 (6.9 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=851에서 피크가 확인되었다.To a flask containing intermediate I-4 (13.1 g) and tert-butyl benzene (160 ml), 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give compound 9 (6.9 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 851.
제조예 10.Preparation Example 10.
1)One)
Figure PCTKR2019013722-appb-I000118
Figure PCTKR2019013722-appb-I000118
1-브로모-2,3-디클로로-5-아이오도벤젠 (70.4 g), 중간체 J-1 (54.4 g), Pd(PPh3)2 (0.51 g), K2CO3 (55.2 g) 및 물 200mL 테트라하이드로퓨란 (1000 ml)이 들어간 플라스크를 환류 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 테트라하이드로퓨란을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(에틸아세테이트/헥산)으로 정제하여 중간체 J-2(73.3 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=453에서 피크가 확인되었다.1-bromo-2,3-dichloro-5-iodobenzene (70.4 g), intermediate J-1 (54.4 g), Pd (PPh 3 ) 2 (0.51 g), K 2 CO 3 (55.2 g) and The flask containing 200 mL tetrahydrofuran (1000 ml) of water was heated to reflux and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and tetrahydrofuran to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (ethyl acetate / hexane) gave intermediate J-2 (73.3 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 453.
2)2)
Figure PCTKR2019013722-appb-I000119
Figure PCTKR2019013722-appb-I000119
중간체 J-2 (67.8 g), CH3SO2OH (96mL) 및 톨루엔 (600 ml)이 들어간 플라스크를 5시간 동안 교반하였다. 반응액을 실온까지 냉각시키고, 물에 반응물을 부은 후 생긴 고체를 여과하여 생성된 고체를 클로로포름과 에탄올로 정제하여 중간체 J-3(59.9 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=435에서 피크가 확인되었다.The flask containing intermediate J-2 (67.8 g), CH 3 SO 2 OH (96 mL) and toluene (600 ml) was stirred for 5 hours. The reaction solution was cooled to room temperature, and the resulting solid was filtered by pouring the reactant into water, and the resulting solid was purified by chloroform and ethanol to obtain intermediate J-3 (59.9 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M + H +] = 435.
3)3)
Figure PCTKR2019013722-appb-I000120
Figure PCTKR2019013722-appb-I000120
중간체 J-3 (43.4 g), 중간체 J-4 (16.9 g), Pd(PtBu3)2 (0.51 g), NaOtBu (19.2 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 J-5(40.8 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=523에서 피크가 확인되었다.The flask containing intermediate J-3 (43.4 g), intermediate J-4 (16.9 g), Pd (P t Bu 3 ) 2 (0.51 g), NaOtBu (19.2 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate J-5 (40.8 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M + H +] = 523.
4)4)
Figure PCTKR2019013722-appb-I000121
Figure PCTKR2019013722-appb-I000121
중간체 J-5 (22.9 g), 중간체 J-6 (8.6 g), Pd(PtBu3)2 (0.22 g), NaOtBu (8.42 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 실리카겔 컬럼 크로마토그래피 (전개액: 헥산/에틸아세테이트 = 50%/50%(부피비))로 정제하여, 중간체 J-7(19.4 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=684에서 피크가 확인되었다.The flask with intermediate J-5 (22.9 g), intermediate J-6 (8.6 g), Pd (P t Bu 3 ) 2 (0.22 g), NaOtBu (8.42 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developer: hexane / ethyl acetate = 50% / 50% (volume ratio)) gave intermediate J-7 (19.4 g). As a result of mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 684.
5)5)
Figure PCTKR2019013722-appb-I000122
Figure PCTKR2019013722-appb-I000122
중간체 J-7 (10.2 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 화합물 10 (6.5 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=657에서 피크가 확인되었다.To a flask containing intermediate J-7 (10.2 g) and tert-butyl benzene (160 ml), a 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give compound 10 (6.5 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 657.
제조예 11.Production Example 11.
1)One)
Figure PCTKR2019013722-appb-I000123
Figure PCTKR2019013722-appb-I000123
1-브로모-2,3-디클로로-5-아이오도벤젠 (70.4 g), 중간체 K-1 (58.0 g), Pd(PPh3)2 (0.51 g), K2CO3 (55.2 g) 및 물 200mL 테트라하이드로퓨란 (1000 ml)이 들어간 플라스크를 환류 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 테트라하이드로퓨란을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(에틸아세테이트/헥산)으로 정제하여 중간체 K-2(73.3 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=471에서 피크가 확인되었다.1-bromo-2,3-dichloro-5-iodobenzene (70.4 g), intermediate K-1 (58.0 g), Pd (PPh 3 ) 2 (0.51 g), K 2 CO 3 (55.2 g) and The flask containing 200 mL tetrahydrofuran (1000 ml) of water was heated to reflux and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and tetrahydrofuran to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (ethyl acetate / hexane) gave intermediate K-2 (73.3 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 471.
2)2)
Figure PCTKR2019013722-appb-I000124
Figure PCTKR2019013722-appb-I000124
중간체 K-2 (70.5 g), CH3SO2OH (96mL) 및 톨루엔 (600 ml)이 들어간 플라스크를 5시간 동안 교반하였다. 반응액을 실온까지 냉각시키고, 물에 반응물을 부은 후 생긴 고체를 여과하여 생성된 고체를 클로로포름과 에탄올로 정제하여 중간체 K-3(61.0 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=453에서 피크가 확인되었다.The flask containing intermediate K-2 (70.5 g), CH 3 SO 2 OH (96 mL) and toluene (600 ml) was stirred for 5 hours. The reaction solution was cooled to room temperature, and the resulting solid was filtered by pouring the reactant into water, and the resulting solid was purified by chloroform and ethanol to obtain intermediate K-3 (61.0 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 453.
3)3)
Figure PCTKR2019013722-appb-I000125
Figure PCTKR2019013722-appb-I000125
중간체 K-3 (45.2 g), 중간체 K-4 (52.6 g), Pd(PtBu3)2 (1.02 g), NaOtBu (38.4 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 K-5(40.5 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=862에서 피크가 확인되었다.The flask containing intermediate K-3 (45.2 g), intermediate K-4 (52.6 g), Pd (P t Bu 3 ) 2 (1.02 g), NaOtBu (38.4 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate K-5 (40.5 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M + H +] = 862.
4)4)
Figure PCTKR2019013722-appb-I000126
Figure PCTKR2019013722-appb-I000126
중간체 K-5 (12.8 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 화합물 11 (4.8 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=835에서 피크가 확인되었다.To a flask containing intermediate K-5 (12.8 g) and tert-butyl benzene (160 ml), 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give compound 11 (4.8 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 835.
제조예 12.Preparation Example 12.
1)One)
Figure PCTKR2019013722-appb-I000127
Figure PCTKR2019013722-appb-I000127
2-브로모-3,4-디클로로-1-아이오도벤젠 (70.4 g), 중간체 L-1 (54.4 g), Pd(PPh3)2 (0.51 g), K2CO3 (55.2 g) 및 물 200mL 테트라하이드로퓨란 (1000 ml)이 들어간 플라스크를 환류 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 테트라하이드로퓨란을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(에틸아세테이트/헥산)으로 정제하여 중간체 L-2(68.1 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=453에서 피크가 확인되었다.2-bromo-3,4-dichloro-1-iodobenzene (70.4 g), intermediate L-1 (54.4 g), Pd (PPh 3 ) 2 (0.51 g), K 2 CO 3 (55.2 g) and The flask containing 200 mL tetrahydrofuran (1000 ml) of water was heated to reflux and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and tetrahydrofuran to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (ethyl acetate / hexane) gave intermediate L-2 (68.1 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 453.
2)2)
Figure PCTKR2019013722-appb-I000128
Figure PCTKR2019013722-appb-I000128
중간체 L-2 (67.8 g), CH3SO2OH (96mL) 및 톨루엔 (600 ml)이 들어간 플라스크를 5시간 동안 교반하였다. 반응액을 실온까지 냉각시키고, 물에 반응물을 부은 후 생긴 고체를 여과하여 생성된 고체를 클로로포름과 에탄올로 정제하여 중간체 L-3(60.1 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=435에서 피크가 확인되었다.The flask containing intermediate L-2 (67.8 g), CH 3 SO 2 OH (96 mL) and toluene (600 ml) was stirred for 5 hours. The reaction solution was cooled to room temperature, and the resulting solid was filtered by pouring the reactant into water, and the resulting solid was purified by chloroform and ethanol to obtain intermediate L-3 (60.1 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M + H +] = 435.
3)3)
Figure PCTKR2019013722-appb-I000129
Figure PCTKR2019013722-appb-I000129
중간체 L-3 (43.4 g), 중간체 L-4 (40.6 g), Pd(PtBu3)2 (0.51 g), NaOtBu (19.2 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 L-5(37.9 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=759에서 피크가 확인되었다.The flask containing intermediate L-3 (43.4 g), intermediate L-4 (40.6 g), Pd (P t Bu 3 ) 2 (0.51 g), NaOtBu (19.2 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate L-5 (37.9 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 759.
4)4)
Figure PCTKR2019013722-appb-I000130
Figure PCTKR2019013722-appb-I000130
중간체 L-5 (33.2 g), 중간체 L-6 (17.8 g), Pd(PtBu3)2 (0.22 g), NaOtBu (8.42 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 실리카겔 컬럼 크로마토그래피 (전개액: 헥산/에틸아세테이트 = 50%/50%(부피비))로 정제하여, 중간체 L-7(18.8 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=1129에서 피크가 확인되었다.The flask with intermediate L-5 (33.2 g), intermediate L-6 (17.8 g), Pd (P t Bu 3 ) 2 (0.22 g), NaOtBu (8.42 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developer: hexane / ethyl acetate = 50% / 50% (volume ratio)) gave intermediate L-7 (18.8 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M + H +] = 1129.
5)5)
Figure PCTKR2019013722-appb-I000131
Figure PCTKR2019013722-appb-I000131
중간체 L-7 (16.8 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 화합물 12 (6.9 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=1102에서 피크가 확인되었다.To a flask containing intermediate L-7 (16.8 g) and tert-butyl benzene (160 ml), a 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to give compound 12 (6.9 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 1102.
제조예 13.Preparation Example 13.
1)One)
Figure PCTKR2019013722-appb-I000132
Figure PCTKR2019013722-appb-I000132
3-브로모-4,5-디클로로페놀 (24.2 g), 중간체 M-1 (16.9 g), Pd(PtBu3)2 (0.51 g), NaOtBu (19.2 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 재결정(메틸 tert-부틸 에테르/헥산)으로 정제하여 중간체 M-2(28.1 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=331에서 피크가 확인되었다.3-bromo-4,5-dichlorophenol (24.2 g), intermediate M-1 (16.9 g), Pd (P t Bu 3 ) 2 (0.51 g), NaOtBu (19.2 g) and toluene (400 ml) The entered flask was heated at 110 ° C. and stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by recrystallization (methyl tert-butyl ether / hexane) gave intermediate M-2 (28.1 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M + H +] = 331.
2)2)
Figure PCTKR2019013722-appb-I000133
Figure PCTKR2019013722-appb-I000133
중간체 M-2 (14.5 g), 중간체 M-3 (16.5 g), Pd(PtBu3)2 (0.22 g), NaOtBu (8.42 g) 및 톨루엔 (400 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 실리카겔 컬럼 크로마토그래피 (전개액: 헥산/에틸아세테이트 = 50%/50%(부피비))로 정제하여, 중간체 M-4(17.9 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=672에서 피크가 확인되었다.The flask with intermediate M-2 (14.5 g), intermediate M-3 (16.5 g), Pd (P t Bu 3 ) 2 (0.22 g), NaOtBu (8.42 g) and toluene (400 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developer: hexane / ethyl acetate = 50% / 50% (volume ratio)) gave intermediate M-4 (17.9 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 672.
3)3)
Figure PCTKR2019013722-appb-I000134
Figure PCTKR2019013722-appb-I000134
중간체 M-4 (10.0 g) 및 tert-부틸 벤젠 (160 ml)이 들어간 플라스크에, 아르곤 분위기 하, 0℃에서 1.7M의 tert-부틸리튬펜탄 용액 (9.2 ml)을 가하였다. 적하 종료 후, 70℃로 승온하여 4시간 교반하여 펜탄을 증류 제거하였다. -40℃로 냉각하고 삼브롬화 붕소 (1.6 ml)를 가하고, 실온으로 승온하며 4시간 교반하였다. 그 후, 다시 0℃까지 냉각하고 N,N-디이소프로필에틸아민 (6.6 ml)을 가하고, 상온에서 교반한 후 80℃에서 4시간 교반하였다. 반응액을 실온까지 냉각시키고, 물 및 에틸아세테이트를 가하여 분액한 후, 용매를 감압 하에서 증류 제거하였다. 아세토나이트릴을 가하여 중간체 M-5 (4.8 g)를 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, M/Z=645에서 피크가 확인되었다.To a flask containing intermediate M-4 (10.0 g) and tert-butyl benzene (160 ml), 1.7 M tert-butyllithium pentane solution (9.2 ml) was added at 0 ° C under an argon atmosphere. After completion of the dropwise addition, the temperature was raised to 70 ° C and stirred for 4 hours to distill off the pentane. After cooling to -40 ° C, boron tribromide (1.6 ml) was added, the temperature was raised to room temperature and stirred for 4 hours. Then, it was cooled to 0 ° C again, N, N-diisopropylethylamine (6.6 ml) was added, and the mixture was stirred at room temperature and then stirred at 80 ° C for 4 hours. The reaction solution was cooled to room temperature, separated by adding water and ethyl acetate, and then the solvent was distilled off under reduced pressure. Acetonitrile was added to obtain Intermediate M-5 (4.8 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at M / Z = 645.
4)4)
Figure PCTKR2019013722-appb-I000135
Figure PCTKR2019013722-appb-I000135
중간체 M-5 (4.1 g), 노나플루오로부탄-1-술포닐 플로라이드 (2.2 g) 및 탄산칼륨 (1.5 g)을 아세토니트릴 (40 ml)에 녹이고 50℃로 가열한 후 4시간 동안 교반하였다. 상온으로 냉각 후 증류수를 투입하여 탄산칼륨을 제거하여 중간체 M-6 (5.5 g)을 얻었다. Dissolve intermediate M-5 (4.1 g), nonafluorobutane-1-sulfonyl fluoride (2.2 g) and potassium carbonate (1.5 g) in acetonitrile (40 ml), heat to 50 ° C. and stir for 4 hours. Did. After cooling to room temperature, distilled water was added to remove potassium carbonate to obtain intermediate M-6 (5.5 g).
5)5)
Figure PCTKR2019013722-appb-I000136
Figure PCTKR2019013722-appb-I000136
중간체 M-6 (13.8 g), 중간체 M-7 (6.4 g), Pd(PtBu3)2 (0.10 g), NaOtBu (3.0 g) 및 톨루엔 (100 ml)이 들어간 플라스크를 110℃에서 가열하고, 30분 동안 교반하였다. 반응액을 실온까지 냉각시키고, sat.aq. NH4Cl 및 톨루엔을 가하여 분액한 후, 용매를 감압하에서 증류제거하였다. 실리카겔 컬럼 크로마토그래피 (전개액: 헥산/에틸아세테이트 = 50%/50%(부피비))로 정제하여, 화합물 13 (11.2 g)을 얻었다. 얻어진 고체의 질량스펙트럼 측정결과, [M+H+]=1055에서 피크가 확인되었다.The flask with intermediate M-6 (13.8 g), intermediate M-7 (6.4 g), Pd (P t Bu 3 ) 2 (0.10 g), NaOtBu (3.0 g) and toluene (100 ml) was heated at 110 ° C. And stirred for 30 minutes. The reaction solution was cooled to room temperature, and sat.aq. After adding NH 4 Cl and toluene to separate, the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developer: hexane / ethyl acetate = 50% / 50% (volume ratio)) gave compound 13 (11.2 g). As a result of the mass spectrum measurement of the obtained solid, a peak was confirmed at [M + H +] = 1055.
<실험예><Experimental Example>
실시예 1.Example 1.
ITO(indium tin oxide)가 1300Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 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 a thin film of indium tin oxide (ITO) at a thickness of 1300 에 was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer Co. was used as a detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice for 10 minutes with distilled water. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and transporting to a plasma cleaner. In addition, after the substrate was cleaned for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 하기 화합물 HAT를 50Å의 두께로 열 진공 증착하여 정공주입층을 형성하였다. 그 위에 제1 정공수송층으로 하기 화합물 HT-A 1000Å을 진공 증착하고, 연이어 제2 정공수송층으로 하기 화합물 HT-B 100Å을 증착하였다. 호스트인 BH-A와 도펀트인 화합물 1을 95 : 5의 중량비로 진공 증착하여 200Å두께의 발광층을 형성하였다. On the prepared ITO transparent electrode, the following compound HAT was thermally vacuum-deposited to a thickness of 50 Pa to form a hole injection layer. Thereafter, the following compound HT-A 1000A was vacuum-deposited as a first hole transport layer, and subsequently the following compound HT-B 100Å was deposited as a second hole transport layer. The host BH-A and the dopant Compound 1 were vacuum deposited at a weight ratio of 95: 5 to form a 200 mm thick light emitting layer.
그 다음에 전자 주입 및 전자 수송을 동시에 하는 층으로 하기 화합물 ET-A 와 하기 화합물 Liq를 1:1 비율로 300Å을 증착하였고, 이 위에 순차적으로 10Å두께로 리튬 플루라이드(LiF)와 1,000Å두께로 알루미늄을 증착하여 음극을 형성하여, 유기 발광 소자를 제조하였다.Subsequently, 300 Å of the following compound ET-A and the following compound Liq were deposited in a 1: 1 ratio as a layer that simultaneously performs electron injection and electron transport, and sequentially, lithium fluoride (LiF) and 1,000 Å thick with a thickness of 10 위에 An anode was formed by depositing aluminum with a furnace, thereby manufacturing an organic light emitting device.
상기의 과정에서 유기물의 증착속도는 0.4 ~ 1.0 Å/sec를 유지하였고, 음극의 리튬플루오라이드는 0.3 Å/sec알루미늄은 2 Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 1 Х 10-7 내지 5 Х 10-8 torr를 유지하여, 유기 발광 소자를 제작하였다.The deposition rate of the organic material in the above process, 0.4 to 1.0 was maintained Å / sec, the lithium fluoride of the cathode was maintained at the deposition speed of 0.3 Å / sec of aluminum is 2 Å / sec, the deposition upon the degree of vacuum is 1 Х 10 - By maintaining 7 to 5 Х 10 -8 torr, an organic light emitting device was manufactured.
Figure PCTKR2019013722-appb-I000137
Figure PCTKR2019013722-appb-I000137
실시예 2 내지 14Examples 2 to 14
상기 실시예 1에서 발광층 물질로 하기 표 1에 기재된 호스트 및 도펀트 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 유기 발광 소자를 제조했다. An organic light-emitting device was manufactured in the same manner as in Example 1, except that the host and dopant compounds described in Table 1 below were used as the light-emitting layer material in Example 1.
Figure PCTKR2019013722-appb-I000138
Figure PCTKR2019013722-appb-I000138
Figure PCTKR2019013722-appb-I000139
Figure PCTKR2019013722-appb-I000139
비교예 1 내지 4Comparative Examples 1 to 4
상기 실시예 1에서 발광층 물질로 하기 표 1에 기재된 호스트 및 도펀트 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 유기 발광 소자를 제조했다.An organic light-emitting device was manufactured in the same manner as in Example 1, except that the host and dopant compounds described in Table 1 below were used as the light-emitting layer material in Example 1.
Figure PCTKR2019013722-appb-I000140
Figure PCTKR2019013722-appb-I000140
실시예 15 내지 19 및 비교예 5Examples 15 to 19 and Comparative Example 5
상기 실시예 1에서 발광층 물질로 하기 표 1에 기재된 호스트 및 도펀트 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 유기 발광 소자를 제조했다. 구체적으로, 호스트는 실시예 1의 BH-A 대신 제1 호스트 및 제2 호스트를 1:1 중량비로 사용하였다. An organic light-emitting device was manufactured in the same manner as in Example 1, except that the host and dopant compounds described in Table 1 below were used as the light-emitting layer material in Example 1. Specifically, the host used the first host and the second host in a 1: 1 weight ratio instead of the BH-A of Example 1.
상기 실시예 1 내지 19 및 비교예 1 내지 5에 의해 제작된 유기 발광 소자를 10 mA/cm2의 전류밀도에서 구동 전압 및 효율을 측정하였고, 20mA/cm2의 전류밀도에서 초기 휘도 대비 97%가 되는 시간(T97)을 측정하였다. 그 결과를 하기 표 1에 나타내었다.The driving voltage and efficiency of the organic light emitting devices manufactured by Examples 1 to 19 and Comparative Examples 1 to 5 were measured at a current density of 10 mA / cm 2 , and 97% of the initial luminance at a current density of 20 mA / cm 2 . Time (T97) was measured. The results are shown in Table 1 below.
제1 호스트(발광층)First host (light emitting layer) 제2 호스트(발광층)2nd host (light emitting layer) 도펀트(발광층)Dopant (light emitting layer) 10mA/cm2 10mA / cm 2 20mA/cm2 20mA / cm 2
구동전압(V)Driving voltage (V) 발광효율(Cd/A)Luminous efficiency (Cd / A) 수명, T97(시간)Lifetime, T97 (hours)
실시예 1Example 1 BH-ABH-A -- 화합물 1 Compound 1 4.3 4.3 5.5 5.5 188188
실시예 2Example 2 BH-ABH-A -- 화합물 3Compound 3 4.2 4.2 5.8 5.8 196 196
실시예 3Example 3 BH-ABH-A -- 화합물 4Compound 4 4.2 4.2 6.1 6.1 230 230
실시예 4Example 4 BH-ABH-A -- 화합물 6Compound 6 4.3 4.3 6.0 6.0 269 269
실시예 5Example 5 BH-ABH-A -- 화합물 9Compound 9 4.2 4.2 6.5 6.5 230 230
실시예 6Example 6 BH-ABH-A -- 화합물 10Compound 10 4.1 4.1 6.0 6.0 238 238
실시예 7Example 7 BH-ABH-A -- 화합물 13Compound 13 3.8 3.8 6.0 6.0 230 230
비교예 1Comparative Example 1 BH-ABH-A -- R-1R-1 4.8 4.8 5.1 5.1 120120
비교예 2Comparative Example 2 BH-ABH-A -- R-2R-2 4.5 4.5 4.8 4.8 146146
실시예 8Example 8 BH-BBH-B -- 화합물 1Compound 1 4.3 4.3 5.2 5.2 201 201
실시예 9Example 9 BH-BBH-B -- 화합물 3Compound 3 4.3 4.3 6.1 6.1 231 231
실시예 10Example 10 BH-BBH-B -- 화합물 4Compound 4 4.1 4.1 6.6 6.6 230 230
비교예 3Comparative Example 3 BH-BBH-B -- R-1R-1 4.4 4.4 5.0 5.0 170 170
실시예 11Example 11 BH-CBH-C -- 화합물 6Compound 6 4.1 4.1 5.9 5.9 180 180
실시예 12Example 12 BH-CBH-C -- 화합물 9Compound 9 4.5 4.5 5.8 5.8 290 290
실시예 13Example 13 BH-CBH-C -- 화합물 10Compound 10 4.0 4.0 6.9 6.9 240 240
실시예 14Example 14 BH-CBH-C -- 화합물 13Compound 13 3.9 3.9 5.9 5.9 218 218
비교예4Comparative Example 4 BH-CBH-C -- R-2R-2 4.4 4.4 5.0 5.0 166 166
실시예 15Example 15 BH-ABH-A BH-DBH-D 화합물 1Compound 1 4.0 4.0 5.5 5.5 185 185
실시예 16Example 16 BH-ABH-A BH-EBH-E 화합물 3Compound 3 4.2 4.2 5.7 5.7 250 250
실시예 17Example 17 BH-ABH-A BH-EBH-E 화합물 4Compound 4 3.8 3.8 6.1 6.1 200 200
실시예 18Example 18 BH-BBH-B BH-DBH-D 화합물 6Compound 6 3.6 3.6 6.2 6.2 209 209
실시예 19Example 19 BH-BBH-B BH-EBH-E 화합물 9Compound 9 3.9 3.9 6.6 6.6 221 221
비교예 5Comparative Example 5 BH-BBH-B BH-EBH-E R-1R-1 4.1 4.1 4.3 4.3 145 145
상기 표 1에서 보는 바와 같이, 화학식 1의 구조를 갖는 화합물을 사용한 실시예 1 내지 19의 소자는 비교예 1 내지 5의 소자보다 저전압, 고효율 및 장수명의 특성을 가지는 것을 확인할 수 있다.As shown in Table 1, it can be seen that the devices of Examples 1 to 19 using the compound having the structure of Formula 1 have characteristics of lower voltage, higher efficiency, and longer life than the devices of Comparative Examples 1 to 5.

Claims (8)

  1. 하기 화학식 1로 표시되는 헤테로고리 화합물:Heterocyclic compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2019013722-appb-I000141
    Figure PCTKR2019013722-appb-I000141
    [화학식 2][Formula 2]
    Figure PCTKR2019013722-appb-I000142
    Figure PCTKR2019013722-appb-I000142
    상기 화학식 1 및 화학식 2에 있어서,In Formula 1 and Formula 2,
    R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, R51 내지 R55, 및 R61 내지 R64는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기, 치환 또는 비치환된 알콕시기, 치환 또는 비치환된 실릴기, 치환 또는 비치환된 포스핀옥사이드기, 치환 또는 비치환된 아민기, 치환 또는 비치환된 붕소기, 치환 또는 비치환의 아릴기, 또는 치환 또는 비치환의 헤테로고리기이거나, 인접한 치환기와 결합하여 치환 또는 비치환된 고리를 형성하고,R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , R 51 to R 55 , And R 61 to R 64 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted Or an unsubstituted silyl group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted amine group, a substituted or unsubstituted boron group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, Combines with adjacent substituents to form a substituted or unsubstituted ring,
    상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 2개의 치환기 그룹; 및 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 치환기가 결합하여 형성된 치환 또는 비치환된 고리의 인접한 2개의 치환기 그룹 중 1 이상의 그룹이 상기 화학식 2의 점선과 결합된다.R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And two adjacent substituent groups among R 51 to R 55 ; And R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And one or more groups of two adjacent substituent groups of a substituted or unsubstituted ring formed by combining adjacent substituents among R 51 to R 55 are bonded to the dotted line of Formula 2.
  2. 청구항 1에 있어서, 상기 화학식 1은 하기 화학식 1-1 내지 1-7 중 어느 하나로 표시되는 것인 헤테로고리 화합물:The method according to claim 1, wherein Formula 1 is a heterocyclic compound represented by any one of the following Formulas 1-1 to 1-7:
    [화학식 1-1][Formula 1-1]
    Figure PCTKR2019013722-appb-I000143
    Figure PCTKR2019013722-appb-I000143
    [화학식 1-2][Formula 1-2]
    Figure PCTKR2019013722-appb-I000144
    Figure PCTKR2019013722-appb-I000144
    [화학식 1-3][Formula 1-3]
    Figure PCTKR2019013722-appb-I000145
    Figure PCTKR2019013722-appb-I000145
    [화학식 1-4][Formula 1-4]
    Figure PCTKR2019013722-appb-I000146
    Figure PCTKR2019013722-appb-I000146
    [화학식 1-5][Formula 1-5]
    Figure PCTKR2019013722-appb-I000147
    Figure PCTKR2019013722-appb-I000147
    [화학식 1-6][Formula 1-6]
    Figure PCTKR2019013722-appb-I000148
    Figure PCTKR2019013722-appb-I000148
    [화학식 1-7][Formula 1-7]
    Figure PCTKR2019013722-appb-I000149
    Figure PCTKR2019013722-appb-I000149
    상기 화학식 1-1 내지 1-7에 있어서, In Chemical Formulas 1-1 to 1-7,
    R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, R51 내지 R55, 및 R61 내지 R64는 화학식 1 및 2에서 정의한 바와 같고,R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43, R 51 to R 55 , and R 61 to R 64 are as defined in Formulas 1 and 2,
    R71 내지 R74, R81 내지 R84, R91 내지 R94, 및 Ra 내지 Re는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기, 치환 또는 비치환된 알콕시기, 치환 또는 비치환된 실릴기, 치환 또는 비치환된 포스핀옥사이드기, 치환 또는 비치환된 아민기, 치환 또는 비치환의 아릴기, 또는 치환 또는 비치환의 헤테로고리기이거나, 인접한 치환기와 결합하여 치환 또는 비치환된 고리를 형성하고,R 71 to R 74 , R 81 to R 84 , R 91 to R 94 , And Ra to Re are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted A substituted silyl group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or in combination with an adjacent substituent, substituted or unsubstituted Form a ring,
    a 및 c는 각각 0 내지 3의 정수이고,a and c are each an integer from 0 to 3,
    b 및 f는 각각 0 또는 1이고,b and f are each 0 or 1,
    d 및 e는 각각 0 내지 2의 정수이고, d and e are each an integer from 0 to 2,
    a, 및 c 내지 e가 각각 2 이상인 경우, 괄호 내의 치환기는 서로 같거나 상이하다.When a, and c to e are each 2 or more, the substituents in parentheses are the same as or different from each other.
  3. 청구항 1에 있어서, 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 2개의 치환기 그룹; 및 상기 R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55 중 인접한 치환기가 결합하여 형성된 치환 또는 비치환된 고리의 인접한 2개의 치환기 그룹 중 1개 내지 4개의 그룹이 상기 화학식 2의 점선과 결합되는 것인 헤테로고리 화합물.The method according to claim 1, R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And two adjacent substituent groups among R 51 to R 55 ; And R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , And one to four groups of two adjacent substituent groups of a substituted or unsubstituted ring formed by combining adjacent substituents among R 51 to R 55 are bonded to the dotted line of Formula 2 above.
  4. 청구항 1에 있어서, 상기 화학식 1은 하기 화학식 2-1 내지 2-5 중 어느 하나로 표시되는 것인 헤테로고리 화합물:The method according to claim 1, wherein Formula 1 is a heterocyclic compound represented by any one of the following Formulas 2-1 to 2-5:
    [화학식 2-1][Formula 2-1]
    Figure PCTKR2019013722-appb-I000150
    Figure PCTKR2019013722-appb-I000150
    [화학식 2-2][Formula 2-2]
    Figure PCTKR2019013722-appb-I000151
    Figure PCTKR2019013722-appb-I000151
    [화학식 2-3][Formula 2-3]
    Figure PCTKR2019013722-appb-I000152
    Figure PCTKR2019013722-appb-I000152
    [화학식 2-4][Formula 2-4]
    Figure PCTKR2019013722-appb-I000153
    Figure PCTKR2019013722-appb-I000153
    [화학식 2-5][Formula 2-5]
    Figure PCTKR2019013722-appb-I000154
    Figure PCTKR2019013722-appb-I000154
    상기 화학식 2-1 내지 2-5에 있어서, In Chemical Formulas 2-1 to 2-5,
    R11 내지 R14, R21 내지 R24, R31 내지 R35, R41 내지 R43, 및 R51 내지 R55는 상기 화학식 1 및 2에서 정의한 바와 같고,R 11 to R 14 , R 21 to R 24 , R 31 to R 35 , R 41 to R 43 , and R 51 to R 55 are the same as defined in Chemical Formulas 1 and 2,
    X1 및 X2는 서로 같거나 상이하고, 각각 독립적으로 O, S 또는 NR이며,X 1 and X 2 are the same as or different from each other, and each independently O, S or NR,
    R, R101 내지 R111, 및 R201 내지 R228는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 니트릴기, 할로겐기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기, 치환 또는 비치환된 알콕시기, 치환 또는 비치환된 실릴기, 치환 또는 비치환된 포스핀옥사이드기, 치환 또는 비치환된 아민기, 치환 또는 비치환된 붕소기, 치환 또는 비치환의 아릴기, 치환 또는 비치환의 헤테로고리기이고,R, R 101 to R 111 , and R 201 to R 228 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted Or an unsubstituted alkoxy group, a substituted or unsubstituted silyl group, a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted amine group, a substituted or unsubstituted boron group, a substituted or unsubstituted aryl group, a substituted or Unsubstituted heterocyclic group,
    n1 내지 n9는 각각 0 내지 2의 정수이며,n1 to n9 are each an integer of 0 to 2,
    n10 및 n11은 각각 0 내지 4의 정수이고,n10 and n11 are each an integer from 0 to 4,
    n1 내지 n11이 각각 2 이상인 경우, 괄호 내의 치환기는 서로 같거나 상이하다.When n1 to n11 are each 2 or more, the substituents in parentheses are the same as or different from each other.
  5. 청구항 1에 있어서, 상기 화학식 1은 하기 화합물 중에서 선택되는 어느 하나인 것인 헤테로고리 화합물: The method according to claim 1, wherein Formula 1 is a heterocyclic compound that is any one selected from the following compounds:
    Figure PCTKR2019013722-appb-I000155
    Figure PCTKR2019013722-appb-I000156
    Figure PCTKR2019013722-appb-I000157
    Figure PCTKR2019013722-appb-I000155
    Figure PCTKR2019013722-appb-I000156
    Figure PCTKR2019013722-appb-I000157
    Figure PCTKR2019013722-appb-I000158
    Figure PCTKR2019013722-appb-I000158
    Figure PCTKR2019013722-appb-I000159
    Figure PCTKR2019013722-appb-I000159
    Figure PCTKR2019013722-appb-I000160
    Figure PCTKR2019013722-appb-I000160
    Figure PCTKR2019013722-appb-I000161
    Figure PCTKR2019013722-appb-I000161
    Figure PCTKR2019013722-appb-I000162
    Figure PCTKR2019013722-appb-I000162
    Figure PCTKR2019013722-appb-I000163
    Figure PCTKR2019013722-appb-I000163
    Figure PCTKR2019013722-appb-I000164
    Figure PCTKR2019013722-appb-I000164
    Figure PCTKR2019013722-appb-I000165
    Figure PCTKR2019013722-appb-I000165
    Figure PCTKR2019013722-appb-I000166
    Figure PCTKR2019013722-appb-I000166
    Figure PCTKR2019013722-appb-I000167
    Figure PCTKR2019013722-appb-I000167
    Figure PCTKR2019013722-appb-I000168
    Figure PCTKR2019013722-appb-I000168
    Figure PCTKR2019013722-appb-I000169
    Figure PCTKR2019013722-appb-I000169
    Figure PCTKR2019013722-appb-I000170
    Figure PCTKR2019013722-appb-I000170
    Figure PCTKR2019013722-appb-I000171
    Figure PCTKR2019013722-appb-I000171
    Figure PCTKR2019013722-appb-I000172
    Figure PCTKR2019013722-appb-I000172
    Figure PCTKR2019013722-appb-I000173
    Figure PCTKR2019013722-appb-I000173
    Figure PCTKR2019013722-appb-I000174
    Figure PCTKR2019013722-appb-I000174
    Figure PCTKR2019013722-appb-I000175
    Figure PCTKR2019013722-appb-I000175
    Figure PCTKR2019013722-appb-I000176
    Figure PCTKR2019013722-appb-I000176
    Figure PCTKR2019013722-appb-I000177
    Figure PCTKR2019013722-appb-I000177
    Figure PCTKR2019013722-appb-I000178
    Figure PCTKR2019013722-appb-I000178
    Figure PCTKR2019013722-appb-I000179
    Figure PCTKR2019013722-appb-I000179
    Figure PCTKR2019013722-appb-I000180
    Figure PCTKR2019013722-appb-I000180
    Figure PCTKR2019013722-appb-I000181
    Figure PCTKR2019013722-appb-I000181
    Figure PCTKR2019013722-appb-I000182
    Figure PCTKR2019013722-appb-I000182
    Figure PCTKR2019013722-appb-I000183
    Figure PCTKR2019013722-appb-I000183
    Figure PCTKR2019013722-appb-I000184
    Figure PCTKR2019013722-appb-I000184
    Figure PCTKR2019013722-appb-I000185
    Figure PCTKR2019013722-appb-I000185
    Figure PCTKR2019013722-appb-I000186
    Figure PCTKR2019013722-appb-I000186
    Figure PCTKR2019013722-appb-I000187
    Figure PCTKR2019013722-appb-I000187
    Figure PCTKR2019013722-appb-I000188
    Figure PCTKR2019013722-appb-I000188
    Figure PCTKR2019013722-appb-I000189
    Figure PCTKR2019013722-appb-I000189
    Figure PCTKR2019013722-appb-I000190
    Figure PCTKR2019013722-appb-I000190
    Figure PCTKR2019013722-appb-I000191
    Figure PCTKR2019013722-appb-I000191
    Figure PCTKR2019013722-appb-I000192
    Figure PCTKR2019013722-appb-I000192
    Figure PCTKR2019013722-appb-I000193
    Figure PCTKR2019013722-appb-I000193
    Figure PCTKR2019013722-appb-I000194
    Figure PCTKR2019013722-appb-I000194
    Figure PCTKR2019013722-appb-I000195
    Figure PCTKR2019013722-appb-I000195
    Figure PCTKR2019013722-appb-I000196
    Figure PCTKR2019013722-appb-I000196
    Figure PCTKR2019013722-appb-I000197
    Figure PCTKR2019013722-appb-I000197
    Figure PCTKR2019013722-appb-I000198
    Figure PCTKR2019013722-appb-I000198
    Figure PCTKR2019013722-appb-I000199
    Figure PCTKR2019013722-appb-I000199
    Figure PCTKR2019013722-appb-I000200
    Figure PCTKR2019013722-appb-I000200
    Figure PCTKR2019013722-appb-I000201
    Figure PCTKR2019013722-appb-I000201
    Figure PCTKR2019013722-appb-I000202
    Figure PCTKR2019013722-appb-I000202
    Figure PCTKR2019013722-appb-I000203
    Figure PCTKR2019013722-appb-I000203
    Figure PCTKR2019013722-appb-I000204
    Figure PCTKR2019013722-appb-I000204
    Figure PCTKR2019013722-appb-I000205
    Figure PCTKR2019013722-appb-I000205
    Figure PCTKR2019013722-appb-I000206
    Figure PCTKR2019013722-appb-I000206
    Figure PCTKR2019013722-appb-I000207
    Figure PCTKR2019013722-appb-I000207
    Figure PCTKR2019013722-appb-I000208
    Figure PCTKR2019013722-appb-I000208
    Figure PCTKR2019013722-appb-I000209
    Figure PCTKR2019013722-appb-I000209
    Figure PCTKR2019013722-appb-I000210
    Figure PCTKR2019013722-appb-I000210
    Figure PCTKR2019013722-appb-I000211
    Figure PCTKR2019013722-appb-I000211
    Figure PCTKR2019013722-appb-I000212
    Figure PCTKR2019013722-appb-I000212
    Figure PCTKR2019013722-appb-I000213
    Figure PCTKR2019013722-appb-I000213
    Figure PCTKR2019013722-appb-I000214
    Figure PCTKR2019013722-appb-I000214
    Figure PCTKR2019013722-appb-I000215
    Figure PCTKR2019013722-appb-I000215
    Figure PCTKR2019013722-appb-I000216
    Figure PCTKR2019013722-appb-I000216
    Figure PCTKR2019013722-appb-I000217
    Figure PCTKR2019013722-appb-I000217
    Figure PCTKR2019013722-appb-I000218
    Figure PCTKR2019013722-appb-I000218
    Figure PCTKR2019013722-appb-I000219
    Figure PCTKR2019013722-appb-I000219
    Figure PCTKR2019013722-appb-I000220
    Figure PCTKR2019013722-appb-I000220
    Figure PCTKR2019013722-appb-I000221
    Figure PCTKR2019013722-appb-I000221
    Figure PCTKR2019013722-appb-I000222
    Figure PCTKR2019013722-appb-I000222
    Figure PCTKR2019013722-appb-I000223
    Figure PCTKR2019013722-appb-I000223
    Figure PCTKR2019013722-appb-I000224
    Figure PCTKR2019013722-appb-I000224
    Figure PCTKR2019013722-appb-I000225
    Figure PCTKR2019013722-appb-I000225
    Figure PCTKR2019013722-appb-I000226
    Figure PCTKR2019013722-appb-I000226
    Figure PCTKR2019013722-appb-I000227
    Figure PCTKR2019013722-appb-I000227
    Figure PCTKR2019013722-appb-I000228
    Figure PCTKR2019013722-appb-I000228
    Figure PCTKR2019013722-appb-I000229
    Figure PCTKR2019013722-appb-I000229
    Figure PCTKR2019013722-appb-I000230
    .
    Figure PCTKR2019013722-appb-I000230
    .
  6. 제1 전극; 상기 제1 전극에 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 또는 2층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1 층 이상은 청구항 1 내지 5 중 어느 한 항의 헤테로고리 화합물을 포함하는 것인 유기 발광 소자.A first electrode; A second electrode provided opposite to the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer comprises the heterocyclic compound of claim 1. Organic light emitting device.
  7. 청구항 6에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 호스트와 도펀트를 99.9:0.1 내지 80:20의 질량비로 포함하는 것인 유기 발광 소자.The method according to claim 6, The organic layer comprises a light emitting layer, the light emitting layer is an organic light emitting device comprising a host and a dopant in a mass ratio of 99.9: 0.1 to 80:20.
  8. 청구항 6에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 헤테로고리 화합물을 포함하는 것인 유기 발광 소자.The method according to claim 6, The organic material layer comprises a light emitting layer, the light emitting layer is an organic light emitting device comprising the heterocyclic compound.
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