WO2016003171A1 - Heterocyclic compound and organic light emitting element using same - Google Patents

Heterocyclic compound and organic light emitting element using same Download PDF

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Publication number
WO2016003171A1
WO2016003171A1 PCT/KR2015/006723 KR2015006723W WO2016003171A1 WO 2016003171 A1 WO2016003171 A1 WO 2016003171A1 KR 2015006723 W KR2015006723 W KR 2015006723W WO 2016003171 A1 WO2016003171 A1 WO 2016003171A1
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unsubstituted
substituted
monocyclic
polycyclic
compound
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PCT/KR2015/006723
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French (fr)
Korean (ko)
Inventor
이정현
정수진
강상규
김기용
김동준
최진석
최대혁
음성진
이주동
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희성소재(주)
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Priority claimed from KR1020140127222A external-priority patent/KR101579289B1/en
Application filed by 희성소재(주) filed Critical 희성소재(주)
Priority to US15/318,901 priority Critical patent/US10446765B2/en
Priority to CN201580035950.0A priority patent/CN106661020B/en
Priority to JP2016575816A priority patent/JP6513719B2/en
Publication of WO2016003171A1 publication Critical patent/WO2016003171A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/165—Electron transporting layers comprising dopants
    • 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]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • 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]
    • H10K50/19—Tandem OLEDs

Definitions

  • the present invention relates to a novel heterocyclic compound and an organic light emitting device using the same.
  • An electroluminescent device is one type of self-luminous display device, and has advantages of wide viewing angle, excellent contrast, and high response speed.
  • the organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes couple to each other in the organic thin film and form a pair, which then extinguishes and emits light.
  • the organic thin film may be composed of a single layer or a multilayer, if necessary.
  • the material of the organic thin film may have a light emitting function as needed.
  • a compound capable of forming a light emitting layer by itself may be used, or a compound capable of serving as a host or a dopant of a host-dopant light emitting layer may be used.
  • a compound capable of performing a role such as hole injection, hole transport, electron blocking, hole blocking, electron transport or electron injection may be used.
  • the present invention provides a novel heterocyclic compound and an organic light emitting device using the same.
  • One embodiment of the present disclosure provides compounds of formula 1:
  • X is NR 3 , CR 4 R 5 , S, O or Se,
  • a is an integer of 0 to 4, and when a is 2 or more, R 1 are the same or different from each other,
  • b is an integer of 0 to 6, and when b is 2 or more, R 2 are the same or different from each other,
  • R 4 to R 9 are the same or different and each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl.
  • one embodiment of the present invention is an organic light emitting device including a cathode, a cathode, and at least one organic layer provided between the anode and the cathode, wherein at least one of the organic layers includes an organic light emitting Device.
  • the compound described in this specification can be used as an organic layer material of an organic light emitting device.
  • the compound can be used as an electron transport layer, a hole blocking layer, a light emitting layer, and the like in an organic light emitting device.
  • the compound of Formula 1 can be used as a material for an electron transport layer, a hole blocking layer, and a light emitting layer of an organic light emitting device.
  • the compound of Formula 1 can be used as an electron transporting layer or a material of a light emitting layer.
  • FIGS. 1 to 3 illustrate a stacking order of electrodes and organic layers of an organic light emitting diode according to embodiments of the present invention.
  • Fig. 5 shows a PL measurement graph of Compound 1-12 at a wavelength of 233 nm.
  • FIG. 9 shows a PL measurement graph of a compound 1-124 at a wavelength of 240 nm.
  • FIG. 10 shows a PL measurement graph of Compound 1-318 at a wavelength of 309 nm.
  • FIG. 11 shows a PL measurement graph of Compound 2-36 at a wavelength of 282 nm.
  • Fig. 13 shows a PL measurement graph of compound 3-39 at a wavelength of 307 nm.
  • 16 shows a PL measurement graph of Compound 4-58 at a wavelength of 290 nm.
  • 17 shows a PL measurement graph of Compound 4-76 at a wavelength of 267 nm.
  • 19 is a graph showing the LTPL measurement at a wavelength of 309 nm of the compound 1-1.
  • 20 is a graph showing the LTPL measurement of Compound 1-12 at a wavelength of 338 nm.
  • 21 is a graph showing the LTPL measurement at a wavelength of 310 nm of Compound 1-36.
  • 24 is a graph showing the LTPL measurement at 408 nm wavelength of Compound 2-38.
  • 25 is a graph showing the LTPL measurement at a wavelength of 307 nm of the compound 3-39.
  • 26 is a graph showing the LTPL measurement at a wavelength of 268 nm of Compound 3-46.
  • 27 is a graph showing the LTPL measurement at 278 nm wavelength of Compound 4-56.
  • 29 is a graph showing the LTPL measurement at 365 nm wavelength of Compound 4-76.
  • the compounds described in this specification can be represented by the above formula (1).
  • the compound of Formula 1 may be used as an organic material layer material of an organic light emitting diode according to the structural features of the core structure and the substituent.
  • substituted or unsubstituted "halogen C 1 to C 60 linear or branched alkyl; C 2 to C 60 straight or branched chain alkenyl; C 2 to C 60 linear or branched alkynyl; C 1 to C 60 straight or branched chain alkoxy; C 3 to C 60 monocyclic or polycyclic cycloalkyl; A C 2 to C 60 monocyclic or polycyclic heterocycloalkyl; C 6 to C 60 monocyclic or polycyclic aryl; C 2 to C 60 monocyclic or polycyclic heteroaryl; A C 1 to C 20 alkylamine, a C 6 to C 60 monocyclic or polycyclic arylamine, and a C 2 to C 60 monocyclic or polycyclic heteroaryl Amine, or substituted or unsubstituted with a substituent having two or more of the substituents bonded thereto, or substituted or unsubstituted with a substituent to which at least
  • R, R 'and R " are the same or different and each independently hydrogen, substituted or unsubstituted C 1 to C 60 linear or branched alkyl, substituted or unsubstituted C 3 to C 60 monocyclic Substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl.
  • R, R 'and R " are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, halogen, C 6 to C 60 aryl and C 2 to C 60 hetero C 1 -C 60 straight or branched chain alkyl substituted or unsubstituted with one or more substituents selected from halogen, C 6 -C 60 aryl and C 2 -C 60 heteroaryl, A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl, substituted or unsubstituted with at least one substituent selected from deuterium, halogen, C 6 to C 60 aryl and C 2 to C 60 heteroaryl, unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or heavy hydrogen, halogen, C 6 to C aryl and at least one selected from the group consisting of heteroaryl of C 2 to C 60 of the 60 substituent is substituted or unsubsti
  • the halogen may be fluorine, chlorine, bromine or iodine.
  • alkyl includes straight or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents.
  • the carbon number of the alkyl may be 1 to 60, specifically 1 to 40, more specifically 1 to 20.
  • alkenyl includes straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents.
  • the carbon number of the alkenyl may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20.
  • alkynyl includes a straight chain or a branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents.
  • the carbon number of the alkynyl may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20.
  • the cycloalkyl includes monocyclic or polycyclic rings having 3 to 60 carbon atoms, and may be further substituted by other substituents.
  • the polycyclic ring means a group in which cycloalkyl is directly connected to another ring group or condensed.
  • the other ring group may be a cycloalkyl group, but may be other ring groups such as heterocycloalkyl, aryl, heteroaryl, and the like.
  • the carbon number of the cycloalkyl may be 3 to 60, specifically 3 to 40, more particularly 5 to 20.
  • heterocycloalkyl includes O, S, Se, N or Si as a heteroatom and includes monocyclic or polycyclic rings having 2 to 60 carbon atoms, and may be further substituted by other substituents.
  • the polycyclic ring means a group in which heterocycloalkyl is directly connected to another ring group or condensed.
  • the other ring group may be heterocycloalkyl, but may be other ring groups such as cycloalkyl, aryl, heteroaryl, and the like.
  • the heterocycloalkyl may have from 2 to 60 carbon atoms, specifically from 2 to 40, more specifically from 3 to 20 carbon atoms.
  • aryl includes monocyclic or polycyclic rings having 6 to 60 carbon atoms and may be further substituted by other substituents.
  • the polycyclic ring means a group in which aryl is directly connected to another ring group or condensed.
  • the other ring group may be aryl, but may be other ring groups such as cycloalkyl, heterocycloalkyl, heteroaryl and the like.
  • Aryl includes a spiro group.
  • the carbon number of the aryl may be 6 to 60, specifically 6 to 40, more specifically 6 to 25.
  • aryl examples include phenyl, biphenyl, triphenyl, naphthyl, anthryl, klycenyl, phenanthrenyl, perylenyl, fluoranthenyl, triphenylenyl, phenalenyl, pyrenyl, tetracenyl, pentacenyl, But are not limited to, fluorenyl, indenyl, acenaphthylenyl, benzofluorenyl, spirobifluorenyl, 2,3-dihydro-1H-indenyl, and condensed rings thereof.
  • the spiro group is a group including a spiro structure and may have from 15 to 60 carbon atoms.
  • a spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro-bonded to a fluorene group.
  • the spiro group includes groups of the following structural formulas.
  • heteroaryl includes S, O, Se, N or Si as a heteroatom and includes monocyclic or polycyclic rings having 2 to 60 carbon atoms and may be further substituted by other substituents.
  • polycyclic means a heteroaryl group directly bonded to another ring group or condensed therewith.
  • the other ring group may be heteroaryl, but may be other ring groups such as cycloalkyl, heterocycloalkyl, aryl, and the like.
  • the heteroaryl may have 2 to 60 carbon atoms, specifically 2 to 40, more specifically 3 to 25 carbon atoms.
  • heteroaryl examples include pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thiophene, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, Thiazolyl, thiazolyl, pyrazinyl, thiopyranyl, diazinyl, oxazinyl, thiazinyl, dioxinyl, triazinyl, tetrazinyl, quinolyl, iso And examples thereof include quinolyl, quinolyl, quinazolinyl, isoquinazolinyl, quinolyl, naphthyridyl, acridyl, phenanthridinyl, imidazopyridyl, diazanaphthyl, triazinene, indolyl,
  • the amine is -NH 2; Dialkylamines; Diarylamine; Diheteroarylamine; Alkylarylamines; Alkylheteroarylamines; And arylheteroarylamine.
  • the number of carbon atoms is not particularly limited, but is preferably 1 to 30.
  • amine examples include methylamine, dimethylamine, ethylamine, diethylamine, phenylamine, naphthylamine, biphenylamine, diviphenylamine, anthracenylamine, 9-methyl-anthracenylamine, diphenylamine, phenyl Naphthylamine, ditolylamine, phenyltolylamine, triphenylamine, and the like, but are not limited thereto.
  • X in the formula (1) is NR 3 , and at least one of Y and R 3 is - (L) m - (Z) n ,
  • X in formula (1) is CR 4 R 5 , S, O or Se, Y is - (L) m - (Z) n ,
  • n 1 to 6
  • n is an integer of 1 to 5
  • R 4 , R 5 and R 10 to R 12 are each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl.
  • X in the formula (1) is NR 3 , and at least one of Y and R 3 is - (L) m - (Z) n ,
  • X is CR 4 R 5 , S, O or Se
  • Y is - (L) m - (Z) n ,
  • n 1 to 6
  • n is an integer of 1 to 5
  • R, R ', R ", R 4, R 5 and R 10 to R 12 are, and the same as or different from each other, each independently represent hydrogen, the heavy hydrogen, halogen, C 6 to monocyclic of C 60 or unsubstituted aryl, and C 2 to C 60 monocyclic or polycyclic heteroaryl, 1-alkyl of at least substituted with a substituent or a straight chain of the unsubstituted C 1 to C 60 unsubstituted or branched chain is selected from; deuterium, halogen, C 6 to C 60 monocyclic or polycyclic aryl and C 2 to C 60 monocyclic or polycyclic heteroaryl group unsubstituted or substituted by one or more substituents selected from C 3 to monocyclic of C 60 or polycyclic cycloalkyl; deuterium, halogen, a monocyclic of C 6 to C 60 or polycyclic aryl and C 2 to C 60 monocyclic or polycyclic heteroaryl group unsubstit
  • L is a direct bond;
  • Z is a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl, wherein said heteroaryl is at least one selected from N, O and S as a heteroatom One.
  • Z is X 1 and X 2 are substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aromatic hydrocarbon rings; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic aromatic heterocyclic ring.
  • Y 1 to Y 5 are the same or different and each independently represent S, NY 'or CY'Y "
  • Y 'and Y are the same or different and each is independently hydrogen, substituted or unsubstituted alkyl, a linear or branched unsubstituted C 1 to C 60; of the substituted or unsubstituted C 6 to C 60 monocyclic or Aryl of a polycyclic ring.
  • X is NR 3
  • at least one of Y and R 3 is - (L) m - (Z) n , Substituted phenylene;
  • heteroarylene substituted or unsubstituted C 5 Z, m and n are the same as in the above-mentioned one condition, wherein Z is bonded at the para or meta position relative to the atom bonded to the core L.
  • X in the above first embodiment is NR 3
  • Y is - (L) m - (Z) n
  • R 3 is the same as in the above- L
  • Z, m and n are the same as in the first embodiment described above
  • Z is bonded to the para position with respect to the atom bonded to the core of L.
  • X in the above first embodiment is NR 3
  • Y is - (L) m - (Z) n
  • R 3 is the same as in the above- L
  • Z, m and n are the same as in the above-mentioned first embodiment
  • Z is bonded to the meta position with respect to the atom bonded to the core of L.
  • X in the above first embodiment is NR 3
  • R 3 is - (L) m - (Z) n
  • X in the above first embodiment is NR 3
  • R 3 is - (L) m - (Z) n
  • X is CR 4 R 5 , S, O or Se
  • Y is - (L) m - (Z) n
  • R 4 , R 5 , Z, m and n are the same as in the above-mentioned one embodiment
  • Z is bonded to the para or meta position with respect to the atom bonded to the core of L.
  • X of the above-described second condition is CR 4 R 5, and S, O or Se
  • Y is - (L) m - (Z ) and n
  • R 4, R 5 , L, Z, m and n are the same as in the second embodiment described above, and Z is bonded to the para position with respect to the atom bonded to the core of L.
  • X of the above-described second condition is CR 4 R 5, and S, O or Se
  • Y is - (L) m - (Z ) and n
  • R 4, R 5 , L, Z, m and n are the same as in the above-mentioned second embodiment
  • Z is bonded to the meta position with respect to the atom bonded to the core of L.
  • L is substituted or unsubstituted phenylene; Or substituted or unsubstituted pyridylenes.
  • L is phenylene; Or pyridylene.
  • Formula 1 according to the above-described embodiment is represented by any one of the following Formulas 2 to 7:
  • Formula 1 according to the above-described embodiment is represented by any one of the following Formulas 8 to 12:
  • Formula 8 according to the above-described embodiment is represented by any one of the following Formulas 13 to 24:
  • R 11 and R 12 are the same or different and each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl,
  • the formulas (2) to (7) according to the above-described embodiments are represented by the following formulas (25) to (30), respectively.
  • X ' represents CR 4 R 5 , O, S or Se
  • R 4 , R 5 , R 11 and R 12 are the same or different from each other, and each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl,
  • the formula (1) may be selected from the following compounds.
  • Ar is bonded to the para position to an atom bonded to the core of the phenyl, and the above formulas (13) and (25) can be selected from the following compounds.
  • Ar is bonded to the meta position with respect to the atom bonded to the core of the phenyl, and the above formulas (13) and (25) can be selected from the following compounds.
  • Ar is bonded to the para position with respect to the atom bonded to the core of the phenyl, and the formula (14) may be selected from the following compounds.
  • Ar is bonded to a meta-position with respect to an atom bonded to the core of the phenyl, and Formula 14 may be selected from the following compounds.
  • Ar is bonded at the meta position with respect to an atom bonded to the core of the phenyl, .
  • Ar is bonded to the para position with respect to an atom bonded to the core of the phenyl, and the formula (17) may be selected from the following compounds.
  • Ar is bonded to the meta position with respect to an atom bonded to the core of the phenyl, and the formula (17) may be selected from the following compounds.
  • Ar is bonded to the para position with respect to the atom bonded to the core of the phenyl, May be selected from the following compounds.
  • Ar is bonded to the meta position with respect to the atom bonded to the core of the phenyl, May be selected from the following compounds.
  • Ar is bonded to the para position with respect to an atom bonded to the core of the phenyl, and Formula 20 may be selected from the following compounds.
  • Ar is bonded to the meta position with respect to the atom bonded to the core of the phenyl, and Formula 20 may be selected from the following compounds.
  • Ar is bonded to the para position with respect to an atom bonded to the core of the phenyl, and the above formulas 24 and 30 may be selected from the following compounds.
  • Ar is bonded to the meta position with respect to the atom bonded to the core of the phenyl, and the above formulas 24 and 30 may be selected from the following compounds.
  • Ar is bonded to a para position with respect to an atom bonded to the core of the phenyl, and the formula (23) may be selected from the following compounds.
  • Ar is bonded to the meta position with respect to an atom bonded to the core of the phenyl, and the formula (23) may be selected from the following compounds.
  • the above-mentioned compounds can be produced on the basis of the preparation examples described later. Exemplary examples are described below in the preparation examples, but substituents can be added or removed as needed, and the position of the substituent can be changed. In addition, based on techniques known in the art, starting materials, reactants, reaction conditions, and the like can be changed. The type or position of the substituent at the remaining positions may be changed as required by those skilled in the art using techniques known in the art.
  • core structures may be prepared as shown in the following general formulas 1 to 9.
  • Substituent groups may be attached by methods known in the art, and the substituent position or number of substituent groups may be varied according to techniques known in the art.
  • X and Y are the same as the general formula (1) according to the above-described embodiment, and are an example of the reaction for producing the core structure of the general formula (2).
  • Ar is the same as the above-described embodiment, and is an example of the reaction for producing the core structure of the general formula (13).
  • Ar is the same as R 3 defined in formula (1) according to the above-described embodiment, and is an example of the reaction for producing the core structure of formula (14).
  • Ar is the same as the above-described embodiment, and is an example of a reaction for producing the core structure of the formulas (15) to (16).
  • Ar is the same as the above-described embodiment, and is an example of the reaction for producing the core structure of the general formula (17).
  • Ar is the same as the above-described embodiment, and is an example of the reaction for producing the core structure of the general formulas (18) to (19).
  • Ar is the same as R 3 defined in formula (1) according to the above-described embodiment, and is an example of a reaction for producing the core structure of formula (20).
  • Ar is the same as R 3 defined in formula (1) according to the above-described embodiment, and is an example of a reaction for producing the core structure represented by formula (23).
  • Ar is the same as the above-described embodiment, and is an example of a reaction for producing the core structure of the general formula (24).
  • the organic light emitting device comprising the compound of Formula 1 described above.
  • the organic light emitting device according to the present application includes a cathode, a cathode, and at least one organic layer provided between the anode and the cathode, and at least one of the organic layers includes the compound of Formula 1.
  • FIGS. 1 to 3 illustrate the stacking process of the electrodes and organic layers of the organic light emitting diode according to the embodiments of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and the structure of the organic light emitting device known in the art can be applied to the present application.
  • an organic light emitting device in which an anode 200, an organic layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is shown.
  • the present invention is not limited to such a structure, and an organic light emitting device in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate may be implemented as shown in FIG.
  • FIG. 3 illustrates the case where the organic material layer is a multilayer. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306.
  • a hole injection layer 301 a hole transport layer 302
  • a light emitting layer 303 a hole transport layer 302
  • a hole blocking layer 304 a hole blocking layer
  • an electron transport layer 305 an electron injection layer 306.
  • the scope of the present application is not limited by such a laminated structure, and if necessary, the remaining layers except the light emitting layer may be omitted, and other necessary functional layers may be further added.
  • the organic light emitting device according to the present invention can be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer contains the compound of the above formula (1).
  • the compound of formula (I) may constitute one or more layers of the organic material layer of the organic light emitting device. However, if necessary, the organic material layer may be formed by mixing with other materials.
  • the compound of Formula 1 may be used as an electron transport layer, a hole blocking layer, and a material of a light emitting layer in an organic light emitting device.
  • the compound of Formula 1 may be used as an electron transport layer or a material of a light emitting layer of an organic light emitting device.
  • the compound of Formula 1 may be used as a material of a phosphorescent host in an electron transport layer or a light emitting layer.
  • the cathode material materials having a relatively large work function can be used, and a transparent conductive oxide, a metal, or a conductive polymer can be used.
  • the cathode material materials having relatively low work functions can be used, and metals, metal oxides, conductive polymers, and the like can be used.
  • a known hole injecting material may be used.
  • a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or a compound described in Advanced Material, 6, p.
  • a pyrazoline derivative an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, or the like may be used, and a low molecular weight or a high molecular weight material may be used.
  • Examples of the electron transporting material include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, Derivatives thereof, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and the like may be used as well as low molecular weight materials and high molecular weight materials.
  • LiF is typically used in the art, but the present application is not limited thereto.
  • red, green or blue light emitting materials may be used, and if necessary, two or more light emitting materials may be mixed and used.
  • a fluorescent material may be used as a light emitting material, but it may be used as a phosphorescent material.
  • the light emitting material a material which emits light by coupling holes and electrons respectively injected from the anode and the cathode may be used. However, materials in which both the host material and the dopant material participate in light emission may also be used.
  • A-2 38.8g (105.0mmol), 2- bromoaniline (2-bromoaniline) 36.1g (210.0mmol ), tetrakis (triphenylphosphine) palladium (0) 6.1g (5.25mmol), K 3 PO 4 67.0 g (315.0 mmol) was refluxed and stirred at 400 ° C in 1,4-dioxane and 80 mL of H 2 O at 120 ° C for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 17.5 g (50%) of the target compound A-3 .
  • reaction mixture was cooled to room temperature, and a solid was formed.
  • the solid was filtered and then washed with dicholoromethane, ethyl acetate (EA), and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount, and then filtered with silica gel to obtain 10.3 g (78%) of the desired compound 1-12 .
  • the organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 19.0 g (81%) of the target compound C-1 .
  • the organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator.
  • the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.5 g (79%) of the desired compound 1-113 .
  • reaction mixture was extracted with distilled water and dichloromethane.
  • the organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator.
  • the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 4.92 g (54%) of the desired compound 1-119 .
  • the organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator.
  • the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.5 g (68%) of the desired compound 1-157 .
  • the organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 21.2 g (89%) of the target compound F-1 .
  • the solvent was dissolved in dichloromethane (150 mL), and the mixture was stirred at room temperature for 16 hours with 10 mL of 30% aqueous H 2 O 2 solution.
  • the organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator.
  • the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 6.3 g (51%) of the title compound 1-190 .
  • reaction mixture was extracted with distilled water and dichloromethane.
  • the organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator.
  • the residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the desired compound 2-107 12.1 g (68%).
  • reaction mixture was extracted with distilled water and dichloromethane.
  • the organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator.
  • the residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the desired compound 2-123 9.79 g (71%).
  • the organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 13.9 g (57%) of the target compound J-1 .
  • K-1 10.0g (20.02mmol), a phenanthrene-9-Daily Nick Acid (phenanthren-9-ylboronic acid) 5.34g (24.03mmol), tetrakis (triphenylphosphine) palladium (0) 1.16g (1.0 mmol) and 12.75 g (60.06 mmol) of K 3 PO 4 were refluxed and stirred at 120 ° C in 200 mL of 1,4-dioxane and 40 mL of H 2 O for 8 hours.
  • reaction mixture was extracted with distilled water and dichloromethane.
  • the organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator.
  • the residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the desired compound 3-43 10.6 g (77%).
  • the solid was filtered and washed with dichloromethane, ethyl acetate (EA), and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount, and then filtered with silica gel to obtain 6.6 g (55%) of the target compound 4-1 .
  • the solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount, and then filtered with silica gel to obtain 4.4 g (55%) of the target compound 2-38 .
  • EA ethyl acetate
  • MeOH methanol
  • the organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator.
  • the solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). After that, the solid was boiled with 1,2-dichloroethane in an excess amount and filtered to obtain 6.6 g (78%) of the target compound 4-56 .
  • EA ethyl acetate
  • MeOH methanol
  • the organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain the target compound 2-148 8.9 g (67%).
  • reaction mixture was extracted with distilled water and dichloromethane.
  • the organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and the residue was purified by column chromatography using dichloromethane and hexane as eluent. g (68%).
  • A-5 A mixture of 10.0 g (20.02 mmol), 9-phenyl-9H, 9'H-3,3'-bicarbazole 7.36 g (18.02 mmol), Pd 2 (dba) 3 1.83 g (2.0 mmol), XPhos 1.9 g And NaOtBu (8.1 g, 40.04 mmol) were stirred in toluene (100 mL) at 120 ⁇ ⁇ for 3 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was purified by column to obtain 8.11 g (49%) of the desired compound 5-55.
  • 9,9 '- (5-bromo-1,3-phenylene) bis (9H-carbazole) was used instead of 2-chloro-4,6-diphenyl-1,3,5- . ≪ / RTI > (Yield: 55%).
  • the organic layer was dried over anhydrous MgSO 4 , the solvent was removed by a rotary evaporator, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 10.9 g (84%) of the target compound 11-36 .

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Abstract

The present specification relates to a novel heterocyclic compound and an organic light emitting element using the same.

Description

헤테로고리 화합물 및 이를 이용한 유기발광소자Heterocyclic compounds and organic light emitting devices using the same
본 출원은 2014년 6월 30일에 한국특허청에 제출된 한국 특허 출원 제10-2014-0081206호, 및 2014년 9월 23일에 한국특허청에 제출된 한국 특허 출원 제10-2014-0127222호의 출원일의 이익을 주장하며, 그 내용 전부는 본 명세서에 포함된다.The present application is based on Korean Patent Application No. 10-2014-0081206 filed on June 30, 2014, and Korean Patent Application No. 10-2014-0127222 filed on September 23, 2014, , The entire contents of which are incorporated herein by reference.
본 명세서는 신규한 헤테로고리 화합물 및 이를 이용한 유기발광소자에 관한 것이다.The present invention relates to a novel heterocyclic compound and an organic light emitting device using the same.
전계 발광 소자는 자체 발광형 표시 소자의 일종으로서, 시야각이 넓고, 콘트라스트가 우수할 뿐만 아니라 응답속도가 빠르다는 장점을 가지고 있다.An electroluminescent device is one type of self-luminous display device, and has advantages of wide viewing angle, excellent contrast, and high response speed.
유기발광소자는 2개의 전극 사이에 유기박막을 배치시킨 구조를 가지고 있다. 이와 같은 구조의 유기발광소자에 전압이 인가되면, 2개의 전극으로부터 주입된 전자와 정공이 유기박막에서 결합하여 쌍을 이룬 후 소멸하면서 빛을 발하게 된다. 상기 유기박막은 필요에 따라 단층 또는 다층으로 구성될 수 있다.The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes couple to each other in the organic thin film and form a pair, which then extinguishes and emits light. The organic thin film may be composed of a single layer or a multilayer, if necessary.
유기박막의 재료는 필요에 따라 발광 기능을 가질 수 있다. 예컨대, 유기박막 재료로는 그 자체가 단독으로 발광층을 구성할 수 있는 화합물이 사용될 수도 있고, 또는 호스트-도펀트계 발광층의 호스트 또는 도펀트 역할을 할 수 있는 화합물이 사용될 수도 있다. 그 외에도, 유기박막의 재료로서, 정공주입, 정공수송, 전자블록킹, 정공블록킹, 전자수송 또는 전자주입 등의 역할을 수행할 수 있는 화합물이 사용될 수도 있다.The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound capable of forming a light emitting layer by itself may be used, or a compound capable of serving as a host or a dopant of a host-dopant light emitting layer may be used. In addition, as the material of the organic thin film, a compound capable of performing a role such as hole injection, hole transport, electron blocking, hole blocking, electron transport or electron injection may be used.
유기발광소자의 성능, 수명 또는 효율을 향상시키기 위하여, 유기박막의 재료의 개발이 지속적으로 요구되고 있다.In order to improve the performance, life or efficiency of an organic light emitting device, development of materials for organic thin films is continuously required.
본 명세서는 신규한 헤테로고리 화합물 및 이를 이용한 유기발광소자를 제공한다.The present invention provides a novel heterocyclic compound and an organic light emitting device using the same.
본 명세서의 일 실시상태는 하기 화학식 1의 화합물을 제공한다:One embodiment of the present disclosure provides compounds of formula 1:
[화학식 1][Chemical Formula 1]
Figure PCTKR2015006723-appb-I000001
Figure PCTKR2015006723-appb-I000001
상기 화학식 1에 있어서,In Formula 1,
X는 NR3, CR4R5, S, O 또는 Se이며,X is NR 3 , CR 4 R 5 , S, O or Se,
Y는 수소; 중수소; 할로겐; -P(=O)R6R7; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,Y is hydrogen; heavy hydrogen; halogen; -P (= O) R 6 R 7; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
R1 및 R2는 서로 같거나 상이하며, 각각 독립적으로 수소; 중수소; 할로겐; -P(=O)R8R9; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C2 내지 C60의 직쇄 또는 분지쇄의 알케닐; 치환 또는 비치환된 C2 내지 C60의 직쇄 또는 분지쇄의 알키닐; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알콕시; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,R 1 and R 2 are the same or different and each independently hydrogen; heavy hydrogen; halogen; -P (= O) R <8> R <9>; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; Substituted or unsubstituted C 2 to C 60 straight or branched chain alkenyl; Substituted or unsubstituted C 2 to C 60 straight or branched chain alkynyl; A substituted or unsubstituted C 1 to C 60 straight or branched chain alkoxy; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heterocycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
a는 0 내지 4의 정수이며, a가 2 이상인 경우 R1은 서로 같거나 상이하고,a is an integer of 0 to 4, and when a is 2 or more, R 1 are the same or different from each other,
b는 0 내지 6의 정수이며, b가 2 이상인 경우 R2는 서로 같거나 상이하고,b is an integer of 0 to 6, and when b is 2 or more, R 2 are the same or different from each other,
R3은 수소; 중수소; 할로겐; -P(=O)R6R7; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되며,R 3 is hydrogen; heavy hydrogen; halogen; -P (= O) R 6 R 7; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
R4 내지 R9은 서로 같거나 상이하며, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴이다.R 4 to R 9 are the same or different and each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl.
또한, 본 명세서의 일 실시상태는 양극, 음극 및 상기 양극과 음극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기발광소자로서, 상기 유기물층 중 1층 이상이 상기 화학식 1의 화합물을 포함하는 유기발광소자를 제공한다.In addition, one embodiment of the present invention is an organic light emitting device including a cathode, a cathode, and at least one organic layer provided between the anode and the cathode, wherein at least one of the organic layers includes an organic light emitting Device.
본 명세서에 기재된 화합물은 유기발광소자의 유기물층 재료로서 사용할 수 있다. 상기 화합물은 유기발광소자에서 전자수송층, 정공저지층, 발광층 등의 재료로서 사용될 수 있다. 특히, 상기 화학식 1의 화합물은 유기발광소자의 전자수송층, 정공저지층, 발광층의 재료로서 사용될 수 있다. 또한, 상기 화학식 1의 화합물은 전자수송층 또는 발광층의 재료로서 사용될 수 있다.The compound described in this specification can be used as an organic layer material of an organic light emitting device. The compound can be used as an electron transport layer, a hole blocking layer, a light emitting layer, and the like in an organic light emitting device. In particular, the compound of Formula 1 can be used as a material for an electron transport layer, a hole blocking layer, and a light emitting layer of an organic light emitting device. Further, the compound of Formula 1 can be used as an electron transporting layer or a material of a light emitting layer.
도 1 내지 3은 본 명세서의 실시상태들에 따른 유기발광소자의 전극과 유기물층의 적층순서를 예시한 것이다.FIGS. 1 to 3 illustrate a stacking order of electrodes and organic layers of an organic light emitting diode according to embodiments of the present invention.
도 4는 화합물 1-1의 274nm 파장에서의 PL 측정 그래프를 나타낸 것이다.4 shows a PL measurement graph of Compound 1-1 at a wavelength of 274 nm.
도 5는 화합물 1-12의 233nm 파장에서의 PL 측정 그래프를 나타낸 것이다.Fig. 5 shows a PL measurement graph of Compound 1-12 at a wavelength of 233 nm.
도 6은 화합물 1-36의 276nm 파장에서의 PL 측정 그래프를 나타낸 것이다.6 shows a PL measurement graph of Compound 1-36 at a wavelength of 276 nm.
도 7은 화합물 1-113의 240nm 파장에서의 PL 측정 그래프를 나타낸 것이다.7 shows a PL measurement graph of Compound 1-113 at a wavelength of 240 nm.
도 8은 화합물 1-119의 270nm 파장에서의 PL 측정 그래프를 나타낸 것이다.8 shows a PL measurement graph of the compound 1-119 at a wavelength of 270 nm.
도 9는 화합물 1-124의 240nm 파장에서의 PL 측정 그래프를 나타낸 것이다.FIG. 9 shows a PL measurement graph of a compound 1-124 at a wavelength of 240 nm.
도 10은 화합물 1-318의 309nm 파장에서의 PL 측정 그래프를 나타낸 것이다.FIG. 10 shows a PL measurement graph of Compound 1-318 at a wavelength of 309 nm.
도 11은 화합물 2-36의 282nm 파장에서의 PL 측정 그래프를 나타낸 것이다.11 shows a PL measurement graph of Compound 2-36 at a wavelength of 282 nm.
도 12는 화합물 2-38의 284nm 파장에서의 PL 측정 그래프를 나타낸 것이다.12 shows a PL measurement graph of Compound 2-38 at a wavelength of 284 nm.
도 13은 화합물 3-39의 307nm 파장에서의 PL 측정 그래프를 나타낸 것이다.Fig. 13 shows a PL measurement graph of compound 3-39 at a wavelength of 307 nm.
도 14는 화합물 3-46의 310nm 파장에서의 PL 측정 그래프를 나타낸 것이다.14 shows a PL measurement graph of Compound 3-46 at a wavelength of 310 nm.
도 15는 화합물 4-56의 278nm 파장에서의 PL 측정 그래프를 나타낸 것이다.15 shows a PL measurement graph of Compound 4-56 at a wavelength of 278 nm.
도 16은 화합물 4-58의 290nm 파장에서의 PL 측정 그래프를 나타낸 것이다.16 shows a PL measurement graph of Compound 4-58 at a wavelength of 290 nm.
도 17은 화합물 4-76의 267nm 파장에서의 PL 측정 그래프를 나타낸 것이다.17 shows a PL measurement graph of Compound 4-76 at a wavelength of 267 nm.
도 18은 화합물 4-169의 264nm 파장에서의 PL 측정 그래프를 나타낸 것이다.18 shows the PL measurement graph of Compound 4-169 at a wavelength of 264 nm.
도 19는 화합물 1-1의 309nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.19 is a graph showing the LTPL measurement at a wavelength of 309 nm of the compound 1-1.
도 20은 화합물 1-12의 338nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.20 is a graph showing the LTPL measurement of Compound 1-12 at a wavelength of 338 nm.
도 21은 화합물 1-36의 310nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.21 is a graph showing the LTPL measurement at a wavelength of 310 nm of Compound 1-36.
도 22는 화합물 1-318의 309nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.22 shows a graph of LTPL measurement at a wavelength of 309 nm of Compound 1-318.
도 23은 화합물 2-36의 409nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.23 is a graph showing the LTPL measurement at 409 nm wavelength of Compound 2-36.
도 24는 화합물 2-38의 408nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.24 is a graph showing the LTPL measurement at 408 nm wavelength of Compound 2-38.
도 25는 화합물 3-39의 307nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.25 is a graph showing the LTPL measurement at a wavelength of 307 nm of the compound 3-39.
도 26은 화합물 3-46의 268nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.26 is a graph showing the LTPL measurement at a wavelength of 268 nm of Compound 3-46.
도 27은 화합물 4-56의 278nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.27 is a graph showing the LTPL measurement at 278 nm wavelength of Compound 4-56.
도 28은 화합물 4-58의 329nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.28 shows a graph of LTPL measurement at a wavelength of 329 nm of Compound 4-58.
도 29는 화합물 4-76의 365nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.29 is a graph showing the LTPL measurement at 365 nm wavelength of Compound 4-76.
도 30은 화합물 4-169의 365nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.30 shows a graph of LTPL measurement at 365 nm wavelength of Compound 4-169.
[부호의 설명][Description of Symbols]
100 기판100 substrate
200 양극200 anode
300 유기물층300 organic layer
301 정공주입층301 hole injection layer
302 정공수송층302 hole transport layer
303 발광층303 luminous layer
304 정공저지층304 hole stop layer
305 전자수송층305 electron transport layer
306 전자주입층306 electron injection layer
400 음극400 cathode
이하, 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 명세서에 기재된 화합물은 상기 화학식 1로 표시될 수 있다. 구체적으로, 상기 화학식 1의 화합물은 상기와 같은 코어 구조 및 치환기의 구조적 특징에 의하여 유기발광소자의 유기물층 재료로 사용될 수 있다.The compounds described in this specification can be represented by the above formula (1). Specifically, the compound of Formula 1 may be used as an organic material layer material of an organic light emitting diode according to the structural features of the core structure and the substituent.
본 명세서에 있어서, "치환 또는 비치환"이란 중수소; 할로겐; C1 내지 C60의 직쇄 또는 분지쇄의 알킬; C2 내지 C60의 직쇄 또는 분지쇄의 알케닐; C2 내지 C60의 직쇄 또는 분지쇄의 알키닐; C1 내지 C60의 직쇄 또는 분지쇄의 알콕시; C3 내지 C60의 단환 또는 다환의 시클로알킬; C2 내지 C60의 단환 또는 다환의 헤테로시클로알킬; C6 내지 C60의 단환 또는 다환의 아릴; C2 내지 C60의 단환 또는 다환의 헤테로아릴; -SiRR'R"; -P(=O)RR'; C1 내지 C20의 알킬아민; C6 내지 C60의 단환 또는 다환의 아릴아민; 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴아민으로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환되거나, 상기 치환기들 중 2 이상이 결합된 치환기로 치환 또는 비치환되거나, 상기 예시된 치환기 중에서 선택된 2 이상의 치환기가 연결된 치환기로 치환 또는 비치환된 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 비페닐기일 수 있다. 즉, 비페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수 있다. 상기 추가의 치환기들은 추가로 더 치환될 수도 있다.As used herein, the term " substituted or unsubstituted &quot;halogen; C 1 to C 60 linear or branched alkyl; C 2 to C 60 straight or branched chain alkenyl; C 2 to C 60 linear or branched alkynyl; C 1 to C 60 straight or branched chain alkoxy; C 3 to C 60 monocyclic or polycyclic cycloalkyl; A C 2 to C 60 monocyclic or polycyclic heterocycloalkyl; C 6 to C 60 monocyclic or polycyclic aryl; C 2 to C 60 monocyclic or polycyclic heteroaryl; A C 1 to C 20 alkylamine, a C 6 to C 60 monocyclic or polycyclic arylamine, and a C 2 to C 60 monocyclic or polycyclic heteroaryl Amine, or substituted or unsubstituted with a substituent having two or more of the substituents bonded thereto, or substituted or unsubstituted with a substituent to which at least two substituents selected from the above exemplified substituents are connected, For example, the "substituent group to which at least two substituents are connected" may be a biphenyl group, that is, the biphenyl group may be an aryl group, and two phenyl groups may be connected to each other. . &Lt; / RTI &gt;
상기 R, R' 및 R"은 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴이다.Wherein R, R 'and R " are the same or different and each independently hydrogen, substituted or unsubstituted C 1 to C 60 linear or branched alkyl, substituted or unsubstituted C 3 to C 60 monocyclic Substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl.
본 발명의 일 실시상태에 따르면, 상기 "치환 또는 비치환"이란 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 아릴 및 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기 또는 상기 치환기 중에서 선택된 2 이상의 치환기가 연결된 치환기로 치환 또는 비치환된 것을 의미하고,According to an exemplary embodiment of the present invention, the "substituted or unsubstituted" is deuterium, halogen, -SiRR'R ", -P (= O ) RR ', the C 6 to C 60 aryl, and C 2 to C 60 of Heteroaryl, or substituted or unsubstituted with a substituent to which at least two substituents selected from the above-mentioned substituents are connected,
본 명세서의 또 하나의 실시상태에 따르면, 상기 R, R' 및 R"은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소, 할로겐, C6 내지 C60의 아릴 및 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 중수소, 할로겐, C6 내지 C60의 아릴 및 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 중수소, 할로겐, C6 내지 C60의 아릴 및 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 중수소, 할로겐, C6 내지 C60의 아릴 및 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴이다.According to another embodiment of the disclosure, R, R 'and R " are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, halogen, C 6 to C 60 aryl and C 2 to C 60 hetero C 1 -C 60 straight or branched chain alkyl substituted or unsubstituted with one or more substituents selected from halogen, C 6 -C 60 aryl and C 2 -C 60 heteroaryl, A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl, substituted or unsubstituted with at least one substituent selected from deuterium, halogen, C 6 to C 60 aryl and C 2 to C 60 heteroaryl, unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or heavy hydrogen, halogen, C 6 to C aryl and at least one selected from the group consisting of heteroaryl of C 2 to C 60 of the 60 substituent is substituted or unsubstituted C 2 To C 60 monoclinic Or heteroaryl.
본 명세서에 있어서, 할로겐은 불소, 염소, 브롬 또는 요오드일 수 있다.In the present specification, the halogen may be fluorine, chlorine, bromine or iodine.
본 명세서에 있어서, 알킬은 탄소수 1 내지 60의 직쇄 또는 분지쇄를 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 알킬의 탄소수는 1 내지 60, 구체적으로 1 내지 40, 더욱 구체적으로, 1 내지 20일 수 있다.In the present specification, alkyl includes straight or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. The carbon number of the alkyl may be 1 to 60, specifically 1 to 40, more specifically 1 to 20.
본 명세서에 있어서, 알케닐은 탄소수 2 내지 60의 직쇄 또는 분지쇄를 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 알케닐의 탄소수는 2 내지 60, 구체적으로 2 내지 40, 더욱 구체적으로, 2 내지 20일 수 있다.In the present specification, alkenyl includes straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The carbon number of the alkenyl may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20.
본 명세서에 있어서, 알키닐은 탄소수 2 내지 60의 직쇄 또는 분지쇄를 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 알키닐의 탄소수는 2 내지 60, 구체적으로 2 내지 40, 더욱 구체적으로, 2 내지 20일 수 있다.In the present specification, alkynyl includes a straight chain or a branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The carbon number of the alkynyl may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20.
본 명세서에 있어서, 시클로알킬은 탄소수 3 내지 60의 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 시클로알킬이 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 시클로알킬일 수도 있으나, 다른 종류의 고리기, 예컨대 헤테로시클로알킬, 아릴, 헤테로아릴 등일 수도 있다. 시클로알킬의 탄소수는 3 내지 60, 구체적으로 3 내지 40, 더욱 구체적으로 5 내지 20일 수 있다.In the present specification, the cycloalkyl includes monocyclic or polycyclic rings having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic ring means a group in which cycloalkyl is directly connected to another ring group or condensed. Here, the other ring group may be a cycloalkyl group, but may be other ring groups such as heterocycloalkyl, aryl, heteroaryl, and the like. The carbon number of the cycloalkyl may be 3 to 60, specifically 3 to 40, more particularly 5 to 20.
본 명세서에 있어서, 헤테로시클로알킬은 헤테로원자로서 O, S, Se, N 또는 Si를 포함하고, 탄소수 2 내지 60의 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 헤테로시클로알킬이 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 헤테로시클로알킬일 수도 있으나, 다른 종류의 고리기, 예컨대 시클로알킬, 아릴, 헤테로아릴 등일 수도 있다. 헤테로시클로알킬의 탄소수는 2 내지 60, 구체적으로 2 내지 40, 더욱 구체적으로 3 내지 20일 수 있다.In the present specification, heterocycloalkyl includes O, S, Se, N or Si as a heteroatom and includes monocyclic or polycyclic rings having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic ring means a group in which heterocycloalkyl is directly connected to another ring group or condensed. Here, the other ring group may be heterocycloalkyl, but may be other ring groups such as cycloalkyl, aryl, heteroaryl, and the like. The heterocycloalkyl may have from 2 to 60 carbon atoms, specifically from 2 to 40, more specifically from 3 to 20 carbon atoms.
본 명세서에 있어서, 아릴은 탄소수 6 내지 60의 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 아릴이 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 아릴일 수도 있으나, 다른 종류의 고리기, 예컨대 시클로알킬, 헤테로시클로알킬, 헤테로아릴 등일 수도 있다. 아릴은 스피로기를 포함한다. 아릴의 탄소수는 6 내지 60, 구체적으로 6 내지 40, 더욱 구체적으로 6 내지 25일 수 있다. 아릴의 구체적인 예로는 페닐, 비페닐, 트리페닐, 나프틸, 안트릴, 크라이세닐, 페난트레닐, 페릴레닐, 플루오란테닐, 트리페닐레닐, 페날레닐, 파이레닐, 테트라세닐, 펜타세닐, 플루오레닐, 인데닐, 아세나프틸레닐, 벤조플루오레닐, 스피로비플루오레닐, 2,3-디하이드로-1H-인데닐 등이나 이들의 축합고리가 있으나, 이에만 한정되는 것은 아니다.In the present specification, aryl includes monocyclic or polycyclic rings having 6 to 60 carbon atoms and may be further substituted by other substituents. Here, the polycyclic ring means a group in which aryl is directly connected to another ring group or condensed. Here, the other ring group may be aryl, but may be other ring groups such as cycloalkyl, heterocycloalkyl, heteroaryl and the like. Aryl includes a spiro group. The carbon number of the aryl may be 6 to 60, specifically 6 to 40, more specifically 6 to 25. Specific examples of aryl include phenyl, biphenyl, triphenyl, naphthyl, anthryl, klycenyl, phenanthrenyl, perylenyl, fluoranthenyl, triphenylenyl, phenalenyl, pyrenyl, tetracenyl, pentacenyl, But are not limited to, fluorenyl, indenyl, acenaphthylenyl, benzofluorenyl, spirobifluorenyl, 2,3-dihydro-1H-indenyl, and condensed rings thereof.
본 명세서에 있어서, 스피로기는 스피로 구조를 포함하는 기로서, 탄소수 15 내지 60일 수 있다. 예컨대, 스피로기는 플루오렌기에 2,3-디하이드로-1H-인덴기 또는 시클로헥산기가 스피로 결합된 구조를 포함할 수 있다. 구체적으로, 스피로기는 하기 구조식의 기를 포함한다.In the present specification, the spiro group is a group including a spiro structure and may have from 15 to 60 carbon atoms. For example, a spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro-bonded to a fluorene group. Specifically, the spiro group includes groups of the following structural formulas.
Figure PCTKR2015006723-appb-I000002
Figure PCTKR2015006723-appb-I000002
본 명세서에 있어서, 헤테로아릴은 헤테로원자로서 S, O, Se, N 또는 Si를 포함하고, 탄소수 2 내지 60인 단환 또는 다환을 포함하며, 다른 치환기에 의하여 추가로 치환될 수 있다. 여기서, 다환이란 헤테로아릴이 다른 고리기와 직접 연결되거나 축합된 기를 의미한다. 여기서, 다른 고리기란 헤테로아릴일 수도 있으나, 다른 종류의 고리기, 예컨대 시클로알킬, 헤테로시클로알킬, 아릴 등일 수도 있다. 헤테로아릴의 탄소수는 2 내지 60, 구체적으로 2 내지 40, 더욱 구체적으로 3 내지 25일 수 있다. 헤테로아릴의 구체적인 예로는 피리딜, 피롤릴, 피리미딜, 피리다지닐, 푸라닐, 티오펜기, 이미다졸릴, 피라졸릴, 옥사졸릴, 이소옥사졸릴, 티아졸릴, 이소티아졸릴, 트리아졸릴, 푸라자닐, 옥사디아졸릴, 티아디아졸릴, 디티아졸릴, 테트라졸릴, 파이라닐, 티오파이라닐, 디아지닐, 옥사지닐, 티아지닐, 디옥시닐, 트리아지닐, 테트라지닐, 퀴놀릴, 이소퀴놀릴, 퀴나졸리닐, 이소퀴나졸리닐, 퀴노졸리릴, 나프티리딜, 아크리딜, 페난트리디닐, 이미다조피리딜, 디아자나프틸, 트리아자인덴, 인돌릴, 인돌리지닐, 벤조티아졸릴, 벤즈옥사졸릴, 벤즈이미다졸릴, 벤조티오펜기, 벤조푸란기, 디벤조티오펜기, 디벤조푸란기, 카바졸릴, 벤조카바졸릴, 디벤조카바졸릴, 페나지닐, 디벤조실롤, 스피로비(디벤조실롤), 디히드로페나지닐, 페녹사지닐, 페난트리딜, 이미다조피리딜, 티에닐, 인돌[2,3-a]카바졸릴, 인돌[2,3-b]카바졸릴, 인돌리닐, 10,11-디하이드로-디벤조[b,f]아제핀기, 9,10-디하이드로아크리딜, 페난트라지닐, 페노티아티아지닐, 프탈라지닐, 나프틸리디닐, 페난트롤리닐, 벤조[c][1,2,5]티아디아졸릴, 5,10-디하이드로디벤조[b,e][1,4]아자실리닐, 피라졸로[1,5-c]퀴나졸리닐, 피리도[1,2-b]인다졸릴, 피리도[1,2-a]이미다조[1,2-e]인돌리닐, 5,11-디하이드로인데노[1,2-b]카바졸릴, 디벤조[c, h]아크리딜 등이나 이들의 축합고리가 있으나, 이에만 한정되는 것은 아니다.As used herein, heteroaryl includes S, O, Se, N or Si as a heteroatom and includes monocyclic or polycyclic rings having 2 to 60 carbon atoms and may be further substituted by other substituents. Herein, the term "polycyclic" means a heteroaryl group directly bonded to another ring group or condensed therewith. Here, the other ring group may be heteroaryl, but may be other ring groups such as cycloalkyl, heterocycloalkyl, aryl, and the like. The heteroaryl may have 2 to 60 carbon atoms, specifically 2 to 40, more specifically 3 to 25 carbon atoms. Specific examples of heteroaryl include pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thiophene, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, Thiazolyl, thiazolyl, pyrazinyl, thiopyranyl, diazinyl, oxazinyl, thiazinyl, dioxinyl, triazinyl, tetrazinyl, quinolyl, iso And examples thereof include quinolyl, quinolyl, quinazolinyl, isoquinazolinyl, quinolyl, naphthyridyl, acridyl, phenanthridinyl, imidazopyridyl, diazanaphthyl, triazinene, indolyl, indolizinyl, A benzothiophene group, a benzothiophene group, a dibenzothiophene group, a dibenzofuran group, a carbazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a phenazinyl group, a dibenzosilyl group, Spirobi (dibenzoylol), dihydrophenazinyl, phenoxazinyl, phenanthridyl, di 2,3-a] carbazolyl, indolinyl, 10,11-dihydro-dibenzo [b, f] azepinyl, Naphthyridinyl, phenanthrolinyl, benzo [c] [1,2,5] thiadiazolyl, 5,10-dihydrocyclohexyl, phenanthrazinyl, phenothiatriazinyl, phthalazinyl, Dihydrodibenzo [b, e] [1,4] azacylinyl, pyrazolo [1,5-c] quinazolinyl, pyrido [1,2- b] indazolyl, pyrido [ a] imidazo [1,2-e] indolinyl, 5,11-dihydroindeno [1,2-b] carbazolyl, dibenzo [c, h] acridyl and the like, , But is not limited thereto.
본 명세서에 있어서, 아민은 -NH2; 디알킬아민; 디아릴아민; 디헤테로아릴아민; 알킬아릴아민; 알킬헤테로아릴아민; 및 아릴헤테로아릴아민으로 이루어진 군으로부터 선택될 수 있으며, 탄소수는 특별히 한정되지 않으나, 1 내지 30인 것이 바람직하다. 아민의 구체적인 예로는 메틸아민, 디메틸아민, 에틸아민, 디에틸아민, 페닐아민, 나프틸아민, 비페닐아민, 디비페닐아민, 안트라세닐아민, 9-메틸-안트라세닐아민, 디페닐아민, 페닐나프틸아민, 디톨릴아민, 페닐톨릴아민, 트리페닐아민 등이 있으나, 이들에만 한정되는 것은 아니다.In this specification, the amine is -NH 2; Dialkylamines; Diarylamine; Diheteroarylamine; Alkylarylamines; Alkylheteroarylamines; And arylheteroarylamine. The number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine include methylamine, dimethylamine, ethylamine, diethylamine, phenylamine, naphthylamine, biphenylamine, diviphenylamine, anthracenylamine, 9-methyl-anthracenylamine, diphenylamine, phenyl Naphthylamine, ditolylamine, phenyltolylamine, triphenylamine, and the like, but are not limited thereto.
본 명세서의 일 실시상태에 따르면,According to one embodiment of the present disclosure,
화학식 1의 X는 NR3이고, Y 와 R3 중 적어도 하나는 -(L)m-(Z)n이거나,X in the formula (1) is NR 3 , and at least one of Y and R 3 is - (L) m - (Z) n ,
화학식 1의 X는 CR4R5, S, O 또는 Se이고, Y는 -(L)m-(Z)n이며, X in formula (1) is CR 4 R 5 , S, O or Se, Y is - (L) m - (Z) n ,
L은 직접결합; -P(=O)R10-; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴렌; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴렌; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,L is a direct bond; -P (= O) R &lt; 10 &gt;-; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic arylene; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroarylene; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Or an unsubstituted amine,
m은 1 내지 6의 정수이며,m is an integer of 1 to 6,
n은 1 내지 5의 정수이고,n is an integer of 1 to 5,
Z는 수소; 중수소; 할로겐; -P(=O)R11R12; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되며,Z is hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
R4, R5 및 R10 내지 R12은 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴이다.R 4 , R 5 and R 10 to R 12 are each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl.
본 명세서의 일 실시상태에 따르면,According to one embodiment of the present disclosure,
상기 화학식 1의 X가 NR3이고, Y 와 R3 중 적어도 하나는 -(L)m-(Z)n이거나,X in the formula (1) is NR 3 , and at least one of Y and R 3 is - (L) m - (Z) n ,
상기 화학식 1의 X는 CR4R5, S, O 또는 Se이고, Y는 -(L)m-(Z)n이고,Wherein X is CR 4 R 5 , S, O or Se, Y is - (L) m - (Z) n ,
L은 직접결합; -P(=O)R10-; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴렌; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴렌; 및 C1 내지 C20의 알킬, C6 내지 C60의 단환 또는 다환의 아릴, 또는 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되며,L is a direct bond; -P (= O) R &lt; 10 &gt;-; Is at least one substituent selected from the group consisting of hydrogen, deuterium, halogen, -SiRR'R ", -P (= O) RR ', monocyclic or polycyclic aryl of C 6 to C 60 and monocyclic or polycyclic heteroaryl of C 2 to C 60 A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic arylene, a monovalent group selected from the group consisting of deuterium, halogen, -SiRR'R ", -P (═O) RR ', C 6 to C 60 monocyclic or polycyclic aryl, A monocyclic or polycyclic heteroarylene of C 2 to C 60 which is substituted or unsubstituted with at least one substituent selected from monocyclic or polycyclic heteroaryl of 2 to 60 carbon atoms; And amines substituted or unsubstituted with C 1 to C 20 alkyl, C 6 to C 60 monocyclic or polycyclic aryl, or C 2 to C 60 monocyclic or polycyclic heteroaryl,
m은 1 내지 6의 정수이고,m is an integer of 1 to 6,
n은 1 내지 5의 정수이며,n is an integer of 1 to 5,
Z는 수소; 중수소; 할로겐; -P(=O)R11R12; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 및 C1 내지 C20의 알킬, C6 내지 C60의 단환 또는 다환의 아릴, 또는 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,Z is hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; Is at least one substituent selected from the group consisting of hydrogen, deuterium, halogen, -SiRR'R ", -P (= O) RR ', monocyclic or polycyclic aryl of C 6 to C 60 and monocyclic or polycyclic heteroaryl of C 2 to C 60 substituted or unsubstituted C 1 to C 60 straight chain alkyl or branched-chain; deuterium, halogen, -SiRR'R ", -P (= O ) RR ', C 6 to C 60 monocyclic or polycyclic aryl and C A C 6 to C 60 monocyclic or polycyclic aryl which is substituted or unsubstituted with at least one substituent selected from monocyclic or polycyclic heteroaryl of 2 to 60 carbon atoms; Is at least one substituent selected from the group consisting of hydrogen, deuterium, halogen, -SiRR'R ", -P (= O) RR ', monocyclic or polycyclic aryl of C 6 to C 60 and monocyclic or polycyclic heteroaryl of C 2 to C 60 Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl, and C 1 to C 20 alkyl, C 6 to C 60 monocyclic or polycyclic aryl, or C 2 to C 60 monocyclic or polycyclic Substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl,
상기 R, R', R", R4, R5 및 R10 내지 R12은 서로 같거나 상이하며, 각각 독립적으로 수소; 중수소, 할로겐, C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 중수소, 할로겐, C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 중수소, 할로겐, C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 중수소, 할로겐, C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴이다.Wherein R, R ', R ", R 4, R 5 and R 10 to R 12 are, and the same as or different from each other, each independently represent hydrogen, the heavy hydrogen, halogen, C 6 to monocyclic of C 60 or unsubstituted aryl, and C 2 to C 60 monocyclic or polycyclic heteroaryl, 1-alkyl of at least substituted with a substituent or a straight chain of the unsubstituted C 1 to C 60 unsubstituted or branched chain is selected from; deuterium, halogen, C 6 to C 60 monocyclic or polycyclic aryl and C 2 to C 60 monocyclic or polycyclic heteroaryl group unsubstituted or substituted by one or more substituents selected from C 3 to monocyclic of C 60 or polycyclic cycloalkyl; deuterium, halogen, a monocyclic of C 6 to C 60 or polycyclic aryl and C 2 to C 60 monocyclic or polycyclic heteroaryl group unsubstituted or substituted by one or more substituents selected from C 6 to C 60 monocyclic or polycyclic aryl group; or heavy hydrogen, halogen, C 6 to C 60 Monocyclic or polycyclic aryl A C 2 to C 60 monocyclic or polycyclic heteroaryl group of C 2 to C 60 unsubstituted or substituted with one or more substituents selected from monocyclic or polycyclic heteroaryl group.
본 명세서의 또 하나의 실시상태에 따르면, 상기 L은 직접결합; 중수소, 할로겐, -SiRR'R", -P(=O)RR', 치환 또는 비치환된 C6 내지 C60의 아릴 및 치환 또는 비치환된 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴렌; 중수소, 할로겐, -SiRR'R", -P(=O)RR', 치환 또는 비치환된 C6 내지 C60의 아릴 및 치환 또는 비치환된 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴렌; -P(=O)R10-; 치환 또는 비치환된 C1 내지 C20의 알킬아민; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴아민; 및 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴아민으로 이루어진 군으로부터 선택되고, 상기 R, R', R" 및 R10은 전술한 바와 동일하다.According to another embodiment of the present disclosure, L is a direct bond; A substituted or unsubstituted C 6 to C 60 aryl, and a substituted or unsubstituted C 2 to C 60 heteroaryl selected from the group consisting of hydrogen, deuterium, halogen, -SiRR'R ", -P (= O) unsubstituted or substituted with a substituent C 6 to C 60 monocyclic or polycyclic arylene; deuterium, halogen, -SiRR'R ", -P (= O ) RR ', a substituted or unsubstituted C 6 to C 60 ring aryl and substituted or unsubstituted C 2 to C 60 heteroaryl group of C 2 to C 60 substituted or unsubstituted by one or more substituents selected from the group consisting of monocyclic or polycyclic heteroarylene; -P (= O) R &lt; 10 &gt;-; A substituted or unsubstituted C 1 to C 20 alkylamine; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic arylamine; And substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl amines, and R, R ', R "and R 10 are the same as defined above.
본 명세서의 또 하나의 실시상태에 따르면, 상기 L은 직접결합; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 아릴 및 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴렌; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 아릴 및 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴렌; -P(=O)R10-; 치환 또는 비치환된 C1 내지 C20의 알킬아민; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴아민; 및 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴아민으로 이루어진 군으로부터 선택되고, 상기 R, R', R" 및 R10은 전술한 바와 동일하다.According to another embodiment of the present disclosure, L is a direct bond; Substituted or unsubstituted C 6 to C 8 heteroaryl substituted with at least one substituent selected from the group consisting of halogen, -SiRR'R ", -P (= O) RR ', aryl of C 6 to C 60 and heteroaryl of C 2 to C 60 . C 60 monocyclic or polycyclic arylene; deuterium, halogen, -SiRR'R ", -P (= O ) RR ', C 6 aryl, and C 2 to to one or more selected from the group consisting of C 60 heteroaryl group of C 60 A C 2 to C 60 monocyclic or polycyclic heteroarylene substituted or unsubstituted with a substituent; -P (= O) R &lt; 10 &gt;-; A substituted or unsubstituted C 1 to C 20 alkylamine; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic arylamine; And substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl amines, and R, R ', R "and R 10 are the same as defined above.
본 명세서의 또 하나의 실시상태에 따르면, 상기 L은 직접결합; -P(=O)R10-; 치환 또는 비치환된 페닐렌; 치환 또는 비치환된 바이페닐렌; 치환 또는 비치환된 나프틸렌; 치환 또는 비치환된 안트릴렌; 치환 또는 비치환된 페난트레닐렌; 치환 또는 비치환된 트리페닐렌; 또는 치환 또는 비치환된 9,9-다이페닐-9H-플루오레닐렌; 치환 또는 비치환된 피리딜렌; 치환 또는 비치환된 피리미딜렌; 치환 또는 비치환된 트리아지닐렌; 치환 또는 비치환된 퀴놀릴렌; 치환 또는 비치환된 퀴나졸리닐렌; 치환 또는 비치환된 벤조티아졸릴렌; 치환 또는 비치환된 벤즈옥사졸릴렌; 치환 또는 비치환된 벤즈이미다졸릴렌; 치환 또는 비치환된 2가의 디벤조티오펜기; 치환 또는 비치환된 디벤조푸라닐렌; 치환 또는 비치환된 카바졸릴렌; 치환 또는 비치환된 인돌로[2, 3-a]카바졸릴렌; 치환 또는 비치환된 나프틸리디닐렌; 치환 또는 비치환된 옥사디아졸릴렌; 치환 또는 비치환된 피라졸로[1, 5-c]퀴나졸리닐렌; 치환 또는 비치환된 피리도[1,2-a]인다졸릴렌; 치환 또는 비치환된 디벤조[c, h]아크리딜; 치환 또는 비치환된 디알킬아민; 치환 또는 비치환된 디아릴아민; 치환 또는 비치환된 디헤테로아릴아민; 치환 또는 비치환된 알킬아릴아민; 치환 또는 비치환된 알킬헤테로아릴아민; 및 치환 또는 비치환된 아릴헤테로아릴아민으로 이루어진 군으로부터 선택되고,According to another embodiment of the present disclosure, L is a direct bond; -P (= O) R &lt; 10 &gt;-; Substituted or unsubstituted phenylene; Substituted or unsubstituted biphenylene; Substituted or unsubstituted naphthylene; Substituted or unsubstituted anthrylene; Substituted or unsubstituted phenanthrenylene; Substituted or unsubstituted triphenylene; Or substituted or unsubstituted 9,9-diphenyl-9H-fluorenylenes; Substituted or unsubstituted pyridylenes; Substituted or unsubstituted pyrimidines; Substituted or unsubstituted thiaziene; Substituted or unsubstituted quinolylenes; Substituted or unsubstituted quinazolinylene; Substituted or unsubstituted benzothiazolylenes; Substituted or unsubstituted benzoxazolylene; Substituted or unsubstituted benzimidazolylene; A substituted or unsubstituted divalent dibenzothiophene group; Substituted or unsubstituted dibenzofuranylenes; Substituted or unsubstituted carbazolylene; Substituted or unsubstituted indolo [2, 3-a] carbazolylene; Substituted or unsubstituted naphthylidenediyl; Substituted or unsubstituted oxadiazolylene; Substituted or unsubstituted pyrazolo [1,5-c] quinazolinylene; Substituted or unsubstituted pyrido [1,2-a] indazolylene; Substituted or unsubstituted dibenzo [c, h] acridyl; Substituted or unsubstituted dialkylamines; A substituted or unsubstituted diarylamine; Substituted or unsubstituted diheteroarylamines; Substituted or unsubstituted alkylarylamines; Substituted or unsubstituted alkylheteroarylamines; And substituted or unsubstituted arylheteroaryl amines,
상기 L이 치환되는 경우, 치환기는 중수소, 할로겐, -SiRR'R", -P(=O)RR', 치환 또는 비치환된 C6 내지 C60의 아릴 및 치환 또는 비치환된 C2 내지 C60의 헤테로아릴 중에서 선택되며, 상기 R, R', R" 및 R10은 전술한 바와 동일하다.If the the L-substituted, the substituent is deuterium, halogen, -SiRR'R ", -P (= O ) RR ', substituted or unsubstituted C 6 to C 60 aryl, and substituted or unsubstituted C 2 to C And R, R ', R " and R &lt; 10 &gt; are as defined above.
본 명세서의 또 하나의 실시상태에 따르면, 상기 L은 직접결합; -P(=O)R10-; 페닐렌; 바이페닐렌; 나프틸렌; 안트릴렌; 페난트레닐렌; 트리페닐렌; 9,9-다이페닐-9H-플루오레닐렌; 피리딜렌; 피리미딜렌; 트리아지닐렌; 퀴놀릴렌; 퀴나졸리닐렌; 벤조티아졸릴렌; 벤즈옥사졸릴렌; 벤즈이미다졸릴렌; 2가의 디벤조티오펜기; 디벤조푸라닐렌; 카바졸릴렌; 인돌로[2, 3-a]카바졸릴렌; 나프틸리디닐렌; 옥사디아졸릴렌; 피라졸로[1, 5-c]퀴나졸리닐렌; 피리도[1,2-a]인다졸릴렌; 디벤조[c, h]아크리딜; 디알킬아민; 디아릴아민; 디헤테로아릴아민; 알킬아릴아민; 알킬헤테로아릴아민; 및 아릴헤테로아릴아민으로 이루어진 군으로부터 선택되고, 상기 R10은 전술한 바와 동일하다.According to another embodiment of the present disclosure, L is a direct bond; -P (= O) R &lt; 10 &gt;-;Phenylene;Biphenylene;Naphthylene;Anthrylene;Phenanthrenylene;Triphenylene;9,9-diphenyl-9H-fluorenylene;Pyridylene;Pyrimidylene;Triazinilene;Quinolylene;Quinazolinylene;Benzothiazolylene;Benzoxazolylene;Benzimidazolylene; A divalent dibenzothiophene group; Dibenzofuranylene; Carbazolylene; Indolo [2, 3-a] carbazolylene; Naphthyridinylene; Oxadiazolylene; Pyrazolo [1,5-c] quinazolinylene; Pyrido [1,2-a] indazolylene; Dibenzo [c, h] acridyl; Dialkylamines; Diarylamine; Diheteroarylamine; Alkylarylamines; Alkylheteroarylamines; And arylheteroarylamines, wherein R &lt; 10 &gt; is the same as described above.
본 명세서의 또 하나의 실시상태에 따르면, 상기 L은 직접결합; -P(=O)R10-; 페닐렌; 바이페닐렌; 나프틸렌; 안트릴렌; 페난트레닐렌; 트리페닐렌; 9,9-다이페닐-9H-플루오레닐렌; 피리딜렌; 피리미딜렌; 트리아지닐렌; 퀴놀릴렌; 퀴나졸리닐렌; 벤조티아졸릴렌; 벤조옥사졸릴렌; 벤조이미다졸릴렌; 2가의 디벤조티오펜기; 디벤조푸라닐렌; 카바졸릴렌; 인돌로[2, 3-a]카바졸릴렌; 나프틸리디닐렌; 옥사디아졸릴렌; 피라졸로[1, 5-c]퀴나졸리닐렌; 피리도[1,2-a]인다졸릴렌; 디벤조[c, h]아크리딜; 디페닐아민; 디비페닐아민; 및 페닐나프틸아민으로 이루어진 군으로부터 선택되고, 상기 R10은 전술한 바와 동일하다.According to another embodiment of the present disclosure, L is a direct bond; -P (= O) R &lt; 10 &gt;-;Phenylene;Biphenylene;Naphthylene;Anthrylene;Phenanthrenylene;Triphenylene;9,9-diphenyl-9H-fluorenylene;Pyridylene;Pyrimidylene;Triazinilene;Quinolylene;Quinazolinylene;Benzothiazolylene;Benzoxazolylene;Benzoimidazolylene; A divalent dibenzothiophene group; Dibenzofuranylene; Carbazolylene; Indolo [2, 3-a] carbazolylene; Naphthyridinylene; Oxadiazolylene; Pyrazolo [1,5-c] quinazolinylene; Pyrido [1,2-a] indazolylene; Dibenzo [c, h] acridyl; Diphenylamine; Dibiphenylamine; And phenyl naphthylamine, wherein R &lt; 10 &gt; is the same as described above.
본 명세서의 또 하나의 실시상태에 따르면, 상기 Z는 수소; 중수소; 할로겐; -P(=O)R11R12; 중수소, 할로겐, -SiRR'R", -P(=O)RR', 치환 또는 비치환된 C6 내지 C60의 아릴 및 치환 또는 비치환된 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 중수소, 할로겐, -SiRR'R", -P(=O)RR', 치환 또는 비치환된 C6 내지 C60의 아릴 및 치환 또는 비치환된 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 중수소, 할로겐, -SiRR'R", -P(=O)RR', 치환 또는 비치환된 C6 내지 C60의 아릴 및 치환 또는 비치환된 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 치환 또는 비치환된 C1 내지 C20의 알킬아민; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴아민; 및 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴아민으로 이루어진 군으로부터 선택되고, 상기 R, R', R", R11 및 R12는 전술한 바와 동일하다.According to another embodiment of the present disclosure, Z is selected from the group consisting of hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; A substituted or unsubstituted C 6 to C 60 aryl, and a substituted or unsubstituted C 2 to C 60 heteroaryl selected from the group consisting of hydrogen, deuterium, halogen, -SiRR'R ", -P (= O) Halogen, -SiRR'R ", -P (= O) RR ', a substituted or unsubstituted C 6 to C 60 substituted or unsubstituted C 1 to C 60 linear or branched alkyl, C 6 to C 60 monocyclic or polycyclic aryl which is substituted or unsubstituted with at least one substituent selected from aryl and substituted or unsubstituted C 2 to C 60 heteroaryl; A substituted or unsubstituted C 6 to C 60 aryl, and a substituted or unsubstituted C 2 to C 60 heteroaryl selected from the group consisting of hydrogen, deuterium, halogen, -SiRR'R ", -P (= O) A substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl, a substituted or unsubstituted C 1 to C 20 alkylamine, a substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl Amine and a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroarylamine, and R, R ', R ", R 11 and R 12 are the same as defined above.
상기 Z는 수소; 중수소; 할로겐; -P(=O)R11R12; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 아릴 및 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 아릴 및 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 아릴 및 C2 내지 C60의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 치환 또는 비치환된 C1 내지 C20의 알킬아민; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴아민; 및 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴아민으로 이루어진 군으로부터 선택되고, 상기 R, R', R", R11 및 R12는 전술한 바와 동일하다.Z is hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; C 1 to C 6 substituted or unsubstituted with one or more substituents selected from deuterium, halogen, -SiRR'R ", -P (= O) RR ', aryl of C 6 to C 60 and heteroaryl of C 2 to C 60 . alkyl of C 60 linear or branched; deuterium, halogen, -SiRR'R ", -P (= O ) RR ', C 6 aryl, and C 2 to to one or more selected from the group consisting of C 60 heteroaryl group of C 60 A C 6 to C 60 monocyclic or polycyclic aryl group substituted or unsubstituted with a substituent group; Deuterium, halogen, -SiRR'R ", -P (= O ) RR ', C 6 to C 60 aryl and C 2 to a substituted or unsubstituted C 2 to by one or more substituents selected from heteroaryl of C 60 C 60 monocyclic or polycyclic heteroaryl; a substituted or unsubstituted C 1 to C 20 alkyl amine group; a substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl amines; and substituted or unsubstituted C 2 To C 60 monocyclic or polycyclic heteroaryl amines, and R, R ', R ", R 11 and R 12 are the same as defined above.
본 명세서의 또 하나의 실시상태에 따르면, 상기 Z는 수소; 중수소; 할로겐; -P(=O)R11R12; 치환 또는 비치환된 에틸; 치환 또는 비치환된 페닐; 치환 또는 비치환된 바이페닐; 치환 또는 비치환된 나프틸; 치환 또는 비치환된 안트릴; 치환 또는 비치환된 페난트레닐; 치환 또는 비치환된 트리페닐레닐; 또는 치환 또는 비치환된 9,9-다이페닐-9H-플루오레닐; 치환 또는 비치환된 피리딜; 치환 또는 비치환된 피리미딜; 치환 또는 비치환된 트리아지닐; 치환 또는 비치환된 퀴놀릴; 치환 또는 비치환된 퀴나졸리닐; 치환 또는 비치환된 벤조티아졸릴; 치환 또는 비치환된 벤즈옥사졸릴; 치환 또는 비치환된 벤즈이미다졸릴; 치환 또는 비치환된 디벤조티오페닐; 치환 또는 비치환된 디벤조푸라닐; 치환 또는 비치환된 카바졸릴; 치환 또는 비치환된 인돌로[2, 3-a]카바졸릴, 치환 또는 비치환된 나프틸리디닐; 치환 또는 비치환된 옥사디아졸릴; 치환 또는 비치환된 피라졸로[1, 5-c]퀴나졸리닐; 치환 또는 비치환된 피리도[1,2-a]인다졸릴; 또는 치환 또는 비치환된 디벤조[c, h]아크리딜; 치환 또는 비치환된 벤조[b]나프토[2,3-d]티오펜기; 치환 또는 비치환된 벤조[h]나프토[2,3-c]아크리딜; 치환 또는 비치환된 벤조[f]퀴놀릴; 치환 또는 비치환된 디알킬아민; 치환 또는 비치환된 디아릴아민; 치환 또는 비치환된 디헤테로아릴아민; 치환 또는 비치환된 알킬아릴아민; 치환 또는 비치환된 알킬헤테로아릴아민; 및 치환 또는 비치환된 아릴헤테로아릴아민으로 이루어진 군으로부터 선택되고,According to another embodiment of the present disclosure, Z is selected from the group consisting of hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; Substituted or unsubstituted ethyl; Substituted or unsubstituted phenyl; Substituted or unsubstituted biphenyl; Substituted or unsubstituted naphthyl; Substituted or unsubstituted anthryl; Substituted or unsubstituted phenanthrenyl; Substituted or unsubstituted triphenylenyl; Or substituted or unsubstituted 9,9-diphenyl-9H-fluorenyl; Substituted or unsubstituted pyridyl; Substituted or unsubstituted pyrimidyl; Substituted or unsubstituted thiazinyl; Substituted or unsubstituted quinolyl; Substituted or unsubstituted quinazolinyl; Substituted or unsubstituted benzothiazolyl; Substituted or unsubstituted benzoxazolyl; Substituted or unsubstituted benzimidazolyl; Substituted or unsubstituted dibenzothiophenyl; Substituted or unsubstituted dibenzofuranyl; Substituted or unsubstituted carbazolyl; Substituted or unsubstituted indolo [2, 3-a] carbazolyl, substituted or unsubstituted naphthyridinyl; Substituted or unsubstituted oxadiazolyl; Substituted or unsubstituted pyrazolo [1,5-c] quinazolinyl; Substituted or unsubstituted pyrido [1,2-a] indazolyl; Or substituted or unsubstituted dibenzo [c, h] acridyl; Substituted or unsubstituted benzo [b] naphtho [2,3-d] thiophene groups; Substituted or unsubstituted benzo [h] naphtho [2,3-c] acridyl; Substituted or unsubstituted benzo [f] quinolyl; Substituted or unsubstituted dialkylamines; A substituted or unsubstituted diarylamine; Substituted or unsubstituted diheteroarylamines; Substituted or unsubstituted alkylarylamines; Substituted or unsubstituted alkylheteroarylamines; And substituted or unsubstituted arylheteroaryl amines,
상기 Z가 치환되는 경우, 치환기는 중수소, 할로겐, -SiRR'R", -P(=O)RR', 치환 또는 비치환된 C6 내지 C60의 아릴 및 치환 또는 비치환된 C2 내지 C60의 헤테로아릴 중에서 선택되며, 상기 R, R', R", R11 및 R12은 전술한 바와 동일하다.Case in which the Z-substituted, the substituent is deuterium, halogen, -SiRR'R ", -P (= O ) RR ', substituted or unsubstituted C 6 to C 60 aryl, and substituted or unsubstituted C 2 to C And R, R ', R &quot;, R 11 and R 12 are the same as defined above.
본 명세서의 또 하나의 실시상태에 따르면, 상기 Z는 수소; 중수소; 할로겐; -P(=O)R11R12; 에틸; 페닐; 바이페닐; 나프틸; 안트릴; 페난트레닐; 트리페닐레닐; 9,9-다이페닐-9H-플루오레닐; 피리딜; 피리미딜; 트리아지닐; 퀴놀릴; 퀴나졸리닐; 벤조티아졸릴; 벤즈옥사졸릴; 벤즈이미다졸릴; 디벤조티오페닐; 디벤조푸라닐; 카바졸릴; 인돌로[2, 3-a]카바졸릴, 나프틸리디닐; 옥사디아졸릴; 피라졸로[1, 5-c]퀴나졸리닐; 피리도[1,2-a]인다졸릴; 디벤조[c, h]아크리딜; 벤조[b]나프토[2,3-d]티오펜기; 벤조[h]나프토[2,3-c]아크리딜; 벤조[f]퀴놀릴; 디알킬아민; 디아릴아민; 디헤테로아릴아민; 알킬아릴아민; 알킬헤테로아릴아민; 및 아릴헤테로아릴아민으로 이루어진 군으로부터 선택되고, 상기 R11 및 R12은 전술한 바와 동일하다.According to another embodiment of the present disclosure, Z is selected from the group consisting of hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; ethyl; Phenyl; Biphenyl; Naphthyl; Anthryl; Phenanthrenyl; Triphenylenyl; 9,9-diphenyl-9H-fluorenyl; Pyridyl; Pyrimidyl; Triazinyl; Quinolyl; Quinazolinyl; Benzothiazolyl; Benzoxazolyl; Benzimidazolyl; Dibenzothiophenyl; Dibenzofuranyl; Carbazolyl; Indolo [2, 3-a] carbazolyl, naphthyridinyl; Oxadiazolyl; Pyrazolo [1,5-c] quinazolinyl; Pyrido [1,2-a] indazolyl; Dibenzo [c, h] acridyl; Benzo [b] naphtho [2,3-d] thiophene group; Benzo [h] naphtho [2,3-c] acridyl; Benzo [f] quinolyl; Dialkylamines; Diarylamine; Diheteroarylamine; Alkylarylamines; Alkylheteroarylamines; And arylheteroarylamine, and R &lt; 11 &gt; and R &lt; 12 &gt; are the same as described above.
본 명세서의 또 하나의 실시상태에 따르면, 상기 Z는 수소; 중수소; 할로겐; -P(=O)R11R12; 에틸; 페닐; 바이페닐; 나프틸; 안트릴; 페난트레닐; 트리페닐레닐; 9,9-다이페닐-9H-플루오레닐; 피리딜; 피리미딜; 트리아지닐; 퀴놀릴; 퀴나졸리닐; 벤조티아졸릴; 벤조옥사졸릴; 벤조이미다졸릴; 디벤조티오페닐; 디벤조푸라닐; 카바졸릴; 인돌로[2, 3-a]카바졸릴, 나프틸리디닐; 옥사디아졸릴; 피라졸로[1, 5-c]퀴나졸리닐; 피리도[1,2-a]인다졸릴; 디벤조[c, h]아크리딜; 벤조[b]나프토[2,3-d]티오펜기; 벤조[h]나프토[2,3-c]아크리딜; 벤조[f]퀴놀릴; 디페닐아민; 디비페닐아민; 및 페닐나프틸아민으로 이루어진 군으로부터 선택되고, 상기 R11 및 R12은 전술한 바와 동일하다. According to another embodiment of the present disclosure, Z is selected from the group consisting of hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; ethyl; Phenyl; Biphenyl; Naphthyl; Anthryl; Phenanthrenyl; Triphenylenyl; 9,9-diphenyl-9H-fluorenyl; Pyridyl; Pyrimidyl; Triazinyl; Quinolyl; Quinazolinyl; Benzothiazolyl; Benzoxazolyl; Benzoimidazolyl; Dibenzothiophenyl; Dibenzofuranyl; Carbazolyl; Indolo [2, 3-a] carbazolyl, naphthyridinyl; Oxadiazolyl; Pyrazolo [1,5-c] quinazolinyl; Pyrido [1,2-a] indazolyl; Dibenzo [c, h] acridyl; Benzo [b] naphtho [2,3-d] thiophene group; Benzo [h] naphtho [2,3-c] acridyl; Benzo [f] quinolyl; Diphenylamine; Dibiphenylamine; And phenyl naphthylamine, and R &lt; 11 &gt; and R &lt; 12 &gt; are the same as described above.
본 명세서의 또 하나의 실시상태에 따르면, 상기 Z는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴이고, 상기 헤테로아릴은 헤테로원자로서 N, O 및 S 중에서 선택되는 적어도 어느 하나를 포함한다.According to another embodiment of the present disclosure, Z is a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl, wherein said heteroaryl is at least one selected from N, O and S as a heteroatom One.
본 명세서의 또 하나의 실시상태에 따르면, 상기 Z는
Figure PCTKR2015006723-appb-I000003
이고, 상기 X1 및 X2는 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 방향족 탄화수소 고리; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 방향족 헤테로 고리이다.According to another embodiment of the present disclosure, Z is
Figure PCTKR2015006723-appb-I000003
X 1 and X 2 are substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aromatic hydrocarbon rings; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic aromatic heterocyclic ring.
본 명세서의 또 하나의 실시상태에 따르면, 상기
Figure PCTKR2015006723-appb-I000004
는 하기 구조식으로 표시된다.According to another embodiment of the present disclosure,
Figure PCTKR2015006723-appb-I000004
Is represented by the following structural formula.
Figure PCTKR2015006723-appb-I000005
Figure PCTKR2015006723-appb-I000005
상기 구조식에 있어서, Y1 내지 Y5는 서로 같거나 상이하고, 각각 독립적으로 S, NY' 또는 CY'Y"이며,Y 1 to Y 5 are the same or different and each independently represent S, NY 'or CY'Y "
상기 Y' 및 Y"는 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 또는 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴이다.Wherein Y 'and Y "are the same or different and each is independently hydrogen, substituted or unsubstituted alkyl, a linear or branched unsubstituted C 1 to C 60; of the substituted or unsubstituted C 6 to C 60 monocyclic or Aryl of a polycyclic ring.
본 명세서의 제 1 실시상태에 따르면, 전술한 일 실시상태의 화학식 1에서 X는 NR3이고, Y와 R3 중 적어도 하나는 -(L)m-(Z)n이며, L은 치환 또는 비치환된 페닐렌; 치환 또는 비치환된 C5의 헤테로아릴렌이고, Z, m 및 n은 전술한 일 실시상태와 동일하며, 상기 Z는 L의 코어에 결합된 원자에 대하여 파라 또는 메타위치에 결합된다.According to a first embodiment of the present invention, in the above-mentioned one embodiment, X is NR 3 , at least one of Y and R 3 is - (L) m - (Z) n , Substituted phenylene; And heteroarylene substituted or unsubstituted C 5, Z, m and n are the same as in the above-mentioned one condition, wherein Z is bonded at the para or meta position relative to the atom bonded to the core L.
본 명세서의 또 하나의 실시상태에 따르면, 전술한 제 1 실시상태의 X는 NR3이고, Y는 -(L)m-(Z)n이며, R3는 전술한 일 실시상태와 동일하고, L, Z, m 및 n은 전술한 제 1 실시상태와 동일하며, 상기 Z는 L의 코어에 결합된 원자에 대하여 파라위치에 결합된다.According to another embodiment of the present invention, X in the above first embodiment is NR 3 , Y is - (L) m - (Z) n , R 3 is the same as in the above- L, Z, m and n are the same as in the first embodiment described above, and Z is bonded to the para position with respect to the atom bonded to the core of L.
본 명세서의 또 하나의 실시상태에 따르면, 전술한 제 1 실시상태의 X는 NR3이고, Y는 -(L)m-(Z)n이며, R3는 전술한 일 실시상태와 동일하고, L, Z, m 및 n은 전술한 제 1 실시상태와 동일하며, 상기 Z는 L의 코어에 결합된 원자에 대하여 메타위치에 결합된다.According to another embodiment of the present invention, X in the above first embodiment is NR 3 , Y is - (L) m - (Z) n , R 3 is the same as in the above- L, Z, m and n are the same as in the above-mentioned first embodiment, and Z is bonded to the meta position with respect to the atom bonded to the core of L.
본 명세서의 또 하나의 실시상태에 따르면, 전술한 제 1 실시상태의 X는 NR3이고, R3는 -(L)m-(Z)n이며, L, Z, m 및 n은 전술한 제 1 실시상태와 동일하고, 상기 Z는 L의 코어에 결합된 원자에 대하여 파라위치에 결합된다.According to another embodiment of the present invention, X in the above first embodiment is NR 3 , R 3 is - (L) m - (Z) n , and L, Z, 1 &lt; / RTI &gt; embodiment, where Z is bonded to the para position with respect to the atom bound to the L core.
본 명세서의 또 하나의 실시상태에 따르면, 전술한 제 1 실시상태의 X는 NR3이고, R3는 -(L)m-(Z)n이며, L, Z, m 및 n은 전술한 제 1 실시상태와 동일하고, 상기 Z는 L의 코어에 결합된 원자에 대하여 메타위치에 결합된다.According to another embodiment of the present invention, X in the above first embodiment is NR 3 , R 3 is - (L) m - (Z) n , and L, Z, 1 &lt; / RTI &gt; embodiment, wherein Z is bonded to the meta position with respect to the atom bonded to the core of L.
본 명세서의 제 2 실시상태에 따르면, 전술한 일 실시상태의 화학식 1에서 X는 CR4R5, S, O 또는 Se이고, Y는 -(L)m-(Z)n이며, L은 전술한 제 1 실시상태와 동일하고, R4, R5, Z, m 및 n은 전술한 일 실시상태와 동일하며, 상기 Z는 L의 코어에 결합된 원자에 대하여 파라 또는 메타위치에 결합된다.According to a second embodiment of the present invention, X is CR 4 R 5 , S, O or Se, Y is - (L) m - (Z) n , R 4 , R 5 , Z, m and n are the same as in the above-mentioned one embodiment, and Z is bonded to the para or meta position with respect to the atom bonded to the core of L.
본 명세서의 또 하나의 실시상태에 따르면, 전술한 제 2 실시상태의 X는 CR4R5, S, O 또는 Se이고, Y는 -(L)m-(Z)n이며, R4, R5, L, Z, m 및 n은 전술한 제 2 실시상태와 동일하고, 상기 Z는 L의 코어에 결합된 원자에 대하여 파라위치에 결합된다.According to yet an embodiment of the present disclosure, X of the above-described second condition is CR 4 R 5, and S, O or Se, Y is - (L) m - (Z ) and n, R 4, R 5 , L, Z, m and n are the same as in the second embodiment described above, and Z is bonded to the para position with respect to the atom bonded to the core of L.
본 명세서의 또 하나의 실시상태에 따르면, 전술한 제 2 실시상태의 X는 CR4R5, S, O 또는 Se이고, Y는 -(L)m-(Z)n이며, R4, R5, L, Z, m 및 n은 전술한 제 2 실시상태와 동일하고, 상기 Z는 L의 코어에 결합된 원자에 대하여 메타위치에 결합된다.According to yet an embodiment of the present disclosure, X of the above-described second condition is CR 4 R 5, and S, O or Se, Y is - (L) m - (Z ) and n, R 4, R 5 , L, Z, m and n are the same as in the above-mentioned second embodiment, and Z is bonded to the meta position with respect to the atom bonded to the core of L.
본 명세서의 제 1 및 제 2 실시상태에 따르면, 상기 L은 치환 또는 비치환된 페닐렌; 또는 치환 또는 비치환된 피리딜렌이다.According to the first and second embodiments of the present invention, L is substituted or unsubstituted phenylene; Or substituted or unsubstituted pyridylenes.
본 명세서의 제 1 및 제 2 실시상태에 따르면, 상기 L은 페닐렌; 또는 피리딜렌이다.According to the first and second embodiments of the present invention, L is phenylene; Or pyridylene.
본 명세서의 일 실시상태에 따르면, 전술한 실시상태에 따른 화학식 1은 하기 화학식 2 내지 7 중 어느 하나로 표시된다:According to one embodiment of the present disclosure, Formula 1 according to the above-described embodiment is represented by any one of the following Formulas 2 to 7:
[화학식 2](2)
Figure PCTKR2015006723-appb-I000006
Figure PCTKR2015006723-appb-I000006
[화학식 3](3)
Figure PCTKR2015006723-appb-I000007
Figure PCTKR2015006723-appb-I000007
[화학식 4][Chemical Formula 4]
Figure PCTKR2015006723-appb-I000008
Figure PCTKR2015006723-appb-I000008
[화학식 5][Chemical Formula 5]
Figure PCTKR2015006723-appb-I000009
Figure PCTKR2015006723-appb-I000009
[화학식 6][Chemical Formula 6]
Figure PCTKR2015006723-appb-I000010
Figure PCTKR2015006723-appb-I000010
[화학식 7](7)
Figure PCTKR2015006723-appb-I000011
Figure PCTKR2015006723-appb-I000011
상기 화학식 2 내지 7에 있어서, X, Y, R1, R2, a 및 b의 전술한 실시상태에 따른 화학식 1과 동일하다.(1) according to the above-described embodiment of X, Y, R 1 , R 2 , a and b in the above formulas 2 to 7.
본 명세서의 또 하나의 실시상태에 따르면, 전술한 실시상태에 따른 화학식 1은 하기 화학식 8 내지 12 중 어느 하나로 표시된다:According to another embodiment of the present disclosure, Formula 1 according to the above-described embodiment is represented by any one of the following Formulas 8 to 12:
[화학식 8][Chemical Formula 8]
Figure PCTKR2015006723-appb-I000012
Figure PCTKR2015006723-appb-I000012
[화학식 9][Chemical Formula 9]
Figure PCTKR2015006723-appb-I000013
Figure PCTKR2015006723-appb-I000013
[화학식 10][Chemical formula 10]
Figure PCTKR2015006723-appb-I000014
Figure PCTKR2015006723-appb-I000014
[화학식 11](11)
Figure PCTKR2015006723-appb-I000015
Figure PCTKR2015006723-appb-I000015
[화학식 12][Chemical Formula 12]
Figure PCTKR2015006723-appb-I000016
Figure PCTKR2015006723-appb-I000016
상기 화학식 8 내지 12에 있어서, Y, a, b, R1 내지 R5는 전술한 실시상태에 따른 화학식 1과 동일하다.In formulas (8) to (12), Y, a, b and R 1 to R 5 are the same as in formula (1) according to the above-described embodiment.
본 명세서의 또 하나의 실시상태에 따르면, 전술한 실시상태에 따른 화학식 8은 하기 화학식 13 내지 24 중 어느 하나로 표시된다:According to another embodiment of the present disclosure, Formula 8 according to the above-described embodiment is represented by any one of the following Formulas 13 to 24:
[화학식 13][Chemical Formula 13]
Figure PCTKR2015006723-appb-I000017
Figure PCTKR2015006723-appb-I000017
[화학식 14][Chemical Formula 14]
Figure PCTKR2015006723-appb-I000018
Figure PCTKR2015006723-appb-I000018
[화학식 15][Chemical Formula 15]
Figure PCTKR2015006723-appb-I000019
Figure PCTKR2015006723-appb-I000019
[화학식 16][Chemical Formula 16]
Figure PCTKR2015006723-appb-I000020
Figure PCTKR2015006723-appb-I000020
[화학식 17][Chemical Formula 17]
Figure PCTKR2015006723-appb-I000021
Figure PCTKR2015006723-appb-I000021
[화학식 18][Chemical Formula 18]
Figure PCTKR2015006723-appb-I000022
Figure PCTKR2015006723-appb-I000022
[화학식 19][Chemical Formula 19]
Figure PCTKR2015006723-appb-I000023
Figure PCTKR2015006723-appb-I000023
[화학식 20][Chemical Formula 20]
Figure PCTKR2015006723-appb-I000024
Figure PCTKR2015006723-appb-I000024
[화학식 21][Chemical Formula 21]
Figure PCTKR2015006723-appb-I000025
Figure PCTKR2015006723-appb-I000025
[화학식 22][Chemical Formula 22]
Figure PCTKR2015006723-appb-I000026
Figure PCTKR2015006723-appb-I000026
[화학식 23](23)
Figure PCTKR2015006723-appb-I000027
Figure PCTKR2015006723-appb-I000027
[화학식 24]&Lt; EMI ID =
Figure PCTKR2015006723-appb-I000028
Figure PCTKR2015006723-appb-I000028
상기 화학식 13 내지 24에 있어서, In Formulas 13 to 24,
Ar은 수소; 중수소; 할로겐; -P(=O)R11R12; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,Ar is hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
R11 및 R12은 서로 같거나 상이하며, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴이고,R 11 and R 12 are the same or different and each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl,
R1, R2, a 및 b의 전술한 실시상태에 따른 화학식 1과 동일하다. 1 &gt;, R &lt; 1 &gt;, R &lt; 2 &gt;, a and b.
본 명세서의 또 하나의 실시상태에 따르면, 전술한 실시상태에 따른 화학식 2 내지 7은 각각 하기 화학식 25 내지 30로 표시된다.According to another embodiment of the present invention, the formulas (2) to (7) according to the above-described embodiments are represented by the following formulas (25) to (30), respectively.
[화학식 25](25)
Figure PCTKR2015006723-appb-I000029
Figure PCTKR2015006723-appb-I000029
[화학식 26](26)
Figure PCTKR2015006723-appb-I000030
Figure PCTKR2015006723-appb-I000030
[화학식 27](27)
Figure PCTKR2015006723-appb-I000031
Figure PCTKR2015006723-appb-I000031
[화학식 28](28)
Figure PCTKR2015006723-appb-I000032
Figure PCTKR2015006723-appb-I000032
[화학식 29][Chemical Formula 29]
Figure PCTKR2015006723-appb-I000033
Figure PCTKR2015006723-appb-I000033
[화학식 30](30)
Figure PCTKR2015006723-appb-I000034
Figure PCTKR2015006723-appb-I000034
상기 화학식 25 내지 30에 있어서, X'는 CR4R5, O, S 또는 Se이고,In the above Formulas 25 to 30, X 'represents CR 4 R 5 , O, S or Se,
Ar은 수소; 중수소; 할로겐; -P(=O)R11R12; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되며,Ar is hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
R4, R5, R11 및 R12은 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴이며,R 4 , R 5 , R 11 and R 12 are the same or different from each other, and each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl,
R1, R2, a 및 b의 전술한 실시상태에 따른 화학식 1과 동일하다. 1 &gt;, R &lt; 1 &gt;, R &lt; 2 &gt;, a and b.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화합물 중에서 선택될 수 있다.According to one embodiment of the present invention, the formula (1) may be selected from the following compounds.
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 13 및 25에서, Ar은 페닐의 코어에 결합된 원자에 대하여 파라위치에 결합되고, 상기 화학식 13 및 25는 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present invention, in the above formulas (13) and (25), Ar is bonded to the para position to an atom bonded to the core of the phenyl, and the above formulas (13) and (25) can be selected from the following compounds.
Figure PCTKR2015006723-appb-I000035
Figure PCTKR2015006723-appb-I000035
Figure PCTKR2015006723-appb-I000036
Figure PCTKR2015006723-appb-I000036
Figure PCTKR2015006723-appb-I000037
Figure PCTKR2015006723-appb-I000037
Figure PCTKR2015006723-appb-I000038
Figure PCTKR2015006723-appb-I000038
Figure PCTKR2015006723-appb-I000039
Figure PCTKR2015006723-appb-I000039
Figure PCTKR2015006723-appb-I000040
Figure PCTKR2015006723-appb-I000040
Figure PCTKR2015006723-appb-I000041
Figure PCTKR2015006723-appb-I000041
Figure PCTKR2015006723-appb-I000042
Figure PCTKR2015006723-appb-I000042
Figure PCTKR2015006723-appb-I000043
Figure PCTKR2015006723-appb-I000043
Figure PCTKR2015006723-appb-I000044
Figure PCTKR2015006723-appb-I000044
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 13 및 25에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 메타위치에 결합되고, 상기 화학식 13 및 25는 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present invention, in the above formulas (13) and (25), Ar is bonded to the meta position with respect to the atom bonded to the core of the phenyl, and the above formulas (13) and (25) can be selected from the following compounds.
Figure PCTKR2015006723-appb-I000045
Figure PCTKR2015006723-appb-I000045
Figure PCTKR2015006723-appb-I000046
Figure PCTKR2015006723-appb-I000046
Figure PCTKR2015006723-appb-I000047
Figure PCTKR2015006723-appb-I000047
Figure PCTKR2015006723-appb-I000048
Figure PCTKR2015006723-appb-I000048
Figure PCTKR2015006723-appb-I000049
Figure PCTKR2015006723-appb-I000049
Figure PCTKR2015006723-appb-I000050
Figure PCTKR2015006723-appb-I000050
Figure PCTKR2015006723-appb-I000051
Figure PCTKR2015006723-appb-I000051
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 14에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 파라위치에 결합되고, 상기 화학식 14는 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present invention, in the above formula (14), Ar is bonded to the para position with respect to the atom bonded to the core of the phenyl, and the formula (14) may be selected from the following compounds.
Figure PCTKR2015006723-appb-I000052
Figure PCTKR2015006723-appb-I000052
Figure PCTKR2015006723-appb-I000053
Figure PCTKR2015006723-appb-I000053
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 14에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 메타위치에 결합되고, 상기 화학식 14는 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present disclosure, in Formula 14, Ar is bonded to a meta-position with respect to an atom bonded to the core of the phenyl, and Formula 14 may be selected from the following compounds.
Figure PCTKR2015006723-appb-I000054
Figure PCTKR2015006723-appb-I000054
Figure PCTKR2015006723-appb-I000055
Figure PCTKR2015006723-appb-I000055
상기 화학식 15, 16 및 26에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 파라위치에 결합되고, 상기 화학식 15, 16 및 26은 하기 화합물 중에서 선택될 수 있다.In the above formulas (15), (16) and (26), Ar is bonded to the para position with respect to an atom bonded to the core of the phenyl, and the above formulas (15), (16) and (26) may be selected from the following compounds.
Figure PCTKR2015006723-appb-I000056
Figure PCTKR2015006723-appb-I000056
Figure PCTKR2015006723-appb-I000057
Figure PCTKR2015006723-appb-I000057
Figure PCTKR2015006723-appb-I000058
Figure PCTKR2015006723-appb-I000058
Figure PCTKR2015006723-appb-I000059
Figure PCTKR2015006723-appb-I000059
Figure PCTKR2015006723-appb-I000060
Figure PCTKR2015006723-appb-I000060
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 15, 16 및 26에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 메타위치에 결합되고, 상기 화학식 15, 16 및 26은 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present disclosure, in the above formulas (15), (16) and (26), Ar is bonded at the meta position with respect to an atom bonded to the core of the phenyl, .
Figure PCTKR2015006723-appb-I000061
Figure PCTKR2015006723-appb-I000061
Figure PCTKR2015006723-appb-I000062
Figure PCTKR2015006723-appb-I000062
Figure PCTKR2015006723-appb-I000063
Figure PCTKR2015006723-appb-I000063
Figure PCTKR2015006723-appb-I000064
Figure PCTKR2015006723-appb-I000064
Figure PCTKR2015006723-appb-I000065
Figure PCTKR2015006723-appb-I000065
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 17에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 파라위치에 결합되고, 상기 화학식 17은 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present invention, in the above formula (17), Ar is bonded to the para position with respect to an atom bonded to the core of the phenyl, and the formula (17) may be selected from the following compounds.
Figure PCTKR2015006723-appb-I000066
Figure PCTKR2015006723-appb-I000066
Figure PCTKR2015006723-appb-I000067
Figure PCTKR2015006723-appb-I000067
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 17에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 메타위치에 결합되고, 상기 화학식 17은 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present invention, in the above formula (17), Ar is bonded to the meta position with respect to an atom bonded to the core of the phenyl, and the formula (17) may be selected from the following compounds.
Figure PCTKR2015006723-appb-I000068
Figure PCTKR2015006723-appb-I000068
Figure PCTKR2015006723-appb-I000069
Figure PCTKR2015006723-appb-I000069
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 18, 19, 28 및 29에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 파라위치에 결합되고, 상기 화학식 18, 19, 28 및 29는 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present disclosure, in the above Chemical Formulas 18, 19, 28 and 29, Ar is bonded to the para position with respect to the atom bonded to the core of the phenyl, May be selected from the following compounds.
Figure PCTKR2015006723-appb-I000070
Figure PCTKR2015006723-appb-I000070
Figure PCTKR2015006723-appb-I000071
Figure PCTKR2015006723-appb-I000071
Figure PCTKR2015006723-appb-I000072
Figure PCTKR2015006723-appb-I000072
Figure PCTKR2015006723-appb-I000073
Figure PCTKR2015006723-appb-I000073
Figure PCTKR2015006723-appb-I000074
Figure PCTKR2015006723-appb-I000074
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 18, 19, 28 및 29에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 메타위치에 결합되고, 상기 화학식 18, 19, 28 및 29은 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present disclosure, in the above Chemical Formulas 18, 19, 28 and 29, Ar is bonded to the meta position with respect to the atom bonded to the core of the phenyl, May be selected from the following compounds.
Figure PCTKR2015006723-appb-I000075
Figure PCTKR2015006723-appb-I000075
Figure PCTKR2015006723-appb-I000076
Figure PCTKR2015006723-appb-I000076
Figure PCTKR2015006723-appb-I000077
Figure PCTKR2015006723-appb-I000077
Figure PCTKR2015006723-appb-I000078
Figure PCTKR2015006723-appb-I000078
Figure PCTKR2015006723-appb-I000079
Figure PCTKR2015006723-appb-I000079
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 20에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 파라위치에 결합되고, 상기 화학식 20은 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present disclosure, in the above Formula 20, Ar is bonded to the para position with respect to an atom bonded to the core of the phenyl, and Formula 20 may be selected from the following compounds.
Figure PCTKR2015006723-appb-I000080
Figure PCTKR2015006723-appb-I000080
Figure PCTKR2015006723-appb-I000081
Figure PCTKR2015006723-appb-I000081
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 20에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 메타위치에 결합되고, 상기 화학식 20은 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present invention, in the above Formula 20, Ar is bonded to the meta position with respect to the atom bonded to the core of the phenyl, and Formula 20 may be selected from the following compounds.
Figure PCTKR2015006723-appb-I000082
Figure PCTKR2015006723-appb-I000082
Figure PCTKR2015006723-appb-I000083
Figure PCTKR2015006723-appb-I000083
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 24 및 30에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 파라위치에 결합되고, 상기 화학식 24 및 30은 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present invention, in the above formulas 24 and 30, Ar is bonded to the para position with respect to an atom bonded to the core of the phenyl, and the above formulas 24 and 30 may be selected from the following compounds.
Figure PCTKR2015006723-appb-I000084
Figure PCTKR2015006723-appb-I000084
Figure PCTKR2015006723-appb-I000085
Figure PCTKR2015006723-appb-I000085
Figure PCTKR2015006723-appb-I000086
Figure PCTKR2015006723-appb-I000086
Figure PCTKR2015006723-appb-I000087
Figure PCTKR2015006723-appb-I000087
Figure PCTKR2015006723-appb-I000088
Figure PCTKR2015006723-appb-I000088
Figure PCTKR2015006723-appb-I000089
Figure PCTKR2015006723-appb-I000089
Figure PCTKR2015006723-appb-I000090
Figure PCTKR2015006723-appb-I000090
Figure PCTKR2015006723-appb-I000091
Figure PCTKR2015006723-appb-I000091
Figure PCTKR2015006723-appb-I000092
Figure PCTKR2015006723-appb-I000092
Figure PCTKR2015006723-appb-I000093
Figure PCTKR2015006723-appb-I000093
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 24 및 30에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 메타위치에 결합되고, 상기 화학식 24 및 30은 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present invention, in the above formulas 24 and 30, Ar is bonded to the meta position with respect to the atom bonded to the core of the phenyl, and the above formulas 24 and 30 may be selected from the following compounds.
Figure PCTKR2015006723-appb-I000094
Figure PCTKR2015006723-appb-I000094
Figure PCTKR2015006723-appb-I000095
Figure PCTKR2015006723-appb-I000095
Figure PCTKR2015006723-appb-I000096
Figure PCTKR2015006723-appb-I000096
Figure PCTKR2015006723-appb-I000097
Figure PCTKR2015006723-appb-I000097
Figure PCTKR2015006723-appb-I000098
Figure PCTKR2015006723-appb-I000098
Figure PCTKR2015006723-appb-I000099
Figure PCTKR2015006723-appb-I000099
Figure PCTKR2015006723-appb-I000100
Figure PCTKR2015006723-appb-I000100
Figure PCTKR2015006723-appb-I000101
Figure PCTKR2015006723-appb-I000101
Figure PCTKR2015006723-appb-I000102
Figure PCTKR2015006723-appb-I000102
Figure PCTKR2015006723-appb-I000103
Figure PCTKR2015006723-appb-I000103
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 23에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 파라위치에 결합되고, 상기 화학식 23은 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present invention, in the formula (23), Ar is bonded to a para position with respect to an atom bonded to the core of the phenyl, and the formula (23) may be selected from the following compounds.
Figure PCTKR2015006723-appb-I000104
Figure PCTKR2015006723-appb-I000104
본 명세서의 또 하나의 실시상태에 따르면, 상기 화학식 23에서, 상기 Ar은 페닐의 코어에 결합된 원자에 대하여 메타위치에 결합되고, 상기 화학식 23은 하기 화합물 중에서 선택될 수 있다.According to another embodiment of the present invention, in the formula (23), Ar is bonded to the meta position with respect to an atom bonded to the core of the phenyl, and the formula (23) may be selected from the following compounds.
Figure PCTKR2015006723-appb-I000105
Figure PCTKR2015006723-appb-I000105
Figure PCTKR2015006723-appb-I000106
Figure PCTKR2015006723-appb-I000106
Figure PCTKR2015006723-appb-I000107
Figure PCTKR2015006723-appb-I000107
Figure PCTKR2015006723-appb-I000108
Figure PCTKR2015006723-appb-I000108
Figure PCTKR2015006723-appb-I000109
Figure PCTKR2015006723-appb-I000109
Figure PCTKR2015006723-appb-I000110
Figure PCTKR2015006723-appb-I000110
Figure PCTKR2015006723-appb-I000111
Figure PCTKR2015006723-appb-I000111
Figure PCTKR2015006723-appb-I000112
Figure PCTKR2015006723-appb-I000112
Figure PCTKR2015006723-appb-I000113
Figure PCTKR2015006723-appb-I000113
Figure PCTKR2015006723-appb-I000114
Figure PCTKR2015006723-appb-I000114
Figure PCTKR2015006723-appb-I000115
Figure PCTKR2015006723-appb-I000115
Figure PCTKR2015006723-appb-I000116
Figure PCTKR2015006723-appb-I000116
Figure PCTKR2015006723-appb-I000117
Figure PCTKR2015006723-appb-I000117
Figure PCTKR2015006723-appb-I000118
Figure PCTKR2015006723-appb-I000118
Figure PCTKR2015006723-appb-I000119
Figure PCTKR2015006723-appb-I000119
Figure PCTKR2015006723-appb-I000120
Figure PCTKR2015006723-appb-I000120
Figure PCTKR2015006723-appb-I000121
Figure PCTKR2015006723-appb-I000121
Figure PCTKR2015006723-appb-I000122
Figure PCTKR2015006723-appb-I000122
Figure PCTKR2015006723-appb-I000123
Figure PCTKR2015006723-appb-I000123
Figure PCTKR2015006723-appb-I000124
Figure PCTKR2015006723-appb-I000124
Figure PCTKR2015006723-appb-I000125
Figure PCTKR2015006723-appb-I000125
Figure PCTKR2015006723-appb-I000126
Figure PCTKR2015006723-appb-I000126
Figure PCTKR2015006723-appb-I000127
Figure PCTKR2015006723-appb-I000127
Figure PCTKR2015006723-appb-I000128
Figure PCTKR2015006723-appb-I000128
Figure PCTKR2015006723-appb-I000129
Figure PCTKR2015006723-appb-I000129
Figure PCTKR2015006723-appb-I000130
Figure PCTKR2015006723-appb-I000130
Figure PCTKR2015006723-appb-I000131
Figure PCTKR2015006723-appb-I000131
Figure PCTKR2015006723-appb-I000132
Figure PCTKR2015006723-appb-I000132
Figure PCTKR2015006723-appb-I000133
Figure PCTKR2015006723-appb-I000133
Figure PCTKR2015006723-appb-I000134
Figure PCTKR2015006723-appb-I000134
Figure PCTKR2015006723-appb-I000135
Figure PCTKR2015006723-appb-I000135
Figure PCTKR2015006723-appb-I000136
Figure PCTKR2015006723-appb-I000136
Figure PCTKR2015006723-appb-I000137
Figure PCTKR2015006723-appb-I000137
Figure PCTKR2015006723-appb-I000138
Figure PCTKR2015006723-appb-I000138
전술한 화합물들은 후술하는 제조예를 기초로 제조될 수 있다. 후술하는 제조예들에서는 대표적인 예시들을 기재하지만, 필요에 따라, 치환기를 추가하거나 제외할 수 있으며, 치환기의 위치를 변경할 수 있다. 또한, 당기술분야에 알려져 있는 기술을 기초로, 출발물질, 반응물질, 반응 조건 등을 변경할 수 있다. 필요에 따라 나머지 위치의 치환기의 종류 또는 위치를 변경하는 것은 당업자가 당 기술분야에 알려져 있는 기술을 이용하여 수행할 수 있다.The above-mentioned compounds can be produced on the basis of the preparation examples described later. Exemplary examples are described below in the preparation examples, but substituents can be added or removed as needed, and the position of the substituent can be changed. In addition, based on techniques known in the art, starting materials, reactants, reaction conditions, and the like can be changed. The type or position of the substituent at the remaining positions may be changed as required by those skilled in the art using techniques known in the art.
이하에서, 실시예를 통하여 본 출원을 더욱 상세하게 설명하지만, 이들은 본 출원을 예시하기 위한 것일 뿐, 본 출원의 범위를 한정하기 위한 것은 아니다.Hereinafter, the present application will be described in more detail by way of examples, but these are for the purpose of illustrating the present application and are not intended to limit the scope of the present application.
예컨데, 상기 화학식 2, 13 내지 20, 23 및 24의 화합물과 관련하여, 하기 일반식 1 내지 9와 같이 코어구조가 제조될 수 있다.For example, with respect to the compounds of the above formulas 2, 13 to 20, 23 and 24, core structures may be prepared as shown in the following general formulas 1 to 9.
치환기는 당 기술분야에 알려져 있는 방법에 의하여 결합될 수 있으며, 치환기 위치나 치환기의 개수는 당 기술 분야에 알려져 있는 기술에 따라 변경될 수 있다.Substituent groups may be attached by methods known in the art, and the substituent position or number of substituent groups may be varied according to techniques known in the art.
[일반식 1][Formula 1]
Figure PCTKR2015006723-appb-I000139
Figure PCTKR2015006723-appb-I000139
일반식 1에 있어서, X 및 Y는 전술한 실시상태에 따른 화학식 1과 동일하고, 화학식 2의 코어구조를 제조하는 반응의 예시이다.In the general formula (1), X and Y are the same as the general formula (1) according to the above-described embodiment, and are an example of the reaction for producing the core structure of the general formula (2).
[일반식 2][Formula 2]
Figure PCTKR2015006723-appb-I000140
Figure PCTKR2015006723-appb-I000140
일반식 2에 있어서, Ar은 전술한 실시상태와 동일하고, 화학식 13의 코어구조를 제조하는 반응의 예시이다.In the general formula (2), Ar is the same as the above-described embodiment, and is an example of the reaction for producing the core structure of the general formula (13).
[일반식 3][Formula 3]
Figure PCTKR2015006723-appb-I000141
Figure PCTKR2015006723-appb-I000141
일반식 3에 있어서, Ar은 전술한 실시상태에 따른 화학식 1에서 정의한 R3와 동일하고, 화학식 14의 코어구조를 제조하는 반응의 예시이다.In the general formula 3, Ar is the same as R 3 defined in formula (1) according to the above-described embodiment, and is an example of the reaction for producing the core structure of formula (14).
[일반식 4][Formula 4]
Figure PCTKR2015006723-appb-I000142
Figure PCTKR2015006723-appb-I000142
일반식 4에 있어서, Ar은 전술한 실시상태와 동일하고, 화학식 15 내지 16의 코어구조를 제조하는 반응의 예시이다.In the general formula (4), Ar is the same as the above-described embodiment, and is an example of a reaction for producing the core structure of the formulas (15) to (16).
[일반식 5][Formula 5]
Figure PCTKR2015006723-appb-I000143
Figure PCTKR2015006723-appb-I000143
일반식 5에 있어서, Ar은 전술한 실시상태와 동일하고, 화학식 17의 코어구조를 제조하는 반응의 예시이다.In the general formula 5, Ar is the same as the above-described embodiment, and is an example of the reaction for producing the core structure of the general formula (17).
[일반식 6][Formula 6]
Figure PCTKR2015006723-appb-I000144
Figure PCTKR2015006723-appb-I000144
일반식 6에 있어서, Ar은 전술한 실시상태와 동일하고, 화학식 18 내지 19의 코어구조를 제조하는 반응의 예시이다.In the general formula (6), Ar is the same as the above-described embodiment, and is an example of the reaction for producing the core structure of the general formulas (18) to (19).
[일반식 7][Formula 7]
Figure PCTKR2015006723-appb-I000145
Figure PCTKR2015006723-appb-I000145
일반식 7에 있어서, Ar은 전술한 실시상태에 따른 화학식 1에서 정의한 R3와 동일하고, 화학식 20의 코어구조를 제조하는 반응의 예시이다.In the general formula (7), Ar is the same as R 3 defined in formula (1) according to the above-described embodiment, and is an example of a reaction for producing the core structure of formula (20).
[일반식 8][Formula 8]
Figure PCTKR2015006723-appb-I000146
Figure PCTKR2015006723-appb-I000146
일반식 8에 있어서, Ar은 전술한 실시상태에 따른 화학식 1에서 정의한 R3와 동일하고, 화학식 23의 코어구조를 제조하는 반응의 예시이다.In the general formula (8), Ar is the same as R 3 defined in formula (1) according to the above-described embodiment, and is an example of a reaction for producing the core structure represented by formula (23).
[일반식 9][Formula 9]
Figure PCTKR2015006723-appb-I000147
Figure PCTKR2015006723-appb-I000147
일반식 9에 있어서, Ar은 전술한 실시상태와 동일하고, 화학식 24의 코어구조를 제조하는 반응의 예시이다.In the general formula (9), Ar is the same as the above-described embodiment, and is an example of a reaction for producing the core structure of the general formula (24).
본 명세서의 또 하나의 실시상태는 전술한 화학식 1의 화합물을 포함하는 유기발광소자를 제공한다. 구체적으로, 본 출원에 따른 유기발광소자는 양극, 음극 및 양극과 음극 사이에 구비된 1층 이상의 유기물층을 포함하고, 상기 유기물층 중 1층 이상은 상기 화학식 1의 화합물을 포함한다. Another embodiment of the present invention provides an organic light emitting device comprising the compound of Formula 1 described above. Specifically, the organic light emitting device according to the present application includes a cathode, a cathode, and at least one organic layer provided between the anode and the cathode, and at least one of the organic layers includes the compound of Formula 1.
도 1 내지 3에 본 출원의 실시상태들에 따른 유기발광소자의 전극과 유기물층의 적층 순서를 예시하였다. 그러나, 이들 도면에 의하여 본 출원의 범위가 한정될 것을 의도한 것은 아니며, 당 기술분야에 알려져 있는 유기발광소자의 구조가 본 출원에도 적용될 수 있다. FIGS. 1 to 3 illustrate the stacking process of the electrodes and organic layers of the organic light emitting diode according to the embodiments of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and the structure of the organic light emitting device known in the art can be applied to the present application.
도 1에 따르면, 기판(100) 상에 양극(200), 유기물층(300) 및 음극(400)이 순차적으로 적층된 유기발광소자가 도시된다. 그러나, 이와 같은 구조에만 한정되는 것은 아니고, 도 2와 같이, 기판 상에 음극, 유기물층 및 양극이 순차적으로 적층된 유기발광소자가 구현될 수도 있다. 1, an organic light emitting device in which an anode 200, an organic layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is shown. However, the present invention is not limited to such a structure, and an organic light emitting device in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate may be implemented as shown in FIG.
도 3은 유기물층이 다층인 경우를 예시한 것이다. 도 3에 따른 유기발광소자는 정공주입층(301), 정공수송층(302), 발광층(303), 정공저지층(304), 전자수송층(305) 및 전자주입층(306)을 포함한다. 그러나, 이와 같은 적층구조에 의하여 본 출원의 범위가 한정되는 것은 아니며, 필요에 따라 발광층을 제외한 나머지 층은 생략될 수도 있고, 필요한 다른 기능층이 더 추가될 수 있다. FIG. 3 illustrates the case where the organic material layer is a multilayer. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by such a laminated structure, and if necessary, the remaining layers except the light emitting layer may be omitted, and other necessary functional layers may be further added.
본 명세서에 따른 유기발광소자는 유기물층 중 1층 이상에 상기 화학식 1의 화합물을 포함하는 것을 제외하고는 당기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다. The organic light emitting device according to the present invention can be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer contains the compound of the above formula (1).
상기 화학식 1의 화합물은 단독으로 유기발광소자의 유기물층 중 1층 이상을 구성할 수 있다. 그러나, 필요에 따라 다른 물질과 혼합하여 유기물층을 구성할 수도 있다. The compound of formula (I) may constitute one or more layers of the organic material layer of the organic light emitting device. However, if necessary, the organic material layer may be formed by mixing with other materials.
상기 화학식 1의 화합물은 유기발광소자에서 전자수송층, 정공저지층, 발광층의 재료 등으로 사용될 수 있다. 한 예로서, 상기 화학식 1의 화합물은 유기발광소자의 전자수송층 또는 발광층의 재료로서 사용될 수 있다. 또한, 상기 화학식 1의 화합물은 전자수송층 또는 발광층의 인광호스트의 재료로서 사용될 수 있다. The compound of Formula 1 may be used as an electron transport layer, a hole blocking layer, and a material of a light emitting layer in an organic light emitting device. As an example, the compound of Formula 1 may be used as an electron transport layer or a material of a light emitting layer of an organic light emitting device. Further, the compound of Formula 1 may be used as a material of a phosphorescent host in an electron transport layer or a light emitting layer.
본 명세서에 따른 유기발광소자에 있어서, 상기 화학식 1의 화합물 이외의 재료를 하기에 예시하지만, 이들은 예시를 위한 것일 뿐 본 출원의 범위를 한정하기 위한 것은 아니며, 당 기술분야에 공지된 재료들로 대체될 수 있다. In the organic light emitting device according to the present invention, materials other than the compound of Formula 1 are exemplified below, but these are for illustrative purposes only and are not intended to limit the scope of the present application and include materials known in the art Can be replaced.
양극 재료로는 비교적 일함수가 큰 재료들을 이용할 수 있으며, 투명 전도성 산화물, 금속 또는 전도성 고분자 등을 사용할 수 있다. As the cathode material, materials having a relatively large work function can be used, and a transparent conductive oxide, a metal, or a conductive polymer can be used.
음극 재료로는 비교적 일함수가 낮은 재료들을 이용할 수 있으며, 금속, 금속 산화물 또는 전도성 고분자 등을 사용할 수 있다. As the cathode material, materials having relatively low work functions can be used, and metals, metal oxides, conductive polymers, and the like can be used.
정공주입재료로는 공지된 정공주입재료를 이용할 수도 있는데, 예를 들면, 미국특허 제4,356,429호에 개시된 구리프탈로시아닌 등의 프탈로시아닌 화합물 또는 문헌 [Advanced Material, 6, p.677 (1994)]에 기재되어 있는 스타버스트형 아민 유도체류, 예컨대 트리스(4-카바조일-9-일페닐)아민(TCTA), 4,4',4"-트리[페닐(m-톨릴)아미노]트리페닐아민(m-MTDATA), 1,3,5-트리스[4-(3-메틸페닐페닐아미노)페닐]벤젠(m-MTDAPB), 용해성이 있는 전도성 고분자인 Pani/DBSA(Polyaniline/Dodecylbenzenesulfonic acid: 폴리아닐린/도데실벤젠술폰산) 또는 PEDOT/PSS(Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate):폴리(3,4-에틸렌디옥시티오펜)/폴리(4-스티렌술포네이트)), Pani/CSA(Polyaniline/Camphor sulfonic acid:폴리아닐린/캠퍼술폰산) 또는 PANI/PSS(Polyaniline/Poly(4-styrene-sulfonate):폴리아닐린/폴리(4-스티렌술포네이트)) 등을 사용할 수 있다.As the hole injecting material, a known hole injecting material may be used. For example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or a compound described in Advanced Material, 6, p. 677 (1994) Star burst type amine derivatives such as tris (4-carbamoyl-9-phenyl) amine (TCTA), 4,4 ', 4 "-tri [phenyl (m- tolyl) amino] triphenylamine MTDAPA), 1,3,5-tris [4- (3-methylphenylphenylamino) phenyl] benzene (m-MTDAPB), and a soluble conductive polymer such as Pani / DBSA (Polyaniline / Dodecylbenzenesulfonic acid: ) Or PEDOT / PSS (poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate) / poly (4-styrenesulfonate)), Pani / CSA (Polyaniline / (Polyaniline / camphorsulfonic acid) or PANI / PSS (polyaniline / poly (4-styrene sulfonate): polyaniline / poly Can be used.
정공수송재료로는 피라졸린 유도체, 아릴아민계 유도체, 스틸벤 유도체, 트리페닐디아민 유도체 등이 사용될 수 있으며, 저분자 또는 고분자 재료가 사용될 수도 있다. As the hole transporting material, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, or the like may be used, and a low molecular weight or a high molecular weight material may be used.
전자수송재료로는 옥사디아졸 유도체, 안트라퀴노디메탄 및 이의 유도체, 벤조퀴논 및 이의 유도체, 나프토퀴논 및 이의 유도체, 안트라퀴논 및 이의 유도체, 테트라시아노안트라퀴노디메탄 및 이의 유도체, 플루오레논 유도체, 디페닐디시아노에틸렌 및 이의 유도체, 디페노퀴논 유도체, 8-히드록시퀴놀린 및 이의 유도체의 금속 착체 등이 사용될 수 있으며, 저분자 물질 뿐만 아니라 고분자 물질이 사용될 수도 있다. Examples of the electron transporting material include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, Derivatives thereof, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and the like may be used as well as low molecular weight materials and high molecular weight materials.
전자주입재료로는 예를 들어, LiF가 당업계 대표적으로 사용되나, 본 출원이 이에 한정되는 것은 아니다. As the electron injecting material, for example, LiF is typically used in the art, but the present application is not limited thereto.
발광재료로는 적색, 녹색 또는 청색 발광재료가 사용될 수 있으며, 필요한 경우 2 이상의 발광재료를 혼합하여 사용할 수 있다. 또한, 발광재료로서 형광 재료를 사용할 수도 있으나, 인광 재료로서 사용할 수도 있다. 발광재료로는 단독으로서 양극과 음극으로부터 각각 주입된 정공과 전자를 결합하여 발광시키는 재료가 사용될 수도 있으나, 호스트 재료와 도펀트 재료가 함께 발광에 관여하는 재료들이 사용될 수도 있다. As the light emitting material, red, green or blue light emitting materials may be used, and if necessary, two or more light emitting materials may be mixed and used. Further, a fluorescent material may be used as a light emitting material, but it may be used as a phosphorescent material. As the light emitting material, a material which emits light by coupling holes and electrons respectively injected from the anode and the cathode may be used. However, materials in which both the host material and the dopant material participate in light emission may also be used.
이하에서, 실시예를 통하여 본 출원을 더욱 상세하게 설명하지만, 이들은 본 출원을 예시하기 위한 것일 뿐, 본 출원의 범위를 한정하기 위한 것은 아니다.Hereinafter, the present application will be described in more detail by way of examples, but these are for the purpose of illustrating the present application and are not intended to limit the scope of the present application.
[제조예 1] 화합물 1-1의 제조[Preparation Example 1] Preparation of Compound 1-1
Figure PCTKR2015006723-appb-I000148
Figure PCTKR2015006723-appb-I000148
화합물 A-1의 합성Synthesis of Compound A-1
4-브로모-9H-카바졸(4-bromo-9H-carbazole) 50g(203.16mmol), 아이오도벤젠(Iodobenzene) 68mL(609.48mmol), Cu 1.3g(20.32mmol), K2CO3 56g(406.32mmol), 18-크라운-6-에테르(18-crown-6-ether) 6.6g(20.32mmol)을 1,2-디클로로벤젠(1,2-dichlorobenzene) 1L와 함께 140℃, 밀봉관(sealed tube)에서 16시간동안 반응하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 A-1 60.0g(92%)을 얻었다.4-Bromo -9H- carbazole (4-bromo-9H-carbazole ) 50g (203.16mmol), iodo-benzene (Iodobenzene) 68mL (609.48mmol), Cu 1.3g (20.32mmol), K 2 CO 3 56g ( 6.6 g (20.32 mmol) of 18-crown-6-ether was added to 1 L of 1,2-dichlorobenzene at 140 占 폚 in a sealed tube tube for 16 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 60.0 g (92%) of the target compound A-1 .
화합물 A-2의 합성Synthesis of Compound A-2
A-1 60g(186.22mmol), 비스(피나콜라토)디보론 94.5g(372.44mmol), 포타슘아세테이트(KOAc) 54.8g(558.66mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II) 6.8g(9.31mmol)을 1,4-디옥산(1,4-dioxane)하에서 120℃로 3시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산으로 씻어주어 목적화합물 A-2 42.0g(61%)을 얻었다. A mixture of 60 g (186.22 mmol) of A-1 , 94.5 g (372.44 mmol) of bis (pinacolato) diboron, 54.8 g (558.66 mmol) of potassium acetate (KOAc), 1,1'-bis (diphenylphosphino) ] Dichloropalladium (II) (6.8 g, 9.31 mmol) was refluxed under stirring at 120 ° C for 3 hours under 1,4-dioxane. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 42.0 g (61%) of the target compound A-2 .
화합물 A-3의 합성Synthesis of Compound A-3
A-2 38.8g(105.0mmol), 2-브로모아닐린(2-bromoaniline) 36.1g(210.0mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 6.1g(5.25mmol), K3PO4 67.0g(315.0mmol)을 1,4-디옥산(1,4-dioxane) 400mL, H2O 80mL하에서 120℃로 2시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산으로 씻어주어 목적화합물 A-3 17.5g(50%)을 얻었다. A-2 38.8g (105.0mmol), 2- bromoaniline (2-bromoaniline) 36.1g (210.0mmol ), tetrakis (triphenylphosphine) palladium (0) 6.1g (5.25mmol), K 3 PO 4 67.0 g (315.0 mmol) was refluxed and stirred at 400 ° C in 1,4-dioxane and 80 mL of H 2 O at 120 ° C for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 17.5 g (50%) of the target compound A-3 .
화합물 A-4의 합성Synthesis of Compound A-4
A-3 20g(59.8mmol), 트리에틸아민(Triethylamine) 8.4mL(59.8mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 4-브로모벤조일클로라이드(4-bromobenzoylchloride) 13.1g(59.8mmol)를 천천히 적가하여 1시간동안 온도를 유지하면서 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 A-4 23.5g(76%)을 얻었다.20 g (59.8 mmol) of A-3 and 8.4 mL (59.8 mmol) of triethylamine were dissolved in dichloromethane and then maintained at 0 ° C. Then, 13.1 g (59.8 mmol) of 4-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off using dichloromethane and hexane as eluent to obtain 23.5 g (76%) of target compound A-4 .
화합물 A-5의 합성Synthesis of Compound A-5
A-4 29.6g(57.21mmol)을 니트로벤젠(Nitrobenzene) 300mL에 전부 녹인 뒤 POCl3 6.45mL(57.21mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 2시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 메탄올(MeOH)로 씻어주어 목적화합물 A-5 25.5g(89%)을 얻었다. A total of 29.6 g (57.21 mmol) of A-4 was dissolved in 300 mL of Nitrobenzene, and 6.45 mL (57.21 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator, followed by washing with methanol (MeOH) to obtain 25.5 g (89%) of the target compound A-5 .
화합물 B-1의 합성Synthesis of Compound B-1
A-5 15g(30.04mmol), 비스(피나콜라토)디보론 15.3g(60.07mmol), 포타슘아세테이트(KOAc) 8.84g(90.12mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II)1.1g(1.5mmol)을 디메틸포름아미드(DMF) 70mL하에서 120℃로 3시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산, 메탄올(MeOH)로 씻어주어 목적화합물 B-1 12.6g(77%)을 얻었다.15.0 g (30.04 mmol) of A-5 , 15.3 g (60.07 mmol) of bis (pinacolato) diboron, 8.84 g (90.12 mmol) of potassium acetate (KOAc), 1,1'-bis (diphenylphosphino) ] 1.1 g (1.5 mmol) of dichloropalladium (II) was stirred in 70 ml of dimethylformamide (DMF) at 120 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was then filtered off with silica gel and washed with hexane and methanol (MeOH) to obtain 12.6 g (77%) of the target compound B-1 .
화합물 1-1의 합성Synthesis of Compound 1-1
B-1 9.0g(16.47mmol), 2-클로로-4,6-디페닐-1,3,5-트리아진(2-chloro-4,6-diphenyl-1,3,5-triazine) 5.3g(19.76mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.9g(1.65mmol), K2CO3 6.8g(49.41mmol)을 톨루엔(Toluene) 90mL, 에탄올(EtOH)/H2O 각 18mL하에서 120℃로 3시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 디클로로메탄(dichloromethane), 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 디클로로메탄(dichloromethane) 과량으로 전부 녹인 뒤 실리카겔로 필터하여 목적화합물 1-1 5.7g(53%)을 얻었다. B-1 , 5.3 g (16.47 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine, (49.71 mmol) of K 2 CO 3 were dissolved in 90 mL of toluene and a solution of ethanol (EtOH) / H 2 O was added to a solution of 1.9 g (1.65 mmol) of tetrakis (triphenylphosphine) palladium And the mixture was stirred at 18O &lt; 0 &gt; C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with dichloromethane, ethyl acetate (EA), and methanol (MeOH). After that, the solid was completely dissolved in dichloromethane in an excess amount, and then filtered with silica gel to obtain 5.7 g (53%) of the objective compound 1-1 .
[제조예 2] 화합물 1-12의 제조[Preparation Example 2] Preparation of Compound 1-12
Figure PCTKR2015006723-appb-I000149
Figure PCTKR2015006723-appb-I000149
A-5 8.0g(16.02mmol), 9,9'-(5-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-일)-1,3-페닐렌)비스(9H-카바졸)(9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole)) 10.3g(19.22mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 0.93g(0.8mmol), K3PO4 10.2g(48.06mmol)을 1,4-디옥산(1,4-dioxane) 160mL, H2O 32mL하에서 120℃로 2시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 디클로로메탄(dicholoromethane), 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 디클로로메탄(dichloromethane) 과량으로 전부 녹인 뒤 실리카겔로 필터하여 목적화합물 1-12 10.3g(78%)을 얻었다.8.0 g (16.02 mmol) of A-5 , 9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaboran- Bis (9H-carbazole) (9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- (0.8 mmol) of tetrakis (triphenylphosphine) palladium (0) and 10.2 g (48.06 mmol) of K 3 PO 4 were dissolved in 1,4-dioxane (1 , 4-dioxane) and 32 mL of H 2 O under reflux at 120 ° C for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and then washed with dicholoromethane, ethyl acetate (EA), and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount, and then filtered with silica gel to obtain 10.3 g (78%) of the desired compound 1-12 .
[제조예 3] 화합물 1-16의 제조[Preparation Example 3] Preparation of Compound 1-16
Figure PCTKR2015006723-appb-I000150
Figure PCTKR2015006723-appb-I000150
A-5 8.0g(16.02mmol), 2-(4-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-일)페닐)벤조[d]카바졸(2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[d]thiazole) 6.48g(19.22mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 0.93g(0.8mmol), K3PO4 10.2g(48.06mmol)을 1,4-디옥산(1,4-dioxane) 160mL, H2O 32mL하에서 120℃로 4시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 디클로로메탄(dichloromethane), 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 디클로로메탄(dichloromethane) 과량으로 전부 녹인 뒤 실리카겔로 필터하여 목적화합물 1-16 7.9g(78%)을 얻었다. A-5 8.0 g (16.02 mmol), 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2- yl) phenyl) benzo [d] 6.48 g (19.22 mmol) of 2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) benzo [d] thiazole, 0.93 g (0.8 mmol) of palladium (0) and 10.2 g (48.06 mmol) of K 3 PO 4 were refluxed in 160 mL of 1,4-dioxane and 32 mL of H 2 O at 120 ° C for 4 hours Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with dichloromethane, ethyl acetate (EA), and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount and then filtered through silica gel to obtain 7.9 g (78%) of the desired compound 1-16 .
[제조예 4] 화합물 1-36의 제조[Preparation Example 4] Preparation of Compound 1-36
Figure PCTKR2015006723-appb-I000151
Figure PCTKR2015006723-appb-I000151
화합물 C-1의 합성Synthesis of Compound C-1
4-브로모-9,9-디메틸-9H-플루오렌 (4-Bromo-9,9-dimethyl-9H-fluorene) 20g(73.21mmol), 비스(피나콜라토)디보론 37.2g(146.43mmol), 포타슘아세테이트(KOAc) 21.5g(219.63mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II)2.68g(3.66mmol)을 디메틸포름아미드(DMF) 200mL하에서 120℃로 16시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산으로 씻어주어 목적화합물 C-1 19.0g(81%)을 얻었다.(73.21 mmol) of 4-bromo-9,9-dimethyl-9H-fluorene and 37.2 g (146.43 mmol) of bis (pinacolato) 2.68 g (3.66 mmol) of 21.6 g (219.63 mmol) of potassium acetate (KOAc) and 1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) were dissolved in 200 ml of dimethylformamide Lt; / RTI &gt; for 16 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 19.0 g (81%) of the target compound C-1 .
화합물 C-2의 합성Synthesis of Compound C-2
C-1 17.3g(54.02mmol), 2-브로모아닐린(2-bromoaniline) 18.6g(108.04mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 3.12g(2.70mmol), K3PO4 34.4g(162.06mmol)을 1,4-디옥산(1,4-dioxane) 170mL, H2O 30mL하에서 120℃로 3시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산 및 메탄올(MeOH)(소량)로 씻어주어 목적화합물 C-2 13.0g(84%)을 얻었다. C-1 17.3g (54.02mmol), 2- bromoaniline (2-bromoaniline) 18.6g (108.04mmol ), tetrakis (triphenylphosphine) palladium (0) 3.12g (2.70mmol), K 3 PO 4 34.4g (162.06mmol) was refluxed and stirred in 170mL of 1,4-dioxane and 30mL of H 2 O at 120 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel, followed by washing with a small amount of hexane and methanol (MeOH) to obtain 13.0 g (84%) of the target compound C-2 .
화합물 C-3의 합성Synthesis of Compound C-3
C-2 13.0g(45.55mmol), 트리에틸아민(Triethylamine) 6.4mL(45.55mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 4-브로모벤조일클로라이드(4-bromobenzoylchloride) 9.99g(45.55mmol)를 천천히 적가하여 1시간동안 온도를 유지하면서 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 C-3 15.0g(76%)을 얻었다.13.0 g (45.55 mmol) of C-2 and 6.4 mL (45.55 mmol) of triethylamine were dissolved in dichloromethane and then maintained at 0 ° C. Thereafter, 9.99 g (45.55 mmol) of 4-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 15.0 g (76%) of the target compound C-3 .
화합물 C-4의 합성Synthesis of Compound C-4
C-3 15.0g(32.02mmol)을 니트로벤젠(Nitrobenzene) 150mL에 전부 녹인 뒤 POCl3 3.6mL(32.02mmol)를 천천히 적가하였다. 그 후 후 150℃로 유지하면서 2시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 C-4 8.8g(61%)을 얻었다.15.0 g (32.02 mmol) of C-3 was completely dissolved in 150 mL of Nitrobenzene, and 3.6 mL (32.02 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 150 ° C. After the reaction was completed After drying the organic layer was back extracted with distilled water and dichloromethane (dichloromethane) with anhydrous MgSO 4 with dichloromethane and hexane as a developing solvent by rotary evaporation and purified by column chromatography to give the objective compound C-4 8.8g (61% ).
화합물 1-36의 합성Synthesis of Compound 1-36
C-4 10.0g(20.10mmol), 2-클로로-4,6-디페닐-1,3,5-트리아진(2-chloro-4,6-diphenyl-1,3,5-triazine) 6.46g(24.12mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 2.3g(2.01mmol), K3PO4 12.8g(60.3mmol)을 1,4-디옥산(1,4-dioxane) 120mL, H2O 20mL하에서 120℃로 2시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 1-36 8.2g(68%)을 얻었다.10.0 g (20.10 mmol) of C-4 , 2-chloro-4,6-diphenyl-1,3,5-triazine 2.3 g (2.01 mmol) of tetrakis (triphenylphosphine) palladium (0) and 12.8 g (60.3 mmol) of K 3 PO 4 were dissolved in 120 mL of 1,4-dioxane, under a H 2 O 20mL was stirred at reflux for 2 hours in 120 ℃. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed by a rotary evaporator, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 8.2 g (68%) of the desired compound 1-36 .
[제조예 5] 화합물 1-113의 제조[Preparation Example 5] Preparation of Compound 1-113
Figure PCTKR2015006723-appb-I000152
Figure PCTKR2015006723-appb-I000152
화합물 D-1의 합성Synthesis of Compound D-1
A-3 20g(59.8mmol), 트리에틸아민(Triethylamine) 8.4mL(59.8mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 3-bromobenzoylchloride 13.1g(59.8mmol)를 천천히 적가하여 1시간동안 온도를 유지하면 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 D-1 24.9g(80%)을 얻었다.20 g (59.8 mmol) of A-3 and 8.4 mL (59.8 mmol) of triethylamine were dissolved in dichloromethane and then maintained at 0 ° C. 13.1 g (59.8 mmol) of 3-bromobenzoylchloride was slowly added dropwise thereto, and the mixture was stirred for 1 hour. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was then purified by column chromatography using dichloromethane and hexane as eluent to obtain 24.9 g (80%) of the target compound D-1 .
화합물 D-2의 합성Synthesis of Compound D-2
D-1 27.0g(52.18mmol)을 니트로벤젠(Nitrobenzene) 300mL에 전부 녹인 뒤 POCl3 5.9mL(52.18mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 2시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 메탄올(MeOH)로 씻어주어 목적화합물 D-2 26.7g(93%)을 얻었다.27.0 g (52.18 mmol) of D-1 was completely dissolved in 300 mL of Nitrobenzene, and 5.9 mL (52.18 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The residue was washed with methanol (MeOH) to obtain 26.7 g (93%) of the target compound D-2 .
화합물 1-113의 합성Synthesis of Compound 1-113
D-2 10g(20.02mmol), 디벤조[b,d]티오펜-4-일보로닉 에시드(dibenzo[b,d]thiophen-4-ylboronic acid) 5.5g(24.03mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 2.3g(2.0mmol), K2CO3 8.3g(60.06mmol)을 톨루엔(Toluene) 200mL, 에탄올(EtOH) 40mL, H2O 40mL하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 1-113 9.5g(79%)을 얻었다. D-2 10g (20.02mmol), dibenzo [b, d] thiophene-4 Daily Nick Acid (dibenzo [b, d] thiophen -4-ylboronic acid) 5.5g (24.03mmol), tetrakis (tri 2.3 g (2.0 mmol) of palladium (0) and 8.3 g (60.06 mmol) of K 2 CO 3 were refluxed in 120 mL of toluene, 40 mL of ethanol (EtOH) and 40 mL of H 2 O at 120 ° C for 6 hours Lt; / RTI &gt; After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.5 g (79%) of the desired compound 1-113 .
[제조예 6] 화합물 1-119의 제조[Preparation Example 6] Preparation of Compound 1-119
Figure PCTKR2015006723-appb-I000153
Figure PCTKR2015006723-appb-I000153
D-2 7g(14.02mmol), 4,4,5,5-테트라메틸-2-(트리페닐렌-2-일)-1,3,2-디옥사보란(4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane) 5.96g(16.82mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.62g(1.4mmol), K2CO3 5.81g(42.06mmol)을 톨루엔(Toluene) 140mL, 에탄올(EtOH) 28mL, H2O 28mL하에서 120℃로 3시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 1-119 4.92g(54%)을 얻었다. D-2 7g (14.02mmol), 4,4,5,5- tetramethyl-2- (triphenylene-2-yl) 1,3,2-dioxa-boran (4,4,5,5 tetramethyl-2- (triphenylen-2- yl) -1,3,2-dioxaborolane) 5.96g (16.82mmol), tetrakis (triphenylphosphine) palladium (0) 1.62g (1.4mmol), K 2 CO 3 5.81 g (42.06 mmol) were refluxed and stirred for 3 hours at 140 DEG C in 140 mL of toluene, 28 mL of ethanol (EtOH) and 28 mL of H 2 O at 120 ° C. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 4.92 g (54%) of the desired compound 1-119 .
[제조예 7] 화합물 1-124의 제조[Preparation Example 7] Preparation of Compound 1-124
Figure PCTKR2015006723-appb-I000154
Figure PCTKR2015006723-appb-I000154
D-2 7g(14.02mmol), 9-(3-(4,4,5,5-테트라메틸-1,3,2-디옥사보란--2-일)페닐)-9H-카바졸(9-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole) 6.21g(16.82mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.62g(1.4mmol), K2CO3 5.81g(42.06mmol)을 톨루엔(Toluene) 140mL, 에탄올(EtOH) 28mL, H2O 28mL하에서 120℃로 4시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 1-124 6.39g(69%)을 얻었다. D-2 7 g (14.02 mmol), 9- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborane-2- yl) phenyl) -9H-carbazole 6.21g (16.82mmol) of tetrakis (triphenylphosphine) palladium (II), 6.21g (16.82mmol) of 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 1.62 g (1.4 mmol) of K 2 CO 3 and 5.81 g (42.06 mmol) of K 2 CO 3 were refluxed and stirred at 120 ° C. for 4 hours in 140 ml of toluene, 28 ml of ethanol (EtOH) and 28 ml of H 2 O for 4 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 6.39 g (69%) of the desired compound 1-124 .
[제조예 8] 화합물 1-157의 제조[Preparation Example 8] Preparation of Compound 1-157
Figure PCTKR2015006723-appb-I000155
Figure PCTKR2015006723-appb-I000155
화합물 E-1의 합성Synthesis of Compound E-1
1-브로모디벤조티오펜(1-bromodibenzothiophene) 50g(190.0mmol), 비스(피나콜라토)디보론 96.5g(380.0mmol), 포타슘아세테이트(KOAc) 55.9g(570.0mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II)6.95g(9.50mmol)을 1,4-디옥산(1,4-dioxane) 500mL하에서 120℃로 16시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산으로 씻어주어 목적화합물 E-1 51.6g(88%)을 얻었다.(190.0 mmol) of 1-bromodibenzothiophene, 96.5 g (380.0 mmol) of bis (pinacolato) diboron, 55.9 g (570.0 mmol) of potassium acetate (KOAc) -Bis (diphenylphosphino) ferrocene] Dichloropalladium (II) (6.95 g, 9.50 mmol) was stirred in 500 mL of 1,4-dioxane at 120 ° C for 16 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 51.6 g (88%) of the target compound E-1 .
화합물 E-2의 합성Synthesis of Compound E-2
E-1 50.0g(161.17mmol), 2-브로모아닐린(2-bromoaniline) 55.5g(322.35mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 9.3g(8.06mmol), K3PO4 102.63g(483.51mmol)을 1,4-디옥산(1,4-dioxane) 500mL, H2O 100mL하에서 120℃로 6시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산으로 씻어주어 목적화합물 E-2 33.8g(76%)을 얻었다. E-1 50.0g (161.17mmol), 2- bromoaniline (2-bromoaniline) 55.5g (322.35mmol ), tetrakis (triphenylphosphine) palladium (0) 9.3g (8.06mmol), K 3 PO 4 the 102.63g (483.51mmol) in 120 ℃ under 1, 4-dioxane (1,4-dioxane) 500mL, 100mL H 2 O and stirred at reflux for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and then washed with hexane to obtain 33.8 g (76%) of the target compound E-2 .
화합물 E-3의 합성Synthesis of Compound E-3
E-2 30g(108.94mmol), 트리에틸아민(Triethylamine) 15.3mL(108.94mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 3-브로모벤조일클로라이드(3-bromobenzoylchloride) 23.9g(108.94mmol)를 천천히 적가하여 2시간동안 온도를 유지하면서 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 E-3 43.7g(87%)을 얻었다.30 g (108.94 mmol) of E-2 and 15.3 mL (108.94 mmol) of triethylamine were dissolved in dichloromethane and maintained at 0 ° C. After that, 23.9 g (108.94 mmol) of 3-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred for 2 hours while maintaining the temperature. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 43.7 g (87%) of the desired compound E-3 .
화합물 E-4의 합성Synthesis of Compound E-4
E-3 43.0g(93.8mmol)을 니트로벤젠(Nitrobenzene) 430mL에 전부 녹인 뒤 POCl3 10.6mL(93.8mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 1시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 메탄올(MeOH)로 씻어주어 목적화합물 E-4 37.5g(91%)을 얻었다.43.0 g (93.8 mmol) of E-3 was dissolved in 430 mL of Nitrobenzene and 10.6 mL (93.8 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 1 hour while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator, followed by washing with methanol (MeOH) to obtain 37.5 g (91%) of the target compound E-4 .
화합물 1-157의 합성Synthesis of Compound 1-157
E-4 8.0g(18.17mmol), 9,9'-(5-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-일)-1,3-페닐렌)비스(9H-카바졸)(9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole)) 11.85g(21.8mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.05g(0.91mmol), K3PO4 11.57g(54.51mmol)을 1,4-디옥산(1,4-dioxane) 160mL, H2O 32mL하에서 120℃로 7시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 1-157 9.5g(68%)을 얻었다.8.0 g (18.17 mmol) of E-4 , 9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaboran- Bis (9H-carbazole) (9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- 11.57 g (54.51 mmol) of K 3 PO 4 were dissolved in 1, 4 -dioxane (1, 1, 1 -dimethylformamide) , 4-dioxane) and 32 mL of H 2 O under reflux at 120 ° C. for 7 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.5 g (68%) of the desired compound 1-157 .
[제조예 9] 화합물 1-190의 제조[Preparation Example 9] Preparation of Compound 1-190
Figure PCTKR2015006723-appb-I000156
Figure PCTKR2015006723-appb-I000156
화합물 F-1의 합성Synthesis of Compound F-1
4-브로모-9H-카바졸(4-bromo-9H-carbazole) 20g(81.26mmol), 비스(피나콜라토)디보론 41.3g(162.52mmol), 포타슘아세테이트(KOAc) 23.9g(243.78mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II)2.97g(4.1mmol)을 1,4-디옥산(1,4-dioxane) 100mL하에서 120℃로 6시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산으로 씻어주어 목적화합물 F-1 21.2g(89%)을 얻었다.(81.26 mmol) of 4-bromo-9H-carbazole, 41.3 g (162.52 mmol) of bis (pinacolato) diboron and 23.9 g (243.78 mmol) of potassium acetate (KOAc) 2.97 g (4.1 mmol) of [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) was refluxed in 100 mL of 1,4-dioxane at 120 ° C. for 6 hours Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 21.2 g (89%) of the target compound F-1 .
화합물 F-2의 합성Synthesis of Compound F-2
F-1 20.0g(68.22mmol), 2-브로모아닐린(2-bromoaniline) 23.5g(136.44mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 3.94g(3.41mmol), K3PO4 43.44g(204.66mmol)을 1,4-디옥산(1,4-dioxane) 200mL, H2O 40mL하에서 120℃로 8시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 F-2 11.7g(66%)을 얻었다. F-1 20.0g (68.22mmol), 2- bromoaniline (2-bromoaniline) 23.5g (136.44mmol ), tetrakis (triphenylphosphine) palladium (0) 3.94g (3.41mmol), K 3 PO 4 43.44 g (204.66 mmol) was refluxed with stirring in 120 mL of 1,4-dioxane (200 mL) and H 2 O at 120 ° C for 8 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 11.7 g (66%) of the desired compound F-2 .
화합물 F-3의 합성Synthesis of Compound F-3
F-2 11.7g(45.3mmol), 트리에틸아민(Triethylamine) 6.37mL(45.3mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 벤조일클로라이드(benzoylchloride) 6.37g(45.3mmol)를 천천히 적가하여 1시간동안 온도를 유지하면 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 F-3 14.5g(88%)을 얻었다.11.7 g (45.3 mmol) of F-2 and 6.37 mL (45.3 mmol) of triethylamine were dissolved in dichloromethane and maintained at 0 ° C. Then, 6.37 g (45.3 mmol) of benzoylchloride was slowly added dropwise, and the mixture was stirred for 1 hour. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 14.5 g (88%) of the desired compound F-3 .
화합물 F-4의 합성Synthesis of Compound F-4
F-3 14.0g(38.63mmol)을 니트로벤젠(Nitrobenzene) 140mL에 전부 녹인 뒤 POCl3 4.36mL(38.63mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 2시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 메탄올(MeOH)로 씻어주어 목적화합물 F-4 10.5g(79%)을 얻었다.14.0 g (38.63 mmol) of F-3 was dissolved in 140 mL of Nitrobenzene, and 4.36 mL (38.63 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator, followed by washing with methanol (MeOH) to obtain 10.5 g (79%) of the target compound F-4 .
화합물 F-5의 합성Synthesis of Compound F-5
F-4 10.0g(29.03mmol), 1-아이오도-4-브로모벤젠(1-Iodo-4-bromobenzene) 9.84g(34.84mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.68g(1.45mmol), K3PO4 18.49g(87.09mmol)을 1,4-디옥산(1,4-dioxane) 100mL, H2O 20mL하에서 120℃로 3시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 F-5 12.7g(87%)을 얻었다. A mixture of 10.0 g (29.03 mmol) of F-4 , 9.84 g (34.84 mmol) of 1-iodo-4-bromobenzene, 1.68 g of tetrakis (triphenylphosphine) palladium 18.49 g (87.09 mmol) of K 3 PO 4 were stirred under reflux for 3 hours at 120 ° C. in 100 mL of 1,4-dioxane and 20 mL of H 2 O. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 12.7 g (87%) of the desired compound F-5 .
화합물 1-190의 합성Synthesis of Compound 1-190
F-5 10g(20.02mmol)을 테트라히드로푸란(THF) 30mL에 전부 녹인 뒤 -78를 유지하면서 n-부틸리튬(n-BuLi)(2.5M in 헥산) 10.4mL(26.02mmol)을 천천히 적가한 뒤 1시간동안 교반하였다. 이 용액에 클로로디페닐포스핀(Chlorodiphenylphosphine) 4.8mL(26.02mmol)을 적가하고 실온에서 12시간동안 교반하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄(dichloromethane) 150mL에 녹인 뒤 30% H2O2 수용액 10mL와 함께 실온에서 16시간동안 교반하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 1-190 6.3g(51%)을 얻었다.10.4 mL (26.02 mmol) of n-butyllithium (n-BuLi) (2.5 M in hexane) was slowly added dropwise while dissolving 10 g (20.02 mmol) of F-5 in 30 mL of tetrahydrofuran The mixture was stirred for 1 hour. To this solution, 4.8 mL (26.02 mmol) of chlorodiphenylphosphine was added dropwise, and the mixture was stirred at room temperature for 12 hours. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was dissolved in dichloromethane (150 mL), and the mixture was stirred at room temperature for 16 hours with 10 mL of 30% aqueous H 2 O 2 solution. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 6.3 g (51%) of the title compound 1-190 .
[제조예 10] 화합물 2-3의 제조[Preparation Example 10] Preparation of Compound 2-3
Figure PCTKR2015006723-appb-I000157
Figure PCTKR2015006723-appb-I000157
화합물 G-1의 합성Synthesis of Compound G-1
(9-페닐-9H-카바졸-3-일)보로닉 에시드((9-Phenyl-9H-carbazol-3-yl)boronic acid) 38.8g(105.0mmol), 2-브로모아닐린(2-bromoaniline) 36.1g(210.0mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 6.1g(5.25mmol), K3PO4 67.0g(315.0mmol)을 1,4-디옥산(1,4-dioxane) 400mL, H2O 80mL하에서 120℃로 2시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산으로 씻어주어 목적화합물 G-1 22.3g(63%)을 얻었다.38.8 g (105.0 mmol) of (9-phenyl-9H-carbazol-3-yl) boronic acid, 2-bromoaniline 6.1 g (5.25 mmol) of tetrakis (triphenylphosphine) palladium (0) and 67.0 g (315.0 mmol) of K 3 PO 4 were dissolved in 1,4-dioxane ), And the mixture was stirred under reflux for 2 hours at 80 ° C in 80 mL of H 2 O. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and then washed with hexane to obtain 22.3 g (63%) of the target compound G-1 .
화합물 G-2의 합성Synthesis of Compound G-2
G-1 20g(59.8mmol), 트리에틸아민(Triethylamine) 8.4mL(59.8mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 4-브로모벤조일클로라이드(4-bromobenzoylchloride) 13.1g(59.8mmol)를 천천히 적가하여 1시간동안 온도를 유지하면서 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 G-2 28.0g(91%)을 얻었다.20 g (59.8 mmol) of G-1 and 8.4 mL (59.8 mmol) of triethylamine were dissolved in dichloromethane and maintained at 0 ° C. Then, 13.1 g (59.8 mmol) of 4-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed by rotary evaporation. The solvent was distilled off using dichloromethane and hexane as eluent to obtain 28.0 g (91%) of the target compound G-2 .
화합물 G-3 및 G-3'의 합성Synthesis of compounds G-3 and G-3 '
G-2 29.6g(57.21mmol)을 니트로벤젠(Nitrobenzene) 300mL에 전부 녹인 뒤 POCl3 6.45mL(57.21mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 2시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 G-3 18.9g(66%) 및 G-3' 6.24(22%)로 얻었다.29.6 g (57.21 mmol) of G-2 was completely dissolved in 300 mL of Nitrobenzene, and 6.45 mL (57.21 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and the residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the target compound G-3 18.9 g (66%) and G-3 ' 6.24 (22%).
화합물 2-3의 합성Synthesis of Compound 2-3
G-3 10.0g(20.02mmol), 4-([1,1'-비페닐]-4-일)-2-페닐-6-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-일)피리미딘(4-([1,1'-biphenyl]-4-yl)-2-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidine) 10.4g(24.03mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 2.3g(2.0mmol), K3PO4 12.75g(60.06mmol)을 1,4-디옥산(1,4-dioxane) 200mL, H2O 40mL하에서 120℃로 8시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 2-3 9.6g(66%)로 얻었다. G-3 (10.0 g, 20.02 mmol), 4 - ([1,1'-biphenyl] 4-yl) -2-phenyl-6- (4,4,5,5-tetramethyl-1,3-dioxaborolan-2-yl) pyrimidine , 2-dioxaborolan-2-yl ) pyrimidine) to 10.4g (24.03mmol), tetrakis (triphenylphosphine) palladium (0) 2.3g (2.0mmol), K 3 PO 4 12.75g (60.06mmol) 1, Dioxane (1,4-dioxane) and 40 mL of H 2 O at 120 ° C for 8 hours. After completion of the reaction was purified in distilled water and dichloromethane (dichloromethane) After drying the organic layer was back extracted with anhydrous MgSO 4 The solvent was removed by rotary evaporation of dichloromethane and hexane as a developing solvent of column chromatography and the target compound 2-3 9.6 g (66%).
[제조예 11] 화합물 2-44의 제조[Preparation Example 11] Preparation of Compound 2-44
Figure PCTKR2015006723-appb-I000158
Figure PCTKR2015006723-appb-I000158
G-3' 6.0g(12.01mmol), 4,6-디페닐-2-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-일)피리미딘(4,6-diphenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidine) 5.16g(14.42mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.39g(1.2mmol), K3PO4 7.65g(36.03mmol)을 1,4-디옥산(1,4-dioxane) 120mL, H2O 24mL하에서 120℃로 2시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 2-44 6.64g(85%)로 얻었다. G-3 ' 6.0 g (12.01 mmol), 4,6-diphenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2- yl) pyrimidine , 5.16 g (14.42 mmol) of tetrakis (triphenylphosphine) palladium (0), 6-diphenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 1.39 g (1.2 mmol) of K 3 PO 4 and 7.65 g (36.03 mmol) of K 3 PO 4 were stirred under reflux for 2 hours at 120 ° C. in 120 mL of 1,4-dioxane and 24 mL of H 2 O. After completion of the reaction distilled water and dichloromethane (dichloromethane) and then dried the organic layer was back extracted with anhydrous MgSO 4 The solvent was removed by rotary evaporation with dichloromethane and hexane as a developing solvent was purified by column chromatography the desired compound 2-44 6.64 g (85%).
[제조예 12] 화합물 2-107의 제조[Preparation Example 12] Preparation of Compound 2-107
Figure PCTKR2015006723-appb-I000159
Figure PCTKR2015006723-appb-I000159
화합물 H-1의 합성Synthesis of Compound H-1
디벤조푸란-2-일 보로닉 에시드(dibenzofuran-2-yl boronic acid) 20.0g(94.33mmol), 2-브로모아닐린(2-bromoaniline) 32.45g(188.66mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 5.45g(4.72mmol), K3PO4 60.07g(282.99mmol)을 1,4-디옥산(1,4-dioxane) 400mL, H2O 80mL하에서 120℃로 3시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산으로 씻어주어 목적화합물 H-1 21.5g(88%)을 얻었다.(94.33 mmol) of dibenzofuran-2-yl boronic acid, 32.45 g (188.66 mmol) of 2-bromoaniline, tetrakis (triphenylphosphine ) Of palladium (0) and 60.07 g (282.99 mmol) of K 3 PO 4 were refluxed in 400 mL of 1,4-dioxane and 80 mL of H 2 O at 120 ° C for 3 hours Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 21.5 g (88%) of the target compound H-1 .
화합물 H-2의 합성Synthesis of Compound H-2
H-1 20g(77.13mmol), 트리에틸아민(Triethylamine) 10.8mL(77.13mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 4-브로모벤조일클로라이드(4-bromobenzoylchloride) 16.9g(77.13mmol)를 천천히 적가하여 1시간동안 온도를 유지하면서 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 H-2 32.4g(95%)을 얻었다.20 g (77.13 mmol) of H-1 and 10.8 mL (77.13 mmol) of triethylamine were dissolved in dichloromethane and maintained at 0 ° C. Then, 16.9 g (77.13 mmol) of 4-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred for 1 hour while maintaining the temperature. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off using dichloromethane and hexane as eluent to obtain 32.4 g (95%) of the target compound H-2 .
화합물 H-3의 합성Synthesis of Compound H-3
H-2 32.0g(72.35mmol)을 니트로벤젠(Nitrobenzene) 600mL에 전부 녹인 뒤 POCl3 8.16mL(72.35mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 2시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 H-3 17.8g(58%)로 얻었다.32.0 g (72.35 mmol) of H-2 was completely dissolved in 600 mL of Nitrobenzene, and 8.16 mL (72.35 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 150 캜. After completion of the reaction was purified in distilled water and dichloromethane (dichloromethane) in dichloromethane and column chromatography with hexane as a developing solvent to behind the organic layer and then removing the solvent on a rotary evaporator after drying over anhydrous MgSO 4, extracted with the desired compound H-3 17.8 g (58%).
화합물 2-107의 합성Synthesis of Compound 2-107
H-3 10.0g(23.57mmol), 9,9'-(5-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-일)-1,3-페닐렌)비스(9H-카바졸)(9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole)) 15.1g(28.28mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.36g(1.18mmol), K3PO4 15.0g(70.71mmol)을 1,4-디옥산(1,4-dioxane) 200mL, H2O 40mL하에서 120℃로 2시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 2-107 12.1g(68%)로 얻었다. H-3 10.0 g (23.57 mmol), 9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaboran- Bis (9H-carbazole) (9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- 1.34 g (1.18 mmol) of tetrakis (triphenylphosphine) palladium (0) and 15.0 g (70.71 mmol) of K 3 PO 4 were dissolved in 1,4-dioxane (1 , 4-dioxane) and 40 mL of H 2 O was stirred at 120 ° C for 2 hours under reflux. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the desired compound 2-107 12.1 g (68%).
[제조예 13] 화합물 2-123의 제조[Preparation Example 13] Preparation of Compound 2-123
Figure PCTKR2015006723-appb-I000160
Figure PCTKR2015006723-appb-I000160
화합물 I-1의 합성Synthesis of Compound I-1
G-1 20g(59.8mmol), 트리에틸아민(Triethylamine) 8.4mL(59.8mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 4-브로모벤조일클로라이드(4-bromobenzoylchloride) 13.1g(59.8mmol)를 천천히 적가하여 1시간동안 온도를 유지하면서 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 I-1 29.0g(94%)을 얻었다.20 g (59.8 mmol) of G-1 and 8.4 mL (59.8 mmol) of triethylamine were dissolved in dichloromethane and maintained at 0 ° C. Then, 13.1 g (59.8 mmol) of 4-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 29.0 g (94%) of the desired compound I-1 .
화합물 I-2의 합성Synthesis of Compound I-2
I-1 29.6g(57.21mmol)을 니트로벤젠(Nitrobenzene) 300mL에 전부 녹인 뒤 POCl3 6.45mL(57.21mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 2시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 I-2 21.2g(74%)로 얻었다.29.6 g (57.21 mmol) of I-1 was completely dissolved in 300 mL of Nitrobenzene, and 6.45 mL (57.21 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 150 캜. After completion of the reaction distilled water and dichloromethane (dichloromethane) were dried after the organic layer was extracted with anhydrous MgSO 4 The solvent was removed by rotary evaporation to give the dichloromethane and column chromatography with hexane as a developing solvent the desired compound I-2 21.2 g (74%).
화합물 2-123의 합성Synthesis of Compound 2-123
I-2 10.0g(20.02mmol), 2-페닐-1-(4-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-일)페닐)-1H-벤조[d]이미다졸(2-phenyl-1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole) 9.52g(24.03mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 2.3g(2.0mmol), K3PO4 12.75g(60.06mmol)을 1,4-디옥산(1,4-dioxane) 200mL, H2O 40mL하에서 120℃로 8시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 2-123 9.79g(71%)로 얻었다. I-2 10.0g (20.02mmol), 2- phenyl-1- (4- (4,4,5,5-tetramethyl-1,3,2-dioxa-boran-2-yl) phenyl) -1H- Benzo [d] imidazole) was prepared in a manner similar to that described in Example 1 (b), except that 2-phenyl-1- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 2.3 g (2.0 mmol) of tetrakis (triphenylphosphine) palladium (0) and 12.75 g (60.06 mmol) of K 3 PO 4 were dissolved in 1,4-dioxane, to 120 ℃ under 200mL, 40mL H 2 O was stirred under reflux for 8 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the desired compound 2-123 9.79 g (71%).
[제조예 14] 화합물 2-243의 제조[Preparation Example 14] Preparation of Compound 2-243
Figure PCTKR2015006723-appb-I000161
Figure PCTKR2015006723-appb-I000161
화합물 J-1의 합성Synthesis of Compound J-1
(9H-카바졸-3-일)보로닉 에시드((9H-carbazol-3-yl)bronic acid) 20.0g(94.77mmol), 2-브로모아닐린(2-bromoaniline) 32.6g(189.55mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 5.48g(4.74mmol), K3PO4 60.35g(284.31mmol)을 1,4-디옥산(1,4-dioxane) 400mL, H2O 80mL하에서 120℃로 3시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산으로 씻어주어 목적화합물 J-1 13.9g(57%)을 얻었다.20.0 g (94.77 mmol) of (9H-carbazol-3-yl) bronic acid, 32.6 g (189.55 mmol) of 2-bromoaniline, 5.48 g (4.74 mmol) of tetrakis (triphenylphosphine) palladium (0) and 60.35 g (284.31 mmol) of K 3 PO 4 were dissolved in 400 mL of 1,4-dioxane and 80 mL of H 2 O And the mixture was refluxed and stirred at 120 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 13.9 g (57%) of the target compound J-1 .
화합물 J-2의 합성Synthesis of Compound J-2
J-1 13g(50.32mmol), 트리에틸아민(Triethylamine) 7.07mL(50.32mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 벤조일클로라이드(benzoylchloride) 7.07mL(50.32mmol)를 천천히 적가하여 1시간동안 온도를 유지하면서 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 J-2 16.6g(91%)을 얻었다.13.0 g (50.32 mmol) of J-1 and 7.07 mL (50.32 mmol) of triethylamine were dissolved in dichloromethane and maintained at 0 占 폚. Then, 7.07 mL (50.32 mmol) of benzoylchloride was slowly added dropwise, and the mixture was stirred while maintaining the temperature for 1 hour. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was then purified by column chromatography using dichloromethane and hexane as eluent to obtain 16.6 g (91%) of the target compound J-2 .
화합물 J-3의 합성Synthesis of Compound J-3
J-2 16.0g(44.15mmol)을 니트로벤젠(Nitrobenzene) 320mL에 전부 녹인 뒤 POCl3 4.98mL(44.15mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 1시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 J-3 13.4g(88%)로 얻었다.16.0 g (44.15 mmol) of J-2 was completely dissolved in 320 mL of Nitrobenzene, and 4.98 mL (44.15 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 1 hour while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the desired compound J-3 13.4 g (88%).
화합물 K-1의 합성Synthesis of Compound K-1
J-3 10.0g(29.03mmol), 1-아이오도-4-브로모벤젠(1-Iodo-4-bromobenzene) 9.84g(34.84mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.68g(1.45mmol), K3PO4 18.49g(87.09mmol)을 1,4-디옥산(1,4-dioxane) 100mL, H2O 20mL하에서 120℃로 3시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 K-1 10.2g(70%)을 얻었다. J-3 10.0g (29.03mmol), 1- iodo-4-bromobenzene (1-Iodo-4-bromobenzene ) 9.84g (34.84mmol), tetrakis (triphenylphosphine) palladium (0), 1.68g 18.49 g (87.09 mmol) of K 3 PO 4 were stirred under reflux for 3 hours at 120 ° C. in 100 mL of 1,4-dioxane and 20 mL of H 2 O. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off using dichloromethane and hexane as eluent to obtain 10.2 g (70%) of the desired compound K-1 .
화합물 2-243의 합성Synthesis of Compound 2-243
K-1 10.0g(20.02mmol), 페난트렌-9-일보로닉 에시드(phenanthren-9-ylboronic acid) 5.34g(24.03mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.16g(1.0mmol), K3PO4 12.75g(60.06mmol)을 1,4-디옥산(1,4-dioxane) 200mL, H2O 40mL하에서 120℃로 8시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 2-243 6.93g(58%)로 얻었다. K-1 10.0g (20.02mmol), a phenanthrene-9-Daily Nick Acid (phenanthren-9-ylboronic acid) 5.34g (24.03mmol), tetrakis (triphenylphosphine) palladium (0) 1.16g (1.0 mmol) and 12.75 g (60.06 mmol) of K 3 PO 4 were refluxed and stirred at 120 ° C in 200 mL of 1,4-dioxane and 40 mL of H 2 O for 8 hours. After completion of the reaction distilled water and dichloromethane (dichloromethane) and then dried the organic layer was back extracted with anhydrous MgSO 4 The solvent was removed by rotary evaporation with dichloromethane and hexane as a developing solvent was purified by column chromatography the desired compound 2-243 6.93 g (58%).
[제조예 15] 화합물 3-19의 제조[Preparation Example 15] Preparation of Compound 3-19
Figure PCTKR2015006723-appb-I000162
Figure PCTKR2015006723-appb-I000162
화합물 L-1의 합성Synthesis of Compound L-1
(9-페닐-9H-카바졸-2-일)보로닉 에시드((9-Phenyl-9H-carbazol-2-yl)boronic acid) 40.0g(139.3mmol), 2-브로모아닐린(2-bromoaniline) 35.9g(208.9mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 8.05g(6.96mmol), K3PO4 88.7g(417.9mmol)을 1,4-디옥산(1,4-dioxane) 800mL, H2O 160mL하에서 120℃로 1시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산으로 씻어주어 목적화합물 L-1 36.3g(78%)을 얻었다.(9-phenyl-9H-carbazol-2-yl) boronic acid, 40.0 g (139.3 mmol) of 2-bromoaniline 8.05 g (6.96 mmol) of tetrakis (triphenylphosphine) palladium (0) and 88.7 g (417.9 mmol) of K 3 PO 4 were dissolved in 1,4-dioxane ) And 160 mL of H 2 O under reflux for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 36.3 g (78%) of the target compound L-1 .
화합물 L-2의 합성Synthesis of Compound L-2
L-1 36g(107.6mmol), 트리에틸아민(Triethylamine) 15.1mL(107.6mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 4-브로모벤조일클로라이드(4-bromobenzoylchloride) 23.6g(107.6mmol)를 천천히 적가하여 1시간동안 온도를 유지하면 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 L-2 50.1g(90%)을 얻었다.36 g (107.6 mmol) of L-1 and 15.1 mL (107.6 mmol) of triethylamine were dissolved in dichloromethane and maintained at 0 ° C. After that, 23.6 g (107.6 mmol) of 4-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred for 1 hour. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off using dichloromethane and hexane as eluent to obtain 50.1 g (90%) of the target compound L-2 .
화합물 L-3 및 L-3'의 합성Synthesis of compounds L-3 and L-3 '
L-2 30g(57.97mmol)을 니트로벤젠(Nitrobenzene) 600mL에 전부 녹인 뒤 POCl3 6.54mL(57.97mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 2시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 L-3 20.27g(70%) 및 L-3' 5.21(18%)로 얻었다.30 g (57.97 mmol) of L-2 was dissolved in 600 mL of Nitrobenzene, and then 6.54 mL (57.97 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the desired compound L-3 20.27 g (70%) and L-3 '5.21 (18%).
화합물 3-19의 합성Synthesis of Compound 3-19
L-3' 5.0g(10.01mmol), 2-(9,9-디페닐-9H-플루오렌-2-일)-4,4,5,5-테트라메틸-1,3,2-디옥사보란(2-(9,9-diphenyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane) 5.34g(12.01mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 0.58g(0.5mmol), K3PO4 6.37g(30.0mmol)을 1,4-디옥산(1,4-dioxane) 100mL, H2O 20mL하에서 120℃로 8시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 3-19 6.49g(88%)로 얻었다.5.0 g (10.01 mmol) of L-3 ', 2- (9,9-diphenyl-9H-fluoren-2-yl) -4,4,5,5-tetramethyl- 5.34 g (12.01 mmol) of 2- (9,9-diphenyl-9H-fluoren-2-yl) -4,4,5,5-tetramethyl-1,3,2- dioxaborolane, 0.57 g (0.5 mmol) of palladium (0) and 6.37 g (30.0 mmol) of K 3 PO 4 were dissolved in 100 mL of 1,4-dioxane and 20 mL of H 2 O at 120 ° C. for 8 hours Lt; / RTI &gt; After completion of the reaction distilled water and dichloromethane (dichloromethane) and then dried the organic layer was back extracted with anhydrous MgSO 4 The solvent was removed by rotary evaporation with dichloromethane and hexane as a developing solvent was purified by column chromatography the desired compound 3-19 6.49 g (88%).
[제조예 16] 화합물 3-43의 제조[Preparation Example 16] Preparation of Compound 3-43
Figure PCTKR2015006723-appb-I000163
Figure PCTKR2015006723-appb-I000163
L-3 10.0g(20.02mmol), 2-페닐-1-(4-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-일)페닐)-1H-벤조[d]이미다졸(2-phenyl-1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole) 9.52g(24.03mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.16g(1.0mmol), K3PO4 12.7g(60.06mmol)을 1,4-디옥산(1,4-dioxane) 200mL, H2O 40mL하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 3-43 10.6g(77%)로 얻었다. L-3 10.0g (20.02mmol), 2- phenyl-1- (4- (4,4,5,5-tetramethyl-1,3,2-dioxa-boran-2-yl) phenyl) -1H- Benzo [d] imidazole) was prepared in a manner similar to that described in Example 1 (b), except that 2-phenyl-1- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 1.16 g (1.0 mmol) of tetrakis (triphenylphosphine) palladium (0) and 12.7 g (60.06 mmol) of K 3 PO 4 were dissolved in 1,4-dioxane, to 120 ℃ under 200mL, 40mL H 2 O was stirred at reflux for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the desired compound 3-43 10.6 g (77%).
[제조예 17] 화합물 4-1의 제조[Preparation Example 17] Preparation of Compound 4-1
Figure PCTKR2015006723-appb-I000164
Figure PCTKR2015006723-appb-I000164
화합물 M-1의 합성Synthesis of Compound M-1
(9-페닐-9H-카바졸-1-일)보로닉 에시드((9-Phenyl-9H-carbazol-1-yl)boronic acid) 40.0g(139.3mmol), 2-브로모아닐린(2-bromoaniline) 35.9g(208.9mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 8.05g(6.96mmol), K3PO4 88.7g(417.9mmol)을 1,4-디옥산(1,4-dioxane) 800mL, H2O 160mL하에서 120℃로 1시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산으로 씻어주어 목적화합물 M-1 37.7g(81%)을 얻었다.(9-phenyl-9H-carbazol-1-yl) boronic acid, 40.0 g (139.3 mmol) of 2-bromoaniline 8.05 g (6.96 mmol) of tetrakis (triphenylphosphine) palladium (0) and 88.7 g (417.9 mmol) of K 3 PO 4 were dissolved in 1,4-dioxane ) And 160 mL of H 2 O under reflux for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 37.7 g (81%) of the target compound M-1 .
화합물 M-2의 합성Synthesis of Compound M-2
M-1 36g(107.6mmol), 트리에틸아민(Triethylamine) 15.1mL(107.6mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 4-브로모벤조일클로라이드(4-bromobenzoylchloride) 23.6g(107.6mmol)를 천천히 적가하여 1시간동안 온도를 유지하면서 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 M-2 42.2g(76%)을 얻었다.36 g (107.6 mmol) of M-1 and 15.1 mL (107.6 mmol) of triethylamine were dissolved in dichloromethane and maintained at 0 ° C. Thereafter, 23.6 g (107.6 mmol) of 4-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 42.2 g (76%) of the target compound M-2 .
화합물 M-3의 합성Synthesis of Compound M-3
M-2 30g(57.97mmol)을 니트로벤젠(Nitrobenzene) 600mL에 전부 녹인 뒤 POCl3 6.54mL(57.97mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 2시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 M-3 22.2g(77%)로 얻었다.30 g (57.97 mmol) of M-2 was completely dissolved in 600 mL of Nitrobenzene, and 6.54 mL (57.97 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the target compound M-3 22.2 g (77%).
화합물 M-4의 합성Synthesis of Compound M-4
M-3 20g(40.05mmol), 비스(피나콜라토)디보론 20.3g(80.09mmol), 포타슘아세테이트(KOAc) 11.8g(120.15mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II)1.5g(2.0mmol)을 1,4-디옥산(1,4-dioxane) 100mL하에서 120℃로 6시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산, 메탄올(MeOH)로 씻어주어 목적화합물 M-4 18.8g(86%)을 얻었다. M-3 20g (40.05mmol), bis (pinacolato) diboron 20.3g (80.09mmol), potassium acetate (KOAc) 11.8g (120.15mmol), [1,1'- bis (diphenylphosphino) ferrocene ] 1.5 g (2.0 mmol) of dichloropalladium (II) were stirred in 100 ml of 1,4-dioxane at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel, followed by washing with hexane and methanol (MeOH) to obtain 18.8 g (86%) of the target compound M-4 .
화합물 4-1의 합성Synthesis of Compound 4-1
M-4 10.0g(18.3mmol), 2-클로로-4,6-디페닐-1,3,5-트리아진(2-chloro-4,6-diphenyl-1,3,5-triazine) 5.88g(21.96mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.06g(0.92mmol), K2CO3 7.59g(54.9mmol)을 톨루엔(Toluene) 100mL, 에탄올(EtOH)/H2O 각 20mL하에서 120℃로 3시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 디클로로메탄(dichloromethane), 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 디클로로메탄(dichloromethane) 과량으로 전부 녹인 뒤 실리카겔로 필터하여 목적화합물 4-1 6.6g(55%)을 얻었다.10.0 g (18.3 mmol) of M-4 , 2-chloro-4,6-diphenyl-1,3,5-triazine 1.09 g (0.92 mmol) of tetrakis (triphenylphosphine) palladium (0) and 7.59 g (54.9 mmol) of K 2 CO 3 were dissolved in toluene (100 mL), ethanol (EtOH) / H 2 O And the mixture was stirred at 120 占 폚 under 20 mL for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with dichloromethane, ethyl acetate (EA), and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount, and then filtered with silica gel to obtain 6.6 g (55%) of the target compound 4-1 .
[제조예 18] 화합물 1-318의 제조[Manufacturing Example 18] Preparation of Compound 1-318
Figure PCTKR2015006723-appb-I000165
Figure PCTKR2015006723-appb-I000165
B-1 6.0g(10.98mmol), 5-브로모-2,4-6-트리페닐피리미딘(5-bromo-2,4,6-triphenylpyrimidine) 5.1g(13.18mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.3g(1.1mmol), K3PO4 6.99g(32.94mmol)을 1,4-디옥산(1,4-dioxane) 60mL의 H2O 12mL하에서 120℃로 2시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤고체가 생성되어 필터한 후 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후, 고체를 디클로로메탄(dichloromethane) 과량으로 전부 녹인 뒤 실리카겔로 필터하여 목적화합물 1-318 5.0g(63%)을 얻었다.5.1 g (13.18 mmol) of 5-bromo-2,4,6-triphenylpyrimidine, 6.0 g (10.98 mmol) of B-1 , 1.3 g (1.1 mmol) of palladium (0) and 6.99 g (32.94 mmol) of K 3 PO 4 were dissolved in 12 mL of 1,4-dioxane 60 mL of H 2 O at 120 ° C. for 2 hours Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount, and then filtered with silica gel to obtain 5.0 g (63%) of the target compound 1-318 .
[제조예 19] 화합물 2-36의 제조[Manufacturing Example 19] Preparation of Compound 2-36
Figure PCTKR2015006723-appb-I000166
Figure PCTKR2015006723-appb-I000166
화합물 N-1의 제조Preparation of Compound N-1
G-3' 20g(40.05mmol), 비스(피나콜라토)디보론 20.3g(80.09mmol), 포타슘아세테이트(KOAc) 11.8g(120.15mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II)1.5g(2.0mmol)을 1,4-디옥산(1,4-dioxane) 100mL하에서 120℃로 3시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산, 메탄올(MeOH)로 씻어주어 목적화합물 N-1 20.1g(92%)을 얻었다. G-3 '20g (40.05mmol) , bis (pinacolato) diboron 20.3g (80.09mmol), potassium acetate (KOAc) 11.8g (120.15mmol), [1,1'- bis (diphenylphosphino) Ferrocene] 1.5 g (2.0 mmol) of dichloropalladium (II) was stirred in 100 mL of 1,4-dioxane at 120 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel, followed by washing with hexane and methanol (MeOH) to obtain 20.1 g (92%) of the target compound N-1 .
화합물 2-36의 제조Preparation of compound 2-36
N-1 6.0g(10.98mmol), 2-클로로-4,6-디페닐-1,3,5-트리아진(2-chloro-4,6-diphenyl-1,3,5-triazine) 3.5g (13.18mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.3g(1.1mmol), K3PO4 6.99g(32.94mmol)을 1,4-디옥산(1,4-dioxane) 60mL, H2O 12mL하에서 120℃로 8시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤고체가 생성되어 필터한 후 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 디클로로메탄(dichloromethane) 과량으로 전부 녹인 뒤 실리카겔로 필터하여 목적화합물 2-36 4.7g(66%)을 얻었다.3.5 g (10.98 mmol) of N-1 , 2-chloro-4,6-diphenyl-1,3,5-triazine 1.3 g (1.1 mmol) of tetrakis (triphenylphosphine) palladium (0) and 6.99 g (32.94 mmol) of K 3 PO 4 were dissolved in 60 mL of 1,4-dioxane, And the mixture was refluxed and stirred at 12 DEG C under 12 mL of H 2 O for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount, and then filtered through silica gel to obtain 4.7 g (66%) of the desired compound 2-36 .
[제조예 20] 화합물 2-38의 제조[Manufacturing Example 20] Preparation of Compound 2-38
Figure PCTKR2015006723-appb-I000167
Figure PCTKR2015006723-appb-I000167
N-1 6.0g(10.98mmol), 4-([1,1'-비페닐]-4-일)-6-브로모-2-페닐피리미딘(4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine) 5.1g (13.18mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.3g(1.1mmol), K3PO4 6.99g(32.94mmol)을 1,4-디옥산(1,4-dioxane) 60mL,H2O 12mL하에서 120℃로 8시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤고체가 생성되어 필터한 후 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 디클로로메탄(dichloromethane) 과량으로 전부 녹인 뒤 실리카겔로 필터하여 목적화합물 2-38 4.4g(55%)을 얻었다. N-1 6.0g (10.98mmol), 4 - ([1,1'- biphenyl] -4-yl) -6-bromo-2-phenyl-pyrimidine (4 - ([1,1'-biphenyl ] (1.1 mmol) of tetrakis (triphenylphosphine) palladium (0), 6.99 g (32.94 mmol) of K 3 PO 4 , Dioxane (60 mL) and H 2 O (12 mL) at 120 ° C for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount, and then filtered with silica gel to obtain 4.4 g (55%) of the target compound 2-38 .
[제조예 21] 화합물 3-39의 제조[Manufacturing Example 21] Preparation of Compound 3-39
Figure PCTKR2015006723-appb-I000168
Figure PCTKR2015006723-appb-I000168
화합물 O-1의 제조Preparation of compound O-1
L-3 20g(40.05mmol), 비스(피나콜라토)디보론 20.3g(80.09mmol), 포타슘아세테이트(KOAc) 11.8g(120.15mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II)1.5g(2.0mmol)을 1,4-디옥산(1,4-dioxane) 100mL하에서 120℃로 7시간 동안교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산, 메탄올(MeOH)로 씻어주어 목적화합물 O-1 18.8g(86%)을 얻었다. L 3-20g (40.05mmol), bis (pinacolato) diboron 20.3g (80.09mmol), potassium acetate (KOAc) 11.8g (120.15mmol), [1,1'- bis (diphenylphosphino) ferrocene ] 1.5 g (2.0 mmol) of dichloropalladium (II) were stirred in 100 ml of 1,4-dioxane at 120 ° C for 7 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel, followed by washing with hexane and methanol (MeOH) to obtain 18.8 g (86%) of the target compound O-1 .
화합물 3-39의 제조Preparation of compound 3-39
O-1 6.0g(10.98mmol), 4-([1,1'-비페닐]-4-일)-6-브로모-2-페닐피리미딘 (4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine) 5.1g (13.18mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.3g(1.1mmol), K3PO4 6.99g(32.94mmol)을 1,4-디옥산(1,4-dioxane) 60mL,H2O 12mL하에서 120℃로 2시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 디클로로메탄(dichloromethane) 과량으로 전부 녹인 뒤 실리카겔로 필터하여 목적화합물 3-39 6.1g(85%)을 얻었다. O-1 6.0g (10.98mmol), 4 - ([1,1'- biphenyl] -4-yl) -6-bromo-2-phenyl-pyrimidine (4 - ([1,1'-biphenyl ] (1.1 mmol) of tetrakis (triphenylphosphine) palladium (0), 6.99 g (32.94 mmol) of K 3 PO 4 , Dioxane (60 mL) and H 2 O (12 mL) at 120 ° C for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount, and then the mixture was filtered through silica gel to obtain 6.1 g (85%) of the desired compound 3-39 .
[제조예 22] 화합물 3-46의 제조[Preparation Example 22] Preparation of compound 3-46
Figure PCTKR2015006723-appb-I000169
Figure PCTKR2015006723-appb-I000169
L-3 10.0g(20.02mmol) 1-페닐-2-(4-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)페닐)-1H-벤조[d]이미다졸(1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole) 9.52g(24.03mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.16g(1.0mmol), K3PO4 12.7g(60.06mmol)을 1,4-디옥산(1,4-dioxane) 200mL, H2O 40mL하에서 120℃로 4시간동안 환류교반하였다. 반응종료 후 증류수와 클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 3-46 8.7g(63%)로 얻었다 L-3 10.0 g (20.02 mmol) 1-phenyl-2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan- -Benzo [d] imidazole (1-phenyl-2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 1.63 g (1.0 mmol) of tetrakis (triphenylphosphine) palladium (0) and 12.7 g (60.06 mmol) of K 3 PO 4 were dissolved in 1,4-dioxane ) under 200mL, 40mL H 2 O to 120 ℃ was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the desired compound 3-46 8.7 g (63%) of
[제조예 23] 화합물 4-56의 제조[Manufacturing Example 23] Preparation of compound 4-56
Figure PCTKR2015006723-appb-I000170
Figure PCTKR2015006723-appb-I000170
화합물 P-1의 제조Preparation of Compound P-1
디벤조[b,d]티오펜-4-일보로닉 에시드 (dibenzo[b,d]thiophen-4-ylboronic acid) 50.0g(219.2mmol), 2-브로모아닐린(2-bromoaniline) 56.5g(328.8mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 25.0g(10.96mmol), K3PO4 140.0g(657.6mmol)을 1,4-디옥산(1,4-dioxane) 500mL, H2O 100mL하에서 120℃로 3시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 (디클로로메탄:헥산=1:4)로 컬럼정제하여 목적화합물 P-1 54.08g(89%)을 얻었다., 50.0 g (219.2 mmol) of dibenzo [b, d] thiophen-4-ylboronic acid and 56.5 g (2-bromoaniline) of dibenzo [ 25.0 g (10.96 mmol) of tetrakis (triphenylphosphine) palladium (0) and 140.0 g (657.6 mmol) of K 3 PO 4 were dissolved in 500 mL of 1,4-dioxane, And the mixture was refluxed and stirred at 120 占 폚 under 100 mL of 2 O for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel (dichloromethane: hexane = 1: 4) to obtain 54.08 g (89%) of the target compound P-1 .
화합물 P-2의 제조Preparation of Compound P-2
P-1 54g(196.1mmol), 트리에틸아민(Triethylamine) 27.5mL(196.1mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 4-브로모벤조일클로라이드(4-bromobenzoylchloride) 43.0g(196.1mmol)를 천천히 적가하여 2시간동안 온도를 유지하면서 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 목적화합물 P-2 85.0g(95%)을 얻었다.54 g (196.1 mmol) of P-1 and 27.5 mL (196.1 mmol) of triethylamine were dissolved in dichloromethane and maintained at 0 ° C. Then, 43.0 g (196.1 mmol) of 4-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred at the same temperature for 2 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed by a rotary evaporator to obtain 85.0 g (95%) of the target compound P-2 .
화합물 P-3의 제조Preparation of Compound P-3
P-2 85.0g(185.44mmol)을 니트로벤젠(Nitrobenzene) 600mL에 전부 녹인 뒤 POCl3 21.0mL(185.44mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 3시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)으로 추출한 뒤유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 메탄올(MeOH)로 씻어주어 목적화합물 P-3 55.0g(67%)을 얻었다.85.0 g (185.44 mmol) of P-2 was dissolved in 600 mL of Nitrobenzene and 21.0 mL (185.44 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 3 hours while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator, followed by washing with methanol (MeOH) to obtain 55.0 g (67%) of the target compound P-3 .
화합물 P-4의 제조Preparation of Compound P-4
P-3 20g(45.4mmol), 비스(피나콜라토)디보론 23.0g(90.8mmol), 포타슘아세테이트(KOAc) 13.3g(136.2mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II) 1.6g(2.27mmol)을 1,4-디옥산(1,4-dioxane) 200mL하에서 120℃로 3시간동안교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산, 메탄올(MeOH)로 씻어주어 목적화합물 P-4 16.0g(72%)을 얻었다.20 g (45.4 mmol) of P-3 , 23.0 g (90.8 mmol) of bis (pinacolato) diboron, 13.3 g (136.2 mmol) of potassium acetate (KOAc) ] 1.6 g (2.27 mmol) of dichloropalladium (II) was stirred in 200 mL of 1,4-dioxane at 120 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel, followed by washing with hexane and methanol (MeOH) to obtain 16.0 g (72%) of the desired compound P-4 .
화합물 4-56의 제조Preparation of compound 4-56
P-4 7.0g(14.36mmol), 2-클로로-4,6-디페닐-1,3,5-트리아진(2-chloro-4,6-diphenyl-1,3,5-triazine) 3.8g (14.36mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.6g(1.44mmol), K3PO4 9.1g(43.08mmol)을 1,4-디옥산(1,4-dioxane) 100mL,H2O 20mL하에서 120℃로 2시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤고체가 생성되어 필터한 후 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 1,2-디클로로에탄(1,2-Dichloroethane)을 과량으로 끓인 뒤 필터하여 목적화합물 4-56 6.6g(78%)을 얻었다.3.8 g (14.36 mmol) of P-4 and 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6- 1.6 g (1.44 mmol) of tetrakis (triphenylphosphine) palladium (0) and 9.1 g (43.08 mmol) of K 3 PO 4 were dissolved in 100 mL of 1,4-dioxane, under a H 2 O 20mL was stirred at reflux for 2 hours in 120 ℃. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). After that, the solid was boiled with 1,2-dichloroethane in an excess amount and filtered to obtain 6.6 g (78%) of the target compound 4-56 .
[제조예 24] 화합물 4-58의 제조[Production Example 24] Preparation of compound 4-58
Figure PCTKR2015006723-appb-I000171
Figure PCTKR2015006723-appb-I000171
P-4 6.3g(12.91mmol), 4-([1,1'-비페닐]-4-일)-6-브로모-2-페닐피리미딘 (4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine) 5.0g (12.91mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.5g(1.29mmol), K3PO4 8.2g(38.73mmol)을 1,4-디옥산(1,4-dioxane) 100mL, H2O 20mL하에서 120℃로 2시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 1,2-디클로로에탄(1,2-Dichloroethane)을 과량으로 끓인 뒤 필터하여 목적화합물 4-58 5.7g(66%)을 얻었다. P-4 6.3g (12.91mmol), 4 - ([1,1'- biphenyl] -4-yl) -6-bromo-2-phenyl-pyrimidine (4 - ([1,1'-biphenyl ] (1.29 mmol) of tetrakis (triphenylphosphine) palladium (0), 8.2 g (38.73 mmol) of K 3 PO 4 , Dioxane (100 mL) and H 2 O (20 mL) at 120 ° C for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). The solid was then boiled with an excess of 1,2-dichloroethane and then filtered to obtain 5.7 g (66%) of the desired compound 4-58 .
[제조예 25] 화합물 4-76의 제조[Production Example 25] Preparation of compound 4-76
Figure PCTKR2015006723-appb-I000172
Figure PCTKR2015006723-appb-I000172
화합물 Q-1의 제조Preparation of Compound Q-1
디벤조푸란-4-일 보로닉 에시드(dibenzofuran-4-yl boronic acid) 20.0g(94.33mmol), 2-브로모아닐린(2-bromoaniline) 32.45g(188.66mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 5.45g(4.72mmol), K3PO4 60.07g(282.99mmol)을 1,4-디옥산(1,4-dioxane) 400mL, H2O 80mL하에서 120℃로 3시간동안 환류교반하였다. 반응완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산으로 씻어주어 목적화합물 Q-1 21.5g(88%)을 얻었다.20.0 g (94.33 mmol) of dibenzofuran-4-yl boronic acid, 32.45 g (188.66 mmol) of 2-bromoaniline, ) Of palladium (0) and 60.07 g (282.99 mmol) of K 3 PO 4 were refluxed in 400 mL of 1,4-dioxane and 80 mL of H 2 O at 120 ° C for 3 hours Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 21.5 g (88%) of the desired compound Q-1 .
화합물 Q-2의 제조Preparation of Compound Q-2
Q-1 20g(77.13mmol), 트리에틸아민(Triethylamine) 10.8mL(77.13mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 4-브로모벤조일클로라이드(4-bromobenzoylchloride) 16.9g(77.13mmol)를 천천히 적가하여 1시간동안 온도를 유지하면서 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 Q-2 32.4g(95%)을 얻었다.20 g (77.13 mmol) of Q-1 and 10.8 mL (77.13 mmol) of triethylamine were dissolved in dichloromethane and maintained at 0 占 폚. Then, 16.9 g (77.13 mmol) of 4-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred for 1 hour while maintaining the temperature. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was then purified by column chromatography using dichloromethane and hexane as eluent to obtain 32.4 g (95%) of the desired compound Q-2 .
화합물 Q-3의 제조Preparation of Compound Q-3
Q-2 32.0g(72.35mmol)을 니트로벤젠(Nitrobenzene) 600mL에 전부 녹인 뒤 POCl3 8.16mL(72.35mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 2시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 Q-3 17.8g(58%)로 얻었다.32.0 g (72.35 mmol) of Q-2 was dissolved in 600 mL of Nitrobenzene, and 8.16 mL (72.35 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the desired compound Q-3 17.8 g (58%).
화합물 Q-4의 제조Preparation of compound Q-4
Q-3 18.3g(43.1mmol), 비스(피나콜라토)디보론 21.9g(86.3mmol), 포타슘아세테이트(KOAc) 12.7g(129.3mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II) 1.6g(2.16mmol)을 1,4-디옥산(1,4-dioxane) 150mL하에서 120℃로 2시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산, 메탄올(MeOH)로 씻어주어 목적화합물 Q-4 20.0g(84%)을 얻었다.18.3 g (43.1 mmol) of Q-3 , 21.9 g (86.3 mmol) of bis (pinacolato) diboron, 12.7 g (129.3 mmol) of potassium acetate (KOAc) Ferrocene] 1.6 g (2.16 mmol) of dichloropalladium (II) was stirred in 150 mL of 1,4-dioxane at 120 ° C for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel, followed by washing with hexane and methanol (MeOH) to obtain 20.0 g (84%) of the target compound Q-4 .
화합물 4-76의 제조Preparation of compound 4-76
Q-4 8.0g(16.9mmol), 2-클로로-4,6-디페닐-1,3,5-트리아진(2-chloro-4,6-diphenyl-1,3,5-triazine) 5.45g (20.37mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.96g(1.7mmol), K3PO4 10.8g(50.91mmol)을 1,4-디옥산(1,4-dioxane) 160mL,H2O 30mL하에서 120℃로 3시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 톨루엔을 과량으로 끓인 뒤 필터하여 목적화합물 4-76 3.3g(34%)을 얻었다.8.0 g (16.9 mmol) of Q-4, 2.45 g of 2-chloro-4,6-diphenyl-1,3,5-triazine 1.96 g (1.7 mmol) of tetrakis (triphenylphosphine) palladium (0) and 10.8 g (50.91 mmol) of K 3 PO 4 were dissolved in 160 mL of 1,4-dioxane, And the mixture was refluxed and stirred for 3 hours at 120 캜 in 30 mL of H 2 O. [ After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). The solid was then boiled with an excess amount of toluene and then filtered to obtain 3.3 g (34%) of the target compound 4-76.
[제조예 26] 화합물 4-169의 제조[Preparation Example 26] Preparation of Compound 4-169
Figure PCTKR2015006723-appb-I000173
Figure PCTKR2015006723-appb-I000173
화합물 R-1의 제조Preparation of compound R-1
Q-1 20g(77.13mmol), 트리에틸아민(Triethylamine) 10.8mL(77.13mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 3-브로모벤조일클로라이드(3-bromobenzoylchloride) 16.9g(77.13mmol)를 천천히 적가하여 1시간동안 온도를 유지하면서 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 R-1 32.4g(95%)을 얻었다.20 g (77.13 mmol) of Q-1 and 10.8 mL (77.13 mmol) of triethylamine were dissolved in dichloromethane and maintained at 0 占 폚. Thereafter, 16.9 g (77.13 mmol) of 3-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred for 1 hour while maintaining the temperature. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off using dichloromethane and hexane as eluent to obtain 32.4 g (95%) of the target compound R-1 .
화합물 R-2의 제조Preparation of compound R-2
R-1 32.0g(72.35mmol)을 니트로벤젠(Nitrobenzene) 600mL에 전부 녹인 뒤 POCl3 8.16mL(72.35mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 2시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 R-2 17.8g(58%)로 얻었다.32.0 g (72.35 mmol) of R-1 was completely dissolved in 600 mL of Nitrobenzene, and 8.16 mL (72.35 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the target compound R-2 17.8 g (58%).
화합물 R-3의 제조Preparation of compound R-3
R-2 18.3g(43.1mmol), 비스(피나콜라토)디보론 21.9g(86.3mmol), 포타슘아세테이트(KOAc) 12.7g(129.3mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II) 1.6g(2.16mmol)을 1,4-디옥산(1,4-dioxane) 150mL하에서 120℃로 2시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산, 메탄올(MeOH)로 씻어주어 목적화합물 R-3 20.0g(84%)을 얻었다.18.3 g (43.1 mmol) of R-2 , 21.9 g (86.3 mmol) of bis (pinacolato) diboron, 12.7 g (129.3 mmol) of potassium acetate (KOAc) Ferrocene] 1.6 g (2.16 mmol) of dichloropalladium (II) was stirred in 150 mL of 1,4-dioxane at 120 ° C for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel, followed by washing with hexane and methanol (MeOH) to obtain 20.0 g (84%) of the target compound R-3 .
화합물 4-169의 제조Preparation of compound 4-169
R-3 8.0g(16.9mmol), 4-([1,1'-비페닐]-4-일)-6-브로모-2-페닐피리미딘4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 6.34g (20.37mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.96g(1.7mmol), K3PO4 10.8g(50.91mmol)을 1,4-디옥산(1,4-dioxane) 160mL,H2O 30mL하에서 120℃로 3시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 에틸아세테이트(EA),메탄올(MeOH)로 씻어주었다. 그 후 고체를 톨루엔을 과량으로 끓인 뒤 필터하여 목적화합물 4-169 6.4g(66%)을 얻었다.4 - ([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine, 8.0 g (16.9 mmol) 4-yl) -6-bromo- 2-phenylpyrimidine 6.34g (20.37mmol), tetrakis (triphenylphosphine) palladium (0) 1.96g (1.7mmol), K 3 PO 4 with 10.8g (50.91mmol) 1 , 1,4-dioxane (160 mL) and H 2 O (30 mL) at 120 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). The solid was then boiled with an excess amount of toluene and then filtered to obtain 6.4 g (66%) of the target compound 4-169.
[제조예 27] 화합물 1-482의 제조[Preparation Example 27] Preparation of compound 1-482
Figure PCTKR2015006723-appb-I000174
Figure PCTKR2015006723-appb-I000174
F-4 8.0g(23.23mmol), 4-(4-브로모페닐)-2,6-디페닐피리딘(4-(4-bromophenyl)-2,6-diphenylpyrimidine) 9.9g(25.55mmol), Pd2(dba)3 2.1g(2.323mmol), P(t-Bu)3 0.22g(2.323mmol), 소듐 터트-부톡사이드 14.1g(69.69mmol)을 톨루엔 150mL하에서 120℃로 6시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 Toluene 과량으로 끓인 뒤 필터하여 목적화합물 1-482 10.8g(71%)을 얻었다. F-4 8.0g (23.23mmol), 4- (4- bromophenyl) -2,6-diphenyl-pyridine (4- (4-bromophenyl) -2,6 -diphenylpyrimidine) 9.9g (25.55mmol), Pd 2 (dba) 3 2.1g (2.323mmol ), P (t-Bu) 3 0.22g (2.323mmol), sodium tert-butoxide under reflux for 6 hours and 14.1g (69.69mmol) in 150mL toluene and the mixture was stirred under 120 ℃ . After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). The solid was then boiled with an excess of toluene and then filtered to obtain 10.8 g (71%) of the desired compound 1-482 .
[제조예 28] 화합물 1-483의 제조[Production Example 28] Synthesis of Compound 1-483
Figure PCTKR2015006723-appb-I000175
Figure PCTKR2015006723-appb-I000175
F-4 8.0g(23.23mmol), 4-브로모-2-페닐퀴나졸린(4-bromo-2-phenylquinazoline) 7.28g(25.55mmol), Pd2(dba)3 2.1g(2.323mmol), P(t-Bu)3 0.22g(2.323mmol), 소듐 터트-부톡사이드 14.1g(69.69mmol)을 톨루엔 150mL하에서 120℃로 3시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 톨루엔을 과량으로 끓인 뒤 필터하여 목적화합물 1-483 9.1g(71%)을 얻었다. F-4 8.0g (23.23mmol), 4- bromo-2-phenyl-quinazoline (4-bromo-2-phenylquinazoline ) 7.28g (25.55mmol), Pd 2 (dba) 3 2.1g (2.323mmol), P 0.22 g (2.323 mmol) of (t-Bu) 3 and 14.1 g (69.69 mmol) of sodium tert-butoxide were stirred under reflux in 150 mL of toluene at 120 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). The solid was then boiled with an excess amount of toluene and then filtered to obtain 9.1 g (71%) of the desired compound 1-483 .
[제조예 29] 화합물 2-127의 제조[Preparation Example 29] Preparation of Compound 2-127
Figure PCTKR2015006723-appb-I000176
Figure PCTKR2015006723-appb-I000176
I-2 10.0g(20.02mmol), 9,9'-(5-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-일)-1,3-페닐렌)비스(9H-카바졸)(9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole)) 12.9g(24.03mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 2.3g(2.0mmol), K3PO4 12.75g(60.06mmol)을 1,4-디옥산(1,4-dioxane) 200mL, H2O 40mL하에서 120℃로 8시간동안 환류교반하였다. 반응종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 2-127 13.8g(83%)로 얻었다.10.0 g (20.02 mmol) of I-2 , 9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaboran- Bis (9H-carbazole) (9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- 2.3 g (2.0 mmol) of tetrakis (triphenylphosphine) palladium (0) and 12.75 g (60.06 mmol) of K 3 PO 4 were dissolved in 1,4-dioxane (1 , 4-dioxane) and 40 mL of H 2 O at 120 ° C for 8 hours. After completion of the reaction distilled water and dichloromethane (dichloromethane) to give the organic layer was back extracted with anhydrous MgSO 4 and then dried to remove the solvent by rotary evaporation column with dichloromethane and hexane as a developing solvent chromatography the desired compound 13.8 2-127 g (83%).
[제조예 30] 화합물 2-148의 제조[Manufacturing Example 30] Preparation of Compound 2-148
Figure PCTKR2015006723-appb-I000177
Figure PCTKR2015006723-appb-I000177
I-2 10.0g(20.02mmol), (9-페닐-9H-카바졸-3-일)보로닉 에시드((9-phenyl-9H-carbazol-3-yl)boronic acid) 6.9g(24.03mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 2.3g(2.0mmol), K3PO4 12.75g(60.06mmol)을 1,4-디옥산(1,4-dioxane) 200mL, H2O 40mL하에서 120℃로 8시간동안 환류교반하였다. 반응종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 2-148 8.9g(67%)로 얻었다. I-2 10.0g (20.02mmol), (9- phenyl -9H- carbazol-3-yl) Boro Nick Acid ((9-phenyl-9H- carbazol-3-yl) boronic acid) 6.9g (24.03mmol) 2.3 g (2.0 mmol) of tetrakis (triphenylphosphine) palladium (0) and 12.75 g (60.06 mmol) of K 3 PO 4 were dissolved in 200 mL of 1,4-dioxane, 40 mL of H 2 O At 120 &lt; 0 &gt; C for 8 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain the target compound 2-148 8.9 g (67%).
[제조예 31] 화합물 3-12의 제조[Manufacturing Example 31] Preparation of Compound 3-12
Figure PCTKR2015006723-appb-I000178
Figure PCTKR2015006723-appb-I000178
L-3' 5.0g(10.01mmol), 9,9'-(5-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-일)-1,3-페닐렌)비스(9H-카바졸)(9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole)) 6.42g(12.01mmol), 테트라키스(트리페닐포스핀)팔라듐(0)0.58g(0.5mmol), K3PO4 6.37g(30.0mmol)을 1,4-디옥산(1,4-dioxane) 100mL, H2O 20mL하에서 120℃로 8시간동안 환류교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한 뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 3-12 5.6g(68%)로 얻었다. L-3 ' 5.0 g (10.01 mmol), 9,9' - (5- (4,4,5,5-tetramethyl-1,3,2-dioxaboran- Bis (9H-carbazole) (9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- (0.5 mmol) of tetrakis (triphenylphosphine) palladium (0) and 6.37 g (30.0 mmol) of K 3 PO 4 were dissolved in 1,4-dioxane (10 ml) 1,4-dioxane) and 20 mL of H 2 O was refluxed and stirred at 120 ° C for 8 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and the residue was purified by column chromatography using dichloromethane and hexane as eluent. g (68%).
[제조예 32] 화합물 4-109의 제조[Manufacturing Example 32] Production of Compound 4-109
Figure PCTKR2015006723-appb-I000179
Figure PCTKR2015006723-appb-I000179
화합물 S-1의 제조Preparation of compound S-1
M-1 36g(107.6mmol), 트리에틸아민(Triethylamine) 15.1mL(107.6mmol)을 디클로로메탄(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 3-브로모벤조일클로라이드(3-bromobenzoylchloride) 23.6g(107.6mmol)를 천천히 적가하여 1시간동안 온도를 유지하면서 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 S-1 42.2g(76%)을 얻었다.36 g (107.6 mmol) of M-1 and 15.1 mL (107.6 mmol) of triethylamine were dissolved in dichloromethane and maintained at 0 ° C. Thereafter, 23.6 g (107.6 mmol) of 3-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred for 1 hour while maintaining the temperature. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 42.2 g (76%) of the desired compound S-1 .
화합물 S-2의 제조Preparation of compound S-2
S-1 30g(57.97mmol)을 니트로벤젠(Nitrobenzene) 600mL에 전부 녹인 뒤 POCl3 6.54mL(57.97mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 2시간동안 교반하였다. 반응 종료 후 증류수와 디클로로메탄(dichloromethane)로 추출한뒤 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 S-2 22.2g(77%)로 얻었다.30 g (57.97 mmol) of S-1 was completely dissolved in 600 mL of Nitrobenzene, and 6.54 mL (57.97 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The residue was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain the target compound S-2 22.2 g (77%).
화합물 S-3의 제조Preparation of compound S-3
S-2 20g(40.05mmol), 비스(피나콜라토)디보론 20.3g(80.09mmol), 포타슘아세테이트(KOAc) 11.8g(120.15mmol), [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II)1.5g(2.0mmol)을 1,4-디옥산(1,4-dioxane) 100mL하에서 120℃로 6시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 디클로로메탄(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 실리카겔로 필터한 뒤 헥산, 메탄올(MeOH)로 씻어주어 목적화합물 S-3 18.8g(86%)을 얻었다.20.0 g (40.05 mmol) of S-2 , 20.3 g (80.09 mmol) of bis (pinacolato) diboron, 11.8 g (120.15 mmol) of potassium acetate (KOAc), 1,1'-bis (diphenylphosphino) ] 1.5 g (2.0 mmol) of dichloropalladium (II) were stirred in 100 ml of 1,4-dioxane at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was then filtered off with silica gel and washed with hexane and methanol (MeOH) to obtain 18.8 g (86%) of the target compound S-3 .
화합물 4-109의 제조Preparation of compound 4-109
S-3 6.0g(10.98mmol), 2-브로모-9,9-디페닐-9H-플루오렌(2-bromo-9,9-diphenyl-9H-fluorene) 5.2g(13.18mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.3g(1.1mmol), K3PO4 6.99g(32.94mmol)을 1,4-디옥산(1,4-dioxane) 60mL,H2O 12mL하에서 120℃로 2시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 디클로로메탄(dichloromethane) 과량으로 전부 녹인 뒤 실리카겔로 필터하여 목적화합물 4-109 7.1g(88%)을 얻었다. S-3 6.0g (10.98mmol), 2- bromo-9,9-diphenyl--9H- fluorene (2-bromo-9,9-diphenyl -9H-fluorene) 5.2g (13.18mmol), tetrakis 1.3 g (1.1 mmol) of (triphenylphosphine) palladium (0) and 6.99 g (32.94 mmol) of K 3 PO 4 were dissolved in 60 mL of 1,4-dioxane and 12 mL of H 2 O at 120 ° C. Lt; / RTI &gt; for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount, and then filtered with silica gel to obtain 7.1 g (88%) of the target compound 4-109 .
[제조예 33] 화합물 4-113의 제조[Manufacturing Example 33] Preparation of compound 4-113
Figure PCTKR2015006723-appb-I000180
Figure PCTKR2015006723-appb-I000180
S-3 6.0g(10.98mmol), 4-브로모디벤조[b,d]티오펜(4-bromodibenzo[b,d]thiophene) 3.5g(13.18mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.3g(1.1mmol), K3PO4 6.99g(32.94mmol)을 1,4-디옥산(1,4-dioxane) 60mL,H2O 12mL하에서 120℃로 2시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 디클로로메탄(dichloromethane) 과량으로 전부 녹인 뒤 실리카겔로 필터하여 목적화합물 4-113 4.3g(65%)을 얻었다. A mixture of 6.0 g (10.98 mmol) of S-3 , 3.5 g (13.18 mmol) of 4-bromodibenzo [b, d] thiophene, tetrakis (triphenylphosphine) palladium 0) and 6.99 g (32.94 mmol) of K 3 PO 4 were refluxed and stirred at 120 ° C in 60 mL of 1,4-dioxane and 12 mL of H 2 O for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount, and then the mixture was filtered through silica gel to obtain 4.3 g (65%) of the target compound 4-113 .
[제조예 34] 화합물 4-119의 제조[Manufacturing Example 34] Preparation of Compound 4-119
Figure PCTKR2015006723-appb-I000181
Figure PCTKR2015006723-appb-I000181
S-3 6.0g(10.98mmol), 2-브로모트리페닐렌(2-bromotriphenylene) 4.05g(13.18mmol), 테트라키스(트리페닐포스핀)팔라듐(0) 1.3g(1.1mmol), K3PO4 6.99g(32.94mmol)을 1,4-디옥산(1,4-dioxane) 60mL,H2O 12mL하에서 120℃로 2시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 에틸아세테이트(EA), 메탄올(MeOH)로 씻어주었다. 그 후 고체를 디클로로메탄(dichloromethane) 과량으로 전부 녹인 뒤 실리카겔로 필터하여 목적화합물 4-119 4.8g(68%)을 얻었다. S-3 6.0g (10.98mmol), 2- bromo-triphenylene (2-bromotriphenylene) 4.05g (13.18mmol ), tetrakis (triphenylphosphine) palladium (0) 1.3g (1.1mmol), K 3 6.99 g (32.94 mmol) of PO 4 was refluxed with stirring in 120 mL of 120 mL of H 2 O and 60 mL of 1,4-dioxane. After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed. The solid was filtered and washed with ethyl acetate (EA) and methanol (MeOH). Thereafter, the solid was completely dissolved in dichloromethane in an excess amount, and then the mixture was filtered through silica gel to obtain 4.8 g (68%) of the target compound 4-119 .
[제조예 35] 화합물 5-15의 제조[Production Example 35] Preparation of compound 5-15
Figure PCTKR2015006723-appb-I000182
Figure PCTKR2015006723-appb-I000182
A-5 10.0g(20.02mmol), N,9-diphenyl-9H-carbazol-3-amine 6.03g(18.02mmol), Pd2(dba)3 1.83g(2.0mmol), XPhos 1.9g(4.0mmol), NaOtBu 8.1g(40.04mmol)을 Toluene 100mL하에서 120℃로 2시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 oil을 Column정제하여 목적화합물 5-15 9.65g(64%)을 얻었다.(2.0 mmol) of Pd 2 (dba) 3 , 1.9 g (4.0 mmol) of XPhos, 6.03 g (18.02 mmol) of N, 9-diphenyl-9H-carbazol- And 8.1 g (40.04 mmol) of NaOtBu were stirred at 120 占 폚 in 100 ml of toluene for 2 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting oil was purified by column to obtain 9.65 g (64%) of the target compound 5-15.
[제조예 36] 화합물 5-20의 제조[Production Example 36] Synthesis of Compound 5-20
Figure PCTKR2015006723-appb-I000183
Figure PCTKR2015006723-appb-I000183
A-5 10.0g(20.02mmol), N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine 6.51g(18.02mmol), Pd2(dba)3 1.83g(2.0mmol), XPhos 1.9g(4.0mmol), NaOtBu 8.1g(40.04mmol)을 Toluene 100mL하에서 120℃로 2시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 oil을 Column정제하여 목적화합물 5-20 8.53g(55%)을 얻었다.A-5 10.0g (20.02mmol), N - ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine 6.51g (18.02mmol), Pd 2 ( a dba) 3 1.83g (2.0mmol), XPhos 1.9g (4.0mmol), NaOtBu 8.1g (40.04mmol) in 120 ℃ under Toluene 100mL stirred for 2 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting oil was purified by column purification to obtain 8.53 g (55%) of the target compound 5-20.
[제조예 37] 화합물 5-33의 제조[Manufacturing Example 37] Production of Compound 5-33
Figure PCTKR2015006723-appb-I000184
Figure PCTKR2015006723-appb-I000184
A-5 10.0g(20.02mmol), bis(9-phenyl-9H-carbazol-3-yl)amine 9.0g(18.02mmol), Pd2(dba)3 1.83g(2.0mmol), XPhos 1.9g(4.0mmol), NaOtBu 8.1g(40.04mmol)을 Toluene 100mL하에서 120℃로 6시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 고체을 Column정제하여 목적화합물 5-33 14.1g(77%)을 얻었다.9.0 g (18.02 mmol) of the amine bis (9-phenyl-9H-carbazol-3-yl) amine and 1.83 g (2.0 mmol) of Pd 2 (dba) 3 , XPhos 1.9 g (4.0 mmol) mmol) and NaOtBu (8.1 g, 40.04 mmol) were stirred in 100 mL of toluene at 120 DEG C for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was purified by column to obtain 14.1 g (77%) of the desired compound 5-33.
[제조예 38] 화합물 5-55의 제조[Manufacturing Example 38] Production of Compound 5-55
Figure PCTKR2015006723-appb-I000185
Figure PCTKR2015006723-appb-I000185
A-5 10.0g(20.02mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole 7.36g(18.02mmol), Pd2(dba)3 1.83g(2.0mmol), XPhos 1.9g(4.0mmol), NaOtBu 8.1g(40.04mmol)을 Toluene 100mL하에서 120℃로 3시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 고체을 Column정제하여 목적화합물 5-55 8.11g(49%)을 얻었다.A-5 A mixture of 10.0 g (20.02 mmol), 9-phenyl-9H, 9'H-3,3'-bicarbazole 7.36 g (18.02 mmol), Pd 2 (dba) 3 1.83 g (2.0 mmol), XPhos 1.9 g And NaOtBu (8.1 g, 40.04 mmol) were stirred in toluene (100 mL) at 120 占 폚 for 3 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was purified by column to obtain 8.11 g (49%) of the desired compound 5-55.
[제조예 39] 화합물 5-82의 제조[Production Example 39] Preparation of compound 5-82
Figure PCTKR2015006723-appb-I000186
Figure PCTKR2015006723-appb-I000186
A-5 10.0g(20.02mmol), N-([1,1'-biphenyl]-3-yl)-9,9-diphenyl-9H-fluoren-2-amine 8.75g(18.02mmol), Pd2(dba)3 1.83g(2.0mmol), XPhos 1.9g(4.0mmol), NaOtBu 8.1g(40.04mmol)을 Toluene 100mL하에서 120℃로 7시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 고체을 Column정제하여 목적화합물 5-82 7.60g(42%)을 얻었다.A-5 10.0g (20.02mmol), N - ([1,1'-biphenyl] -3-yl) -9,9-diphenyl-9H-fluoren-2-amine 8.75g (18.02mmol), Pd 2 ( a dba) 3 1.83g (2.0mmol), XPhos 1.9g (4.0mmol), NaOtBu 8.1g (40.04mmol) in 120 ℃ under Toluene 100mL the mixture was stirred for 7 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was subjected to column purification to obtain 7.60 g (42%) of the target compound 5-82.
[제조예 39] 화합물 6-14의 제조[Manufacturing Example 39] Preparation of Compound 6-14
Figure PCTKR2015006723-appb-I000187
Figure PCTKR2015006723-appb-I000187
T-1의 합성Synthesis of T-1
SM 30.0g(141.5mmol), 2-bromoaniline 29.2g(169.8mmol), Pd(PPh3)4 8.2g(7.07mmol), K3PO4 90.1g(424.5mmol)을 1,4-dioxane 300mL, H2O 60mL하에서 120℃로 3시간동안 환류 교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 실리카겔로 필터한 뒤 Hexane으로 씻어주어 목적화합물 T-1 29.0g(79%)을 얻었다.Pd (PPh3) 4, 8.2 g (7.07 mmol) of K3PO4, and 300 ml of 1,4-dioxane in 60 ml of H2O at 120 DEG C At reflux for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4, and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 29.0 g (79%) of the target compound T-1.
T-2의 합성Synthesis of T-2
T-1 29g(111.84mmol), Triethylamine 15.7mL(111.84mmol)을 MC(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 4-bromobenzoylchloride 26.9g(123.02mmol)를 천천히 적가하여 1시간동안 온도를 유지하면 교반하였다. 반응 종료 후 Hexane을 과량 첨가하여 생성된 고체를 필터하였다. 목적화합물 T-2 39.6g(80%)을 얻었다.29 g (111.84 mmol) of T-1 and 15.7 mL (111.84 mmol) of triethylamine were dissolved in MC (dichloromethane) and maintained at 0 ° C. 26.9 g (123.02 mmol) of 4-bromobenzoylchloride was slowly added dropwise thereto, and the mixture was stirred for 1 hour. After completion of the reaction, excess hexane was added to filter the resulting solid. 39.6 g (80%) of the desired compound T-2 was obtained.
T-3의 합성Synthesis of T-3
T-2 39.6g(89.53mmol)을 Nitrobenzene 300mL에 전부 녹인 뒤 POCl3 10.0mL(89.53mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 16시간동안 교반하였다. 반응 종료 후 실온으로 식힌 뒤 Hexane을 과량 첨가하였다. 목적화합물 1-3 22.6g(59%)로 얻었다.After dissolving 39.6 g (89.53 mmol) of T-2 in 300 mL of Nitrobenzene, 10.0 mL (89.53 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 16 hours while maintaining the temperature at 150 캜. After completion of the reaction, the mixture was cooled to room temperature, and then excess hexane was added. 22.6 g (59%) of the desired compound 1-3 was obtained.
Figure PCTKR2015006723-appb-I000188
Figure PCTKR2015006723-appb-I000188
6-14의 합성Synthesis of 6-14
T-3 10.0g(23.57mmol), N-phenyldibenzo[b,d]furan-3-amine 5.5g(21.21mmol), Pd2(dba)3 2.11g(2.3mmol), XPhos 2.19g(4.6mmol), NaOtBu 9.54g(47.14mmol)을 Toluene 100mL하에서 120℃로 3시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 고체을 Column정제하여 목적화합물 6-14 9.38g(66%)을 얻었다.(21.21 mmol) of N-phenyldibenzo [b, d] furan-3-amine, 2.11 g (2.3 mmol) of Pd 2 (dba) 3 , 2.19 g (4.6 mmol) of XPhos, And 9.54 g (47.14 mmol) of NaOtBu were stirred at 100 占 폚 in 100 ml of toluene for 3 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was purified by column to obtain 9.38 g (66%) of the desired compound 6-14.
[제조예 40] 화합물 6-37의 제조[Production Example 40] Preparation of compound 6-37
Figure PCTKR2015006723-appb-I000189
Figure PCTKR2015006723-appb-I000189
T-3 10.0g(23.57mmol), N-phenyldibenzo[b,d]furan-3-amine 9.34g(21.21mmol), Pd2(dba)3 2.11g(2.3mmol), XPhos 2.19g(4.6mmol), NaOtBu 9.54g(47.14mmol)을 Toluene 100mL하에서 120℃로 5시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 고체을 Column정제하여 목적화합물 6-37 13.7g(74%)을 얻었다.(2.1 mmol) of Pd 2 (dba) 3 , 2.19 g (4.6 mmol) of XPhos, 10.3 g (23.57 mmol) of N-phenyldibenzo [b, d] furan- And 9.54 g (47.14 mmol) of NaOtBu were stirred in 100 mL of toluene at 120 DEG C for 5 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was purified by column to obtain 13.7 g (74%) of the desired compound 6-37.
[제조예 41] 화합물 6-55의 제조[Manufacturing Example 41] Preparation of Compound 6-55
Figure PCTKR2015006723-appb-I000190
Figure PCTKR2015006723-appb-I000190
T-3 10.0g(23.57mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole 8.66g(21.21mmol), Pd2(dba)3 2.11g(2.3mmol), XPhos 2.19g(4.6mmol), NaOtBu 9.54g(47.14mmol)을 Toluene 100mL하에서 120℃로 2시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 고체을 Column정제하여 목적화합물 6-55 6.91g(39%)을 얻었다.(2.3 mmol) of Pd 2 (dba) 3 , 2.19 g (2.3 mmol) of 9-phenyl-9H, 9'H-3,3'- bicarbazole and 10.0 g (23.57 mmol) of T- 9.54 g (47.14 mmol) of NaOtBu were stirred at 120 占 폚 in 100 ml of toluene for 2 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was purified by column to obtain 6.91 g (39%) of the desired compound 6-55.
[제조예 41] 화합물 6-65의 제조[Manufacturing Example 41] Preparation of Compound 6-65
Figure PCTKR2015006723-appb-I000191
Figure PCTKR2015006723-appb-I000191
T-3 10.0g(23.57mmol), 9,9-dimethyl-N-(naphthalen-2-yl)-9H-fluoren-2-amine 7.11g(21.21mmol), Pd2(dba)3 2.11g(2.3mmol), XPhos 2.19g(4.6mmol), NaOtBu 9.54g(47.14mmol)을 Toluene 100mL하에서 120℃로 5시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 고체을 Column정제하여 목적화합물 6-65 8.8g(55%)을 얻었다.(21.21 mmol), Pd 2 (dba) 3, 2.11 g (2.3 mmol) of 9,9-dimethyl-N- (naphthalen- mmol), 2.19 g (4.6 mmol) of XPhos and 9.54 g (47.14 mmol) of NaOtBu were stirred in 100 mL of toluene at 120 DEG C for 5 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was purified by column to obtain 8.8 g (55%) of the desired compound 6-65.
[제조예 42] 화합물 6-85의 제조[Production Example 42] Preparation of compound 6-85
Figure PCTKR2015006723-appb-I000192
Figure PCTKR2015006723-appb-I000192
T-3 10.0g(23.57mmol), (4-(9H-carbazol-9-yl)phenyl)boronic acid 6.09g(21.21mmol), Pd(PPh3)4 2.72g(2.3mmol), K3PO4 15.0g(70.71mmol)을 1,4-Dioxane 100mL와 H2O 20mL 하에서 120℃로 2시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 고체을 Column정제하여 목적화합물 6-85 10.6g(77%)을 얻었다.T-3 10.0g (23.57mmol), (4- (9H-carbazol-9-yl) phenyl) boronic acid 6.09g (21.21mmol), Pd (PPh 3) 4 2.72g (2.3mmol), K3PO4 15.0g ( 70.71 mmol) were stirred in 100 mL of 1,4-dioxane and 20 mL of H2O at 120 占 폚 for 2 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was purified by column to obtain 10.6 g (77%) of the desired compound 6-85.
[제조예 43] 화합물 7-24의 제조[Preparation Example 43] Preparation of Compound 7-24
Figure PCTKR2015006723-appb-I000193
Figure PCTKR2015006723-appb-I000193
U-1의 합성Synthesis of U-1
SM 50.0g(219.2mmol), 2-bromoaniline 56.5g(328.8mmol), Pd(PPh3)4 25.0g(10.96mmol), K3PO4 140.0g(657.6mmol)을 1,4-dioxane 500mL, H2O 100mL하에서 120℃로 3시간동안 환류 교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 실리카겔로 필터한 뒤 Hexane으로 씻어주어 목적화합물 U-1 54.0g(89%)을 얻었다.SM 50.0g (219.2mmol), 2- bromoaniline 56.5g (328.8mmol), Pd (PPh 3) 4 25.0g (10.96mmol), K 3 PO 4 140.0g (657.6mmol) of 1,4-dioxane 500mL, H And the mixture was refluxed and stirred at 120 占 폚 under 100 mL of 2 O for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration through silica gel and washed with hexane to obtain 54.0 g (89%) of the target compound U-1.
U-2의 합성Synthesis of U-2
U-1 54.0g(196.1mmol), Triethylamine 27.5mL(196.1mmol)을 MC(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 4-bromobenzoylchloride 43.0g(196.1mmol)를 천천히 적가하여 1시간동안 온도를 유지하면 교반하였다. 반응 종료 후 Hexane을 과량 첨가하여 생성된 고체를 필터하였다. 목적화합물 U-2 85.0g(95%)을 얻었다.54.0 g (196.1 mmol) of U-1 and 27.5 mL (196.1 mmol) of triethylamine were dissolved in MC (dichloromethane) and maintained at 0 ° C. Then, 43.0 g (196.1 mmol) of 4-bromobenzoylchloride was slowly added dropwise, and the mixture was stirred for 1 hour. After completion of the reaction, excess hexane was added to filter the resulting solid. 85.0 g (95%) of the desired compound U-2 was obtained.
U-3의 합성Synthesis of U-3
U-2 85.0g(185.44mmol)을 Nitrobenzene 600mL에 전부 녹인 뒤 POCl3 21.0mL(185.44mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 3시간동안 교반하였다. 반응 종료 후 실온으로 식힌 뒤 EA를 과량 첨가하였다. 목적화합물 U-3 55.0g(67%)로 얻었다.85.0 g (185.44 mmol) of U-2 was dissolved in 600 mL of Nitrobenzene and 21.0 mL (185.44 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 3 hours while maintaining the temperature at 150 캜. After completion of the reaction, the reaction mixture was cooled to room temperature, and then excess EA was added. To obtain 55.0 g (67%) of the desired compound U-3.
Figure PCTKR2015006723-appb-I000194
Figure PCTKR2015006723-appb-I000194
7-24의 합성Synthesis of 7-24
U-3 10.0g(22.57mmol), N-([1,1'-biphenyl]-4-yl)-9-phenyl-9H-carbazol-3-amine 8.71g(20.3mmol), Pd2(dba)3 2.01g(2.2mmol), XPhos 2.19g(4.6mmol), NaOtBu 9.13g(45.14mmol)을 Toluene 100mL하에서 120℃로 1시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 고체을 Column정제하여 목적화합물 7-24 15.6g(86%)을 얻었다.9-phenyl-9H-carbazol-3-amine 8.71 g (20.3 mmol), Pd 2 (dba), 10.0 g (22.57 mmol) of N- 3 2.01g (2.2mmol), XPhos 2.19g (4.6mmol), and the mixture was stirred for 1 hour NaOtBu 9.13g (45.14mmol) in 120 ℃ under Toluene 100mL. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was purified by column to obtain 15.6 g (86%) of the target compound 7-24.
[제조예 44] 화합물 7-48의 제조[Manufacturing Example 44] Preparation of Compound 7-48
Figure PCTKR2015006723-appb-I000195
Figure PCTKR2015006723-appb-I000195
U-3 10.0g(22.57mmol), N-([1,1'-biphenyl]-4-yl)-9-phenyl-9H-carbazol-3-amine 8.71g(20.3mmol), Pd(PPh3)4 2.72g(2.3mmol), K3PO4 14.4g(67.71mmol)을 1,4-Dioxane 100mL와 H2O 20mL 하에서 120℃로 2시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 고체을 Column정제하여 목적화합물 7-48 6.67g(39%)을 얻었다.9.7 g (20.3 mmol) of Pd (PPh 3 ), 10.0 g (22.57 mmol) of U- 3 , 4 and 14.4 g (67.71 mmol) of K 3 PO 4 were stirred in 100 mL of 1,4-dioxane and 20 mL of H 2 O at 120 ° C for 2 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was purified by column to obtain 6.67 g (39%) of the desired compound 7-48.
[제조예 45] 화합물 7-75의 제조[Manufacturing Example 45] Preparation of Compound 7-75
Figure PCTKR2015006723-appb-I000196
Figure PCTKR2015006723-appb-I000196
U-3 10.0g(22.57mmol), 9,9-diphenyl-N-(4-(9-phenyl-9H-carbazol-2-yl)phenyl)-9H-fluoren-3-amine 13.8g(21.21mmol), Pd2(dba)3 2.01g(2.3mmol), XPhos 2.19g(4.6mmol), NaOtBu 9.13g(45.14mmol)을 Toluene 100mL하에서 120℃로 8시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 고체을 Column정제하여 목적화합물 7-75 11.2g(47%)을 얻었다.U-3 13.8 g (21.21 mmol) of 9,0-diphenyl-N- (4- (9-phenyl-9H-carbazol-2- 2.09 g (2.3 mmol) of Pd 2 (dba) 3 , 2.19 g (4.6 mmol) of XPhos and 9.13 g (45.14 mmol) of NaOtBu were stirred at 120 ° C in 100 mL of toluene for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was purified by column to obtain 11.2 g (47%) of the desired compound 7-75.
[제조예 46] 화합물 7-88의 제조[Production Example 46] Synthesis of Compound 7-88
Figure PCTKR2015006723-appb-I000197
Figure PCTKR2015006723-appb-I000197
U-3 10.0g(22.57mmol), 9,9-diphenyl-N-(4-(9-phenyl-9H-carbazol-2-yl)phenyl)-9H-fluoren-3-amine 13.8g(20.3mmol), Pd(PPh3)4 2.72g(2.3mmol), K3PO4 14.4g(67.71mmol)을 1,4-Dioxane 100mL와 H2O 20mL 하에서 120℃로 2시간동안 교반하였다. 반응 완료 후 실온으로 식힌 뒤 MC로 추출하여 전부 날려주었다. 생성된 고체을 Column정제하여 목적화합물 7-88 12.0g(88%)을 얻었다.(20.3 mmol) of 9,9-diphenyl-N- (4- (9-phenyl-9H-carbazol-2-yl) phenyl) -9H- 2.72 g (2.3 mmol) of Pd (PPh 3 ) 4 and 14.4 g (67.71 mmol) of K 3 PO 4 were stirred at 120 ° C. in 100 mL of 1,4-dioxane and 20 mL of H 2 O for 2 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted with MC to completely blow it. The resulting solid was purified by column to obtain 12.0 g (88%) of the desired compound 7-88.
[제조예 47] 화합물 1-3의 제조[Manufacturing Example 47] Preparation of Compound 1-3
화합물 1-1의 제조방법 중 2-클로로-4,6-디페닐-1,3,5-트리아진(2-chloro-4,6-diphenyl-1,3,5-triazine) 대신 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:54%)(2-chloro-4,6-diphenyl-1,3,5-triazine) instead of 2-chloro-4,6-diphenyl- [1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine. (Yield: 54%).
[제조예 48] 화합물 1-4의 제조[Manufacturing Example 48] Preparation of Compound 1-4
화합물 1-1의 제조방법 중 2-클로로-4,6-디페닐-1,3,5-트리아진(2-chloro-4,6-diphenyl-1,3,5-triazine) 대신 4-bromo-2,6-diphenylpyrimidine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:50%)(2-chloro-4,6-diphenyl-1,3,5-triazine) instead of 2-chloro-4,6-diphenyl- -2,6-diphenylpyrimidine was used as the starting material. (Yield: 50%).
[제조예 49] 화합물 1-8의 제조[Manufacturing Example 49] Preparation of Compound 1-8
화합물 1-1의 제조방법 중 2-클로로-4,6-디페닐-1,3,5-트리아진(2-chloro-4,6-diphenyl-1,3,5-triazine) 대신 1-(4-bromophenyl)-2-phenyl-1H-benzo[d]imidazole을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:71%)(2-chloro-4,6-diphenyl-1,3,5-triazine) instead of 2-chloro-4,6-diphenyl- 4-bromophenyl) -2-phenyl-1H-benzo [d] imidazole. (Yield: 71%).
[제조예 50] 화합물 1-10의 제조[Manufacturing Example 50] Preparation of Compound 1-10
화합물 1-65의 제조방법 중 6-(4-bromophenyl)benzo[4,5]thieno[2,3-k]phenanthridine 대신 6-(4-bromophenyl)-9-phenyl-9H-indolo[2,3-k]phenanthridine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:38%)6- (4-bromophenyl) -9-phenyl-9H-indolo [2,3-b] pyridine instead of 6- (4-bromophenyl) benzo [4,5] thieno [ -k] phenanthridine was used as the starting material. (Yield: 38%).
[제조예 51] 화합물 1-100의 제조[Manufacturing Example 51] Preparation of Compound 1-100
화합물 1-65의 제조방법 중 6-(3-bromophenyl)benzo[4,5]thieno[2,3-k]phenanthridine 대신 6-(4-bromophenyl)-9-phenyl-9H-indolo[2,3-k]phenanthridine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:44%)6- (4-bromophenyl) -9-phenyl-9H-indolo [2,3-b] pyridine instead of 6- (3-bromophenyl) benzo [4,5] thieno [ -k] phenanthridine was used as the starting material. (Yield: 44%)
[제조예 52] 화합물 1-102의 제조[Production Example 52] Synthesis of Compound 1-102
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 (3,5-di(9H-carbazol-9-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:88%)Except that (3,5-di (9H-carbazol-9-yl) phenyl) boronic acid was used instead of dibenzo [b, d] thiophen-4-ylboronic acid in the preparation of Compound 1-113 Respectively. (Yield: 88%).
[제조예 53] 화합물 1-109의 제조[Manufacturing Example 53] Preparation of Compound 1-109
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 (9,9-diphenyl-9H-fluoren-2-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:49%)Except that 9,9-diphenyl-9H-fluoren-2-yl) boronic acid was used instead of dibenzo [b, d] thiophen-4-ylboronic acid in the preparation of Compound 1-113. (Yield: 49%).
[제조예 54] 화합물 1-123의 제조[Production Example 54] Synthesis of Compound 1-123
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 (9-phenyl-9H-carbazol-3-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:58%)(9-phenyl-9H-carbazol-3-yl) boronic acid was used instead of dibenzo [b, d] thiophen-4-ylboronic acid in the preparation of Compound 1-113. (Yield: 58%).
[제조예 55] 화합물 1-175의 제조[Production Example 55] Synthesis of Compound 1-175
화합물 1-65의 제조방법 중 6-(4-bromophenyl)benzo[4,5]thieno[2,3-k]phenanthridine 대신 6-(3-bromophenyl)benzofuro[2,3-k]phenanthridine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:51%)(3-bromophenyl) benzofuro [2,3-k] phenanthridine was used in place of 6- (4-bromophenyl) benzo [4,5] thieno [2,3-k] phenanthridine Were prepared in the same manner. (Yield: 51%).
[제조예 56] 화합물 1-251의 제조[Manufacturing Example 56] Preparation of Compound 1-251
화합물 1-1의 제조방법 중 2-클로로-4,6-디페닐-1,3,5-트리아진(2-chloro-4,6-diphenyl-1,3,5-triazine) 대신 2-bromo-9,10-di(naphthalen-2-yl)anthracene을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:81%)(2-chloro-4,6-diphenyl-1,3,5-triazine) instead of 2-chloro-4,6-diphenyl- -9,10-di (naphthalen-2-yl) anthracene. (Yield: 81%).
[제조예 57] 화합물 1-366의 제조[Production Example 57] Synthesis of Compound 1-366
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 (9,10-di(naphthalen-2-yl)anthracen-2-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:71%)Except that 9,10-di (naphthalen-2-yl) anthracen-2-yl) boronic acid was used instead of dibenzo [b, d] thiophen-4-ylboronic acid in the preparation method of Compound 1-113. . (Yield: 71%).
[제조예 58] 화합물 1-369의 제조[Production Example 58] Synthesis of Compound 1-369
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 (10-phenylanthracen-9-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:51%)(10-phenylanthracen-9-yl) boronic acid was used instead of dibenzo [b, d] thiophen-4-ylboronic acid in the preparation of Compound 1-113. (Yield: 51%).
[제조예 59] 화합물 1-391의 제조[Production Example 59] Synthesis of Compound 1-391
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 (4-(4,6-diphenylpyrimidin-2-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:71%)Except that 4- (4,6-diphenylpyrimidin-2-yl) phenyl) boronic acid was used instead of dibenzo [b, d] thiophen-4-ylboronic acid in the preparation of Compound 1-113 . (Yield: 71%).
[제조예 60] 화합물 1-401의 제조[Production Example 60] Synthesis of Compound 1-401
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 (3,5-di(phenanthren-9-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:71%)(3,5-di (phenanthren-9-yl) phenyl) boronic acid was used instead of dibenzo [b, d] thiophen-4-ylboronic acid in the preparation method of Compound 1-113. (Yield: 71%).
[제조예 61] 화합물 1-416의 제조[Manufacturing Example 61] Production of Compound 1-416
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 (4-(6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:47%)(4- (6 - ([1,1'-biphenyl] -4-yl) -2-phenylpyrimidin-4-yl) dibenzo [b, d] thiophen- phenyl) boronic acid was used as the starting material. (Yield: 47%).
[제조예 62] 화합물 1-451의 제조[Preparation Example 62] Preparation of Compound 1-451
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 (4-(1,10-phenanthrolin-2-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:63%)Except that (4- (1,10-phenanthrolin-2-yl) phenyl) boronic acid was used instead of dibenzo [b, d] thiophen-4-ylboronic acid in the preparation of Compound 1-113 . (Yield: 63%).
[제조예 63] 화합물 1-452의 제조[Production Example 63] Synthesis of Compound 1-452
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 (4-(imidazo[1,2-a]pyridin-2-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:50%)Except that (4- (imidazo [l, 2-a] pyridin-2-yl) phenyl) boronic acid was used instead of dibenzo [b, d] thiophen-4-ylboronic acid in the preparation of Compound 1-113 &Lt; / RTI &gt; (Yield: 50%).
[제조예 64] 화합물 1-459의 제조[Production Example 64] Synthesis of Compound 1-459
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 (4-(2-phenyl-1H-benzo[d]imidazol-1-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:54%)Except that (4- (2-phenyl-1H-benzo [d] imidazol-1-yl) phenyl) boronic acid was used in place of dibenzo [b, d] thiophen- Were prepared in the same manner. (Yield: 54%).
[제조예 65] 화합물 1-460의 제조[Production Example 65] Preparation of compound 1-460
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 (4-(2-ethyl-1H-benzo[d]imidazol-1-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:49%)Except that (4- (2-ethyl-1H-benzo [d] imidazol-1-yl) phenyl) boronic acid was used instead of dibenzo [b, d] thiophen- Were prepared in the same manner. (Yield: 49%).
[제조예 66] 화합물 1-471의 제조[Preparation Example 66] Preparation of compound 1-471
화합물 1-113의 제조방법 중 dibenzo[b,d]thiophen-4-ylboronic acid 대신 [2,2':6',2''-terpyridin]-4'-ylboronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:55%)Except that [2,2 ': 6', 2 "-terpyridin] -4'-ylboronic acid was used instead of dibenzo [b, d] thiophen-4-ylboronic acid in the preparation method of Compound 1-113 . (Yield: 55%).
[제조예 67] 화합물 1-39의 제조[Manufacturing Example 67] Production of Compound 1-39
화합물 1-36의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 (2,6-diphenylpyrimidin-4-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:47%)Was prepared in the same manner except that (2,6-diphenylpyrimidin-4-yl) boronic acid was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in the preparation of Compound 1-36 . (Yield: 47%).
[제조예 68] 화합물 1-41의 제조[Production Example 68] Synthesis of Compound 1-41
화합물 1-36의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 quinolin-2-ylboronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:55%)Was prepared in the same manner except that quinolin-2-ylboronic acid was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in the preparation of Compound 1-36. (Yield: 55%).
[제조예 69] 화합물 1-43의 제조[Production Example 69] Synthesis of Compound 1-43
화합물 1-36의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 (4-(2-phenyl-1H-benzo[d]imidazol-1-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:74%)(2-phenyl-1H-benzo [d] imidazol-1-yl) phenyl) boronic acid instead of 2-chloro-4,6- Was prepared in the same manner. (Yield: 74%).
[제조예 70] 화합물 1-44의 제조[Manufacturing Example 70] Preparation of Compound 1-44
화합물 1-36의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 (4,6-diphenylpyrimidin-2-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:69%)Except that (4,6-diphenylpyrimidin-2-yl) boronic acid was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in the preparation method of Compound 1-36 . (Yield: 69%).
[제조예 71] 화합물 1-47의 제조[Manufacturing Example 71] Preparation of Compound 1-47
화합물 1-36의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 (3,5-di(9H-carbazol-9-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:84%)Except that (3,5-di (9H-carbazol-9-yl) phenyl) boronic acid was used instead of 2-chloro-4,6-diphenyl-1,3,5- Were prepared in the same manner. (Yield: 84%)
[제조예 72] 화합물 1-67의 제조[Production Example 72] Synthesis of Compound 1-67
화합물 1-56의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 (3,5-di(9H-carbazol-9-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:77%)Except that (3,5-di (9H-carbazol-9-yl) phenyl) boronic acid was used instead of 2-chloro-4,6-diphenyl-1,3,5- Were prepared in the same manner. (Yield: 77%)
[제조예 73] 화합물 1-58의 제조[Manufacturing Example 73] [ 0156 ] A mixture of the compound
화합물 1-56의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 (3,5-di(9H-carbazol-9-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:77%)Except that (3,5-di (9H-carbazol-9-yl) phenyl) boronic acid was used instead of 2-chloro-4,6-diphenyl-1,3,5- Were prepared in the same manner. (Yield: 77%)
[제조예 74] 화합물 1-67의 제조[Preparative Example 74] Preparation of Compound 1-67
화합물 1-56의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:70%)(6 - ([1,1'-biphenyl] -4-yl) -2-phenylpyrimidin-4-ylidene- yl) boronic acid was used as the starting material. (Yield: 70%).
[제조예 75] 화합물 1-74의 제조[Manufacturing Example 75] Preparation of Compound 1-74
화합물 1-56의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 (2,6-diphenylpyrimidin-4-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:49%)Was prepared in the same manner except that (2,6-diphenylpyrimidin-4-yl) boronic acid was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in the preparation of Compound 1-56 . (Yield: 49%).
[제조예 76] 화합물 1-146의 제조[Production Example 76] Synthesis of Compound 1-146
화합물 1-157의 제조방법 중 9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole) 2-chloro-4,6-diphenyl-1,3,5-triazine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:77%)(9H) - (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3- phenylene) bis carbazole) 2-chloro-4,6-diphenyl-1,3,5-triazine. (Yield: 77%)
[제조예 77] 화합물 1-155의 제조[Production Example 77] Production of Compound 1-155
화합물 1-65의 제조방법 중 6-(4-bromophenyl)benzo[4,5]thieno[2,3-k]phenanthridine 대신 중 6-(3-bromophenyl)benzo[4,5]thieno[2,3-k]phenanthridine 을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:47%)Preparation of 6- (4-bromophenyl) benzo [4,5] thieno [2,3-k] phenanthridine in place of 6- (3-bromophenyl) benzo [4,5] thieno [2,3 -k] phenanthridine was used as the starting material. (Yield: 47%).
[제조예 78] 화합물 1-166의 제조[Production Example 78] Synthesis of Compound 1-166
화합물 1-177의 제조방법 중 9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole) 대신 2-((l4-oxidanylidene)boranyl)-4,6-diphenyl-1,3,5-triazine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:49%)Synthesis of 9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (9H- (l4-oxidanylidene) boranyl) -4,6-diphenyl-1,3,5-triazine was used in place of carbazole. (Yield: 49%).
[제조예 78] 화합물 1-168의 제조[Production Example 78] Synthesis of Compound 1-168
화합물 1-177의 제조방법 중 9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole) 대신 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:63%)Synthesis of 9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (9H- carbazole was used instead of (6 - ([1,1'-biphenyl] -4-yl) -2-phenylpyrimidin-4-yl) boronic acid. (Yield: 63%).
[제조예 79] 화합물 1-169의 제조[Production Example 79] Synthesis of Compound 1-169
화합물 1-177의 제조방법 중 9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole) 대신 (2,6-diphenylpyrimidin-4-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:74%)Synthesis of 9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (9H- 4-yl) boronic acid instead of (2,6-diphenylpyrimidin-4-yl) boronic acid. (Yield: 74%).
[제조예 80] 화합물 1-178의 제조[Manufacturing Example 80] Preparation of Compound 1-178
화합물 1-177의 제조방법 중 9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole) 대신 phenanthren-9-ylboronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:41%)Synthesis of 9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (9H- 9-ylboronic acid instead of phenanthren-9-yl-carbazole. (Yield: 41%).
[제조예 81] 화합물 1-179의 제조[Manufacturing Example 81] Production of Compound 1-179
화합물 1-177의 제조방법 중 9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole) 대신 [2,2'-binaphthalen]-6-ylboronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:71%)Synthesis of 9,9 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (9H- carbazole) instead of [2,2'-binaphthalen] -6-ylboronic acid. (Yield: 71%).
[제조예 82] 화합물 4-3의 제조[Manufacturing Example 82] Production of Compound 4-3
화합물 4-1의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:55%)([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine instead of 2-chloro-4,6-diphenyl-1,3,5- Was prepared in the same manner. (Yield: 55%).
[제조예 83] 화합물 4-4의 제조[Manufacturing Example 83] Preparation of compound 4-4
화합물 4-1의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 4-bromo-2,6-diphenylpyrimidine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:87%)Was prepared in the same manner except that 4-bromo-2,6-diphenylpyrimidine was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in the preparation of Compound 4-1. (Yield: 87%).
[제조예 84] 화합물 4-8의 제조[Manufacturing Example 84] Production of Compound 4-8
화합물 4-1의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 1-(4-bromophenyl)-2-phenyl-1H-benzo[d]imidazole을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:77%)Except that 1- (4-bromophenyl) -2-phenyl-1H-benzo [d] imidazole was used in place of 2-chloro-4,6-diphenyl-1,3,5- Were prepared in the same manner. (Yield: 77%)
[제조예 85] 화합물 4-9의 제조[Production Example 85] Production of compound 4-9
화합물 4-1의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 2-bromo-4,6-diphenylpyrimidine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:64%)Was prepared in the same manner except that 2-bromo-4,6-diphenylpyrimidine was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in the preparation of Compound 4-1. (Yield: 64%).
[제조예 86] 화합물 4-10의 제조[Production Example 86] Preparation of compound 4-10
화합물 1-65의 제조방법 중 6-(4-bromophenyl)benzo[4,5]thieno[2,3-k]phenanthridine 대신 6-(4-bromophenyl)-13-phenyl-13H-indolo[3,2-k]phenanthridine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:38%)(4-bromophenyl) -13-phenyl-13H-indolo [3,2-b] pyridine instead of 6- (4-bromophenyl) benzo [4,5] thieno [2,3- -k] phenanthridine was used as the starting material. (Yield: 38%).
[제조예 87] 화합물 4-12의 제조[Preparation Example 87] Preparation of Compound 4-12
화합물 4-1의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 9,9'-(5-bromo-1,3-phenylene)bis(9H-carbazole)을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:55%)9,9 '- (5-bromo-1,3-phenylene) bis (9H-carbazole) was used instead of 2-chloro-4,6-diphenyl-1,3,5- . &Lt; / RTI &gt; (Yield: 55%).
[제조예 88] 화합물 4-15의 제조[Production Example 88] Production of Compound 4-15
화합물 4-1의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 9-bromo-10-(naphthalen-2-yl)anthracene을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:70%)The same procedure was followed except that 9-bromo-10- (naphthalen-2-yl) anthracene was used instead of 2-chloro-4,6-diphenyl- Respectively. (Yield: 70%).
[제조예 89] 화합물 4-19의 제조[Manufacturing Example 89] Production of Compound 4-19
화합물 4-1의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 2-bromo-9,9-diphenyl-9H-fluorene을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:70%)Except that 2-bromo-9,9-diphenyl-9H-fluorene was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in the preparation of Compound 4-1 . (Yield: 70%).
[제조예 90] 화합물 4-22의 제조[Manufacturing Example 90] Preparation of Compound 4-22
화합물 4-1의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 4-bromodibenzo[b,d]furan을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:70%)The same procedure was followed except that 4-bromodibenzo [b, d] furan was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in the preparation of Compound 4-1. (Yield: 70%).
[제조예 91] 화합물 4-29의 제조[Manufacturing Example 91] Preparation of Compound 4-29
화합물 4-1의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 2-bromotriphenylene을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:87%)The same procedure was followed except that 2-bromotriphenylene was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in the preparation of Compound 4-1. (Yield: 87%).
[제조예 92] 화합물 4-33의 제조[Manufacturing Example 92] Preparation of compound 4-33
화합물 4-1의 제조방법 중 2-chloro-4,6-diphenyl-1,3,5-triazine 대신 3-bromo-9-phenyl-9H-carbazole을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:74%)Was prepared in the same manner except that 3-bromo-9-phenyl-9H-carbazole was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in the preparation of Compound 4-1. (Yield: 74%).
[제조예 93] 화합물 4-91의 제조[Manufacturing Example 93] Production of Compound 4-91
화합물 4-119의 제조방법 중 2-bromotriphenylene 대신 2-chloro-4,6-diphenyl-1,3,5-triazine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:74%)Was prepared in the same manner except that 2-chloro-4,6-diphenyl-1,3,5-triazine was used instead of 2-bromotriphenylene in the preparation of Compound 4-119. (Yield: 74%).
[제조예 94] 화합물 4-93의 제조[Manufacturing Example 94] Preparation of compound 4-93
화합물 4-119의 제조방법 중 2-bromotriphenylene 대신 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:59%)Except that 4 - ([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine was used instead of 2-bromotriphenylene in the preparation of Compound 4-119. (Yield: 59%)
[제조예 95] 화합물 4-94의 제조[Manufacturing Example 95] Production of Compound 4-94
화합물 4-119의 제조방법 중 2-bromotriphenylene 대신 4-bromo-2,6-diphenylpyrimidine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:57%)The same procedure was followed except that 4-bromo-2,6-diphenylpyrimidine was used instead of 2-bromotriphenylene in the preparation of Compound 4-119. (Yield: 57%).
[제조예 96] 화합물 4-99의 제조[Manufacturing Example 96] Preparation of Compound 4-99
화합물 4-119의 제조방법 중 2-bromotriphenylene 대신 2-bromo-4,6-diphenylpyrimidine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:51%)Was prepared in the same manner except that 2-bromo-4,6-diphenylpyrimidine was used instead of 2-bromotriphenylene in the preparation of Compound 4-119. (Yield: 51%).
[제조예 97] 화합물 4-100의 제조[Manufacturing Example 97] Preparation of Compound 4-100
화합물 1-65의 제조방법 중 6-(4-bromophenyl)benzo[4,5]thieno[2,3-k]phenanthridine 대신 6-(3-bromophenyl)-13-phenyl-13H-indolo[3,2-k]phenanthridine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:38%)(3-bromophenyl) -13-phenyl-13H-indolo [3,2] pyridine instead of 6- (4-bromophenyl) benzo [4,5] thieno [2,3- -k] phenanthridine was used as the starting material. (Yield: 38%).
[제조예 98] 화합물 4-101의 제조[Manufacturing Example 98] Preparation of compound 4-101
화합물 4-119의 제조방법 중 2-bromotriphenylene 대신 2-(4-bromophenyl)-1-phenyl-1H-benzo[d]imidazole을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:77%)Was prepared in the same manner except that 2- (4-bromophenyl) -1-phenyl-1H-benzo [d] imidazole was used instead of 2-bromotriphenylene in the preparation of Compound 4-119. (Yield: 77%)
[제조예 99] 화합물 4-102의 제조[Production Example 99] Production of compound 4-102
화합물 4-119의 제조방법 중 2-bromotriphenylene 대신 9,9'-(5-bromo-1,3-phenylene)bis(9H-carbazole)을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:66%)Except that 9,9 '- (5-bromo-1,3-phenylene) bis (9H-carbazole) was used instead of 2-bromotriphenylene in the preparation of Compound 4-119. (Yield: 66%).
[제조예 100] 화합물 4-106의 제조[Manufacturing Example 100] Preparation of Compound 4-106
화합물 4-119의 제조방법 중 2-bromotriphenylene 대신 7-bromoquinoline을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:40%)The same procedure was followed except that 7-bromoquinoline was used instead of 2-bromotriphenylene in the preparation of Compound 4-119. (Yield: 40%).
[제조예 101] 화합물 4-109의 제조[Production Example 101] Production of Compound 4-109
화합물 4-119의 제조방법 중 2-bromotriphenylene 대신 2-bromo-9,9-diphenyl-9H-fluorene을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:81%)Was prepared in the same manner except that 2-bromo-9,9-diphenyl-9H-fluorene was used instead of 2-bromotriphenylene in the preparation method of Compound 4-119. (Yield: 81%).
[제조예 102] 화합물 4-113의 제조[Production Example 102] Preparation of compound 4-113
화합물 4-119의 제조방법 중 2-bromotriphenylene 대신 4-bromodibenzo[b,d]thiophene을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:91%)The same procedure was followed except that 4-bromodibenzo [b, d] thiophene was used instead of 2-bromotriphenylene in the preparation of Compound 4-119. (Yield: 91%).
[제조예 103] 화합물 4-36의 제조[Manufacturing Example 103] Production of Compound 4-36
화합물 4-46의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 (4,6-diphenyl-1,3,5-triazin-2-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:49%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole Was prepared in the same manner except that (4,6-diphenyl-1,3,5-triazin-2-yl) boronic acid was used instead. (Yield: 49%).
[제조예 104] 화합물 4-38의 제조[Manufacturing Example 104] Production of Compound 4-38
화합물 4-46의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:53%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole Except that (6 - ([1,1'-biphenyl] -4-yl) -2-phenylpyrimidin-4-yl) boronic acid was used. (Yield: 53%).
[제조예 104] 화합물 4-39의 제조[Manufacturing Example 104] Production of Compound 4-39
화합물 4-46의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 (2,6-diphenylpyrimidin-4-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:51%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole Was prepared in the same manner except that (2,6-diphenylpyrimidin-4-yl) boronic acid was used instead. (Yield: 51%).
[제조예 105] 화합물 4-43의 제조[Manufacturing Example 105] Production of Compound 4-43
화합물 4-46의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 (4-(2-phenyl-1H-benzo[d]imidazol-1-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:49%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole Was prepared in the same manner except that (4- (2-phenyl-1H-benzo [d] imidazol-1-yl) phenyl) boronic acid was used. (Yield: 49%).
[제조예 106] 화합물 4-49의 제조[Manufacturing Example 106] Production of Compound 4-49
화합물 4-46의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 [2,2'-binaphthalen]-6-ylboronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:71%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole The title compound was prepared in the same manner except that [2,2'-binaphthalen] -6-ylboronic acid was used instead. (Yield: 71%).
[제조예 107] 화합물 4-59의 제조[Manufacturing Example 107] Production of Compound 4-59
화합물 4-66의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 (2,6-diphenylpyrimidin-4-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:59%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole Was prepared in the same manner except that (2,6-diphenylpyrimidin-4-yl) boronic acid was used instead. (Yield: 59%)
[제조예 108] 화합물 4-61의 제조[Manufacturing Example 108] Production of Compound 4-61
화합물 4-66의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 2-bromoquinoline을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:37%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole The same procedure was followed except that 2-bromoquinoline was used instead. (Yield: 37%).
[제조예 109] 화합물 4-63의 제조[Manufacturing Example 109] Production of Compound 4-63
화합물 4-66의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 (4-(2-phenyl-1H-benzo[d]imidazol-1-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:69%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole Was prepared in the same manner except that (4- (2-phenyl-1H-benzo [d] imidazol-1-yl) phenyl) boronic acid was used. (Yield: 69%).
[제조예 110] 화합물 4-64의 제조[Manufacturing Example 110] Production of Compound 4-64
화합물 4-66의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 (4,6-diphenylpyrimidin-2-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:60%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole Was prepared in the same manner except that (4,6-diphenylpyrimidin-2-yl) boronic acid was used instead. (Yield: 60%).
[제조예 111] 화합물 4-65의 제조[Manufacturing Example 111] Preparation of Compound 4-65
화합물 1-65의 제조방법 중 6-(4-bromophenyl)benzo[4,5]thieno[2,3-k]phenanthridine 대신 6-(3-bromophenyl)benzo[4,5]thieno[3,2-k]phenanthridine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:48%)(3-bromophenyl) benzo [4,5] thieno [3,2-b] pyridine instead of 6- (4-bromophenyl) benzo [4,5] thieno [ k] phenanthridine was used as the starting material. (Yield: 48%).
[제조예 112] 화합물 4-72의 제조[Manufacturing Example 112] Production of Compound 4-72
화합물 4-66의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 dibenzo[b,d]thiophen-4-ylboronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:60%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole Was prepared in the same manner except that dibenzo [b, d] thiophen-4-ylboronic acid was used instead. (Yield: 60%).
[제조예 113] 화합물 4-251의 제조[Manufacturing Example 113] Production of Compound 4-251
화합물 4-66의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 (9,10-di(naphthalen-2-yl)anthracen-2-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:55%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole Except that (9,10-di (naphthalen-2-yl) anthracen-2-yl) boronic acid was used instead of (Yield: 55%).
[제조예 114] 화합물 4-254의 제조[Manufacturing Example 114] Production of Compound 4-254
화합물 4-66의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 (10-phenylanthracen-9-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:61%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole Except that (10-phenylanthracen-9-yl) boronic acid was used instead of (10-phenylanthracen-9-yl) boronic acid. (Yield: 61%).
[제조예 115] 화합물 4-336의 제조[Manufacturing Example 115] Production of Compound 4-336
화합물 4-66의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 (3-(1,10-phenanthrolin-2-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:49%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole Except that (3- (1,10-phenanthrolin-2-yl) phenyl) boronic acid was used instead of (3- (Yield: 49%).
[제조예 116] 화합물 4-362의 제조[Manufacturing Example 116] Production of Compound 4-362
화합물 4-66의 제조방법 중 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole 대신 [2,3'-bipyridin]-6-ylboronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:80%)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1H-benzo [d] imidazole Was prepared in the same manner except that [2,3'-bipyridin] -6-ylboronic acid was used instead. (Yield: 80%).
[제조예 117] 화합물 4-79의 제조[Manufacturing Example 117] Production of Compound 4-79
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 (2,6-diphenylpyrimidin-4-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:70%)Preparation of Compound 4-78 According to the same manner as that described in (4- (2-phenylpyrimidin-4-yl) boronic acid Was prepared in the same manner. (Yield: 70%).
[제조예 118] 화합물 4-84의 제조[Manufacturing Example 118] Production of Compound 4-84
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 (4,6-diphenylpyrimidin-2-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:73%)(4,6-diphenylpyrimidin-2-yl) boronic acid instead of (6 - ([1,1'-biphenyl] -4-yl) -2-phenylpyrimidin- Was prepared in the same manner. (Yield: 73%)
[제조예 119] 화합물 4-85의 제조[Manufacturing Example 119] Production of Compound 4-85
*화합물 1-65의 제조방법 중 6-(4-bromophenyl)benzo[4,5]thieno[2,3-k]phenanthridine 대신 6-(3-bromophenyl)benzofuro[3,2-k]phenanthridine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:44%)* Using 6- (3-bromophenyl) benzofuro [3,2-k] phenanthridine instead of 6- (4-bromophenyl) benzo [4,5] thieno [2,3- . &Lt; / RTI &gt; (Yield: 44%)
[제조예 120] 화합물 4-89의 제조[Manufacturing Example 120] Preparation of Compound 4-89
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 [2,2'-binaphthalen]-6-ylboronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:47%)Preparation of Compound 4-78 [2,2'-binaphthalen] -6-ylboronic acid (6-fluoropyrimidin-4-yl) Was prepared in the same manner. (Yield: 47%).
[제조예 121] 화합물 4-166의 제조[Manufacturing Example 121] Production of Compound 4-166
화합물 4-168의 제조방법 중 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 대신 2-chloro-4,6-diphenyl-1,3,5-triazine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:73%)2-chloro-4,6-diphenyl-1,3,5-triazine was used instead of 4 - ([1,1'-biphenyl] -4-yl) -6-bromo- Was prepared in the same manner. (Yield: 73%)
[제조예 122] 화합물 4-174의 제조[Manufacturing Example 122] Production of Compound 4-174
화합물 4-168의 제조방법 중 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 대신 2-bromo-4,6-diphenylpyrimidine을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:44%)Except that 2-bromo-4,6-diphenylpyrimidine was used instead of 4 - ([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine in the preparation method of Compound 4-168 . (Yield: 44%)
[제조예 123] 화합물 4-177의 제조[Manufacturing Example 123] Production of Compound 4-177
화합물 4-168의 제조방법 중 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 대신 9,9'-(5-bromo-1,3-phenylene)bis(9H-carbazole)을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:54%)(5-bromo-1, 3-phenylene) bis (4-bromo-2-phenylpyrimidine) (9H-carbazole) was used as the starting material. (Yield: 54%).
[제조예 124] 화합물 4-179의 제조[Manufacturing Example 124] Production of Compound 4-179
화합물 4-168의 제조방법 중 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 대신 6-bromo-2,2'-binaphthalene을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:54%)Except that 6-bromo-2,2'-binaphthalene was used instead of 4 - ([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine in the preparation method of Compound 4-168 &Lt; / RTI &gt; (Yield: 54%).
[제조예 125] 화합물 4-481의 제조[Production Example 125] Production of Compound 4-481
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 (9,10-di(naphthalen-2-yl)anthracen-2-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:40%)(9,10-di (naphthalen-2-yl) -2-phenylpyrimidin-4-yl) boronic acid was prepared in the same manner as in (4- (1- anthracen-2-yl) boronic acid. (Yield: 40%).
[제조예 126] 화합물 4-484의 제조[Manufacturing Example 126] Production of Compound 4-484
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 (10-phenylanthracen-9-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:49%)(10-phenylanthracen-9-yl) boronic acid was used instead of (6 - ([1,1'-biphenyl] -4-yl) -2-phenylpyrimidin- . &Lt; / RTI &gt; (Yield: 49%).
[제조예 126] 화합물 4-485의 제조[Production Example 126] Production of Compound 4-485
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 (4-(diphenylphosphoryl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:62%)(4- (diphenylphosphoryl) phenyl) boronic acid was used instead of (6 - ([1,1'-biphenyl] -4-yl) -2-phenylpyrimidin- Were prepared in the same manner. (Yield: 62%).
[제조예 127] 화합물 4-564의 제조[Manufacturing Example 127] Production of Compound 4-564
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 (1,10-phenanthrolin-2-yl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:49%)Preparation of Compound 4-78 Using (1,10-phenanthrolin-2-yl) boronic acid instead of (6 - ([1,1'-biphenyl] -4-yl) -2-phenylpyrimidin- Was prepared in the same manner. (Yield: 49%).
[제조예 128] 화합물 4-565의 제조[Manufacturing Example 128] Production of Compound 4-565
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 (4-(1,10-phenanthrolin-2-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:39%)(4- (1,10-phenanthrolin-2-yl) -2-phenylpyrimidin-4-yl) boronic acid in place of (6- ) phenyl) boronic acid was used as the starting material. (Yield: 39%).
[제조예 129] 화합물 4-574의 제조[Manufacturing Example 129] Production of Compound 4-574
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 (4-(2-phenyl-1H-benzo[d]imidazol-1-yl)phenyl)boronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:39%)(4- (2-phenyl-1H-benzo [d (1, 1'-biphenyl) -4-yl) -2-phenylpyrimidin- ] imidazol-1-yl) phenyl) boronic acid was used as the starting material. (Yield: 39%).
[제조예 130] 화합물 4-576의 제조[Manufacturing Example 130] Preparation of compound 4-576
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 1-(3-(borino-l3-oxidanyl)phenyl)-2-ethyl-1H-benzo[d]imidazole을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:66%)(3- (borino-13-oxidanyl) phenyl (2-phenylpyrimidin-4-yl) ) -2-ethyl-1H-benzo [d] imidazole. (Yield: 66%).
[제조예 131] 화합물 4-578의 제조[Manufacturing Example 131] Production of Compound 4-578
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 1-(3-(borino-l3-oxidanyl)phenyl)-2-phenyl-1H-benzo[d]imidazole을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:66%)(3- (borino-13-oxidanyl) phenyl (2-phenylpyrimidin-4-yl) ) -2-phenyl-1H-benzo [d] imidazole. (Yield: 66%).
[제조예 132] 화합물 4-590의 제조[Manufacturing Example 132] Production of Compound 4-590
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 [2,2'-bipyridin]-6-ylboronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:76%)Preparation of compound 4-78 [2,2'-bipyridin] -6-ylboronic acid (6-fluorophenyl) -4-yl) Was prepared in the same manner. (Yield: 76%).
[제조예 133] 화합물 4-591의 제조[Manufacturing Example 133] Production of Compound 4-591
화합물 4-78의 제조방법 중 (6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)boronic acid 대신 [2,3'-bipyridin]-6-ylboronic acid을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:76%)Preparation of Compound 4-78 [2,3'-bipyridinyl] -6-ylboronic acid (6'- [1,1'-biphenyl] -4-yl) -2-phenylpyrimidin- Was prepared in the same manner. (Yield: 76%).
[제조예 134] 화합물 4-599의 제조[Manufacturing Example 134] Preparation of Compound 4-599
화합물 4-168의 제조방법 중 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 대신 9-bromo-10-phenylanthracene을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:81%)Except that 9-bromo-10-phenylanthracene was used instead of 4 - ([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine in the preparation of Compound 4-168 Respectively. (Yield: 81%).
[제조예 135] 화합물 4-600의 제조[Manufacturing Example 135] Production of Compound 4-600
화합물 4-168의 제조방법 중 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 대신 (4-bromophenyl)diphenylphosphine oxide을 사용한 것을 제외하고는 동일한 방법으로 제조하였다. (수율:88%)Except that (4-bromophenyl) diphenylphosphine oxide was used instead of 4 - ([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine in the preparation of Compound 4-168 Respectively. (Yield: 88%).
[제조예 136] 화합물 10-1의 제조[Manufacturing Example 136] Production of Compound 10-1
Figure PCTKR2015006723-appb-I000198
Figure PCTKR2015006723-appb-I000198
X-1의 합성Synthesis of X-1
2-Bromo-9,9-diphenyl-9H-fluorene 61g(153.5mmol), Dioxaborolane 58.5g(230.3mmol), PdCl2(dppf) 5.6g(7.7mmol), KOAc 45.2g(460.6mmol)을 1,4-dioxane 600mL하에서 120℃로 2시간동안 환류 교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 실리카겔로 필터한 뒤 Hexane으로 씻어주어 목적화합물 X-1 63.6g(93%)을 얻었다.2-Bromo-9,9-diphenyl- 9H-fluorene 61g (153.5mmol), Dioxaborolane 58.5g (230.3mmol), PdCl a 2 (dppf) 5.6g (7.7mmol) , KOAc 45.2g (460.6mmol) 1,4 -dioxane (600 mL) at 120 ° C for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 63.6 g (93%) of the target compound X-1 .
X-2의 합성Synthesis of X-2
X-1 63.6g(143.1mmol), 2-bromoaniline 27.1g(157.4mmol), Pd(PPh3)4 8.3g(7.2mmol), K3PO4 91.1g(429.4mmol)을 1,4-dioxane 500mL, H2O 100mL하에서 120℃로 17시간동안 환류 교반하였다. 반응 완료 후 실온으로 식힌 뒤 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 실리카겔로 필터한 뒤 Hexane으로 씻어주어 목적화합물 X-2 42.3g(75%)을 얻었다.X-1 63.6g (143.1mmol), 2-bromoaniline 27.1g (157.4mmol), Pd (PPh 3) 4 8.3g (7.2mmol), K 3 PO 4 91.1g (429.4mmol) of 1,4-dioxane 500mL , And the mixture was refluxed and stirred at 100 占 폚 under H 2 O for 17 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by filtration with silica gel and washed with hexane to obtain 42.3 g (75%) of the target compound X-2 .
X-3의 합성Synthesis of X-3
X-2 42.3g(103.3mmol), Triethylamine 43.2mL(309.9mmol)을 MC(dichloromethane)로 전부 녹인 뒤 0℃를 유지하였다. 그 후 3-bromobenzoylchloride 34.0g(154.9mmol)를 천천히 적가하여 1시간동안 온도를 유지하면 교반하였다. 반응 종료 후 Hexane을 과량 첨가하여 생성된 고체를 필터하였다. 목적화합물 X-3 59.3g(97%)을 얻었다.42.3 g (103.3 mmol) of X-2 and 43.2 mL (309.9 mmol) of triethylamine were dissolved in MC (dichloromethane) and maintained at 0 ° C. 34.0 g (154.9 mmol) of 3-bromobenzoylchloride was slowly added dropwise thereto, and the mixture was stirred for 1 hour. After completion of the reaction, excess hexane was added to filter the resulting solid. 59.3 g (97%) of the desired compound X-3 was obtained.
X-4의 합성Synthesis of X-4
X-3 59.3g(100.0mmol)을 Nitrobenzene 600L에 전부 녹인 뒤 POCl3 10.3mL(110.1mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 16시간동안 교반하였다. 반응 종료 후 실온으로 식힌 뒤 Hexane을 과량 첨가하였다. 목적화합물 X-4 55.1g(92%)로 얻었다.59.3 g (100.0 mmol) of X-3 was completely dissolved in 600 L of Nitrobenzene, and then 10.3 mL (110.1 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 16 hours while maintaining the temperature at 150 캜. After completion of the reaction, the mixture was cooled to room temperature, and then excess hexane was added. To obtain 55.1 g (92%) of the desired compound X-4 .
X-5의 합성Synthesis of X-5
2-Bromo-9,9-diphenyl-9H-fluorene 대신 X-4 55.1g(95.9mmol)을 사용하여 X-1의 합성법과 동일하게 진행하였다. 목적화합물 X-5 59.6g(100%)을 얻었다.1 was used instead of 2-bromo-9,9-diphenyl-9H-fluorene in the synthesis of X-1. 59.6 g (100%) of the desired compound X-5 was obtained.
Figure PCTKR2015006723-appb-I000199
Figure PCTKR2015006723-appb-I000199
10-1의 합성Synthesis of 10-1
X-5 10.0g(16.1mmol), 9-bromo-10-phenylanthracene 5.9g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-1 9.97g(82%)을 얻었다.An X-5 10.0g (16.1mmol), 9-bromo-10-phenylanthracene 5.9g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2g (48.3mmol) 1, 4-Dioxane and 30 mL of H 2 O at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.97 g (82%) of the target compound 10-1 .
[제조예 137] 화합물 10-3의 제조[Manufacturing Example 137] Production of Compound 10-3
Figure PCTKR2015006723-appb-I000200
Figure PCTKR2015006723-appb-I000200
X-5 10.0g(16.1mmol), Diphenyl phosphineoxide 6.5g(32.2mmol), Pd(PPh3)4 1.9g(1.6mmol), TEA 3.1mL(22.5mmol)을 Toluene 100mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 MC, EA, MeOH로 씻어주었다. 그 후 디클로로메탄과 EA를 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-3 4.7g(42%)을 얻었다.1.9 g (1.6 mmol) of Pd (PPh 3 ) 4 and 3.1 mL (22.5 mmol) of TEA were added to 100 mL of toluene at 120 ° C. for 5 hours under reflux Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed, filtered and washed with MC, EA and MeOH. Thereafter, the residue was purified by column chromatography using dichloromethane and EA as eluting solvents to obtain 4.7 g (42%) of the desired compound 10-3 .
[제조예 138] 화합물 10-5의 제조[Manufacturing Example 138] Production of Compound 10-5
Figure PCTKR2015006723-appb-I000201
Figure PCTKR2015006723-appb-I000201
X-5 10.0g(16.1mmol), 9,9'-(5-bromo-1,3-phenylene)bis(9H-carbazole) 8.6g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-5 11.5g(79%)을 얻었다.X-5 10.0g (16.1mmol), 9,9 '- (5-bromo-1,3-phenylene) bis (9H-carbazole) 8.6g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol ) And 10.2 g (48.3 mmol) of K 3 PO 4 were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 11.5 g (79%) of the desired compound 10-5 .
[제조예 139] 화합물 10-6의 제조[Production Example 139] Synthesis of Compound 10-6
Figure PCTKR2015006723-appb-I000202
Figure PCTKR2015006723-appb-I000202
X-5 10.0g(16.1mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-6 9.8g(84%)을 얻었다.X-5 10.0g (16.1mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 (10.3 g, 48.3 mmol) was refluxed and stirred at 170 ° C in 1,4-dioxane and 30 ml of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was then purified by column chromatography using dichloromethane and hexane as developing solvents to obtain 9.8 g (84%) of the desired compound 10-6 .
[제조예 140] 화합물 10-12의 제조[Manufacturing Example 140] Preparation of Compound 10-12
Figure PCTKR2015006723-appb-I000203
Figure PCTKR2015006723-appb-I000203
X-5 10.0g(16.1mmol), 4-bromo-2,6-diphenylpyrimidine 5.5g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 4시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-12 10.2g(87%)을 얻었다.An X-5 10.0g (16.1mmol), 4-bromo-2,6-diphenylpyrimidine 5.5g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2g (48.3mmol) 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 4 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed by a rotary evaporator. The solvent was distilled off using dichloromethane and hexane as eluent to obtain 10.2 g (87%) of the target compound 10-12 .
[제조예 141] 화합물 10-13의 제조[Manufacturing Example 141] Preparation of Compound 10-13
Figure PCTKR2015006723-appb-I000204
Figure PCTKR2015006723-appb-I000204
X-5 10.0g(16.1mmol), 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 6.9g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-13 11.1g(86%)을 얻었다.X-5 10.0g (16.1mmol), 4 - ([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine 6.9g (17.7mmol), Pd (PPh 3) 4 0.9g ( 0.8 mmol) and K 3 PO 4 (10.2 g, 48.3 mmol) were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 ml of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 11.1 g (86%) of the target compound 10-13 .
[제조예 142] 화합물 10-37의 제조[Manufacturing Example 142] Production of Compound 10-37
Figure PCTKR2015006723-appb-I000205
Figure PCTKR2015006723-appb-I000205
X-5 10.0g(16.1mmol), 2-(4-bromophenyl)-1-ethyl-1H-benzo[d]imidazole 5.3g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 7시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-37 9.0g(78%)을 얻었다.X-5 10.0g (16.1mmol), 2- (4-bromophenyl) -1-ethyl-1H-benzo [d] imidazole 5.3g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 (10.3 g, 48.3 mmol) were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 7 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.0 g (78%) of the target compound 10-37 .
[제조예 143] 화합물 10-46의 제조[Manufacturing Example 143] Production of Compound 10-46
Figure PCTKR2015006723-appb-I000206
Figure PCTKR2015006723-appb-I000206
X-5 10.0g(16.1mmol), 4-bromobenzonitrile 3.2g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 8시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-46 6.8g(71%)을 얻었다.X-5 10.0g (16.1mmol), 4-bromobenzonitrile 3.2g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 to PO 4 10.2g (48.3mmol) 1,4- Dioxane 170mL And 30 mL of H 2 O at 120 ° C for 8 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 6.8 g (71%) of the target compound 10-46 .
[제조예 144] 화합물 10-48의 제조[Manufacturing Example 144] Preparation of Compound 10-48
Figure PCTKR2015006723-appb-I000207
Figure PCTKR2015006723-appb-I000207
X-5 10.0g(16.1mmol), 2-bromopyridine 2.8g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-48 7.5g(81%)을 얻었다.X-5 10.0g (16.1mmol), 2-bromopyridine 2.8g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 to PO 4 10.2g (48.3mmol) 1,4- Dioxane 170mL And 30 mL of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 7.5 g (81%) of the target compound 10-48 .
[제조예 145] 화합물 10-49의 제조Production Example 145 Production of Compound 10-49
Figure PCTKR2015006723-appb-I000208
Figure PCTKR2015006723-appb-I000208
X-5 10.0g(16.1mmol), 3-bromo-2-phenylimidazo[1,2-a]pyridine 4.8g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-49 9.5g(86%)을 얻었다.X-5 10.0g (16.1mmol), 3-bromo-2-phenylimidazo [1,2-a] pyridine 4.8g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2 g (48.3 mmol) was refluxed with stirring in a solution of 170 mL of 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.5 g (86%) of the desired compound 10-49 .
[제조예 146] 화합물 10-51의 제조[Manufacturing Example 146] Production of Compound 10-51
Figure PCTKR2015006723-appb-I000209
Figure PCTKR2015006723-appb-I000209
Y-3의 합성Synthesis of Y-3
3-Bromobenzoylchloride 대신 4-bromobenzoylchloride 32.0g(145.7mmol)을 사용하여 A-3의 합성법과 동일하게 진행하였다. 목적화합물 Y-3 56.0g(97%)을 얻었다.The same procedure as in the synthesis of A-3 was conducted using 32.0 g (145.7 mmol) of 4-bromobenzoylchloride instead of 3-bromobenzoylchloride. 56.0 g (97%) of the desired compound Y-3 was obtained.
Y-4의 합성Synthesis of Y-4
X-3 대신 Y-3 56.0g(94.5mmol)을 사용하여 X-4의 합성법과 동일하게 진행하였다. 목적화합물 Y-4 50.0g(92%)을 얻었다.The same procedure as in the synthesis of X-4 was conducted using 56.0 g (94.5 mmol) of Y-3 instead of X-3. To obtain 50.0 g (92%) of the desired compound Y-4 .
Y-5의 합성Synthesis of Y-5
X-4 대신 Y-4 50.0g(87.0mmol)을 사용하여 X-5의 합성법과 동일하게 진행하였다. 목적화합물 Y-5 54.1g(100%)을 얻었다.5 was carried out in the same manner as in the synthesis of X-5 using 50.0 g (87.0 mmol) of Y-4 instead of X-4. 54.1 g (100%) of the desired compound Y-5 was obtained.
Figure PCTKR2015006723-appb-I000210
Figure PCTKR2015006723-appb-I000210
10-51의 합성Synthesis of 10-51
Y-5 10.0g(16.1mmol), 9-bromo-10-phenylanthracene 5.9g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-51 10.1g(83%)을 얻었다.The Y-5 10.0g (16.1mmol), 9-bromo-10-phenylanthracene 5.9g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2g (48.3mmol) 1, 4-Dioxane and 30 mL of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was removed by column chromatography using dichloromethane and hexane as eluent to obtain 10.1 g (83%) of the desired compound 10-51 .
[제조예 147] 화합물 10-53의 제조[Manufacturing Example 147] Production of Compound 10-53
Figure PCTKR2015006723-appb-I000211
Figure PCTKR2015006723-appb-I000211
Y-5 10.0g(16.1mmol), Diphenyl phosphineoxide 6.5g(32.2mmol), Pd(PPh3)4 1.9g(1.6mmol), TEA 3.1mL(22.5mmol)을 Toluene 100mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 MC, EA, MeOH로 씻어주었다. 그 후 디클로로메탄과 EA를 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-53 5.0g(45%)을 얻었다.1.9 g (1.6 mmol) of Pd (PPh 3 ) 4 and 3.1 mL (22.5 mmol) of TEA were dissolved in 100 mL of toluene at 120 ° C. for 6 hours under reflux Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed, filtered and washed with MC, EA and MeOH. Thereafter, purification was carried out by column chromatography using dichloromethane and EA as developing solvents to obtain 5.0 g (45%) of the target compound 10-53 .
[제조예 148] 화합물 10-55의 제조[Production Example 148] Production of Compound 10-55
Figure PCTKR2015006723-appb-I000212
Figure PCTKR2015006723-appb-I000212
Y-5 10.0g(16.1mmol), 9,9'-(5-bromo-1,3-phenylene)bis(9H-carbazole) 8.6g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-55 11.6g(80%)을 얻었다.Y-5 10.0g (16.1mmol), 9,9 '- (5-bromo-1,3-phenylene) bis (9H-carbazole) 8.6g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol ) And 10.2 g (48.3 mmol) of K 3 PO 4 were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 11.6 g (80%) of the target compound 10-55 .
[제조예 149] 화합물 10-56의 제조[Manufacturing Example 149] Preparation of Compound 10-56
Figure PCTKR2015006723-appb-I000213
Figure PCTKR2015006723-appb-I000213
Y-5 10.0g(16.1mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-56 9.6g(82%)을 얻었다.Y-5 10.0g (16.1mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 (10.3 g, 48.3 mmol) was refluxed and stirred at 170 ° C in 1,4-dioxane and 30 ml of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 9.6 g (82%) of the target compound 10-56 .
[제조예 150] 화합물 10-62의 제조[Manufacturing Example 150] Preparation of Compound 10-62
Figure PCTKR2015006723-appb-I000214
Figure PCTKR2015006723-appb-I000214
Y-5 10.0g(16.1mmol), 4-bromo-2,6-diphenylpyrimidine 5.5g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-62 10.3g(88%)을 얻었다.The Y-5 10.0g (16.1mmol), 4-bromo-2,6-diphenylpyrimidine 5.5g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2g (48.3mmol) 1,4-Dioxane and 30 mL of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off using dichloromethane and hexane as eluent to obtain 10.3 g (88%) of the desired compound 10-62 .
[제조예 151] 화합물 10-63의 제조[Production Example 151] Production of Compound 10-63
Figure PCTKR2015006723-appb-I000215
Figure PCTKR2015006723-appb-I000215
Y-5 10.0g(16.1mmol), 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 6.9g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-63 11.0g(85%)을 얻었다.Y-5 10.0g (16.1mmol), 4 - ([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine 6.9g (17.7mmol), Pd (PPh 3) 4 0.9g ( 0.83 mmol) and K 3 PO 4 (10.2 g, 48.3 mmol) were refluxed under stirring at 120 ° C. for 6 hours in 170 mL of 1,4-dioxane and 30 mL of H 2 O. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 11.0 g (85%) of the desired compound 10-63 .
[제조예 152] 화합물 10-87의 제조Production Example 152 Production of Compound 10-87
Figure PCTKR2015006723-appb-I000216
Figure PCTKR2015006723-appb-I000216
Y-5 10.0g(16.1mmol), 2-(4-bromophenyl)-1-ethyl-1H-benzo[d]imidazole 5.3g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-87 9.2g(80%)을 얻었다.Y-5 10.0g (16.1mmol), 2- (4-bromophenyl) -1-ethyl-1H-benzo [d] imidazole 5.3g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 (10.3 g, 48.3 mmol) were refluxed under stirring at 120 ° C in 170 mL of 1,4-dioxane and 30 mL of H 2 O for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 9.2 g (80%) of the target compound 10-87 .
[제조예 153] 화합물 10-96의 제조Production Example 153 Production of Compound 10-96
Figure PCTKR2015006723-appb-I000217
Figure PCTKR2015006723-appb-I000217
Y-5 10.0g(16.1mmol), 4-bromobenzonitrile 3.2g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-96 6.3g(74%)을 얻었다.Y-5 10.0g (16.1mmol), 4-bromobenzonitrile 3.2g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 to PO 4 10.2g (48.3mmol) 1,4- Dioxane 170mL And 30 mL of H 2 O at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 6.3 g (74%) of the desired compound 10-96 .
[제조예 154] 화합물 10-98의 제조[Production Example 154] Synthesis of Compound 10-98
Figure PCTKR2015006723-appb-I000218
Figure PCTKR2015006723-appb-I000218
Y-5 10.0g(16.1mmol), 2-bromopyridine 2.8g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-98 7.7g(83%)을 얻었다.Y-5 10.0g (16.1mmol), 2-bromopyridine 2.8g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 to PO 4 10.2g (48.3mmol) 1,4- Dioxane 170mL And 30 mL of H 2 O at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 7.7 g (83%) of the target compound 10-98 .
[제조예 155] 화합물 10-99의 제조Production Example 155 Production of Compound 10-99
Figure PCTKR2015006723-appb-I000219
Figure PCTKR2015006723-appb-I000219
Y-5 10.0g(16.1mmol), 3-bromo-2-phenylimidazo[1,2-a]pyridine 4.8g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 7시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 10-99 9.4g(85%)을 얻었다.Y-5 10.0g (16.1mmol), 3-bromo-2-phenylimidazo [1,2-a] pyridine 4.8g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2 g (48.3 mmol) was refluxed with stirring in a solution of 170 mL of 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 7 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 9.4 g (85%) of the target compound 10-99 .
[제조예 156] 화합물 11-26의 제조[Production Example 156] Production of Compound 11-26
Figure PCTKR2015006723-appb-I000220
Figure PCTKR2015006723-appb-I000220
V-1의 합성Synthesis of V-1
2-Bromo-9,9-diphenyl-9H-fluorene 대신 3-bromo-9,9-diphenyl-9H-fluorene 120g(302.0mmol)을 사용하여 X-1의 합성법과 동일하게 진행하였다. 목적화합물 V-1 134.2g(100%)을 얻었다.1 was synthesized by using 120 g (302.0 mmol) of 3-bromo-9,9-diphenyl-9H-fluorene instead of 2-bromo-9,9-diphenyl-9H-fluorene. 134.2 g (100%) of the desired compound V-1 was obtained.
V-2의 합성Synthesis of V-2
X-1 대신 V-1 134.2g(302.0mmol)을 사용하여 X-2의 합성법과 동일하게 진행하였다. 목적화합물 V-2 91.5g(74%)을 얻었다.The same procedure as in the synthesis of X-2 was conducted using 134.2 g (302.0 mmol) of V-1 instead of X-1. 91.5 g (74%) of the desired compound V-2 was obtained.
V-3의 합성Synthesis of V-3
X-2 대신 V-2 91.5g(223.4mmol)을 사용하여 X-3의 합성법과 동일하게 진행하였다. 목적화합물 V-3 119.2g(90%)을 얻었다.The same procedure as in the synthesis of X-3 was conducted using 91.5 g (223.4 mmol) of V-2 instead of X-2. 119.2 g (90%) of the desired compound V-3 was obtained.
V-4 및 W-4의 합성Synthesis of V-4 and W-4
V-3 119.2g(201.2mmol)을 Nitrobenzene 1200L에 전부 녹인 뒤 POCl3 20.6mL(221.3mmol)를 천천히 적가하였다. 그 후 150℃로 유지하면서 16시간동안 교반하였다. 반응 종료 후 실온으로 식힌 뒤 Hexane을 과량 첨가하였다. 생성된 고체를 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 V-4 42.8g(37%) 및 W-4 63.6g(55%)로 얻었다.After dissolving 119.2 g (201.2 mmol) of V-3 in 1200 L of Nitrobenzene, 20.6 mL (221.3 mmol) of POCl 3 was slowly added dropwise. Thereafter, the mixture was stirred for 16 hours while maintaining the temperature at 150 캜. After completion of the reaction, the mixture was cooled to room temperature, and then excess hexane was added. The resulting solid was purified by column chromatography using dichloromethane and hexane as eluent to give 42.8 g (37%) of the target compound V-4 and 63.6 g (55%) of W-4 .
V-5의 합성Synthesis of V-5
X-4 대신 V-4 42.8g(74.5mmol)을 사용하여 X-1의 합성법과 동일하게 진행하였다. 목적화합물 V-5 46.3g(100%)을 얻었다.1 was used in place of 42.8 g (74.5 mmol) of V-4 instead of X-4. 46.3 g (100%) of the desired compound V-5 was obtained.
W-5의 합성Synthesis of W-5
X-4 대신 W-4 63.6g(110.7mmol)을 사용하여 X-1의 합성법과 동일하게 진행하였다. 목적화합물 W-5 68.8g(100%)을 얻었다.The same procedure as in the synthesis of X-1 was conducted using 63.6 g (110.7 mmol) of W-4 instead of X-4. 68.8 g (100%) of the desired compound W-5 was obtained.
Figure PCTKR2015006723-appb-I000221
Figure PCTKR2015006723-appb-I000221
11-26의 합성Synthesis of 11-26
W-5 10.0g(16.1mmol), 9-bromo-10-phenylanthracene 5.9g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-26 10.0g(82%)을 얻었다.The W-5 10.0g (16.1mmol), 9-bromo-10-phenylanthracene 5.9g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2g (48.3mmol) 1, 4-Dioxane and 30 mL of H 2 O at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 10.0 g (82%) of the target compound 11-26 .
[제조예 157] 화합물 11-28의 제조[Manufacturing Example 157] Production of Compound 11-28
Figure PCTKR2015006723-appb-I000222
Figure PCTKR2015006723-appb-I000222
W-5 10.0g(16.1mmol), Diphenyl phosphineoxide 6.5g(32.2mmol), Pd(PPh3)4 1.9g(1.6mmol), TEA 3.1mL(22.5mmol)을 Toluene 100mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 MC, EA, MeOH로 씻어주었다. 그 후 디클로로메탄과 EA를 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-28 4.7g(42%)을 얻었다.W-5 10.0g (16.1mmol), Diphenyl phosphineoxide 6.5g (32.2mmol), Pd (PPh 3) 4 1.9g (1.6mmol), refluxed for 5 hours the TEA 3.1mL (22.5mmol) in 100mL 120 ℃ under Toluene Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed, filtered and washed with MC, EA and MeOH. Thereafter, purification was conducted by column chromatography using dichloromethane and EA as developing solvents to obtain 4.7 g (42%) of the target compound 11-28 .
[제조예 158] 화합물 11-29의 제조[Manufacturing Example 158] Production of Compound 11-29
Figure PCTKR2015006723-appb-I000223
Figure PCTKR2015006723-appb-I000223
W-5 10.0g(16.1mmol), 9,9'-(5-bromo-1,3-phenylene)bis(9H-carbazole) 8.6g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-29 12.0g(83%)을 얻었다.W-5 10.0g (16.1mmol), 9,9 '- (5-bromo-1,3-phenylene) bis (9H-carbazole) 8.6g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol ) And 10.2 g (48.3 mmol) of K 3 PO 4 were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 12.0 g (83%) of the desired compound 11-29 .
[제조예 159] 화합물 11-30의 제조[Manufacturing Example 159] Production of Compound 11-30
Figure PCTKR2015006723-appb-I000224
Figure PCTKR2015006723-appb-I000224
W-5 10.0g(16.1mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 4시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-30 9.2g(79%)을 얻었다.W-5 10.0g (16.1mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 (10.3 g, 48.3 mmol) was refluxed and stirred at 170 ° C in 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 4 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.2 g (79%) of the target compound 11-30 .
[제조예 160] 화합물 11-35의 제조[Manufacturing Example 160] Preparation of Compound 11-35
Figure PCTKR2015006723-appb-I000225
Figure PCTKR2015006723-appb-I000225
W-5 10.0g(16.1mmol), 4-bromo-2,6-diphenylpyrimidine 5.5g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-35 9.9g(85%)을 얻었다.The W-5 10.0g (16.1mmol), 4-bromo-2,6-diphenylpyrimidine 5.5g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2g (48.3mmol) 1,4-Dioxane and 30 mL of H 2 O at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 9.9 g (85%) of the desired compound 11-35 .
[제조예 161] 화합물 11-36의 제조Production Example 161 Production of Compound 11-36
Figure PCTKR2015006723-appb-I000226
Figure PCTKR2015006723-appb-I000226
W-5 10.0g(16.1mmol), 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 6.9g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-36 10.9g(84%)을 얻었다.W-5 10.0g (16.1mmol), 4 - ([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine 6.9g (17.7mmol), Pd (PPh 3) 4 0.9g ( 0.8 mmol) and K 3 PO 4 (10.2 g, 48.3 mmol) were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 ml of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , the solvent was removed by a rotary evaporator, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 10.9 g (84%) of the target compound 11-36 .
[제조예 162] 화합물 11-45의 제조[Manufacturing Example 162] Preparation of the compound 11-45
Figure PCTKR2015006723-appb-I000227
Figure PCTKR2015006723-appb-I000227
W-5 10.0g(16.1mmol), 2-(4-bromophenyl)-1-ethyl-1H-benzo[d]imidazole 5.3g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-45 9.8g(85%)을 얻었다.W-5 10.0g (16.1mmol), 2- (4-bromophenyl) -1-ethyl-1H-benzo [d] imidazole 5.3g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 (10.3 g, 48.3 mmol) were refluxed under stirring at 120 ° C in 170 mL of 1,4-dioxane and 30 mL of H 2 O for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off using dichloromethane and hexane as eluent to obtain 9.8 g (85%) of the desired compound 11-45 .
[제조예 163] 화합물 11-48의 제조[Manufacturing Example 163] Production of Compound 11-48
Figure PCTKR2015006723-appb-I000228
Figure PCTKR2015006723-appb-I000228
W-5 10.0g(16.1mmol), 4-bromobenzonitrile 3.2g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-48 6.8g(80%)을 얻었다.W-5 10.0g (16.1mmol), 4-bromobenzonitrile 3.2g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 to PO 4 10.2g (48.3mmol) 1,4- Dioxane 170mL And 30 mL of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 6.8 g (80%) of the target compound 11-48 .
[제조예 164] 화합물 11-49의 제조[Manufacturing Example 164] Production of Compound 11-49
Figure PCTKR2015006723-appb-I000229
Figure PCTKR2015006723-appb-I000229
W-5 10.0g(16.1mmol), 2-bromopyridine 2.8g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 7시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-49 7.3g(79%)을 얻었다.W-5 10.0g (16.1mmol), 2-bromopyridine 2.8g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 to PO 4 10.2g (48.3mmol) 1,4- Dioxane 170mL And 30 mL of H 2 O at 120 ° C for 7 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 7.3 g (79%) of the target compound 11-49 .
[제조예 165] 화합물 11-50의 제조[Manufacturing Example 165] Production of Compound 11-50
Figure PCTKR2015006723-appb-I000230
Figure PCTKR2015006723-appb-I000230
W-5 10.0g(16.1mmol), 3-bromo-2-phenylimidazo[1,2-a]pyridine 4.8g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-50 9.2g(83%)을 얻었다.W-5 10.0g (16.1mmol), 3-bromo-2-phenylimidazo [1,2-a] pyridine 4.8g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2 g (48.3 mmol) was refluxed with stirring in a solution of 170 mL of 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 9.2 g (83%) of the desired compound 11-50 .
[제조예 166] 화합물 11-76의 제조[Manufacturing Example 166] Synthesis of Compound 11-76
Figure PCTKR2015006723-appb-I000231
Figure PCTKR2015006723-appb-I000231
Z-3의 합성Synthesis of Z-3
Y-2 대신 V-2 93.2g(227.6mmol)을 사용하여 X-3의 합성법과 동일하게 진행하였다. 목적화합물 Z-3 125.4g(93%)을 얻었다.The same procedure as in the synthesis of X-3 was conducted using 93.2 g (227.6 mmol) of V-2 instead of Y-2. 125.4 g (93%) of the desired compound Z-3 was obtained.
Z-4 및 Z-1-4의 합성Synthesis of Z-4 and Z-1-4
V-3 대신 Z-3 125.4g(211.6mmol)을 사용하여 V-4의 합성법과 동일하게 진행하였다. 각각 목적화합물 Z-4 48.6g(40%) 및 Z-1-4 64.4g(53%)로 얻었다.4 was synthesized by using 125.4 g (211.6 mmol) of Z-3 instead of V-3. 48.6 g (40%) of the objective compound Z-4 and 64.4 g (53%) of Z-1-4 , respectively.
Z-5의 합성Synthesis of Z-5
Y-4 대신 Z-4 48.6g(84.6mmol)을 사용하여 X-1의 합성법과 동일하게 진행하였다. 목적화합물 Z-5 52.6g(100%)을 얻었다.The same procedure as in the synthesis of X-1 was carried out using 48.6 g (84.6 mmol) of Z-4 instead of Y-4. 52.6 g (100%) of the desired compound Z-5 was obtained.
Z-1-5의 합성Synthesis of Z-1-5
Y-4 대신 Z-1-4 64.4g(112.1mmol)을 사용하여 X-1의 합성법과 동일하게 진행하였다. 목적화합물 Z-1-5 69.7g(100%)을 얻었다.1 was prepared in the same manner as in the synthesis of X-1 using 64.4 g (112.1 mmol) of Z-1-4 instead of Y-4. 69.7 g (100%) of the desired compound Z-1-5 was obtained.
Figure PCTKR2015006723-appb-I000232
Figure PCTKR2015006723-appb-I000232
11-76의 합성Synthesis of 11-76
Z-1-5 10.0g(16.1mmol), 9-bromo-10-phenylanthracene 5.9g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-76 9.8g(80%)을 얻었다.Z-1-5 10.0g (16.1mmol), 9-bromo-10-phenylanthracene 5.9g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2g (48.3mmol) of 1,4-Dioxane and 30 mL of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.8 g (80%) of the target compound 11-76 .
[제조예 167] 화합물 11-78의 제조[Manufacturing Example 167] Synthesis of Compound 11-78
Figure PCTKR2015006723-appb-I000233
Figure PCTKR2015006723-appb-I000233
Z-1-5 10.0g(16.1mmol), Diphenyl phosphineoxide 6.5g(32.2mmol), Pd(PPh3)4 1.9g(1.6mmol), TEA 3.1mL(22.5mmol)을 Toluene 100mL 하에서 120℃로 4시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 MC, EA, MeOH로 씻어주었다. 그 후 디클로로메탄과 EA를 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-78 4.5g(40%)을 얻었다.A Z-1-5 10.0g (16.1mmol), Diphenyl phosphineoxide 6.5g (32.2mmol), Pd (PPh 3) 4 1.9g (1.6mmol), TEA 3.1mL (22.5mmol) in 100mL 4 Toluene 120 ℃ under sigan Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed, filtered and washed with MC, EA and MeOH. Thereafter, purification was carried out by column chromatography using dichloromethane and EA as developing solvents to obtain 4.5 g (40%) of the target compound 11-78 .
[제조예 168] 화합물 11-79의 제조[Manufacturing Example 168] Production of Compound 11-79
Figure PCTKR2015006723-appb-I000234
Figure PCTKR2015006723-appb-I000234
Z-1-5 10.0g(16.1mmol), 9,9'-(5-bromo-1,3-phenylene)bis(9H-carbazole) 8.6g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-79 12.3g(85%)을 얻었다.Z-1-5 10.0g (16.1mmol), 9,9 '- (5-bromo-1,3-phenylene) bis (9H-carbazole) 8.6g (17.7mmol), Pd (PPh 3) 4 0.9g ( 0.83 mmol) and K 3 PO 4 (10.2 g, 48.3 mmol) were refluxed under stirring at 120 ° C. for 6 hours in 170 mL of 1,4-dioxane and 30 mL of H 2 O. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 12.3 g (85%) of the desired compound 11-79 .
[제조예 169] 화합물 11-80의 제조[Manufacturing Example 169] Synthesis of Compound 11-80
Figure PCTKR2015006723-appb-I000235
Figure PCTKR2015006723-appb-I000235
Z-1-5 10.0g(16.1mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 3시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-80 9.3g(80%)을 얻었다.Z-1-5 10.0g (16.1mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 (10.3 g, 48.3 mmol) were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 3 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.3 g (80%) of the target compound 11-80 .
[제조예 170] 화합물 11-85의 제조[Manufacturing Example 170] Preparation of Compound 11-85
Figure PCTKR2015006723-appb-I000236
Figure PCTKR2015006723-appb-I000236
Z-1-5 10.0g(16.1mmol), 4-bromo-2,6-diphenylpyrimidine 5.5g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-85 10.2g(88%)을 얻었다.Z-1-5 10.0g (16.1mmol), 4-bromo-2,6-diphenylpyrimidine 5.5g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2g (48.3mmol ) Was refluxed and stirred at 170 ° C in 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 10.2 g (88%) of the target compound 11-85 .
[제조예 171] 화합물 11-86의 제조[Manufacturing Example 171] Production of Compound 11-86
Figure PCTKR2015006723-appb-I000237
Figure PCTKR2015006723-appb-I000237
Z-1-5 10.0g(16.1mmol), 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 6.9g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-86 10.6g(82%)을 얻었다.Z-1-5 10.0g (16.1mmol), 4 - ([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine 6.9g (17.7mmol), Pd (PPh 3) 4 0.9 g (0.8 mmol) of K 3 PO 4 and 10.2 g (48.3 mmol) of K 3 PO 4 were refluxed under stirring at 120 ° C. for 6 hours in 170 mL of 1,4-dioxane and 30 mL of H 2 O. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 10.6 g (82%) of the desired compound 11-86 .
[제조예 172] 화합물 11-95의 제조[Manufacturing Example 172] Production of Compound 11-95
Figure PCTKR2015006723-appb-I000238
Figure PCTKR2015006723-appb-I000238
Z-1-5 10.0g(16.1mmol), 2-(4-bromophenyl)-1-ethyl-1H-benzo[d]imidazole 5.3g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-95 10.0g(87%)을 얻었다.Z-1-5 10.0g (16.1mmol), 2- (4-bromophenyl) -1-ethyl-1H-benzo [d] imidazole 5.3g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol) And K 3 PO 4 (10.2 g, 48.3 mmol) were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off using dichloromethane and hexane as eluent to obtain 10.0 g (87%) of the desired compound 11-95 .
[제조예 173] 화합물 11-98의 제조[Manufacturing Example 173] Production of Compound 11-98
Figure PCTKR2015006723-appb-I000239
Figure PCTKR2015006723-appb-I000239
Z-1-5 10.0g(16.1mmol), 4-bromobenzonitrile 3.2g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-98 7.2g(85%)을 얻었다.Z-1-5 10.0g (16.1mmol), 4-bromobenzonitrile 3.2g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 1,4- the 10.2g (48.3mmol) to 120 ℃ under Dioxane 170mL and 30mL H 2 O was stirred at reflux for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 7.2 g (85%) of the target compound 11-98 .
[제조예 174] 화합물 11-99의 제조[Manufacturing Example 174] Synthesis of Compound 11-99
Figure PCTKR2015006723-appb-I000240
Figure PCTKR2015006723-appb-I000240
Z-1-5 10.0g(16.1mmol), 2-bromopyridine 2.8g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-99 7.6g(82%)을 얻었다.Z-1-5 10.0g (16.1mmol), 2-bromopyridine 2.8g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 1,4- the 10.2g (48.3mmol) And the mixture was stirred under reflux for 5 hours at 170 ° C in dioxane and 30 ml of H 2 O at 120 ° C. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 7.6 g (82%) of the target compound 11-99 .
[제조예 175] 화합물 11-100의 제조[Manufacturing Example 175] Production of Compound 11-100
Figure PCTKR2015006723-appb-I000241
Figure PCTKR2015006723-appb-I000241
Z-1-5 10.0g(16.1mmol), 3-bromo-2-phenylimidazo[1,2-a]pyridine 4.8g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 7시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 11-100 9.4g(85%)을 얻었다.Z-1-5 10.0g (16.1mmol), 3-bromo-2-phenylimidazo [1,2-a] pyridine 4.8g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO a 4 10.2g (48.3mmol) in 1,4-Dioxane 170mL 120 ℃ under and H 2 O 30mL was stirred at reflux for 7 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.4 g (85%) of the target compound 11-100 .
[제조예 176] 화합물 12-1의 제조[Manufacturing Example 176] Synthesis of Compound 12-1
Figure PCTKR2015006723-appb-I000242
Figure PCTKR2015006723-appb-I000242
G-1-1의 합성Synthesis of G-1-1
2-Bromo-9,9-diphenyl-9H-fluorene 대신 4-Bromo-9,9-diphenyl-9H-fluorene 60.0g(151.0mmol)을 사용하여 X-1의 합성법과 동일하게 진행하였다. 목적화합물 G-1-1 65.1g(97%)을 얻었다.1 was prepared in the same manner as in the synthesis of X-1 by using 60.0 g (151.0 mmol) of 4-bromo-9,9-diphenyl-9H-fluorene instead of 2-bromo-9,9-diphenyl-9H-fluorene. 65.1 g (97%) of the target compound G-1-1 was obtained.
G-1-2의 합성Synthesis of G-1-2
X-1 대신 G-1-1 65.1g(146.5mmol)을 사용하여 X-2의 합성법과 동일하게 진행하였다. 목적화합물 G-1-2 51.0g(85%)을 얻었다.2 was prepared in the same manner as in the synthesis of X-2 by using 65.1 g (146.5 mmol) of G-1-1 instead of X-1. 51.0 g (85%) of the target compound G-1-2 was obtained.
G-1-3의 합성Synthesis of G-1-3
X-2 대신 G-1-2 51.0g(124.5mmol)을 사용하여 X-3의 합성법과 동일하게 진행하였다. 목적화합물 G-1-3 70.1g(95%)을 얻었다.3 was prepared in the same manner as in the synthesis of X-3 by using 51.0 g (124.5 mmol) of G-1-2 instead of X-2. 70.1 g (95%) of the target compound G-1-3 was obtained.
G-1-4의 합성Synthesis of G-1-4
X-3 대신 G-1-3 70.1g(118.3mmol)을 사용하여 X-4의 합성법과 동일하게 진행하였다. 목적화합물 G-1-4 61.9g(91%)을 얻었다.4 was prepared in the same manner as in the synthesis of X-4 by using 70.1 g (118.3 mmol) of G-1-3 instead of X-3. 61.9 g (91%) of the desired compound G-1-4 was obtained.
G-1-5의 합성Synthesis of G-1-5
X-4 대신 G-1-4 61.9g(107.7mmol)을 사용하여 X-5의 합성법과 동일하게 진행하였다. 목적화합물 G-1-5 67.0g(100%)을 얻었다.The procedure of synthesis of X-5 was carried out by using 61.9 g (107.7 mmol) of G-1-4 instead of X-4. 67.0 g (100%) of the desired compound G-1-5 was obtained.
Figure PCTKR2015006723-appb-I000243
Figure PCTKR2015006723-appb-I000243
12-1의 합성Synthesis of 12-1
G-1-5 10.0g(16.1mmol), 9-bromo-10-phenylanthracene 5.9g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-1 10.2g(83%)을 얻었다.The G-1-5 10.0g (16.1mmol), 9-bromo-10-phenylanthracene 5.9g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2g (48.3mmol) 1,4-Dioxane and 30 mL of H 2 O at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 10.2 g (83%) of the target compound 12-1 .
[제조예 177] 화합물 12-3의 제조[Manufacturing Example 177] Production of Compound 12-3
Figure PCTKR2015006723-appb-I000244
Figure PCTKR2015006723-appb-I000244
G-1-5 10.0g(16.1mmol), Diphenyl phosphineoxide 6.5g(32.2mmol), Pd(PPh3)4 1.9g(1.6mmol), TEA 3.1mL(22.5mmol)을 Toluene 100mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 MC, EA, MeOH로 씻어주었다. 그 후 디클로로메탄과 EA를 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-3 4.8g(43%)을 얻었다.1.9 g (1.6 mmol) of Pd (PPh 3 ) 4 and 3.1 mL (22.5 mmol) of TEA were dissolved in 100 mL of toluene at 120 ° C. for 6 hours Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed, filtered and washed with MC, EA and MeOH. Thereafter, purification was carried out by column chromatography using dichloromethane and EA as developing solvents to obtain 4.8 g (43%) of the desired compound 12-3 .
[제조예 178] 화합물 12-5의 제조[Manufacturing Example 178] Synthesis of Compound 12-5
Figure PCTKR2015006723-appb-I000245
Figure PCTKR2015006723-appb-I000245
G-1-5 10.0g(16.1mmol), 9,9'-(5-bromo-1,3-phenylene)bis(9H-carbazole) 8.6g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-5 12.7g(88%)을 얻었다.G-1-5 10.0g (16.1mmol), 9,9 '- (5-bromo-1,3-phenylene) bis (9H-carbazole) 8.6g (17.7mmol), Pd (PPh 3) 4 0.9g ( 0.83 mmol) and K 3 PO 4 (10.2 g, 48.3 mmol) were refluxed under stirring at 120 ° C. for 6 hours in 170 mL of 1,4-dioxane and 30 mL of H 2 O. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 12.7 g (88%) of the target compound 12-5 .
[제조예 179] 화합물 12-6의 제조[Manufacturing Example 179] Production of Compound 12-6
Figure PCTKR2015006723-appb-I000246
Figure PCTKR2015006723-appb-I000246
G-1-5 10.0g(16.1mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 4시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-6 9.9g(85%)을 얻었다.G-1-5 10.0g (16.1mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 (10.3 g, 48.3 mmol) were refluxed with stirring in a solution of 170 mL of 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 4 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 9.9 g (85%) of the target compound 12-6 .
[제조예 180] 화합물 12-12의 제조[Manufacturing Example 180] Preparation of Compound 12-12
Figure PCTKR2015006723-appb-I000247
Figure PCTKR2015006723-appb-I000247
G-1-5 10.0g(16.1mmol), 4-bromo-2,6-diphenylpyrimidine 5.5g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-12 10.4g(90%)을 얻었다.G-1-5 10.0g (16.1mmol), 4-bromo-2,6-diphenylpyrimidine 5.5g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2g (48.3mmol ) Was refluxed with stirring in a solution of 170 mL of 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 10.4 g (90%) of the desired compound 12-12 .
[제조예 181] 화합물 12-13의 제조[Manufacturing Example 181] Synthesis of Compound 12-13
Figure PCTKR2015006723-appb-I000248
Figure PCTKR2015006723-appb-I000248
G-1-5 10.0g(16.1mmol), 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 6.9g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-13 11.0g(85%)을 얻었다.G-1-5 10.0g (16.1mmol), 4 - ([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine 6.9g (17.7mmol), Pd (PPh 3) 4 0.9 g (0.8 mmol) of K 3 PO 4 and 10.2 g (48.3 mmol) of K 3 PO 4 were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 ml of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 11.0 g (85%) of the target compound 12-13 .
[제조예 182] 화합물 12-37의 제조[Manufacturing Example 182] Synthesis of Compound 12-37
Figure PCTKR2015006723-appb-I000249
Figure PCTKR2015006723-appb-I000249
G-1-5 10.0g(16.1mmol), 2-(4-bromophenyl)-1-ethyl-1H-benzo[d]imidazole 5.3g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-37 9.8g(85%)을 얻었다.G-1-5 10.0g (16.1mmol), 2- (4-bromophenyl) -1-ethyl-1H-benzo [d] imidazole 5.3g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol) And K 3 PO 4 (10.2 g, 48.3 mmol) were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.8 g (85%) of the target compound 12-37 .
[제조예 183] 화합물 12-46의 제조[Manufacturing Example 183] Synthesis of Compound 12-46
Figure PCTKR2015006723-appb-I000250
Figure PCTKR2015006723-appb-I000250
G-1-5 10.0g(16.1mmol), 4-bromobenzonitrile 3.2g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-46 7.5g(88%)을 얻었다.G-1-5 10.0g (16.1mmol), 4-bromobenzonitrile 3.2g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 1,4- the 10.2g (48.3mmol) And the mixture was stirred under reflux for 5 hours at 170 ° C in dioxane and 30 ml of H 2 O at 120 ° C. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 7.5 g (88%) of the target compound 12-46 .
[제조예 184] 화합물 12-48의 제조[Manufacturing Example 184] Synthesis of Compound 12-48
Figure PCTKR2015006723-appb-I000251
Figure PCTKR2015006723-appb-I000251
G-1-5 10.0g(16.1mmol), 2-bromopyridine 2.8g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-48 7.9g(85%)을 얻었다.G-1-5 10.0g (16.1mmol), 2-bromopyridine 2.8g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 1,4- the 10.2g (48.3mmol) to 120 ℃ under Dioxane 170mL and 30mL H 2 O was stirred at reflux for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 7.9 g (85%) of the target compound 12-48 .
[제조예 185] 화합물 12-49의 제조[Manufacturing Example 185] Synthesis of Compound 12-49
Figure PCTKR2015006723-appb-I000252
Figure PCTKR2015006723-appb-I000252
G-1-5 10.0g(16.1mmol), 3-bromo-2-phenylimidazo[1,2-a]pyridine 4.8g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-49 9.6g(87%)을 얻었다.G-1-5 10.0g (16.1mmol), 3-bromo-2-phenylimidazo [1,2-a] pyridine 4.8g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 (10.3 g, 48.3 mmol) was refluxed and stirred at 170 ° C in 1,4-dioxane and 30 ml of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. Purification by column chromatography using dichloromethane and hexane as eluent gave 9.6 g (87%) of the target compound 12-49 .
[제조예 185] 화합물 12-51의 제조[Manufacturing Example 185] Preparation of Compound 12-51
Figure PCTKR2015006723-appb-I000253
Figure PCTKR2015006723-appb-I000253
H-1-3의 합성Synthesis of H-1-3
Y-2 대신 G-1-2 40.0g(97.7mmol)을 사용하여 X-3의 합성법과 동일하게 진행하였다. 목적화합물 H-1-3 55.0g(95%)을 얻었다.The synthesis was carried out in the same manner as in the synthesis of X-3 by using 40.0 g (97.7 mmol) of G-1-2 instead of Y-2. 55.0 g (95%) of the desired compound H-1-3 was obtained.
H-1-4의 합성Synthesis of H-1-4
Y-3 대신 H-1-3 55.0g(92.8mmol)을 사용하여 X-4의 합성법과 동일하게 진행하였다. 목적화합물 H-1-4 50.1g(94%)을 얻었다.4 was prepared in the same manner as in the synthesis of X-4 by using 55.0 g (92.8 mmol) of H-1-3 instead of Y-3. 50.1 g (94%) of the objective compound H-1-4 was obtained.
H-1-5의 합성Synthesis of H-1-5
Y-4 대신 H-1-4 50.1g(87.2mmol)을 사용하여 X-5의 합성법과 동일하게 진행하였다. 목적화합물 H-1-5 54.2g(100%)을 얻었다.The same procedure as in the synthesis of X-5 was conducted using 50.1 g (87.2 mmol) of H-1-4 instead of Y-4. 54.2 g (100%) of the desired compound H-1-5 was obtained.
Figure PCTKR2015006723-appb-I000254
Figure PCTKR2015006723-appb-I000254
12-51의 합성Synthesis of 12-51
H-1-5 10.0g(16.1mmol), 9-bromo-10-phenylanthracene 5.9g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-51 10.2g(83%)을 얻었다.H-1-5 10.0g (16.1mmol), 9-bromo-10-phenylanthracene 5.9g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2g (48.3mmol) of 1,4-Dioxane and 30 mL of H 2 O at 120 ° C for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 10.2 g (83%) of the target compound 12-51 .
[제조예 186] 화합물 12-53의 제조[Manufacturing Example 186] Synthesis of Compound 12-53
Figure PCTKR2015006723-appb-I000255
Figure PCTKR2015006723-appb-I000255
H-1-5 10.0g(16.1mmol), Diphenyl phosphineoxide 6.5g(32.2mmol), Pd(PPh3)4 1.9g(1.6mmol), TEA 3.1mL(22.5mmol)을 Toluene 100mL 하에서 120℃로 7시간동안 환류교반하였다. 반응 완료 후 실온으로 식힌 뒤 고체가 생성되어 필터한 후 MC, EA, MeOH로 씻어주었다. 그 후 디클로로메탄과 EA를 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-53 5.4g(48%)을 얻었다.The H-1-5 10.0g (16.1mmol), Diphenyl phosphineoxide 6.5g (32.2mmol), Pd (PPh 3) 4 1.9g (1.6mmol), TEA 3.1mL (22.5mmol) in 100mL 7 Toluene 120 ℃ under sigan Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature, and a solid was formed, filtered and washed with MC, EA and MeOH. Thereafter, the product was purified by column chromatography using dichloromethane and EA as eluent, to obtain 5.4 g (48%) of the desired compound 12-53 .
[제조예 187] 화합물 12-55의 제조[Manufacturing Example 187] Synthesis of Compound 12-55
Figure PCTKR2015006723-appb-I000256
Figure PCTKR2015006723-appb-I000256
H-1-5 10.0g(16.1mmol), 9,9'-(5-bromo-1,3-phenylene)bis(9H-carbazole) 8.6g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-55 12.3g(85%)을 얻었다.H-1-5 10.0g (16.1mmol), 9,9 '- (5-bromo-1,3-phenylene) bis (9H-carbazole) 8.6g (17.7mmol), Pd (PPh 3) 4 0.9g ( 0.8 mmol) and K 3 PO 4 (10.2 g, 48.3 mmol) were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 ml of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 12.3 g (85%) of the target compound 12-55 .
[제조예 188] 화합물 12-56의 제조[Manufacturing Example 188] Synthesis of Compound 12-56
Figure PCTKR2015006723-appb-I000257
Figure PCTKR2015006723-appb-I000257
H-1-5 10.0g(16.1mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 3시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-56 9.7g(83%)을 얻었다.H-1-5 10.0g (16.1mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine 4.7g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 (10.3 g, 48.3 mmol) were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 3 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.7 g (83%) of the target compound 12-56 .
[제조예 188] 화합물 12-62의 제조[Manufacturing Example 188] Synthesis of Compound 12-62
Figure PCTKR2015006723-appb-I000258
Figure PCTKR2015006723-appb-I000258
H-1-5 10.0g(16.1mmol), 4-bromo-2,6-diphenylpyrimidine 5.5g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-62 10.2g(88%)을 얻었다.H-1-5 10.0g (16.1mmol), 4-bromo-2,6-diphenylpyrimidine 5.5g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 10.2g (48.3mmol ) Was refluxed and stirred at 170 ° C in 1,4-dioxane and 30 mL of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 10.2 g (88%) of the target compound 12-62 .
[제조예 189] 화합물 12-63의 제조[Manufacturing Example 189] Synthesis of Compound 12-63
Figure PCTKR2015006723-appb-I000259
Figure PCTKR2015006723-appb-I000259
H-1-5 10.0g(16.1mmol), 4-([1,1'-biphenyl]-4-yl)-6-bromo-2-phenylpyrimidine 6.9g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 5시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-63 11.4g(88%)을 얻었다.H-1-5 10.0g (16.1mmol), 4 - ([1,1'-biphenyl] -4-yl) -6-bromo-2-phenylpyrimidine 6.9g (17.7mmol), Pd (PPh 3) 4 0.9 g (0.8 mmol) of K 3 PO 4 and 10.2 g (48.3 mmol) of K 3 PO 4 were refluxed and stirred at 170 ° C in 1,4-dioxane and 30 ml of H 2 O at 120 ° C for 5 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , the solvent was removed by a rotary evaporator, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 11.4 g (88%) of the target compound 12-63 .
[제조예 190] 화합물 12-87의 제조[Manufacturing Example 190] Preparation of Compound 12-87
Figure PCTKR2015006723-appb-I000260
Figure PCTKR2015006723-appb-I000260
H-1-5 10.0g(16.1mmol), 2-(4-bromophenyl)-1-ethyl-1H-benzo[d]imidazole 5.3g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-87 9.5g(82%)을 얻었다.H-1-5 10.0g (16.1mmol), 2- (4-bromophenyl) -1-ethyl-1H-benzo [d] imidazole 5.3g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol) And 10.3 g (48.3 mmol) of K 3 PO 4 were refluxed under stirring at 120 ° C. in 170 mL of 1,4-dioxane and 30 mL of H 2 O for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.5 g (82%) of the target compound 12-87 .
[제조예 191] 화합물 12-96의 제조[Manufacturing Example 191] Synthesis of Compound 12-96
Figure PCTKR2015006723-appb-I000261
Figure PCTKR2015006723-appb-I000261
H-1-5 10.0g(16.1mmol), 4-bromobenzonitrile 3.2g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-96 7.7g(90%)을 얻었다.H-1-5 10.0g (16.1mmol), 4-bromobenzonitrile 3.2g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 1,4- the 10.2g (48.3mmol) to 120 ℃ under Dioxane 170mL and 30mL H 2 O was stirred at reflux for 6 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 7.7 g (90%) of the target compound 12-96 .
[제조예 192] 화합물 12-98의 제조[Manufacturing Example 192] Preparation of Compound 12-98
Figure PCTKR2015006723-appb-I000262
Figure PCTKR2015006723-appb-I000262
H-1-5 10.0g(16.1mmol), 2-bromopyridine 2.8g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 7시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-98 7.7g(83%)을 얻었다.H-1-5 10.0g (16.1mmol), 2-bromopyridine 2.8g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 1,4- the 10.2g (48.3mmol) to 120 ℃ under Dioxane 170mL and 30mL H 2 O was stirred at reflux for 7 hours. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , the solvent was removed by a rotary evaporator, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 7.7 g (83%) of the target compound 12-98 .
[제조예 193] 화합물 12-99의 제조[Manufacturing Example 193] Synthesis of Compound 12-99
Figure PCTKR2015006723-appb-I000263
Figure PCTKR2015006723-appb-I000263
H-1-5 10.0g(16.1mmol), 3-bromo-2-phenylimidazo[1,2-a]pyridine 4.8g(17.7mmol), Pd(PPh3)4 0.9g(0.8mmol), K3PO4 10.2g(48.3mmol)을 1,4-Dioxane 170mL와 H2O 30mL 하에서 120℃로 6시간동안 환류교반하였다. 반응 종료 후 증류수와 MC(dichloromethane)로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 12-99 9.8g(89%)을 얻었다.H-1-5 10.0g (16.1mmol), 3-bromo-2-phenylimidazo [1,2-a] pyridine 4.8g (17.7mmol), Pd (PPh 3) 4 0.9g (0.8mmol), K 3 PO 4 (10.3 g, 48.3 mmol) was refluxed under stirring at 120 캜 for 6 hours in 170 mL of 1,4-dioxane and 30 mL of H 2 O. After completion of the reaction, the reaction mixture was extracted with distilled water and dichloromethane (MC). The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using dichloromethane and hexane as eluent to obtain 9.8 g (89%) of the target compound 12-99 .
상기 제조예들과 같은 방법으로 화합물을 제조하고, 그 합성확인결과를 표 1 및 표 2에 나타내었다. 표 1은 1H NMR(CDCl3, 200Mz)의 측정값이고, 표 2는 FD-질량분석계(FD-MS: Field desorption mass spectrometry)의 측정값이다.The compounds were prepared in the same manner as in the above Preparation Examples, and the results of the confirmation of the synthesis were shown in Tables 1 and 2. Table 1 shows the measured values of 1 H NMR (CDCl 3 , 200 Mz) and Table 2 shows the measured values of FD-MS (field desorption mass spectrometry).
[표 1][Table 1]
Figure PCTKR2015006723-appb-I000264
Figure PCTKR2015006723-appb-I000264
Figure PCTKR2015006723-appb-I000265
Figure PCTKR2015006723-appb-I000265
Figure PCTKR2015006723-appb-I000266
Figure PCTKR2015006723-appb-I000266
Figure PCTKR2015006723-appb-I000267
Figure PCTKR2015006723-appb-I000267
Figure PCTKR2015006723-appb-I000268
Figure PCTKR2015006723-appb-I000268
Figure PCTKR2015006723-appb-I000269
Figure PCTKR2015006723-appb-I000269
Figure PCTKR2015006723-appb-I000270
Figure PCTKR2015006723-appb-I000270
Figure PCTKR2015006723-appb-I000271
Figure PCTKR2015006723-appb-I000271
Figure PCTKR2015006723-appb-I000272
Figure PCTKR2015006723-appb-I000272
[표 2][Table 2]
Figure PCTKR2015006723-appb-I000273
Figure PCTKR2015006723-appb-I000273
Figure PCTKR2015006723-appb-I000274
Figure PCTKR2015006723-appb-I000274
Figure PCTKR2015006723-appb-I000275
Figure PCTKR2015006723-appb-I000275
Figure PCTKR2015006723-appb-I000276
Figure PCTKR2015006723-appb-I000276
Figure PCTKR2015006723-appb-I000277
Figure PCTKR2015006723-appb-I000277
Figure PCTKR2015006723-appb-I000278
Figure PCTKR2015006723-appb-I000278
Figure PCTKR2015006723-appb-I000279
Figure PCTKR2015006723-appb-I000279
Figure PCTKR2015006723-appb-I000280
Figure PCTKR2015006723-appb-I000280
Figure PCTKR2015006723-appb-I000281
Figure PCTKR2015006723-appb-I000281
Figure PCTKR2015006723-appb-I000282
Figure PCTKR2015006723-appb-I000282
Figure PCTKR2015006723-appb-I000283
Figure PCTKR2015006723-appb-I000283
Figure PCTKR2015006723-appb-I000284
Figure PCTKR2015006723-appb-I000284
Figure PCTKR2015006723-appb-I000285
Figure PCTKR2015006723-appb-I000285
Figure PCTKR2015006723-appb-I000286
Figure PCTKR2015006723-appb-I000286
Figure PCTKR2015006723-appb-I000287
Figure PCTKR2015006723-appb-I000287
Figure PCTKR2015006723-appb-I000288
Figure PCTKR2015006723-appb-I000288
Figure PCTKR2015006723-appb-I000289
Figure PCTKR2015006723-appb-I000289
Figure PCTKR2015006723-appb-I000290
Figure PCTKR2015006723-appb-I000290
Figure PCTKR2015006723-appb-I000291
Figure PCTKR2015006723-appb-I000291
Figure PCTKR2015006723-appb-I000292
Figure PCTKR2015006723-appb-I000292
Figure PCTKR2015006723-appb-I000293
Figure PCTKR2015006723-appb-I000293
Figure PCTKR2015006723-appb-I000294
Figure PCTKR2015006723-appb-I000294
Figure PCTKR2015006723-appb-I000295
Figure PCTKR2015006723-appb-I000295
Figure PCTKR2015006723-appb-I000296
Figure PCTKR2015006723-appb-I000296
Figure PCTKR2015006723-appb-I000297
Figure PCTKR2015006723-appb-I000297
Figure PCTKR2015006723-appb-I000298
Figure PCTKR2015006723-appb-I000298
Figure PCTKR2015006723-appb-I000299
Figure PCTKR2015006723-appb-I000299
Figure PCTKR2015006723-appb-I000300
Figure PCTKR2015006723-appb-I000300
Figure PCTKR2015006723-appb-I000301
Figure PCTKR2015006723-appb-I000301
Figure PCTKR2015006723-appb-I000302
Figure PCTKR2015006723-appb-I000302
Figure PCTKR2015006723-appb-I000303
Figure PCTKR2015006723-appb-I000303
Figure PCTKR2015006723-appb-I000304
Figure PCTKR2015006723-appb-I000304
Figure PCTKR2015006723-appb-I000305
Figure PCTKR2015006723-appb-I000305
Figure PCTKR2015006723-appb-I000306
Figure PCTKR2015006723-appb-I000306
Figure PCTKR2015006723-appb-I000307
Figure PCTKR2015006723-appb-I000307
한편, 도 4 내지 30은 특정 UV파장 영역에서의 PL(Photoluminescence) 또는 LTPL(Low Temperature Photoluminescence)측정 발광 흡수스펙트럼을 나타낸 그래프이다. PL의 측정은 Perkin Elmer사의 모델명 LS55 분광기를 사용하여 상온에서 측정하였고, LTPL 측정은 HITACHI사의 모델명 F7000 기기를 사용하였으며, 액체질소를 사용하여 -196℃(77K) 저온 조건에서 분석하였다.4 to 30 are graphs showing PL absorption spectra measured by PL (Photoluminescence) or LTPL (Low Temperature Photoluminescence) in a specific UV wavelength region. PL was measured at room temperature using a model LS55 spectrophotometer of Perkin Elmer, and LTPL was measured at -196 ° C (77K) using liquid nitrogen at a temperature of -196 ° C (77K) using a HITACHI model F7000 instrument.
도 4는 화합물 1-1의 274nm 파장에서의 PL 측정 그래프를 나타낸 것이다.4 shows a PL measurement graph of Compound 1-1 at a wavelength of 274 nm.
도 5는 화합물 1-12의 233nm 파장에서의 PL 측정 그래프를 나타낸 것이다.Fig. 5 shows a PL measurement graph of Compound 1-12 at a wavelength of 233 nm.
도 6은 화합물 1-36의 276nm 파장에서의 PL 측정 그래프를 나타낸 것이다.6 shows a PL measurement graph of Compound 1-36 at a wavelength of 276 nm.
도 7은 화합물 1-113의 240nm 파장에서의 PL 측정 그래프를 나타낸 것이다.7 shows a PL measurement graph of Compound 1-113 at a wavelength of 240 nm.
도 8은 화합물 1-119의 270nm 파장에서의 PL 측정 그래프를 나타낸 것이다.8 shows a PL measurement graph of the compound 1-119 at a wavelength of 270 nm.
도 9는 화합물 1-124의 240nm 파장에서의 PL 측정 그래프를 나타낸 것이다.FIG. 9 shows a PL measurement graph of a compound 1-124 at a wavelength of 240 nm.
도 10은 화합물 1-318의 309nm 파장에서의 PL 측정 그래프를 나타낸 것이다.FIG. 10 shows a PL measurement graph of Compound 1-318 at a wavelength of 309 nm.
도 11은 화합물 2-36의 282nm 파장에서의 PL 측정 그래프를 나타낸 것이다.11 shows a PL measurement graph of Compound 2-36 at a wavelength of 282 nm.
도 12는 화합물 2-38의 284nm 파장에서의 PL 측정 그래프를 나타낸 것이다.12 shows a PL measurement graph of Compound 2-38 at a wavelength of 284 nm.
도 13은 화합물 3-39의 307nm 파장에서의 PL 측정 그래프를 나타낸 것이다.Fig. 13 shows a PL measurement graph of compound 3-39 at a wavelength of 307 nm.
도 14는 화합물 3-46의 310nm 파장에서의 PL 측정 그래프를 나타낸 것이다.14 shows a PL measurement graph of Compound 3-46 at a wavelength of 310 nm.
도 15는 화합물 4-56의 278nm 파장에서의 PL 측정 그래프를 나타낸 것이다.15 shows a PL measurement graph of Compound 4-56 at a wavelength of 278 nm.
도 16은 화합물 4-58의 290nm 파장에서의 PL 측정 그래프를 나타낸 것이다.16 shows a PL measurement graph of Compound 4-58 at a wavelength of 290 nm.
도 17은 화합물 4-76의 267nm 파장에서의 PL 측정 그래프를 나타낸 것이다.17 shows a PL measurement graph of Compound 4-76 at a wavelength of 267 nm.
도 18은 화합물 4-169의 264nm 파장에서의 PL 측정 그래프를 나타낸 것이다.18 shows the PL measurement graph of Compound 4-169 at a wavelength of 264 nm.
도 19는 화합물 1-1의 309nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.19 is a graph showing the LTPL measurement at a wavelength of 309 nm of the compound 1-1.
도 20은 화합물 1-12의 338nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.20 is a graph showing the LTPL measurement of Compound 1-12 at a wavelength of 338 nm.
도 21은 화합물 1-36의 310nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.21 is a graph showing the LTPL measurement at a wavelength of 310 nm of Compound 1-36.
도 22는 화합물 1-318의 309nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.22 shows a graph of LTPL measurement at a wavelength of 309 nm of Compound 1-318.
도 23은 화합물 2-36의 409nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.23 is a graph showing the LTPL measurement at 409 nm wavelength of Compound 2-36.
도 24는 화합물 2-38의 408nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.24 is a graph showing the LTPL measurement at 408 nm wavelength of Compound 2-38.
도 25는 화합물 3-39의 307nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.25 is a graph showing the LTPL measurement at a wavelength of 307 nm of the compound 3-39.
도 26은 화합물 3-46의 268nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.26 is a graph showing the LTPL measurement at a wavelength of 268 nm of Compound 3-46.
도 27은 화합물 4-56의 278nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.27 is a graph showing the LTPL measurement at 278 nm wavelength of Compound 4-56.
도 28은 화합물 4-58의 329nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.28 shows a graph of LTPL measurement at a wavelength of 329 nm of Compound 4-58.
도 29는 화합물 4-76의 365nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.29 is a graph showing the LTPL measurement at 365 nm wavelength of Compound 4-76.
도 30은 화합물 4-169의 365nm 파장에서의 LTPL 측정 그래프를 나타낸 것이다.30 shows a graph of LTPL measurement at 365 nm wavelength of Compound 4-169.
상기 도 4 내지 18의 그래프에서 각각 y축은 강도(intensity)이고, x축은 파장(단위: ㎚)이다.In the graphs of FIGS. 4 to 18, the y-axis is the intensity and the x-axis is the wavelength (unit: nm).
유기 전계 발광 소자의 제작Fabrication of Organic Electroluminescent Device
[비교예 1][Comparative Example 1]
하기의 같은 방법으로 유기 전계 발광 소자를 제조하였다.An organic electroluminescent device was prepared in the following manner.
1500 Å의 두께로 인듐 틴 옥사이드(ITO)가 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 아세톤, 메탄올, 이소프로필 알코올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV 세정기에서 UV를 이용하여 5분간 UVO처리한다. 이후 기판을 플라즈마 세정기(PT)로 이송시킨후, 진공상태에서 인듐 틴 옥사이드(ITO) 일함수 및 잔막제거를 위해 플라즈마 처리를 하여, 유기증착용 열증착 장비로 이송하였다.A glass substrate coated with a thin film of indium tin oxide (ITO) at a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing with distilled water, ultrasonic cleaning is performed with a solvent such as acetone, methanol, isopropyl alcohol, etc., followed by UVO treatment for 5 minutes using UV in a UV scrubber. Subsequently, the substrate was transferred to a plasma cleaner (PT), plasma treatment was performed to remove indium tin oxide (ITO) work function and residual film in a vacuum state, and transferred to a thermal vapor deposition apparatus for vapor deposition.
상기와 같이 준비된 인듐 틴 옥사이드(ITO) 투명 전극(양극)위에 공통층인 정공주입층 4,4',4"-트리스(N,N-(2-나프틸)-페닐아미노)트리페닐 아민(4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA) 및 정공수송층 N,N'-비스(α-나프틸)-N,N'-디페닐-4,4'-디아민(N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine: NPB)을 순차적으로 형성하였다On the indium tin oxide (ITO) transparent electrode (anode) prepared as described above, a hole injection layer 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenyl amine 2-TNATA) and a hole transport layer N, N'- (N, N'-bis (? -Naphthyl) -N, N'-diphenyl-4,4'-diamine: NPB)
상기 정공수송층 상에 발광층을 다음과 같이 열 진공 증착시켰다. 상기 정공수송층 상에 발광층은 호스트로 CBP(4,4'-N,N'-dicarbazole-biphenyl), 도펀트로 Ir(ppy)3(tris(2-phenylpyridine)iridium)을 93:7의 비율로 사용하여 400Å 증착하였다. 이 후, 상기 발광층 상에 정공저지층으로 BCP를 60Å 증착하였으며, 상기 정공저지층 상에 전자수송층으로 Alq3 를 200Å 증착하였다. 마지막으로 전자수송층 상에 리튬 플루오라이드(lithium fluoride: LiF)를 10Å 두께로 증착하여 전자주입층을 형성한 후, 전자주입층 위에 알루미늄(Al) 음극을 1200Å의 두께로 증착하여 음극을 형성함으로써 유기 전계 발광 소자를 제조하였다.A light emitting layer was formed on the hole transporting layer by thermal vacuum deposition as follows. On the hole transport layer, CBP (4,4'-N, N'-dicarbazole-biphenyl) as a host and Ir (ppy) 3 (tris (2-phenylpyridine) iridium) as a dopant were used in a ratio of 93: 7 . Thereafter, BCP was deposited to a thickness of 60Å as a hole blocking layer on the light emitting layer, and Alq 3 . Finally, lithium fluoride (LiF) was deposited to a thickness of 10 Å on the electron transport layer to form an electron injection layer. An aluminum (Al) cathode was deposited on the electron injection layer to a thickness of 1200 Å to form a cathode Thereby preparing an electroluminescent device.
한편, OLED 소자 제작에 필요한 모든 유기 화합물은 재료 별로 각각 10-6~10-8torr 하에서 진공 승화 정제하여 OLED 제작에 사용하였다.On the other hand, all the organic compounds required for OLED device fabrication were vacuum sublimated and refined under 10 -6 ~ 10 - 8 torr for each material and used for OLED fabrication.
Figure PCTKR2015006723-appb-I000308
Figure PCTKR2015006723-appb-I000308
[비교예 2][Comparative Example 2]
OLED용 글래스(삼성-코닝사 제조)로부터 얻어진 투명전극 ITO 박막을 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 각 5분간 초음파 세척을 실시한 후, 이소프로판올에 넣어 보관한 후 사용하였다.The transparent electrode ITO thin film obtained from the glass for OLED (manufactured by Samsung Corning) was ultrasonically cleaned for 5 minutes each using trichlorethylene, acetone, ethanol and distilled water sequentially, and stored in isopropanol before use.
다음으로 ITO 기판을 진공 증착 장비 내에 설치하였다. 그 후에, 진공챔버 내에서, 상기 ITO 상에 4,4',4"-트리스(N,N-(2-나프틸)-페닐아미노)트리페닐 아민(4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA)을 600Å 두께로 진공 증착하여 정공주입층을 형성하였다.Next, ITO The substrate was placed in a vacuum deposition apparatus. Then, in a vacuum chamber, 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine (4,4' N, N- (2-naphthyl) -phenylamino) triphenyl amine: 2-TNATA) was vacuum deposited to a thickness of 600 Å to form a hole injection layer .
그 후에, 상기 정공주입층 상에 N,N'-비스(α-나프틸)-N,N'-디페닐-4,4'-디아민(N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine: NPB)을 300Å 두께로 진공 증착하여 정공수송층을 형성하였다.Thereafter, an N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine , N'-diphenyl-4,4'-diamine: NPB) was vacuum-deposited to a thickness of 300 Å to form a hole transport layer .
그리고 나서, 상기 정공수송층 상에 청색 발광 호스트 재료 H1 및 청색 발광 도펀트 재료 D1을 95:5 비율로 하여 200 Å 두께의 발광층을 진공 증착하였다.Then, a 200 Å thick light emitting layer was vacuum deposited on the hole transport layer with the ratio of the blue light emitting host material H1 and the blue light emitting dopant material D1 being 95: 5.
Figure PCTKR2015006723-appb-I000309
Figure PCTKR2015006723-appb-I000309
이어서 상기 발광층 상에 하기 구조식 E1의 화합물을 300Å 두께로 증착하여 전자수송층을 형성하였다.Then, a compound of the following structural formula E1 was deposited on the light emitting layer to a thickness of 300 Å to form an electron transporting layer .
Figure PCTKR2015006723-appb-I000310
Figure PCTKR2015006723-appb-I000310
그 후에, 상기 전자수송층 상에 전자주입층으로 리튬 플루오라이드(lithium fluoride: LiF)를 10Å 두께로 증착하였고, 상기 전자주입층 상에 Al을 1000Å의 두께로 하여 음극을 형성하여 OLED 소자를 제작하였다.Thereafter, lithium fluoride, an electron injection layer on the electron transport layer: a (lithium fluoride LiF) was deposited to a 10Å thick, to form a negative electrode to the Al on the electron injection layer to a thickness of 1000Å to manufacture an OLED device .
한편, OLED 소자 제작에 필요한 모든 유기 화합물은 재료 별로 각각 10-6~10-8 torr 하에서 진공 승화 정제하여 OLED 제작에 사용하였다.On the other hand, all organic compounds required for OLED device fabrication were vacuum sublimated and refined under 10 -6 ~ 10 - 8 torr for each material, and used for OLED fabrication.
[실시예 1-1 내지 1-10][Examples 1-1 to 1-10]
비교예 1에서 발광층 형성 시 사용된 호스트 CPB 대신에 본 발명에서 합성된 화합물을 이용하는 것을 제외하고는, 비교예 1과 동일하게 수행하여 유기 전계 발광 소자를 제작하였다.An organic electroluminescent device was fabricated in the same manner as in Comparative Example 1, except that the compound synthesized in the present invention was used in place of the host CPB used in forming the light emitting layer in Comparative Example 1.
[실시예 2-1 내지 2-267][Examples 2-1 to 2-267]
상기 비교예 2에서의 전자수송층 형성시 사용된 E1 대신 본 발명에서 합성된 화합물을 사용하는 것을 제외하고는, 비교예 2와 동일하게 수행하여 유기 전계 발광 소자를 제작하였다.An organic electroluminescent device was fabricated in the same manner as in Comparative Example 2 except that the compound synthesized in the present invention was used instead of E1 used in forming the electron transport layer in Comparative Example 2. [
유기 전계 발광 소자의 구동 전압 및 발광 효율Driving voltage and luminous efficiency of organic electroluminescent device
[실험예 1][Experimental Example 1]
상기와 같이 제조된 실시예 1-1 내지 1-10 및 비교예 1에서 각각 제작된 유기 전계 발광 소자에 대하여 맥사이언스사의 M7000으로 전계발광(EL)특성을 측정하였으며, 그 측정 결과를 가지고 맥사이언스사에서 제조된 수명장비측정장비(M6000)를 통해 기준 휘도가 6000 cd/m2 일 때, 수명(T90)을 측정하였다. 본 발명의 유기전계발광소자의 특성은 표 3과 같다.The electroluminescence (EL) characteristics of the organic electroluminescent devices fabricated in Examples 1-1 to 1-10 and Comparative Example 1 were measured with a M7000 M7000, The lifetime (T 90 ) was measured at a reference luminance of 6000 cd / m 2 through a lifetime measuring instrument (M6000) manufactured by Mitsubishi Electric Corporation. Table 3 shows the characteristics of the organic electroluminescent device of the present invention.
[표 3][Table 3]
Figure PCTKR2015006723-appb-I000311
Figure PCTKR2015006723-appb-I000311
상기 표 3의 결과로부터 알 수 있듯이, 본 발명의 유기전계발광소자 발광층 재료를 이용한 유기전계발광소자는 비교예 1에 비해 구동 전압이 낮고, 발광효율이 향상되었을 뿐만 아니라 수명도 현저히 개선되었다.As can be seen from the results of Table 3, the organic electroluminescent device using the organic electroluminescent light emitting layer material of the present invention has a lower driving voltage, improved luminous efficiency, and significantly improved lifetime as compared with Comparative Example 1. [
[실험예 2][Experimental Example 2]
비교예 2 및 실시예 2-1 내지 2-267 에서 각각 제작된 유기 전계 발광 소자에 대하여, 발광휘도가 700 cd/m2 에서의 구동전압, 효율, 색좌표, 수명을 측정하여 평가하였으며, 그 결과는 하기 표 4와 같다. 이때, 수명은 맥사이언스사의 M6000PMX을 사용하여 측정하였다.The driving voltage, efficiency, color coordinate, and lifetime at the luminance of 700 cd / m 2 were measured and evaluated for the organic EL device fabricated in each of the comparative example 2 and the example 2-1 to 2-267, Are shown in Table 4 below. At this time, the lifetime was measured using M6000PMX manufactured by Mac Science.
[표 4][Table 4]
Figure PCTKR2015006723-appb-I000312
Figure PCTKR2015006723-appb-I000312
Figure PCTKR2015006723-appb-I000313
Figure PCTKR2015006723-appb-I000313
Figure PCTKR2015006723-appb-I000314
Figure PCTKR2015006723-appb-I000314
Figure PCTKR2015006723-appb-I000315
Figure PCTKR2015006723-appb-I000315
Figure PCTKR2015006723-appb-I000316
Figure PCTKR2015006723-appb-I000316
Figure PCTKR2015006723-appb-I000317
Figure PCTKR2015006723-appb-I000317
Figure PCTKR2015006723-appb-I000318
Figure PCTKR2015006723-appb-I000318
Figure PCTKR2015006723-appb-I000319
Figure PCTKR2015006723-appb-I000319
Figure PCTKR2015006723-appb-I000320
Figure PCTKR2015006723-appb-I000320
Figure PCTKR2015006723-appb-I000321
Figure PCTKR2015006723-appb-I000321
Figure PCTKR2015006723-appb-I000322
Figure PCTKR2015006723-appb-I000322
Figure PCTKR2015006723-appb-I000323
Figure PCTKR2015006723-appb-I000323
상기 표 4에서와 같이 본 발명에 따른 화합물을 사용한 실시예 2-1 내지 2-267에서의 유기 전계 발광 소자는 비교예의 E1 전자수송층 재료를 사용한 유기전계발광 소자에 비하여 구동전압이 낮고, 발광 효율이 높은 것으로 나타났다. 또한, 소자 내구성, 즉 수명특성이 비교예보다 우수한 것으로 나타났다.As shown in Table 4, the organic electroluminescent devices in Examples 2-1 to 2-267 using the compound according to the present invention had lower driving voltage and lower emission efficiency than the organic electroluminescent device using the E1 electron transport layer material of the comparative example Respectively. In addition, it was found that the device durability, that is, the life characteristics was superior to the comparative example.

Claims (17)

  1. 하기 화학식 1의 화합물:A compound of formula
    [화학식 1][Chemical Formula 1]
    Figure PCTKR2015006723-appb-I000324
    Figure PCTKR2015006723-appb-I000324
    상기 화학식 1에 있어서, In Formula 1,
    X는 NR3, CR4R5, S, O 또는 Se이며,X is NR 3 , CR 4 R 5 , S, O or Se,
    Y는 수소; 중수소; 할로겐; -P(=O)R6R7; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,Y is hydrogen; heavy hydrogen; halogen; -P (= O) R 6 R 7; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
    R1 및 R2는 서로 같거나 상이하며, 각각 독립적으로 수소; 중수소; 할로겐; -P(=O)R8R9; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C2 내지 C60의 직쇄 또는 분지쇄의 알케닐; 치환 또는 비치환된 C2 내지 C60의 직쇄 또는 분지쇄의 알키닐; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알콕시; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,R 1 and R 2 are the same or different and each independently hydrogen; heavy hydrogen; halogen; -P (= O) R <8> R <9>; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; Substituted or unsubstituted C 2 to C 60 straight or branched chain alkenyl; Substituted or unsubstituted C 2 to C 60 straight or branched chain alkynyl; A substituted or unsubstituted C 1 to C 60 straight or branched chain alkoxy; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heterocycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
    a는 0 내지 4의 정수이며, a가 2 이상인 경우 R1은 서로 같거나 상이하고,a is an integer of 0 to 4, and when a is 2 or more, R 1 are the same or different from each other,
    b는 0 내지 6의 정수이며, b가 2 이상인 경우 R2는 서로 같거나 상이하고,b is an integer of 0 to 6, and when b is 2 or more, R 2 are the same or different from each other,
    R3은 수소; 중수소; 할로겐; -P(=O)R6R7; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되며,R 3 is hydrogen; heavy hydrogen; halogen; -P (= O) R 6 R 7; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
    R4 내지 R9은 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴이다.R 4 to R 9 are the same or different and each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl.
  2. 청구항 1에 있어서, 상기 "치환 또는 비치환된"이란 중수소; 할로겐; C1 내지 C60의 직쇄 또는 분지쇄의 알킬; C2 내지 C60의 직쇄 또는 분지쇄의 알케닐; C2 내지 C60의 직쇄 또는 분지쇄의 알키닐; C1 내지 C60의 직쇄 또는 분지쇄의 알콕시; C3 내지 C60의 단환 또는 다환의 시클로알킬; C2 내지 C60의 단환 또는 다환의 헤테로시클로알킬; C6 내지 C60의 단환 또는 다환의 아릴; C2 내지 C60의 단환 또는 다환의 헤테로아릴; -SiRR'R"; -P(=O)RR'; C1 내지 C20의 알킬아민; C6 내지 C60의 단환 또는 다환의 아릴아민; 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴아민으로 이루어진 군으로부터 선택된 1 이상의 치환기 또는 상기 치환기 중에서 선택된 2 이상의 치환기가 연결된 치환기로 치환 또는 비치환된 것을 의미하고,[Claim 4] The method according to claim 1, wherein the " substituted or unsubstituted &quot;halogen; C 1 to C 60 linear or branched alkyl; C 2 to C 60 straight or branched chain alkenyl; C 2 to C 60 linear or branched alkynyl; C 1 to C 60 straight or branched chain alkoxy; C 3 to C 60 monocyclic or polycyclic cycloalkyl; A C 2 to C 60 monocyclic or polycyclic heterocycloalkyl; C 6 to C 60 monocyclic or polycyclic aryl; C 2 to C 60 monocyclic or polycyclic heteroaryl; A C 1 to C 20 alkylamine, a C 6 to C 60 monocyclic or polycyclic arylamine, and a C 2 to C 60 monocyclic or polycyclic heteroaryl Amines, or substituted or unsubstituted with a substituent to which at least two substituents selected from the above-mentioned substituents are connected,
    상기 R, R' 및 R"은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소, 할로겐, C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 중수소, 할로겐, C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 중수소, 할로겐, C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 중수소, 할로겐, C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴인 것인 화합물.Wherein R, R 'and R "are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, halogen, C 6 to C 60 monocyclic or polycyclic aryl and C 2 to C 60 mono- or polycyclic heteroaryl Halogen, C 6 to C 60 monocyclic or polycyclic aryl, and C 2 to C 60 monocyclic or polycyclic heteroaromatic rings substituted or unsubstituted with one or more substituents selected from C 1 to C 60 , A C 3 to C 60 monocyclic or polycyclic cycloalkyl which is substituted or unsubstituted with at least one substituent selected from the group consisting of hydrogen, halogen, C 6 to C 60 monocyclic or polycyclic aryl, and C 2 to C 60 monocyclic or A C 6 to C 60 monocyclic or polycyclic aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of halogen, C 6 to C 60 monocyclic or polycyclic aryl, and C 2 to C 60 Monotone Or a C 2 to C 60 monocyclic or polycyclic heteroaryl which is unsubstituted or substituted with at least one substituent selected from the group consisting of a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteroaryl, or a substituted or unsubstituted heteroaryl.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1의 X가 NR3이고, Y 와 R3 중 적어도 하나는 -(L)m-(Z)n이거나,X in the formula (1) is NR 3 , and at least one of Y and R 3 is - (L) m - (Z) n ,
    상기 화학식 1의 X는 CR4R5, S, O 또는 Se이고, Y는 -(L)m-(Z)n이고,Wherein X is CR 4 R 5 , S, O or Se, Y is - (L) m - (Z) n ,
    L은 직접결합; -P(=O)R10-; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴렌; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴렌; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되며,L is a direct bond; -P (= O) R &lt; 10 &gt;-; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic arylene; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroarylene; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
    m은 1 내지 6의 정수이고,m is an integer of 1 to 6,
    n은 1 내지 5의 정수이며,n is an integer of 1 to 5,
    Z는 수소; 중수소; 할로겐; -P(=O)R11R12; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,Z is hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
    상기 R4, R5 및 R10 내지 R12은 서로 같거나 상이하며, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴인 것인 화합물.R 4 , R 5 and R 10 to R 12 are the same or different from each other, and each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl.
  4. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1의 X가 NR3이고, Y 와 R3 중 적어도 하나는 -(L)m-(Z)n이거나,X in the formula (1) is NR 3 , and at least one of Y and R 3 is - (L) m - (Z) n ,
    상기 화학식 1의 X는 CR4R5, S, O 또는 Se이고, Y는 -(L)m-(Z)n이고,Wherein X is CR 4 R 5 , S, O or Se, Y is - (L) m - (Z) n ,
    L은 직접결합; -P(=O)R10-; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴렌; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴렌; 및 C1 내지 C20의 알킬, C6 내지 C60의 단환 또는 다환의 아릴, 또는 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되며,L is a direct bond; -P (= O) R &lt; 10 &gt;-; Is at least one substituent selected from the group consisting of hydrogen, deuterium, halogen, -SiRR'R ", -P (= O) RR ', monocyclic or polycyclic aryl of C 6 to C 60 and monocyclic or polycyclic heteroaryl of C 2 to C 60 A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic arylene, a monovalent group selected from the group consisting of deuterium, halogen, -SiRR'R ", -P (═O) RR ', C 6 to C 60 monocyclic or polycyclic aryl, A monocyclic or polycyclic heteroarylene of C 2 to C 60 which is substituted or unsubstituted with at least one substituent selected from monocyclic or polycyclic heteroaryl of 2 to 60 carbon atoms; And amines substituted or unsubstituted with C 1 to C 20 alkyl, C 6 to C 60 monocyclic or polycyclic aryl, or C 2 to C 60 monocyclic or polycyclic heteroaryl,
    m은 1 내지 6의 정수이고,m is an integer of 1 to 6,
    n은 1 내지 5의 정수이며,n is an integer of 1 to 5,
    Z는 수소; 중수소; 할로겐; -P(=O)R11R12; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 중수소, 할로겐, -SiRR'R", -P(=O)RR', C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 및 C1 내지 C20의 알킬, C6 내지 C60의 단환 또는 다환의 아릴, 또는 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,Z is hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; Is at least one substituent selected from the group consisting of hydrogen, deuterium, halogen, -SiRR'R ", -P (= O) RR ', monocyclic or polycyclic aryl of C 6 to C 60 and monocyclic or polycyclic heteroaryl of C 2 to C 60 substituted or unsubstituted C 1 to C 60 straight chain alkyl or branched-chain; deuterium, halogen, -SiRR'R ", -P (= O ) RR ', C 6 to C 60 monocyclic or polycyclic aryl and C A C 6 to C 60 monocyclic or polycyclic aryl which is substituted or unsubstituted with at least one substituent selected from monocyclic or polycyclic heteroaryl of 2 to 60 carbon atoms; Is at least one substituent selected from the group consisting of hydrogen, deuterium, halogen, -SiRR'R ", -P (= O) RR ', monocyclic or polycyclic aryl of C 6 to C 60 and monocyclic or polycyclic heteroaryl of C 2 to C 60 Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl, and C 1 to C 20 alkyl, C 6 to C 60 monocyclic or polycyclic aryl, or C 2 to C 60 monocyclic or polycyclic Substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl,
    상기 R, R', R", R4, R5 및 R10 내지 R12은 서로 같거나 상이하며, 각각 독립적으로 수소; 중수소, 할로겐, C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 중수소, 할로겐, C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 중수소, 할로겐, C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 중수소, 할로겐, C6 내지 C60의 단환 또는 다환의 아릴 및 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴인 것인 화합물.Wherein R, R ', R ", R 4, R 5 and R 10 to R 12 are, and the same as or different from each other, each independently represent hydrogen, the heavy hydrogen, halogen, C 6 to monocyclic of C 60 or unsubstituted aryl, and C 2 to C 60 monocyclic or polycyclic heteroaryl, 1-alkyl of at least substituted with a substituent or a straight chain of the unsubstituted C 1 to C 60 unsubstituted or branched chain is selected from; deuterium, halogen, C 6 to C 60 monocyclic or polycyclic aryl and C 2 to C 60 monocyclic or polycyclic heteroaryl group unsubstituted or substituted by one or more substituents selected from C 3 to monocyclic of C 60 or polycyclic cycloalkyl; deuterium, halogen, a monocyclic of C 6 to C 60 or polycyclic aryl and C 2 to C 60 monocyclic or polycyclic heteroaryl group unsubstituted or substituted by one or more substituents selected from C 6 to C 60 monocyclic or polycyclic aryl group; or heavy hydrogen, halogen, C 6 to C 60 Monocyclic or polycyclic aryl C 2 to C 60 monocyclic or polycyclic heteroaryl group of compounds at least one substituted or unsubstituted C 2 to C 60 of monocyclic ring or is a substituent selected from the group consisting of unsubstituted heteroaryl ones.
  5. 청구항 3에 있어서,The method of claim 3,
    상기 L 은 직접결합; -P(=O)R10-; 치환 또는 비치환된 페닐렌; 치환 또는 비치환된 바이페닐렌; 치환 또는 비치환된 나프틸렌; 치환 또는 비치환된 안트릴렌; 치환 또는 비치환된 페난트레닐렌; 치환 또는 비치환된 트리페닐렌; 또는 치환 또는 비치환된 9,9-다이페닐-9H-플루오레닐렌; 치환 또는 비치환된 피리딜렌; 치환 또는 비치환된 피리미딜렌; 치환 또는 비치환된 트리아지닐렌; 치환 또는 비치환된 퀴놀릴렌; 치환 또는 비치환된 퀴나졸리닐렌; 치환 또는 비치환된 벤조티아졸릴렌; 치환 또는 비치환된 벤즈옥사졸릴렌; 치환 또는 비치환된 벤즈이미다졸릴렌; 치환 또는 비치환된 2가의 디벤조티오펜기; 치환 또는 비치환된 디벤조푸라닐렌; 치환 또는 비치환된 카바졸릴렌; 치환 또는 비치환된 인돌로[2, 3-a]카바졸릴렌; 치환 또는 비치환된 나프틸리디닐렌; 치환 또는 비치환된 옥사디아졸릴렌; 치환 또는 비치환된 피라졸로[1, 5-c]퀴나졸리닐렌; 치환 또는 비치환된 피리도[1,2-a]인다졸릴렌; 치환 또는 비치환된 디벤조[c, h]아크리딜; 치환 또는 비치환된 디알킬아민; 치환 또는 비치환된 디아릴아민; 치환 또는 비치환된 디헤테로아릴아민; 치환 또는 비치환된 알킬아릴아민; 치환 또는 비치환된 알킬헤테로아릴아민; 및 치환 또는 비치환된 아릴헤테로아릴아민으로 이루어진 군으로부터 선택되고,L is a direct bond; -P (= O) R &lt; 10 &gt;-; Substituted or unsubstituted phenylene; Substituted or unsubstituted biphenylene; Substituted or unsubstituted naphthylene; Substituted or unsubstituted anthrylene; Substituted or unsubstituted phenanthrenylene; Substituted or unsubstituted triphenylene; Or substituted or unsubstituted 9,9-diphenyl-9H-fluorenylenes; Substituted or unsubstituted pyridylenes; Substituted or unsubstituted pyrimidines; Substituted or unsubstituted thiaziene; Substituted or unsubstituted quinolylenes; Substituted or unsubstituted quinazolinylene; Substituted or unsubstituted benzothiazolylenes; Substituted or unsubstituted benzoxazolylene; Substituted or unsubstituted benzimidazolylene; A substituted or unsubstituted divalent dibenzothiophene group; Substituted or unsubstituted dibenzofuranylenes; Substituted or unsubstituted carbazolylene; Substituted or unsubstituted indolo [2, 3-a] carbazolylene; Substituted or unsubstituted naphthylidenediyl; Substituted or unsubstituted oxadiazolylene; Substituted or unsubstituted pyrazolo [1,5-c] quinazolinylene; Substituted or unsubstituted pyrido [1,2-a] indazolylene; Substituted or unsubstituted dibenzo [c, h] acridyl; Substituted or unsubstituted dialkylamines; A substituted or unsubstituted diarylamine; Substituted or unsubstituted diheteroarylamines; Substituted or unsubstituted alkylarylamines; Substituted or unsubstituted alkylheteroarylamines; And substituted or unsubstituted arylheteroaryl amines,
    상기 L이 치환되는 경우, 치환기는 중수소, 할로겐, -SiRR'R", -P(=O)RR', 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴 및 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되며,When L is substituted, the substituent is selected from the group consisting of deuterium, halogen, -SiRR'R ", -P (= O) RR ', substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, C 2 to C 60 monocyclic or polycyclic heteroaryl,
    상기 R, R', R" 및 R10은 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴인 것인 화합물.Wherein R, R ', R "and R 10 are the same as or different from each other, each independently represent hydrogen, substituted or unsubstituted C 1 to C 60 straight-chain or alkyl branched chain; substituted or unsubstituted C 3 to C A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl.
  6. 청구항 3에 있어서,The method of claim 3,
    상기 Z는 수소; 중수소; 할로겐; -P(=O)R11R12; 치환 또는 비치환된 에틸; 치환 또는 비치환된 페닐; 치환 또는 비치환된 바이페닐; 치환 또는 비치환된 나프틸; 치환 또는 비치환된 안트릴; 치환 또는 비치환된 페난트레닐; 치환 또는 비치환된 트리페닐레닐; 또는 치환 또는 비치환된 9,9-다이페닐-9H-플루오레닐; 치환 또는 비치환된 피리딜; 치환 또는 비치환된 피리미딜; 치환 또는 비치환된 트리아지닐; 치환 또는 비치환된 퀴놀릴; 치환 또는 비치환된 퀴나졸리닐; 치환 또는 비치환된 벤조티아졸릴; 치환 또는 비치환된 벤즈옥사졸릴; 치환 또는 비치환된 벤즈이미다졸릴; 치환 또는 비치환된 디벤조티오페닐; 치환 또는 비치환된 디벤조푸라닐; 치환 또는 비치환된 카바졸릴; 치환 또는 비치환된 인돌로[2, 3-a]카바졸릴, 치환 또는 비치환된 나프틸리디닐; 치환 또는 비치환된 옥사디아졸릴; 치환 또는 비치환된 피라졸로[1, 5-c]퀴나졸리닐; 치환 또는 비치환된 피리도[1,2-a]인다졸릴; 치환 또는 비치환된 디벤조[c, h]아크리딜; 치환 또는 비치환된 벤조[b]나프토[2,3-d]티오펜기; 치환 또는 비치환된 벤조[h]나프토[2,3-c]아크리딜; 치환 또는 비치환된 벤조[f]퀴놀릴; 치환 또는 비치환된 디알킬아민; 치환 또는 비치환된 디아릴아민; 치환 또는 비치환된 디헤테로아릴아민; 치환 또는 비치환된 알킬아릴아민; 치환 또는 비치환된 알킬헤테로아릴아민; 및 치환 또는 비치환된 아릴헤테로아릴아민으로 이루어진 군으로부터 선택되고,Z is hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; Substituted or unsubstituted ethyl; Substituted or unsubstituted phenyl; Substituted or unsubstituted biphenyl; Substituted or unsubstituted naphthyl; Substituted or unsubstituted anthryl; Substituted or unsubstituted phenanthrenyl; Substituted or unsubstituted triphenylenyl; Or substituted or unsubstituted 9,9-diphenyl-9H-fluorenyl; Substituted or unsubstituted pyridyl; Substituted or unsubstituted pyrimidyl; Substituted or unsubstituted thiazinyl; Substituted or unsubstituted quinolyl; Substituted or unsubstituted quinazolinyl; Substituted or unsubstituted benzothiazolyl; Substituted or unsubstituted benzoxazolyl; Substituted or unsubstituted benzimidazolyl; Substituted or unsubstituted dibenzothiophenyl; Substituted or unsubstituted dibenzofuranyl; Substituted or unsubstituted carbazolyl; Substituted or unsubstituted indolo [2, 3-a] carbazolyl, substituted or unsubstituted naphthyridinyl; Substituted or unsubstituted oxadiazolyl; Substituted or unsubstituted pyrazolo [1,5-c] quinazolinyl; Substituted or unsubstituted pyrido [1,2-a] indazolyl; Substituted or unsubstituted dibenzo [c, h] acridyl; Substituted or unsubstituted benzo [b] naphtho [2,3-d] thiophene groups; Substituted or unsubstituted benzo [h] naphtho [2,3-c] acridyl; Substituted or unsubstituted benzo [f] quinolyl; Substituted or unsubstituted dialkylamines; A substituted or unsubstituted diarylamine; Substituted or unsubstituted diheteroarylamines; Substituted or unsubstituted alkylarylamines; Substituted or unsubstituted alkylheteroarylamines; And substituted or unsubstituted arylheteroaryl amines,
    상기 Z가 치환되는 경우, 치환기는 중수소, 할로겐, -SiRR'R", -P(=O)RR', 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴 및 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴 중에서 선택되며,When Z is substituted, the substituent is selected from the group consisting of deuterium, halogen, -SiRR'R ", -P (= O) RR ', substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl and substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl,
    상기 R, R', R", R11 및 R12는 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴인 것인 화합물.Wherein R, R ', R &quot;, R 11 and R 12 are the same or different and each independently hydrogen, substituted or unsubstituted C 1 to C 60 linear or branched alkyl, substituted or unsubstituted C 3 to 60 carbon atoms, a substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl. compound.
  7. 청구항 3에 있어서, 상기 Z는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴이고, 상기 헤테로아릴은 헤테로원자로서 N, O 및 S 중에서 선택되는 적어도 어느 하나를 포함하는 것인 화합물.4. The compound according to claim 3, wherein Z is a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl, and the heteroaryl includes at least any one selected from N, O and S as a hetero atom compound.
  8. 청구항 3에 있어서, 상기 화학식 1에서 X는 NR3이고, 4. The compound according to claim 3, wherein X is NR &lt; 3 &gt;
    Y와 R3 중 적어도 하나는 -(L)m-(Z)n이며,At least one of Y and R 3 is - (L) m - (Z) n ,
    L은 치환 또는 비치환된 페닐렌; 치환 또는 비치환된 C5의 헤테로아릴렌이고,L is substituted or unsubstituted phenylene; Substituted or unsubstituted C 5 heteroarylene,
    상기 Z는 L의 코어에 결합된 원자에 대하여 파라 또는 메타위치에 결합되는 것인 화합물.Lt; RTI ID = 0.0 &gt; Z &lt; / RTI &gt; is bonded to the para or meta position relative to the atom bound to the core of L.
  9. 청구항 1에 있어서, 상기 화학식 1에서 X는 CR4R5, S, O 또는 Se이고,The method according to claim 1, wherein in Formula 1, X is CR 4 R 5, S, O or Se,
    Y는 -(L)m-(Z)n이며, Y is - (L) m - (Z) n ,
    L은 치환 또는 비치환된 페닐렌; 치환 또는 비치환된 피리딜렌이고,L is substituted or unsubstituted phenylene; Substituted or unsubstituted pyridylenes,
    R4 및 R5은 화학식 1과 동일하며, R 4 and R 5 are the same as in the formula (1)
    m은 1 내지 6의 정수이고,m is an integer of 1 to 6,
    n은 1 내지 5의 정수이며,n is an integer of 1 to 5,
    Z는 수소; 중수소; 할로겐; -P(=O)R11R12; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,Z is hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
    상기 R11 및 R12은 서로 같거나 상이하며, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴이고,R 11 and R 12 are the same or different from each other and each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl,
    상기 Z는 L의 코어에 결합된 원자에 대하여 파라 또는 메타위치에 결합되는 것인 화합물.Lt; RTI ID = 0.0 &gt; Z &lt; / RTI &gt; is bonded to the para or meta position relative to the atom bound to the core of L.
  10. 청구항 1에 있어서, 상기 화학식 1은 하기 화학식 2 내지 7 중 어느 하나로 표시되는 것인 화합물:The compound according to claim 1, wherein the formula (1) is represented by any one of the following formulas (2) to (7):
    [화학식 2](2)
    Figure PCTKR2015006723-appb-I000325
    Figure PCTKR2015006723-appb-I000325
    [화학식 3](3)
    Figure PCTKR2015006723-appb-I000326
    Figure PCTKR2015006723-appb-I000326
    [화학식 4][Chemical Formula 4]
    Figure PCTKR2015006723-appb-I000327
    Figure PCTKR2015006723-appb-I000327
    [화학식 5][Chemical Formula 5]
    Figure PCTKR2015006723-appb-I000328
    Figure PCTKR2015006723-appb-I000328
    [화학식 6][Chemical Formula 6]
    Figure PCTKR2015006723-appb-I000329
    Figure PCTKR2015006723-appb-I000329
    [화학식 7](7)
    Figure PCTKR2015006723-appb-I000330
    Figure PCTKR2015006723-appb-I000330
    상기 화학식 2 내지 7에 있어서, X, Y, R1, R2, a 및 b의 정의는 화학식 1과 동일하다.In the general formulas (2) to (7), X, Y, R 1 , R 2 , a and b are the same as in the general formula (1).
  11. 청구항 1에 있어서, 상기 화학식 1은 하기 화학식 8 내지 12 중 어느 하나로 표시되는 것인 화합물:The compound according to claim 1, wherein the formula (1) is represented by any one of the following formulas (8) to (12):
    [화학식 8][Chemical Formula 8]
    Figure PCTKR2015006723-appb-I000331
    Figure PCTKR2015006723-appb-I000331
    [화학식 9][Chemical Formula 9]
    Figure PCTKR2015006723-appb-I000332
    Figure PCTKR2015006723-appb-I000332
    [화학식 10][Chemical formula 10]
    Figure PCTKR2015006723-appb-I000333
    Figure PCTKR2015006723-appb-I000333
    [화학식 11](11)
    Figure PCTKR2015006723-appb-I000334
    Figure PCTKR2015006723-appb-I000334
    [화학식 12][Chemical Formula 12]
    Figure PCTKR2015006723-appb-I000335
    Figure PCTKR2015006723-appb-I000335
    상기 화학식 8 내지 12에 있어서, Y, a, b, R1 내지 R5는 상기 화학식 1과 동일하다.In Formulas 8 to 12, Y, a, b, and R 1 to R 5 are the same as in Formula 1.
  12. 청구항 11에 있어서, 상기 화학식 8은 하기 화학식 13 내지 24 중 어느 하나로 표시되는 것인 화합물:The compound according to claim 11, wherein the formula (8) is represented by any one of the following formulas (13) to
    [화학식 13][Chemical Formula 13]
    Figure PCTKR2015006723-appb-I000336
    Figure PCTKR2015006723-appb-I000336
    [화학식 14][Chemical Formula 14]
    Figure PCTKR2015006723-appb-I000337
    Figure PCTKR2015006723-appb-I000337
    [화학식 15][Chemical Formula 15]
    Figure PCTKR2015006723-appb-I000338
    Figure PCTKR2015006723-appb-I000338
    [화학식 16][Chemical Formula 16]
    Figure PCTKR2015006723-appb-I000339
    Figure PCTKR2015006723-appb-I000339
    [화학식 17][Chemical Formula 17]
    Figure PCTKR2015006723-appb-I000340
    Figure PCTKR2015006723-appb-I000340
    [화학식 18][Chemical Formula 18]
    Figure PCTKR2015006723-appb-I000341
    Figure PCTKR2015006723-appb-I000341
    [화학식 19][Chemical Formula 19]
    Figure PCTKR2015006723-appb-I000342
    Figure PCTKR2015006723-appb-I000342
    [화학식 20][Chemical Formula 20]
    Figure PCTKR2015006723-appb-I000343
    Figure PCTKR2015006723-appb-I000343
    [화학식 21][Chemical Formula 21]
    Figure PCTKR2015006723-appb-I000344
    Figure PCTKR2015006723-appb-I000344
    [화학식 22][Chemical Formula 22]
    Figure PCTKR2015006723-appb-I000345
    Figure PCTKR2015006723-appb-I000345
    [화학식 23](23)
    Figure PCTKR2015006723-appb-I000346
    Figure PCTKR2015006723-appb-I000346
    [화학식 24]&Lt; EMI ID =
    Figure PCTKR2015006723-appb-I000347
    Figure PCTKR2015006723-appb-I000347
    상기 화학식 13 내지 24에 있어서, In Formulas 13 to 24,
    R1 및 R2는 서로 같거나 상이하며, 각각 독립적으로 수소; 중수소; 할로겐; -P(=O)R8R9; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C2 내지 C60의 직쇄 또는 분지쇄의 알케닐; 치환 또는 비치환된 C2 내지 C60의 직쇄 또는 분지쇄의 알키닐; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알콕시; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,R 1 and R 2 are the same or different and each independently hydrogen; heavy hydrogen; halogen; -P (= O) R <8> R <9>; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; Substituted or unsubstituted C 2 to C 60 straight or branched chain alkenyl; Substituted or unsubstituted C 2 to C 60 straight or branched chain alkynyl; A substituted or unsubstituted C 1 to C 60 straight or branched chain alkoxy; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heterocycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
    a는 0 내지 4의 정수이며, a가 2 이상인 경우 R1은 서로 같거나 상이하고,a is an integer of 0 to 4, and when a is 2 or more, R 1 are the same or different from each other,
    b는 0 내지 6의 정수이며, b가 2 이상인 경우 R2는 서로 같거나 상이하고,b is an integer of 0 to 6, and when b is 2 or more, R 2 are the same or different from each other,
    Ar은 수소; 중수소; 할로겐; -P(=O)R11R12; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,Ar is hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
    R8, R9, R11 및 R12은 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴인 것인 화합물.R 8 , R 9 , R 11 and R 12 are the same or different from each other, and each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl.
  13. 청구항 10에 있어서, 상기 화학식 2 내지 7은 각각 하기 화학식 25 내지 30으로 표시되는 것인 화합물:The compound according to claim 10, wherein each of the formulas (2) to (7) is represented by the following formulas (25) to (30)
    [화학식 25](25)
    Figure PCTKR2015006723-appb-I000348
    Figure PCTKR2015006723-appb-I000348
    [화학식 26](26)
    Figure PCTKR2015006723-appb-I000349
    Figure PCTKR2015006723-appb-I000349
    [화학식 27](27)
    Figure PCTKR2015006723-appb-I000350
    Figure PCTKR2015006723-appb-I000350
    [화학식 28](28)
    Figure PCTKR2015006723-appb-I000351
    Figure PCTKR2015006723-appb-I000351
    [화학식 29][Chemical Formula 29]
    Figure PCTKR2015006723-appb-I000352
    Figure PCTKR2015006723-appb-I000352
    [화학식 30](30)
    Figure PCTKR2015006723-appb-I000353
    Figure PCTKR2015006723-appb-I000353
    상기 화학식 25 내지 30에 있어서, X'는 CR4R5, O, S 또는 Se이고, In the above Formulas 25 to 30, X 'represents CR 4 R 5 , O, S or Se,
    R1 및 R2는 서로 같거나 상이하며, 각각 독립적으로 수소; 중수소; 할로겐; -P(=O)R8R9; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C2 내지 C60의 직쇄 또는 분지쇄의 알케닐; 치환 또는 비치환된 C2 내지 C60의 직쇄 또는 분지쇄의 알키닐; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알콕시; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,R 1 and R 2 are the same or different and each independently hydrogen; heavy hydrogen; halogen; -P (= O) R <8> R <9>; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; Substituted or unsubstituted C 2 to C 60 straight or branched chain alkenyl; Substituted or unsubstituted C 2 to C 60 straight or branched chain alkynyl; A substituted or unsubstituted C 1 to C 60 straight or branched chain alkoxy; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heterocycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
    a는 0 내지 4의 정수이며, a가 2 이상인 경우 R1은 서로 같거나 상이하고,a is an integer of 0 to 4, and when a is 2 or more, R 1 are the same or different from each other,
    b는 0 내지 6의 정수이며, b가 2 이상인 경우 R2는 서로 같거나 상이하고,b is an integer of 0 to 6, and when b is 2 or more, R 2 are the same or different from each other,
    Ar은 수소; 중수소; 할로겐; -P(=O)R11R12; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 및 치환 또는 비치환된 C1 내지 C20의 알킬, 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴, 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 아민으로 이루어진 군으로부터 선택되고,Ar is hydrogen; heavy hydrogen; halogen; -P (= O) R 11 R 12; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; And substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl, or substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl Substituted or unsubstituted amines,
    R4, R5, R8, R9, R11 및 R12은 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; 치환 또는 비치환된 C3 내지 C60의 단환 또는 다환의 시클로알킬; 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 치환 또는 비치환된 C2 내지 C60의 단환 또는 다환의 헤테로아릴인 것인 화합물.R 4, R 5 , R 8 , R 9 , R 11 and R 12 are the same or different from each other, and each independently hydrogen; Substituted or unsubstituted C 1 to C 60 straight or branched alkyl; A substituted or unsubstituted C 3 to C 60 monocyclic or polycyclic cycloalkyl; A substituted or unsubstituted C 6 to C 60 monocyclic or polycyclic aryl; Or a substituted or unsubstituted C 2 to C 60 monocyclic or polycyclic heteroaryl.
  14. 청구항 1에 있어서, 상기 화학식 1의 화합물은 하기 화합물 중에서 선택되는 것인 화합물:The compound according to claim 1, wherein the compound of formula (1) is selected from the following compounds:
    Figure PCTKR2015006723-appb-I000354
    Figure PCTKR2015006723-appb-I000354
    Figure PCTKR2015006723-appb-I000355
    Figure PCTKR2015006723-appb-I000355
    Figure PCTKR2015006723-appb-I000356
    Figure PCTKR2015006723-appb-I000356
    Figure PCTKR2015006723-appb-I000357
    Figure PCTKR2015006723-appb-I000357
    Figure PCTKR2015006723-appb-I000358
    Figure PCTKR2015006723-appb-I000358
    Figure PCTKR2015006723-appb-I000359
    Figure PCTKR2015006723-appb-I000359
    Figure PCTKR2015006723-appb-I000360
    Figure PCTKR2015006723-appb-I000360
    Figure PCTKR2015006723-appb-I000361
    Figure PCTKR2015006723-appb-I000361
    Figure PCTKR2015006723-appb-I000362
    Figure PCTKR2015006723-appb-I000362
    Figure PCTKR2015006723-appb-I000363
    Figure PCTKR2015006723-appb-I000363
    Figure PCTKR2015006723-appb-I000364
    Figure PCTKR2015006723-appb-I000364
    Figure PCTKR2015006723-appb-I000365
    Figure PCTKR2015006723-appb-I000365
    Figure PCTKR2015006723-appb-I000366
    Figure PCTKR2015006723-appb-I000366
    Figure PCTKR2015006723-appb-I000367
    Figure PCTKR2015006723-appb-I000367
    Figure PCTKR2015006723-appb-I000368
    Figure PCTKR2015006723-appb-I000368
    Figure PCTKR2015006723-appb-I000369
    Figure PCTKR2015006723-appb-I000369
    Figure PCTKR2015006723-appb-I000370
    Figure PCTKR2015006723-appb-I000370
    Figure PCTKR2015006723-appb-I000371
    Figure PCTKR2015006723-appb-I000371
    Figure PCTKR2015006723-appb-I000372
    Figure PCTKR2015006723-appb-I000372
    Figure PCTKR2015006723-appb-I000373
    Figure PCTKR2015006723-appb-I000373
    Figure PCTKR2015006723-appb-I000374
    Figure PCTKR2015006723-appb-I000374
    Figure PCTKR2015006723-appb-I000375
    Figure PCTKR2015006723-appb-I000375
    Figure PCTKR2015006723-appb-I000376
    Figure PCTKR2015006723-appb-I000376
    Figure PCTKR2015006723-appb-I000377
    Figure PCTKR2015006723-appb-I000377
    Figure PCTKR2015006723-appb-I000378
    Figure PCTKR2015006723-appb-I000378
    Figure PCTKR2015006723-appb-I000379
    Figure PCTKR2015006723-appb-I000379
    Figure PCTKR2015006723-appb-I000380
    Figure PCTKR2015006723-appb-I000380
    Figure PCTKR2015006723-appb-I000381
    Figure PCTKR2015006723-appb-I000381
    Figure PCTKR2015006723-appb-I000382
    Figure PCTKR2015006723-appb-I000382
    Figure PCTKR2015006723-appb-I000383
    Figure PCTKR2015006723-appb-I000383
    Figure PCTKR2015006723-appb-I000384
    Figure PCTKR2015006723-appb-I000384
    Figure PCTKR2015006723-appb-I000385
    Figure PCTKR2015006723-appb-I000385
    Figure PCTKR2015006723-appb-I000386
    Figure PCTKR2015006723-appb-I000386
    Figure PCTKR2015006723-appb-I000387
    Figure PCTKR2015006723-appb-I000387
    Figure PCTKR2015006723-appb-I000388
    Figure PCTKR2015006723-appb-I000388
    Figure PCTKR2015006723-appb-I000389
    Figure PCTKR2015006723-appb-I000389
    Figure PCTKR2015006723-appb-I000390
    Figure PCTKR2015006723-appb-I000390
    Figure PCTKR2015006723-appb-I000391
    Figure PCTKR2015006723-appb-I000391
    Figure PCTKR2015006723-appb-I000392
    Figure PCTKR2015006723-appb-I000392
    Figure PCTKR2015006723-appb-I000393
    Figure PCTKR2015006723-appb-I000393
    Figure PCTKR2015006723-appb-I000394
    Figure PCTKR2015006723-appb-I000394
    Figure PCTKR2015006723-appb-I000395
    Figure PCTKR2015006723-appb-I000395
    Figure PCTKR2015006723-appb-I000396
    Figure PCTKR2015006723-appb-I000396
    Figure PCTKR2015006723-appb-I000397
    Figure PCTKR2015006723-appb-I000397
    Figure PCTKR2015006723-appb-I000398
    Figure PCTKR2015006723-appb-I000398
    Figure PCTKR2015006723-appb-I000399
    Figure PCTKR2015006723-appb-I000399
    Figure PCTKR2015006723-appb-I000400
    Figure PCTKR2015006723-appb-I000400
    Figure PCTKR2015006723-appb-I000401
    Figure PCTKR2015006723-appb-I000401
    Figure PCTKR2015006723-appb-I000402
    Figure PCTKR2015006723-appb-I000402
    Figure PCTKR2015006723-appb-I000403
    Figure PCTKR2015006723-appb-I000403
    Figure PCTKR2015006723-appb-I000404
    Figure PCTKR2015006723-appb-I000404
    Figure PCTKR2015006723-appb-I000405
    Figure PCTKR2015006723-appb-I000405
    Figure PCTKR2015006723-appb-I000406
    Figure PCTKR2015006723-appb-I000406
    Figure PCTKR2015006723-appb-I000407
    Figure PCTKR2015006723-appb-I000407
    Figure PCTKR2015006723-appb-I000408
    Figure PCTKR2015006723-appb-I000408
    Figure PCTKR2015006723-appb-I000409
    Figure PCTKR2015006723-appb-I000409
    Figure PCTKR2015006723-appb-I000410
    Figure PCTKR2015006723-appb-I000410
    Figure PCTKR2015006723-appb-I000411
    Figure PCTKR2015006723-appb-I000411
    Figure PCTKR2015006723-appb-I000412
    Figure PCTKR2015006723-appb-I000412
    Figure PCTKR2015006723-appb-I000413
    Figure PCTKR2015006723-appb-I000413
    Figure PCTKR2015006723-appb-I000414
    Figure PCTKR2015006723-appb-I000414
    Figure PCTKR2015006723-appb-I000415
    Figure PCTKR2015006723-appb-I000415
    Figure PCTKR2015006723-appb-I000416
    Figure PCTKR2015006723-appb-I000416
    Figure PCTKR2015006723-appb-I000417
    Figure PCTKR2015006723-appb-I000417
    Figure PCTKR2015006723-appb-I000418
    Figure PCTKR2015006723-appb-I000418
    Figure PCTKR2015006723-appb-I000419
    Figure PCTKR2015006723-appb-I000419
    Figure PCTKR2015006723-appb-I000420
    Figure PCTKR2015006723-appb-I000420
    Figure PCTKR2015006723-appb-I000421
    Figure PCTKR2015006723-appb-I000421
    Figure PCTKR2015006723-appb-I000422
    Figure PCTKR2015006723-appb-I000422
    Figure PCTKR2015006723-appb-I000423
    Figure PCTKR2015006723-appb-I000423
    Figure PCTKR2015006723-appb-I000424
    Figure PCTKR2015006723-appb-I000424
    Figure PCTKR2015006723-appb-I000425
    Figure PCTKR2015006723-appb-I000425
    Figure PCTKR2015006723-appb-I000426
    Figure PCTKR2015006723-appb-I000426
    Figure PCTKR2015006723-appb-I000427
    Figure PCTKR2015006723-appb-I000427
    Figure PCTKR2015006723-appb-I000428
    Figure PCTKR2015006723-appb-I000428
    Figure PCTKR2015006723-appb-I000429
    Figure PCTKR2015006723-appb-I000429
    Figure PCTKR2015006723-appb-I000430
    Figure PCTKR2015006723-appb-I000430
    Figure PCTKR2015006723-appb-I000431
    Figure PCTKR2015006723-appb-I000431
    Figure PCTKR2015006723-appb-I000432
    Figure PCTKR2015006723-appb-I000432
    Figure PCTKR2015006723-appb-I000433
    Figure PCTKR2015006723-appb-I000433
    Figure PCTKR2015006723-appb-I000434
    Figure PCTKR2015006723-appb-I000434
    Figure PCTKR2015006723-appb-I000435
    Figure PCTKR2015006723-appb-I000435
    Figure PCTKR2015006723-appb-I000436
    Figure PCTKR2015006723-appb-I000436
    Figure PCTKR2015006723-appb-I000437
    Figure PCTKR2015006723-appb-I000437
    Figure PCTKR2015006723-appb-I000438
    Figure PCTKR2015006723-appb-I000438
    Figure PCTKR2015006723-appb-I000439
    Figure PCTKR2015006723-appb-I000439
    Figure PCTKR2015006723-appb-I000440
    Figure PCTKR2015006723-appb-I000440
    Figure PCTKR2015006723-appb-I000441
    Figure PCTKR2015006723-appb-I000441
    Figure PCTKR2015006723-appb-I000442
    Figure PCTKR2015006723-appb-I000442
    Figure PCTKR2015006723-appb-I000443
    Figure PCTKR2015006723-appb-I000443
    Figure PCTKR2015006723-appb-I000444
    Figure PCTKR2015006723-appb-I000444
    Figure PCTKR2015006723-appb-I000445
    Figure PCTKR2015006723-appb-I000445
    Figure PCTKR2015006723-appb-I000446
    Figure PCTKR2015006723-appb-I000446
    Figure PCTKR2015006723-appb-I000447
    Figure PCTKR2015006723-appb-I000447
    Figure PCTKR2015006723-appb-I000448
    Figure PCTKR2015006723-appb-I000448
    Figure PCTKR2015006723-appb-I000449
    Figure PCTKR2015006723-appb-I000449
    Figure PCTKR2015006723-appb-I000451
    Figure PCTKR2015006723-appb-I000451
    Figure PCTKR2015006723-appb-I000452
    Figure PCTKR2015006723-appb-I000452
    Figure PCTKR2015006723-appb-I000453
    Figure PCTKR2015006723-appb-I000453
    Figure PCTKR2015006723-appb-I000454
    Figure PCTKR2015006723-appb-I000454
    Figure PCTKR2015006723-appb-I000455
    Figure PCTKR2015006723-appb-I000455
    Figure PCTKR2015006723-appb-I000456
    Figure PCTKR2015006723-appb-I000456
    Figure PCTKR2015006723-appb-I000457
    Figure PCTKR2015006723-appb-I000457
  15. 양극, 음극 및 상기 양극과 음극 사이에 구비된 1층 이상의 유기물층을 포함하고, 상기 유기물층 중 1층 이상이 청구항 1 내지 14 중 어느 하나의 항에 따른 화학식 1의 화합물을 포함하는 유기발광소자. 1. An organic light emitting device comprising: a cathode; a cathode; and at least one organic layer disposed between the anode and the cathode, wherein at least one of the organic layers includes the compound of Formula 1 according to any one of claims 1 to 14.
  16. 청구항 15에 있어서, 상기 화학식 1의 화합물을 포함하는 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 중에서 선택되는 적어도 하나의 층인 것인 유기발광소자.[17] The organic light emitting device according to claim 15, wherein the organic compound layer comprising the compound of Formula 1 is at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  17. 청구항 15에 있어서, 상기 화학식 1의 화합물을 포함하는 유기물층은 전자수송층 또는 발광층인 것인 유기발광소자. 16. The organic light emitting device according to claim 15, wherein the organic material layer containing the compound of Formula 1 is an electron transporting layer or a light emitting layer.
PCT/KR2015/006723 2014-06-30 2015-06-30 Heterocyclic compound and organic light emitting element using same WO2016003171A1 (en)

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Publication number Priority date Publication date Assignee Title
JP2017537085A (en) * 2014-11-11 2017-12-14 メルク パテント ゲーエムベーハー Materials for organic electroluminescent devices
CN110036013A (en) * 2016-11-30 2019-07-19 喜星素材株式会社 Heterocyclic compound and the organic light emitting apparatus for using this heterocyclic compound
TWI764958B (en) * 2016-11-30 2022-05-21 南韓商Ｌｔ素材股份有限公司 Hetero-cyclic compound and organic light emitting device using the same
JP2020504911A (en) * 2016-12-26 2020-02-13 エルティー・マテリアルズ・カンパニー・リミテッドＬＴ Ｍａｔｅｒｉａｌｓ Ｃｏ．， Ｌｔｄ． Organic light emitting device
EP3561892A4 (en) * 2016-12-26 2020-07-29 LT Materials Co., Ltd. Organic light-emitting device
WO2021103769A1 (en) * 2019-11-25 2021-06-03 广东阿格蕾雅光电材料有限公司 Compound and organic electroluminescence device containing the compound
CN113735848A (en) * 2020-05-27 2021-12-03 上海和辉光电股份有限公司 Electroluminescent compound and preparation method and application thereof
CN113735848B (en) * 2020-05-27 2023-04-07 上海和辉光电股份有限公司 Electroluminescent compound and preparation method and application thereof

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