WO2015034140A1 - Polycyclic compound containing pyrazole and organic light-emitting device using same - Google Patents

Polycyclic compound containing pyrazole and organic light-emitting device using same Download PDF

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WO2015034140A1
WO2015034140A1 PCT/KR2013/012050 KR2013012050W WO2015034140A1 WO 2015034140 A1 WO2015034140 A1 WO 2015034140A1 KR 2013012050 W KR2013012050 W KR 2013012050W WO 2015034140 A1 WO2015034140 A1 WO 2015034140A1
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substituted
compound
unsubstituted
monocyclic
formula
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정수진
김기용
홍장미
음성진
이주동
정정한
김미진
노영석
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희성소재(주)
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Definitions

  • the present invention relates to a novel pyrazole-containing polycyclic compound and an organic light emitting device comprising the same.
  • the electroluminescent device is a kind of self-luminous display device, and has an advantage of having a wide viewing angle, excellent contrast, and fast 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 two electrodes are combined in the organic thin film to form a pair, then disappear and emit light.
  • the organic thin film may be composed of a single layer or multiple layers as necessary.
  • the material of the organic thin film may have a light emitting function as necessary.
  • a compound which may itself constitute a light emitting layer may be used, or a compound which may serve as a host or a dopant of a host-dopant-based 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 pyrazole-containing polycyclic compound and an organic light emitting device comprising the same.
  • the present invention provides a compound of formula
  • R 1 to R 8 are the same as or different from each other, and each independently hydrogen; halogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; C 2 Through C 60 A straight or branched chain substituted or unsubstituted alkenyl; C 2 to C 60 straight or branched substituted or unsubstituted alkynyl; C 1 to C 60 straight or branched chain substituted or unsubstituted alkoxy; C 6 to C 60 straight or branched chain substituted or unsubstituted aryloxy; C 3 to C 60 of monocyclic or polycyclic substituted or unsubstituted cycloalkyl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heterocycloalkyl; C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl
  • the present invention provides an organic light emitting device comprising an anode, a cathode and at least one organic material layer provided between the anode and the cathode, one or more layers of the organic material layer comprises a compound of the formula (1). .
  • the compound described in this specification can be used as an organic material layer material of an organic light emitting element.
  • the compound may serve as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material in the organic light emitting device.
  • the compound may be usefully used as a material for the electron injection and / or transport layer of the organic light emitting device.
  • the compound may be used as a light emitting material.
  • the compound can be used as a phosphorescent host material.
  • 1 to 3 illustrate the stacking order of electrodes and organic material layers of organic light emitting diodes according to exemplary embodiments of the present invention.
  • FIG. 11 shows a PL measurement graph for 320 nm of compound 38.
  • FIG. 13 shows a PL measurement graph for 260 nm of Compound 66.
  • FIG. 14 shows a UV measurement graph of compound 76.
  • FIG. 15 shows a PL measurement graph for 303 nm of compound 76.
  • Compounds described herein may be represented by the formula (1). Specifically, the compound of Formula 1 may be used as the organic material layer material of the organic light emitting device by the structural features of the core structure and substituents as described above.
  • the compound of Formula 1 has a HOMO / LUMO value suitable for electron injection or transport of the organic light emitting device, excellent electron transport ability by the N-N bond and excellent thermal stability.
  • the compound of formula 1 is also suitable for use as a light emitting layer material, in particular as a phosphorescent host material of the light emitting layer.
  • a compound having a bipolar structure may be used as a host material of the light emitting layer of the organic light emitting device.
  • the condensed ring group of the N-containing ring and the S-containing ring is substituted in the core of Formula 1, the condensed ring group includes both a donor and an acceptor, and when used as a light emitting layer material, the light emitting layer ( In EML), holes and electrons can be balanced to form excitons.
  • the condensed ring group heterobands N and S affect the band gap when they are in the same direction and in different directions. When N and S are in the same direction, the conjugation length of ⁇ -electrons is short, and when N and S are in different directions, the conjugation length of ⁇ -electrons is long, affecting the T1 value.
  • substituted or unsubstituted is C 1 to C 60 linear or branched alkyl; C 2 Through C 60 Straight or branched alkenyl; C 2 to C 60 straight or branched alkynyl; C 3 to C 60 monocyclic or polycyclic cycloalkyl; C 2 to C 60 monocyclic or polycyclic heterocycloalkyl; C 6 Through C 60 Monocyclic or polycyclic aryl; C 2 Through C 60 Monocyclic or polycyclic heteroaryl; C 10 to C 60 spiro groups; C 1 to C 20 alkylamines; C 6 Through C 60 Monocyclic or polycyclic arylamine; And it means unsubstituted or substituted with one or more substituents selected from the group consisting of C 2 to C 60 monocyclic or polycyclic heteroarylamine. Said additional substituents may be further substituted further.
  • alkyl includes a 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 a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents.
  • Alkenyl may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, more specifically 2 to 20 carbon atoms.
  • alkynyl includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents.
  • Alkynyl may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, more specifically 2 to 20 carbon atoms.
  • cycloalkyl includes monocyclic or polycyclic having 3 to 60 carbon atoms, and may be further substituted by other substituents.
  • polycyclic means a group in which cycloalkyl is directly connected or condensed with another ring group.
  • the other ring group may be cycloalkyl, but may also be other types of ring groups such as heterocycloalkyl, aryl, heteroaryl, and the like.
  • the cycloalkyl may have 3 to 60 carbon atoms, specifically 3 to 40 carbon atoms, more specifically 5 to 20 carbon atoms.
  • the heterocycloalkyl includes S, O, N or Si as a hetero atom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by other substituents.
  • polycyclic means a group in which heterocycloalkyl is directly connected or condensed with another ring group.
  • the other ring group may be heterocycloalkyl, but may also be other types of ring groups such as cycloalkyl, aryl, heteroaryl, and the like.
  • the heterocycloalkyl may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, more specifically 3 to 20 carbon atoms.
  • aryl includes monocyclic or polycyclic having 6 to 60 carbon atoms, and may be further substituted with other substituents.
  • polycyclic means a group in which aryl is directly connected or condensed with another ring group.
  • the other ring group may be aryl, but may also be other types of ring groups such as cycloalkyl, heterocycloalkyl, heteroaryl, and the like.
  • the aryl may have 6 to 60 carbon atoms, specifically 6 to 40 carbon atoms, more specifically 6 to 25 carbon atoms.
  • aryl examples include phenyl, biphenyl, triphenyl, naphthyl, anthryl, chrysenyl, phenanthrenyl, peryllenyl, fluoranthenyl, triphenylenyl, penalenyl, pyrenyl, tetrasenyl, pentacenyl, Fluorenyl, indenyl, acenaphthylenyl, and the like, and condensed rings thereof, but are not limited thereto.
  • the heteroaryl includes S, O, N or Si as a hetero atom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by other substituents.
  • polycyclic means a group in which heteroaryl is directly connected or condensed with another ring group.
  • the other ring group may be heteroaryl, but may also be other types of ring groups such as cycloalkyl, heterocycloalkyl, aryl, and the like.
  • the heteroaryl may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, more specifically 3 to 25 carbon atoms.
  • heteroaryl examples include pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, fura Zanyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl, oxazinyl, thiazinyl, dioxynyl, triazinyl, tetrazinyl, quinolyl, isoqui Nolyl, quinazolinyl, isoquinazolinyl, acridinyl, phenantridinyl, imidazopyridinyl, diazanaphthalenyl, triazaindene, indolyl, indi
  • the spiro group includes a spiro structure, and may have 15 to 60 carbon atoms.
  • the 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 a group of the following structural formula.
  • aryl and heteroaryl are divalent groups.
  • R 1 to R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Or a substituted or unsubstituted C 10 to C 60 spiro group, with the remainder being hydrogen; halogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; C 2 Through C 60 A straight or branched chain substituted or unsubstituted alkenyl; C 2 to C 60 straight or branched substituted or unsubstituted alkynyl; C 1 to C 60 straight or branched chain substituted or unsubstituted alkoxy; C 6 to C 60 straight or branched chain substituted or unsubstituted aryloxy; C 3 to C 60 of monocyclic or polycyclic substituted or unsubstituted cycloalky
  • At least one of R 1 to R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Or a substituted or unsubstituted C 10 to C 60 spiro group.
  • one of R 1 to R 4 is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Or a substituted or unsubstituted C 10 to C 60 spiro group.
  • At least one of R 1 to R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Or a substituted or unsubstituted C 10 to C 60 spiro group, and the rest of R 1 to R 4 are hydrogen, or combine with an adjacent substituent to form an aromatic hydrocarbon ring or heterocycle.
  • At least one of R 1 to R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, and the remainder of R 1 to R 4 is hydrogen, or combines with an adjacent substituent to form an aromatic hydrocarbon ring or heterocycle.
  • R 2 is a C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl.
  • R 2 is a C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, R 1 , R 3 and R 4 are hydrogen.
  • R 2 is a C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, R 1 is hydrogen, and R 3 and R 4 combine with each other to form a substituted or unsubstituted benzene ring.
  • R 2 is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenan Trityl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group.
  • R 2 is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenan Triyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group, which are phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl At least one may be further substituted, and they may further be further substituted with at least one of phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl At least one may be further substituted
  • R 2 is further phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl, pyridyl substituted phenyl, pyrimidyl substituted phenyl, triazinyl substituted Phenyl, quinolyl substituted phenyl, isoquinolyl substituted phenyl, naphthyl substituted phenyl, anthryl substituted phenyl, phenanthryl substituted phenyl, phenyl substituted naphthyl, phenyl substituted anthryl, phenyl substituted phenanthryl, naphthyl substituted anthryl, an Triyl substituted naphthyl, phenyl substituted pyridyl, naphthyl substituted pyridyl, anthryl substituted pyridyl or
  • R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl.
  • R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, and R 1 to R 3 are hydrogen.
  • R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, R 3 is hydrogen, and R 1 and R 2 combine with each other to form a substituted or unsubstituted benzene ring.
  • R 4 is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenan Trityl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group.
  • R 4 is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenan Triyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group, which are phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl At least one may be further substituted, and they may further be further substituted with at least one of phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl At least one may be further substituted
  • R 4 is further phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl, pyridyl substituted phenyl, pyrimidyl substituted phenyl, triazinyl substituted Phenyl, quinolyl substituted phenyl, isoquinolyl substituted phenyl, naphthyl substituted phenyl, anthryl substituted phenyl, phenanthryl substituted phenyl, phenyl substituted naphthyl, phenyl substituted anthryl, phenyl substituted phenanthryl, naphthyl substituted anthryl, an Triyl substituted naphthyl, phenyl substituted pyridyl, naphthyl substituted pyridyl, anthryl substituted pyridyl or
  • R 1 is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl.
  • R 1 is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, and R 2 to R 4 are hydrogen.
  • R 1 is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, R 2 is hydrogen, and R 3 and R 4 combine with each other to form a substituted or unsubstituted benzene ring.
  • R 1 is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenan Trityl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group.
  • R 1 is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenan Triyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group, which are phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl At least one may be further substituted, and they may further be further substituted with at least one of phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl At least one may be further substituted
  • R 1 is further phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl, pyridyl substituted phenyl, pyrimidyl substituted phenyl, triazinyl substituted Phenyl, quinolyl substituted phenyl, isoquinolyl substituted phenyl, naphthyl substituted phenyl, anthryl substituted phenyl, phenanthryl substituted phenyl, phenyl substituted naphthyl, phenyl substituted anthryl, phenyl substituted phenanthryl, naphthyl substituted anthryl, an Triyl substituted naphthyl, phenyl substituted pyridyl, naphthyl substituted pyridyl, anthryl substituted pyridyl or
  • R 1 and R 2 combine with each other to form a substituted or unsubstituted benzene ring.
  • R 2 and R 3 combine with each other to form a substituted or unsubstituted benzene ring.
  • R 3 and R 4 combine with each other to form a substituted or unsubstituted benzene ring.
  • R 5 to R 8 are the same as or different from each other, and each independently hydrogen; halogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; C 2 Through C 60 A straight or branched chain substituted or unsubstituted alkenyl; C 2 to C 60 straight or branched substituted or unsubstituted alkynyl; C 1 to C 60 straight or branched chain substituted or unsubstituted alkoxy; C 6 to C 60 straight or branched chain substituted or unsubstituted aryloxy; C 3 to C 60 of monocyclic or polycyclic substituted or unsubstituted cycloalkyl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heterocycloalkyl; C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted
  • R 5 to R 8 are the same as or different from each other, and each independently hydrogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; C 2 Through C 60 A straight or branched chain substituted or unsubstituted alkenyl; C 2 to C 60 straight or branched substituted or unsubstituted alkynyl; C 3 to C 60 of monocyclic or polycyclic substituted or unsubstituted cycloalkyl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heterocycloalkyl; C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; And substituted or unsubstituted C 10 to C 60 spiro groups.
  • R 5 to R 8 are the same as or different from each other, and each independently hydrogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; And C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl.
  • R 5 to R 8 is hydrogen.
  • Chemical Formula 1 may be represented by one of the following Chemical Formulas 2 to 4.
  • R 1 to R 8 are the same as defined in Formula 1,
  • R is as defined in R 1 to R 8 , u is an integer from 1 to 4,
  • R is the same as or different from each other.
  • Chemical Formula 1 may be represented by one of the following Chemical Formulas 5 to 8.
  • R 5 to R 8 are the same as defined in Formula 1,
  • R is as defined in R 1 to R 4 ,
  • n is an integer of 1 to 3
  • v is an integer of 1 to 5
  • R is the same or different from each other
  • L is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted arylene; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroarylene, p and x are each an integer of 0 to 3, when p or x is 2 or more, L is the same as or different from each other,
  • Ar is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, q and y are each an integer of 0 to 3, and when q or y is 2 or more, Ar is the same as or different from each other.
  • L is a substituted or unsubstituted pyridine group, a substituted or unsubstituted pyrimidine group, a substituted or unsubstituted triazine group, a substituted or unsubstituted anthracene group , A substituted or unsubstituted phenanthrene group, a substituted or unsubstituted naphthalene group, or a substituted or unsubstituted phenylene group.
  • L is a pyridine group, pyrimidine group, triazine group, anthracene group, phenanthrene group, naphthalene group, or phenylene group.
  • L is a pyridine group, pyrimidine group, triazine group, anthracene group, or phenylene group.
  • p and x are each 0 or 1.
  • Ar is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, Substituted or unsubstituted phenanthryl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group.
  • Ar is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, Substituted or unsubstituted phenanthryl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group, which is phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, qui And further substituted with at least one of isnoquinol and isoquinolyl, which are further further substituted with at least one of phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl,
  • q and y are each 1 or 2.
  • q and y are each one.
  • R is hydrogen
  • Chemical Formula 1 may be represented by one of the following Chemical Formulas 9 to 13.
  • R 5 to R 8 are the same as defined in Formula 1,
  • X 1 to X 3 are the same as or different from each other, each independently N or CY 6 , at least one of X 1 to X 3 is N,
  • R, and Y 1 to Y 6 are the same as or different from each other, and each independently, as defined by R 1 to R 4 , at least two adjacent substituents in R, or at least two adjacent ones of Y 1 to Y 6
  • the substituents may be bonded to each other to form an aromatic hydrocarbon ring or heterocycle
  • n is an integer of 1 to 3, when n is 2 or more, R is the same as or different from each other, r is an integer of 1 to 5, when r is 2 or more, Y 3 is the same as or different from each other, s is an integer of 1 to 7, and when s is 2 or more, Y 4 is the same or different from each other, t is an integer of 1 to 9, and t is 2 or more Y 5 is the same as or different from each other,
  • L is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted arylene; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroarylene, p is an integer of 0 to 3, when p is 2 or more, L is the same as or different from each other,
  • Z1 and Z2 are C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aromatic hydrocarbon ring; Or a C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted aromatic hetero ring.
  • the formula (9) May be represented as follows.
  • Y 11 to Y 13 are the same as the definition of Y 6 .
  • Y 11 to Y 13 are each C 6 to C 60 monocyclic or polycyclic aryl or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl C 6 to C of the 60 monocyclic or polycyclic aryl; Or heteroaryl unsubstituted or substituted with C 6 to C 60 monocyclic or polycyclic aryl or C 2 to C 60 monocyclic or polycyclic heteroaryl.
  • T 1 to T 9 are each CRR ', NR, S or O,
  • R and R ' are the same as or different from each other, and each hydrogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; Or C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl.
  • T 1 , T 2 , T 4 , T 7 , T 8 , T 9 are each independently CRR ', NR, S or O, and T 3 , T 5 and T 6 are each Independently S or O.
  • R and R' are the same as or different from each other, and each independently C 1 to C 6 alkyl; Or C 6 to C 20 aryl.
  • R and R' are the same as or different from each other, and are each independently methyl or phenyl.
  • R is C 6 to C 20 aryl.
  • R is phenyl
  • p is an integer of 0 to 2
  • L is phenylene
  • the compound of Formula 1 may be selected from the following compounds.
  • the compounds described above may be prepared based on the preparation examples described below. In the following production examples, representative examples are described, but if necessary, a substituent may be added or excluded, and the position of the substituent may be changed. In addition, based on techniques known in the art, it is possible to change starting materials, reactants, reaction conditions and the like. Changing the type or position of substituents at the remaining positions as needed can be performed by those skilled in the art using techniques known in the art.
  • the organic light emitting device comprises the compound of Formula 1 described above.
  • the organic light emitting device according to the present invention includes one or more organic material layers provided between the anode, the cathode and the anode and the cathode, one or more of the organic material layer comprises a compound of formula (1).
  • FIG. 1 to 3 illustrate the stacking order of electrodes and organic material layers of organic light emitting diodes according to exemplary embodiments of the present invention.
  • these drawings are not intended to limit the scope of the present invention, the structure of the organic light emitting device known in the art can be applied to the present invention.
  • an organic light emitting device in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is illustrated.
  • the present invention is not limited thereto, and as shown in FIG. 2, 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.
  • the organic light emitting diode according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, an electron transport layer 304, and an electron injection layer 305.
  • the scope of the present invention is not limited by such a laminated structure, and other layers except for the light emitting layer may be omitted, and other functional layers may be added as needed.
  • the organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that the compound of Formula 1 is included in at least one layer of the organic material layer.
  • the compound of Formula 1 may constitute one or more layers of the organic material layer of the organic light emitting device alone. However, if necessary, the organic material layer may be mixed with other materials.
  • the compound of Formula 1 may be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material and the like in the organic light emitting device.
  • the organic material layer including the compound of Formula 1 may be a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer or an electron injection layer.
  • the compound of Formula 1 may be used as the electron injection and / or transport layer material of the organic light emitting device.
  • the organic material layer including the compound of Formula 1 is an electron transport layer.
  • the compound of Formula 1 may be used as a light emitting material of an organic light emitting device.
  • the organic material layer including the compound of Formula 1 may be a light emitting layer of the organic light emitting device.
  • the compound of Formula 1 may be used as a phosphorescent host material.
  • the compound of Formula 1 is used together with a light emitting dopant.
  • the light emitting dopant material those known in the art may be used.
  • phosphorescent dopant materials represented by LL'MX, LL'L''M, LMXX ', L 2 MX, and L 3 M can be used, but the scope of the present invention is not limited to these examples.
  • L, L ', L ", X and X' are bidentate ligands different from each other, and M is a metal which forms an 8-sided complex.
  • M may be iridium, platinum, osmium or the like.
  • L is an anionic bidentate ligand coordinated to M by sp 2 carbon and hetero atom, and X may function to trap electrons or holes.
  • Non-limiting examples of L include 2- (1-naphthyl) benzoxazole, (2-phenylbenzooxazole), (2-phenylbenzothiazole), (2-phenylbenzothiazole), (7,8 -Benzoquinoline), (thienylpyridin), phenylpyridine, benzothienylpyridin, 3-methoxy-2-phenylpyridine, thienylpyridin, tolylpyridine and the like.
  • Non-limiting examples of X include acetylacetonate (acac), hexafluoroacetylacetonate, salicylidene, picolinate, 8-hydroxyquinolinate, and the like.
  • anode material materials having a relatively large work function may be used, and a transparent conductive oxide, a metal, or a conductive polymer may be used.
  • the cathode material materials having a relatively low work function may be used, and a metal, a metal oxide, or a conductive polymer may be used.
  • hole injection material a well-known hole injection material may be used, for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or described in Advanced Material, 6, p.677 (1994).
  • Starburst-type amine derivatives such as TCTA, m-MTDATA, m-MTDAPB, polyaniline / dodecylbenzenesulfonic acid (polyaniline / dodecylbenzenesulfonic acid) or PEDOT / PSS (Poly (3, 4-ethylenedioxythiophene) / Poly (4-styrenesulfonate): poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate)), Pani / CSA (Polyaniline / Camphor sulfonic acid: polyaniline / camphorsulfonic acid) or PANI / PSS (Polyaniline / Poly (4-styrene-sulfonate): polyaniline / poly (4-styrenesulfonate)) and the like can be used.
  • Polyaniline / dodecylbenzenesulfonic acid polyaniline / dode
  • pyrazoline derivatives arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, and the like may be used, and low molecular or polymer materials may be used.
  • Examples of the electron transport material include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinomethane and derivatives thereof, and fluorenone Derivatives, diphenyl dicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and the like can be used, as well as high molecular weight materials as well as high molecular materials.
  • LiF is representatively used in the art, but the present invention is not limited thereto.
  • a red, green or blue light emitting material may be used, and if necessary, two or more light emitting materials may be mixed.
  • a fluorescent material can be used as a light emitting material, it can also be used as a phosphorescent material.
  • a material which combines holes and electrons injected from the anode and the cathode, respectively, to emit light may be used, but materials in which both the host material and the dopant material are involved in light emission may be used.
  • the compound of formula 1 may be prepared by introducing a substituent in the same manner as in Scheme 2 or 3.
  • R is as defined in R 1 to R 8 of Formula 1 above.
  • a compound 1, a compound 3, a compound 8, a compound 12, a compound 13, a compound 16, a compound 18, a compound 28 was performed in the same manner as in Preparation Example 1, except that the compound of Table 1 was used as the compound Ar 1 . , Compound 35 and compound 38 were prepared.
  • a compound of Chemical Formula 1 may be prepared according to Scheme 4 below.
  • R is as defined in R 1 to R 8 of Formula 1 above. It will be apparent to those skilled in the art that the position of the substituent can be changed depending on the substituted position of Br.
  • a compound of Chemical Formula 1 may be prepared according to Scheme 5 below.
  • R is as defined in R 1 to R 8 of Formula 1 above. It will be apparent to those skilled in the art that the position of the substituents can be varied depending on the substituted position of Br or the position of the condensed ring of the starting material.
  • a compound of Chemical Formula 1 may be prepared according to Scheme 6 below.
  • R is as defined in R 1 to R 8 of Formula 1 above. It will be apparent to those skilled in the art that the position of the substituents can be varied depending on the substituted position of Br or the position of the condensed ring of the starting material.
  • a compound of Chemical Formula 1 may be prepared according to the following Scheme 7.
  • R is as defined in R 1 to R 8 of Formula 1 above. It will be apparent to those skilled in the art that the type and position of the substituent of the compound of Formula 1 can be changed according to the type and position of the substituent of the starting material.
  • Trifluoroacetic acid (46.5 ml, 2.4 eq) was added to an acetic acid (700 ml) mixture containing Compound 250-1 (68.9 g, 1.0 eq) in one neck rbf and stirred at 100 ° C. for 15 hours. The solution cooled to room temperature was washed with acetic acid and hexane and filtered to obtain an ivory solid compound 250-2 (27.3 g, 42%).
  • Synthesis was performed in the same manner as in the preparation of Compound 236, except that Compound a-5 was used instead of Compound a-1.
  • HOMO, LUMO, and BAND GAP of Compound 38, Compound 66, and Compound 76 were measured using a CV measuring instrument (princeton appied research, model name: Parstat2273) using the following method. Are shown in Tables 9 to 11 below.
  • Electrolyte solution 3.3 g of tetrabutylammonium tetrafluoroborate was precisely weighed and placed in a 100 ml volumetric flask, and methylene chloride was added to make 100 ml.
  • Standard solution Approximately 1 mg of NPB was precisely weighed, placed in a 10 ml volumetric flask, and the electrolyte was added to make 10 ml.
  • Sample solution About 1 mg of the compound was accurately weighed and placed in a 10 ml volumetric flask, and the electrolyte solution was added to 10 ml before being used as a sample solution.
  • the y axis represents current (unit: A), and the x axis represents potential (unit: V).
  • Figure 10 shows a UV measurement graph of the compound 38.
  • FIG. 11 shows a PL measurement graph for 320 nm of compound 38.
  • FIG. 13 shows a PL measurement graph for 260 nm of Compound 66.
  • FIG. 14 shows a UV measurement graph of compound 76.
  • FIG. 15 shows a PL measurement graph for 303 nm of compound 76.
  • the y-axis of FIGS. 10 to 15 are intensity, respectively, and the x-axis is wavelength (unit: nm).
  • the transparent electrode ITO thin film obtained from the glass for OLED was subjected to ultrasonic washing using trichloroethylene, acetone, ethanol and distilled water in sequence, and used after washing in isopropyl alcohol.
  • an ITO substrate is placed in the substrate folder of the vacuum deposition equipment, and evacuated until the vacuum degree in the vacuum deposition equipment reaches 10 -7 torr, and then the following 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine (4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenyl amine: hereinafter referred to as 2-TNATA) by vapor deposition A 600 ⁇ m thick hole injection layer was deposited on the ITO substrate.
  • NPB N, N'-bis ( ⁇ -naphthyl) -N, N'-diphenyl-4,4'-diamine
  • a light emitting layer was deposited thereon as follows.
  • the following ⁇ -ADN was used as a host as a light emitting material in one cell in the vacuum deposition equipment, and the following BD1 was added as a dopant in the other cell.
  • the following tris (8-hydroxyquinoline) aluminum (III) (hereinafter referred to as Alq 3 ) was deposited to an thickness of 200 kPa as the electron transporting layer.
  • lithium fluoride LiF
  • Al cathode was deposited to a thickness of 1200 ⁇ to produce an OLED.
  • An OLED was manufactured in the same manner as in the comparative example, except that the compound of Table 12 was used instead of the tris (8-hydroxyquinoline) aluminum (III) (Alq 3 ) of the comparative example as the electron transport layer material.
  • the driving voltage (V), power efficiency (cd / A) and driving life of the OLED device fabricated as described above at 1,000 cd / m 2 and the time until the efficiency drops to 50% are described in Table 12 below. It was.
  • the organic light emitting device manufactured by using the compound of Preparation Example of the present invention as an electron transporting material from the results of Table 12 the organic light emitting device using tris (8-hydroxyquinoline) aluminum (III) (Alq 3 ) in the Comparative Example Excellent characteristics in driving voltage, efficiency and lifespan were confirmed. Accordingly, it was confirmed that the pyrazole-containing polycyclic derivative represented by Chemical Formula 1 of the present invention was useful as a material of the electron transport layer when manufacturing an organic light emitting device.
  • the transparent electrode ITO thin film obtained from the glass for OLED was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol, and distilled water in sequence, and then stored in isopropanol and used.
  • substrate was installed in the board
  • a current was applied to the cell to evaporate 2-TNATA to deposit a 600 kW hole injection layer on the ITO substrate.
  • NPB was placed in another cell in the vacuum deposition equipment, and a 300 ⁇ thick hole transport layer was deposited on the hole injection layer by applying an electric current to the cell.
  • the phosphorescent green light emitting material having the following structure was deposited on the light emitting layer.
  • CBP 4,4'-bis (carbazol-9-yl) biphenyl
  • Ir (ppy) 3 green light emitting dopant material
  • Tris (2-phenylpyridine) iridium (III)) was 10% vacuum deposited relative to the host material.
  • BCP 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • Alq 3 as an electron transport layer was 200 GPa thick.
  • lithium fluoride was deposited to a thickness of 10 kPa with an electron injection layer.
  • Al cathode was deposited to a thickness of 1000 ⁇ to produce an OLED.
  • Test Example 3 OLED device fabrication
  • a device was fabricated using the same materials as in Comparative Example 2 except for using the materials shown in Table 13 corresponding to the green light emitting layer in Comparative Example instead of CBP.
  • the drive voltage (Op.V) and power efficiency (cd / A) of the OLED device manufactured as described above are described in Table 13 below until the efficiency drops to 50% at 1,000 cd / m 2 .
  • the organic light emitting device manufactured by using the compound of Preparation Example of the present invention as a phosphorescent light emitting layer material compared to the organic light emitting device using the CBP in the comparative example was confirmed excellent characteristics in driving voltage, efficiency and life. Accordingly, it was confirmed that the pyrazole-containing polycyclic derivative represented by Chemical Formula 1 of the present invention is useful as a material of the phosphorescent light emitting layer in fabricating an organic light emitting device.

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Abstract

The present invention relates to a polycyclic compound containing pyrazole and an organic light-emitting device including the same.

Description

피라졸 함유 다환고리 화합물 및 이를 이용한 유기발광소자Pyrazole-containing polycyclic compound and organic light emitting device using the same
본 발명은 신규한 피라졸 함유 다환고리 화합물 및 이를 포함하는 유기발광소자에 관한 것이다.The present invention relates to a novel pyrazole-containing polycyclic compound and an organic light emitting device comprising the same.
전계 발광 소자는 자체 발광형 표시 소자의 일종으로서, 시야각이 넓고, 콘트라스트가 우수할 뿐만 아니라 응답속도가 빠르다는 장점을 가지고 있다. The electroluminescent device is a kind of self-luminous display device, and has an advantage of having a wide viewing angle, excellent contrast, and fast 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 two electrodes are combined in the organic thin film to form a pair, then disappear and emit light. The organic thin film may be composed of a single layer or multiple layers as 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 necessary. For example, as the organic thin film material, a compound which may itself constitute a light emitting layer may be used, or a compound which may serve as a host or a dopant of a host-dopant-based light emitting layer may be used. In addition, as a 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, lifespan or efficiency of the organic light emitting device, the development of the material of the organic thin film is continuously required.
본 발명은 신규한 피라졸 함유 다환고리 화합물 및 이를 포함하는 유기발광소자를 제공한다.The present invention provides a novel pyrazole-containing polycyclic compound and an organic light emitting device comprising the same.
본 발명은 하기 화학식 1의 화합물을 제공한다:The present invention provides a compound of formula
[화학식 1][Formula 1]
Figure PCTKR2013012050-appb-I000001
Figure PCTKR2013012050-appb-I000001
상기 화학식 1에 있어서, In Chemical Formula 1,
R1 내지 R8은 서로 같거나 상이하고, 각각 독립적으로 수소; 할로겐; C1 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알킬; C2 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알케닐; C2 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알키닐; C1 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알콕시; C6 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 아릴옥시; C3 내지 C60의 단환 또는 다환의 치환 또는 비치환된 시클로알킬; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로시클로알킬; C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴; 치환 또는 비치환된 C10 내지 C60의 스피로기; C1 내지 C20의 치환 또는 비치환된 알킬아민; C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴아민; 및 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴아민으로 이루어진 군으로부터 선택되거나, R1 내지 R8 중 인접하는 적어도 2개의 치환기는 서로 결합하여 방향족 탄화수소계 고리 또는 헤테로고리를 형성할 수 있다. R 1 to R 8 are the same as or different from each other, and each independently hydrogen; halogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; C 2 Through C 60 A straight or branched chain substituted or unsubstituted alkenyl; C 2 to C 60 straight or branched substituted or unsubstituted alkynyl; C 1 to C 60 straight or branched chain substituted or unsubstituted alkoxy; C 6 to C 60 straight or branched chain substituted or unsubstituted aryloxy; C 3 to C 60 of monocyclic or polycyclic substituted or unsubstituted cycloalkyl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heterocycloalkyl; C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Substituted or unsubstituted C 10 Through C 60 Spiro group; C 1 to C 20 substituted or unsubstituted alkylamines; C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted arylamine; And C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroarylamine, or at least two adjacent substituents of R 1 to R 8 are bonded to each other to form an aromatic hydrocarbon ring or heterocyclic ring. Can be formed.
또한, 본 발명은 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, the present invention provides an organic light emitting device comprising an anode, a cathode and at least one organic material layer provided between the anode and the cathode, one or more layers of the organic material layer comprises a compound of the formula (1). .
본 명세서에 기재된 화합물은 유기발광소자의 유기물층 재료로서 사용할 수 있다. 상기 화합물은 유기발광소자에서 정공주입재료, 정공수송재료, 발광재료, 전자수송재료, 전자주입재료 등의 역할을 할 수 있다. 특히, 상기 화합물은 유기발광소자의 전자 주입 및/또는 수송층의 재료로서 유용하게 사용될 수 있다. 또한, 상기 화합물은 발광재료로 사용될 수 있다. 예컨대, 상기 화합물은 인광 발광 호스트 재료로서 사용될 수 있다.The compound described in this specification can be used as an organic material layer material of an organic light emitting element. The compound may serve as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material in the organic light emitting device. In particular, the compound may be usefully used as a material for the electron injection and / or transport layer of the organic light emitting device. In addition, the compound may be used as a light emitting material. For example, the compound can be used as a phosphorescent host material.
도 1 내지 3은 본 발명의 실시상태들에 따른 유기발광소자의 전극과 유기물층의 적층순서를 예시한 것이다.1 to 3 illustrate the stacking order of electrodes and organic material layers of organic light emitting diodes according to exemplary embodiments of the present invention.
도 4 및 도 5는 화합물 38의 CV 측정 결과 도출된 Eox값을 나타낸 것이다.4 and 5 show the E ox value derived from the CV measurement of compound 38.
도 6 및 도 7은 화합물 66의 CV 측정 결과 도출된 Eox값을 나타낸 것이다.6 and 7 show E ox values derived as a result of CV measurement of Compound 66.
도 8 및 도 9는 화합물 76의 CV 측정 결과 도출된 Eox값을 나타낸 것이다.8 and 9 show E ox values derived as a result of CV measurement of Compound 76.
도 10은 화합물 38의 UV 측정 그래프를 나타낸 것이다.10 shows a UV measurement graph of compound 38.
도 11은 화합물 38의 320㎚에 대한 PL 측정 그래프를 나타낸 것이다.11 shows a PL measurement graph for 320 nm of compound 38. FIG.
도 12는 화합물 66의 UV 측정 그래프를 나타낸 것이다.12 shows the UV measurement graph of compound 66.
도 13은 화합물 66의 260㎚에 대한 PL 측정 그래프를 나타낸 것이다.FIG. 13 shows a PL measurement graph for 260 nm of Compound 66.
도 14는 화합물 76의 UV 측정 그래프를 나타낸 것이다.FIG. 14 shows a UV measurement graph of compound 76. FIG.
도 15는 화합물 76의 303㎚에 대한 PL 측정 그래프를 나타낸 것이다.15 shows a PL measurement graph for 303 nm of compound 76. FIG.
이하, 본 발명에 대하여 상세히 설명한다. EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated 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. Compounds described herein may be represented by the formula (1). Specifically, the compound of Formula 1 may be used as the organic material layer material of the organic light emitting device by the structural features of the core structure and substituents as described above.
특히, 상기 화학식 1의 화합물은 유기발광소자의 전자 주입 또는 수송을 하기에 적합한 HOMO / LUMO 값을 가지며 N-N 결합에 의한 전자 수송 능력이 뛰어나며 열적 안정성 또한 우수하다. In particular, the compound of Formula 1 has a HOMO / LUMO value suitable for electron injection or transport of the organic light emitting device, excellent electron transport ability by the N-N bond and excellent thermal stability.
또한, 상기 화학식 1의 화합물은 발광층 재료, 특히 발광층의 인광 호스트 재료로서 사용하기에 적합하다. 여기서 T1 값은 저온 PL nmax 값을 통하여 도출될 수 있다. 본 명세서에 있어서, T1 값은 장비 HITACHI-F7000, 온도 -196℃(77K), 희석액 2-메틸 테트라하이드로퓨란, 계산식 [T1(eV) = 1240/ PL 최단 피크 파장(nm)]에 의하여 얻어질 수 있다. 예컨대, 유기발광소자의 발광층의 호스트 물질로서 양극성(bipolar)을 갖는 구조의 화합물을 이용할 수 있다. 상기 화학식 1의 코어에 N 함유 고리와 S 함유 고리의 축합고리기가 치환되는 경우, 상기 축합고리기는 도너(donor)와 억셉터(acceptor)를 모두 포함하고 있으므로, 이를 발광층 재료로서 이용하는 경우, 발광층(EML)내에서 정공과 전자가 균형있게 만나 엑시톤을 형성할 수 있다. 상기 축합고리기에서 헤테로원소 N과 S가 같은 방향일 때와 다른 방향일 때 밴드갭(band gap)에 영향을 준다. N과 S가 같은 방향일 때 π-전자의 컨쥬게이션(conjugation) 길이가 짧아지고, N과 S가 다른 방향이면 π-전자의 컨쥬게이션 길이가 길어져 T1값에 영향을 준다. The compound of formula 1 is also suitable for use as a light emitting layer material, in particular as a phosphorescent host material of the light emitting layer. The T1 value may be derived through the low temperature PL nmax value. In the present specification, the T1 value is obtained by equipment HITACHI-F7000, temperature -196 ° C (77K), diluent 2-methyl tetrahydrofuran, formula [T1 (eV) = 1240 / PL shortest peak wavelength (nm)]. Can be. For example, a compound having a bipolar structure may be used as a host material of the light emitting layer of the organic light emitting device. When the condensed ring group of the N-containing ring and the S-containing ring is substituted in the core of Formula 1, the condensed ring group includes both a donor and an acceptor, and when used as a light emitting layer material, the light emitting layer ( In EML), holes and electrons can be balanced to form excitons. In the condensed ring group, heterobands N and S affect the band gap when they are in the same direction and in different directions. When N and S are in the same direction, the conjugation length of π-electrons is short, and when N and S are in different directions, the conjugation length of π-electrons is long, affecting the T1 value.
본 명세서에 있어서, "치환 또는 비치환"이란 C1 내지 C60의 직쇄 또는 분지쇄의 알킬; C2 내지 C60의 직쇄 또는 분지쇄의 알케닐; C2 내지 C60의 직쇄 또는 분지쇄의 알키닐; 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; C10 내지 C60의 스피로기; 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 비치환된 것을 의미한다. 상기 추가의 치환기들은 추가로 더 치환될 수도 있다. In the present specification, "substituted or unsubstituted" is C 1 to C 60 linear or branched alkyl; C 2 Through C 60 Straight or branched alkenyl; C 2 to C 60 straight or branched alkynyl; C 3 to C 60 monocyclic or polycyclic cycloalkyl; C 2 to C 60 monocyclic or polycyclic heterocycloalkyl; C 6 Through C 60 Monocyclic or polycyclic aryl; C 2 Through C 60 Monocyclic or polycyclic heteroaryl; C 10 to C 60 spiro groups; C 1 to C 20 alkylamines; C 6 Through C 60 Monocyclic or polycyclic arylamine; And it means unsubstituted or substituted with one or more substituents selected from the group consisting of C 2 to C 60 monocyclic or polycyclic heteroarylamine. Said additional substituents may be further substituted further.
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 a 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 a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. Alkenyl may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, more specifically 2 to 20 carbon atoms.
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 or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. Alkynyl may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, more specifically 2 to 20 carbon atoms.
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, cycloalkyl includes monocyclic or polycyclic having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which cycloalkyl is directly connected or condensed with another ring group. Here, the other ring group may be cycloalkyl, but may also be other types of ring groups such as heterocycloalkyl, aryl, heteroaryl, and the like. The cycloalkyl may have 3 to 60 carbon atoms, specifically 3 to 40 carbon atoms, more specifically 5 to 20 carbon atoms.
본 명세서에 있어서, 헤테로시클로알킬은 헤테로원자로서 S, O, N 또는 Si을 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, the heterocycloalkyl includes S, O, N or Si as a hetero atom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which heterocycloalkyl is directly connected or condensed with another ring group. Here, the other ring group may be heterocycloalkyl, but may also be other types of ring groups such as cycloalkyl, aryl, heteroaryl, and the like. The heterocycloalkyl may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, more specifically 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. 아릴의 탄소수는 6 내지 60, 구체적으로 6 내지 40, 더욱 구체적으로 6 내지 25일 수 있다. 아릴의 구체적인 예로는 페닐, 바이페닐, 트리페닐, 나프틸, 안트릴, 크라이세닐, 페난트레닐, 페릴레닐, 플루오란테닐, 트리페닐레닐, 페날레닐, 파이레닐, 테트라세닐, 펜타세닐, 플루오레닐, 인데닐, 아세나프틸레닐 등이나 이들의 축합고리가 있으나, 이에만 한정되는 것은 아니다.In the present specification, aryl includes monocyclic or polycyclic having 6 to 60 carbon atoms, and may be further substituted with other substituents. Here, polycyclic means a group in which aryl is directly connected or condensed with another ring group. Here, the other ring group may be aryl, but may also be other types of ring groups such as cycloalkyl, heterocycloalkyl, heteroaryl, and the like. The aryl may have 6 to 60 carbon atoms, specifically 6 to 40 carbon atoms, more specifically 6 to 25 carbon atoms. Specific examples of aryl include phenyl, biphenyl, triphenyl, naphthyl, anthryl, chrysenyl, phenanthrenyl, peryllenyl, fluoranthenyl, triphenylenyl, penalenyl, pyrenyl, tetrasenyl, pentacenyl, Fluorenyl, indenyl, acenaphthylenyl, and the like, and condensed rings thereof, but are not limited thereto.
본 명세서에 있어서, 헤테로아릴은 헤테로원자로서 S, O, N 또는 Si을 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, 티에닐, 이미다졸릴, 피라졸릴, 옥사졸릴, 이속사졸릴, 티아졸릴, 이소티아졸릴, 트리아졸릴, 푸라자닐, 옥사디아졸릴, 티아디아졸릴, 디티아졸릴, 테트라졸릴, 파이라닐, 티오파이라닐, 디아지닐, 옥사지닐, 티아지닐, 디옥시닐, 트리아지닐, 테트라지닐, 퀴놀릴, 이소퀴놀릴, 퀴나졸리닐, 이소퀴나졸리닐, 아크리디닐, 페난트리디닐, 이미다조피리디닐, 디아자나프탈레닐, 트리아자인덴, 인돌릴, 인돌리지닐, 벤조티아졸릴, 벤즈옥사졸릴, 벤조이미다졸릴, 벤조티오펜기, 벤조푸란기, 디벤조티오펜기, 디벤조푸란기, 카바졸릴, 벤조카바졸릴, 페나지닐 등이나 이들의 축합고리가 있으나, 이에만 한정되는 것은 아니다. In the present specification, the heteroaryl includes S, O, N or Si as a hetero atom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which heteroaryl is directly connected or condensed with another ring group. Here, the other ring group may be heteroaryl, but may also be other types of ring groups such as cycloalkyl, heterocycloalkyl, aryl, and the like. The heteroaryl may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, more specifically 3 to 25 carbon atoms. Specific examples of heteroaryl include pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, fura Zanyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl, oxazinyl, thiazinyl, dioxynyl, triazinyl, tetrazinyl, quinolyl, isoqui Nolyl, quinazolinyl, isoquinazolinyl, acridinyl, phenantridinyl, imidazopyridinyl, diazanaphthalenyl, triazaindene, indolyl, indolizinyl, benzothiazolyl, benzoxazolyl, Benzoimidazolyl, benzothiophene group, benzofuran group, dibenzothiophene group, dibenzofuran group, carbazolyl, benzocarbazolyl, phenazinyl and the like, and condensed rings thereof, but are not limited thereto.
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 includes a spiro structure, and may have 15 to 60 carbon atoms. For example, the 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 a group of the following structural formula.
Figure PCTKR2013012050-appb-I000002
Figure PCTKR2013012050-appb-I000002
본 명세서에 있어서, 아릴렌 및 헤테로아릴렌은 2가기인 것을 제외하고는 각각 전술한 아릴 및 헤테로아릴의 설명이 적용될 수 있다. In the present specification, the description of aryl and heteroaryl described above can be applied except that arylene and heteroarylene are divalent groups.
본 명세서에 있어서, 방향족 탄화수소 및 방향족 헤테로고리는 축합고리를 형성하는 것을 제외하고는 각각 전술한 아릴 및 헤테로아릴의 설명이 적용될 수 있다.In the present specification, the description of the aforementioned aryl and heteroaryl may be applied except that the aromatic hydrocarbon and the aromatic heterocycle form a condensed ring.
본 발명의 일 실시상태에 따르면, R1 내지 R4 중 적어도 하나는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴; 또는 치환 또는 비치환된 C10 내지 C60의 스피로기이고, 나머지는 수소; 할로겐; C1 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알킬; C2 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알케닐; C2 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알키닐; C1 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알콕시; C6 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 아릴옥시; C3 내지 C60의 단환 또는 다환의 치환 또는 비치환된 시클로알킬; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로시클로알킬; C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴; 치환 또는 비치환된 C10 내지 C60의 스피로기; C1 내지 C20의 치환 또는 비치환된 알킬아민; C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴아민; 및 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴아민으로 이루어진 군으로부터 선택되거나, R1 내지 R4 중 인접하는 적어도 2개의 치환기는 서로 결합하여 방향족 탄화수소계 고리 또는 헤테로고리를 형성한다.According to an exemplary embodiment of the present invention, at least one of R 1 to R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Or a substituted or unsubstituted C 10 to C 60 spiro group, with the remainder being hydrogen; halogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; C 2 Through C 60 A straight or branched chain substituted or unsubstituted alkenyl; C 2 to C 60 straight or branched substituted or unsubstituted alkynyl; C 1 to C 60 straight or branched chain substituted or unsubstituted alkoxy; C 6 to C 60 straight or branched chain substituted or unsubstituted aryloxy; C 3 to C 60 of monocyclic or polycyclic substituted or unsubstituted cycloalkyl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heterocycloalkyl; C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Substituted or unsubstituted C 10 Through C 60 Spiro group; C 1 to C 20 substituted or unsubstituted alkylamines; C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted arylamine; And C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroarylamine, or at least two adjacent substituents of R 1 to R 4 are bonded to each other to form an aromatic hydrocarbon ring or heterocyclic ring. Form.
본 발명의 일 실시상태에 따르면, R1 내지 R4 중 적어도 하나는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴; 또는 치환 또는 비치환된 C10 내지 C60의 스피로기이다.According to an exemplary embodiment of the present invention, at least one of R 1 to R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Or a substituted or unsubstituted C 10 to C 60 spiro group.
본 발명의 일 실시상태에 따르면, R1 내지 R4 중 하나는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴; 또는 치환 또는 비치환된 C10 내지 C60의 스피로기이다.According to an exemplary embodiment of the present invention, one of R 1 to R 4 is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Or a substituted or unsubstituted C 10 to C 60 spiro group.
본 발명의 일 실시상태에 따르면, R1 내지 R4 중 적어도 하나는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴; 또는 치환 또는 비치환된 C10 내지 C60의 스피로기이고, R1 내지 R4 중 나머지는 수소이거나, 인접한 치환기와 결합하여 방향족 탄화수소계 고리 또는 헤테로고리를 형성한다.According to an exemplary embodiment of the present invention, at least one of R 1 to R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Or a substituted or unsubstituted C 10 to C 60 spiro group, and the rest of R 1 to R 4 are hydrogen, or combine with an adjacent substituent to form an aromatic hydrocarbon ring or heterocycle.
본 발명의 일 실시상태에 따르면, R1 내지 R4 중 적어도 하나는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이고, R1 내지 R4 중 나머지는 수소이거나, 인접한 치환기와 결합하여 방향족 탄화수소계 고리 또는 헤테로고리를 형성한다.According to an exemplary embodiment of the present invention, at least one of R 1 to R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, and the remainder of R 1 to R 4 is hydrogen, or combines with an adjacent substituent to form an aromatic hydrocarbon ring or heterocycle.
본 발명의 일 실시상태에 따르면, R2는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이다.According to an exemplary embodiment of the present invention, R 2 is a C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl.
본 발명의 일 실시상태에 따르면, R2는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이고, R1, R3 및 R4는 수소이다.According to an exemplary embodiment of the present invention, R 2 is a C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, R 1 , R 3 and R 4 are hydrogen.
본 발명의 일 실시상태에 따르면, R2는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이고, R1는 수소이고, R3 및 R4는 서로 결합하여 치환 또는 비치환된 벤젠 고리를 형성한다. According to an exemplary embodiment of the present invention, R 2 is a C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, R 1 is hydrogen, and R 3 and R 4 combine with each other to form a substituted or unsubstituted benzene ring.
본 발명의 일 실시상태에 따르면, R2는 치환 또는 비치환된 피리딜, 치환 또는 비치환된 피리미딜, 치환 또는 비치환된 트리아지닐, 치환 또는 비치환된 안트릴, 치환 또는 비치환된 페난트릴, 치환 또는 비치환된 나프틸, 또는 치환 또는 비치환된 페닐기이다.According to an exemplary embodiment of the present invention, R 2 is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenan Trityl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group.
본 발명의 일 실시상태에 따르면, R2는 치환 또는 비치환된 피리딜, 치환 또는 비치환된 피리미딜, 치환 또는 비치환된 트리아지닐, 치환 또는 비치환된 안트릴, 치환 또는 비치환된 페난트릴, 치환 또는 비치환된 나프틸, 또는 치환 또는 비치환된 페닐기이고, 이들은 페닐, 나프틸, 바이페닐, 안트릴, 페난트릴, 피리딜, 피리미딜, 트리아지닐, 퀴놀릴, 이소퀴놀릴 중 적어도 하나로 더 치환될 수 있으며, 이들은 추가로 페닐, 나프틸, 바이페닐, 안트릴, 페난트릴, 피리딜, 피리미딜, 트리아지닐, 퀴놀릴, 이소퀴놀릴 중 적어도 하나로 더 치환될 수 있다. According to an exemplary embodiment of the present invention, R 2 is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenan Triyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group, which are phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl At least one may be further substituted, and they may further be further substituted with at least one of phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl.
예컨대, R2는 추가로 페닐, 나프틸, 바이페닐, 안트릴, 페난트릴, 피리딜, 피리미딜, 트리아지닐, 퀴놀릴, 이소퀴놀릴, 피리딜 치환 페닐, 피리미딜 치환 페닐, 트리아지닐 치환 페닐, 퀴놀릴 치환 페닐, 이소퀴놀릴 치환 페닐, 나프틸 치환 페닐, 안트릴 치환 페닐, 페난트릴 치환 페닐, 페닐 치환 나프틸, 페닐 치환 안트릴, 페닐 치환 페난트릴, 나프틸 치환 안트릴, 안트릴 치환 나프틸, 페닐 치환 피리딜, 나프틸 치환 피리딜, 안트릴 치환 피리딜 또는 페난트릴 치환 피리딜, 페닐 치환 피리미딜, 나프틸 치환 피리미딜, 안트릴 치환 피리미딜, 페난트릴 치환 피리미딜, 페닐 치환 트리아지닐, 나프틸 치환 트리아지닐, 안트릴 치환 트리아지닐, 또는 페난트릴 치환 트리아지닐 등으로 치환될 수 있다.For example, R 2 is further phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl, pyridyl substituted phenyl, pyrimidyl substituted phenyl, triazinyl substituted Phenyl, quinolyl substituted phenyl, isoquinolyl substituted phenyl, naphthyl substituted phenyl, anthryl substituted phenyl, phenanthryl substituted phenyl, phenyl substituted naphthyl, phenyl substituted anthryl, phenyl substituted phenanthryl, naphthyl substituted anthryl, an Triyl substituted naphthyl, phenyl substituted pyridyl, naphthyl substituted pyridyl, anthryl substituted pyridyl or phenanthryl substituted pyridyl, phenyl substituted pyrimidyl, naphthyl substituted pyrimidyl, anthryl substituted pyrimidyl, phenanthryl substituted pyrimidyl , Phenyl substituted triazinyl, naphthyl substituted triazinyl, anthryl substituted triazinyl, or phenanthryl substituted triazinyl and the like.
본 발명의 일 실시상태에 따르면, R4는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이다.According to an exemplary embodiment of the present invention, R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl.
본 발명의 일 실시상태에 따르면, R4는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이고, R1 내지 R3는 수소이다.According to an exemplary embodiment of the present invention, R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, and R 1 to R 3 are hydrogen.
본 발명의 일 실시상태에 따르면, R4는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이고, R3는 수소이고, R1 및 R2는 서로 결합하여 치환 또는 비치환된 벤젠 고리를 형성한다. According to an exemplary embodiment of the present invention, R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, R 3 is hydrogen, and R 1 and R 2 combine with each other to form a substituted or unsubstituted benzene ring.
본 발명의 일 실시상태에 따르면, R4는 치환 또는 비치환된 피리딜, 치환 또는 비치환된 피리미딜, 치환 또는 비치환된 트리아지닐, 치환 또는 비치환된 안트릴, 치환 또는 비치환된 페난트릴, 치환 또는 비치환된 나프틸, 또는 치환 또는 비치환된 페닐기이다.According to an exemplary embodiment of the present invention, R 4 is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenan Trityl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group.
본 발명의 일 실시상태에 따르면, R4는 치환 또는 비치환된 피리딜, 치환 또는 비치환된 피리미딜, 치환 또는 비치환된 트리아지닐, 치환 또는 비치환된 안트릴, 치환 또는 비치환된 페난트릴, 치환 또는 비치환된 나프틸, 또는 치환 또는 비치환된 페닐기이고, 이들은 페닐, 나프틸, 바이페닐, 안트릴, 페난트릴, 피리딜, 피리미딜, 트리아지닐, 퀴놀릴, 이소퀴놀릴 중 적어도 하나로 더 치환될 수 있으며, 이들은 추가로 페닐, 나프틸, 바이페닐, 안트릴, 페난트릴, 피리딜, 피리미딜, 트리아지닐, 퀴놀릴, 이소퀴놀릴 중 적어도 하나로 더 치환될 수 있다. According to an exemplary embodiment of the present invention, R 4 is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenan Triyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group, which are phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl At least one may be further substituted, and they may further be further substituted with at least one of phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl.
예컨대, R4는 추가로 페닐, 나프틸, 바이페닐, 안트릴, 페난트릴, 피리딜, 피리미딜, 트리아지닐, 퀴놀릴, 이소퀴놀릴, 피리딜 치환 페닐, 피리미딜 치환 페닐, 트리아지닐 치환 페닐, 퀴놀릴 치환 페닐, 이소퀴놀릴 치환 페닐, 나프틸 치환 페닐, 안트릴 치환 페닐, 페난트릴 치환 페닐, 페닐 치환 나프틸, 페닐 치환 안트릴, 페닐 치환 페난트릴, 나프틸 치환 안트릴, 안트릴 치환 나프틸, 페닐 치환 피리딜, 나프틸 치환 피리딜, 안트릴 치환 피리딜 또는 페난트릴 치환 피리딜, 페닐 치환 피리미딜, 나프틸 치환 피리미딜, 안트릴 치환 피리미딜, 페난트릴 치환 피리미딜, 페닐 치환 트리아지닐, 나프틸 치환 트리아지닐, 안트릴 치환 트리아지닐, 또는 페난트릴 치환 트리아지닐 등으로 치환될 수 있다.For example, R 4 is further phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl, pyridyl substituted phenyl, pyrimidyl substituted phenyl, triazinyl substituted Phenyl, quinolyl substituted phenyl, isoquinolyl substituted phenyl, naphthyl substituted phenyl, anthryl substituted phenyl, phenanthryl substituted phenyl, phenyl substituted naphthyl, phenyl substituted anthryl, phenyl substituted phenanthryl, naphthyl substituted anthryl, an Triyl substituted naphthyl, phenyl substituted pyridyl, naphthyl substituted pyridyl, anthryl substituted pyridyl or phenanthryl substituted pyridyl, phenyl substituted pyrimidyl, naphthyl substituted pyrimidyl, anthryl substituted pyrimidyl, phenanthryl substituted pyrimidyl , Phenyl substituted triazinyl, naphthyl substituted triazinyl, anthryl substituted triazinyl, or phenanthryl substituted triazinyl and the like.
본 발명의 일 실시상태에 따르면, R1은 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이다.According to an exemplary embodiment of the present invention, R 1 is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl.
본 발명의 일 실시상태에 따르면, R1은 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이고, R2 내지 R4는 수소이다.According to an exemplary embodiment of the present invention, R 1 is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, and R 2 to R 4 are hydrogen.
본 발명의 일 실시상태에 따르면, R1은 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이고, R2는 수소이고, R3 및 R4는 서로 결합하여 치환 또는 비치환된 벤젠 고리를 형성한다. According to an exemplary embodiment of the present invention, R 1 is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, R 2 is hydrogen, and R 3 and R 4 combine with each other to form a substituted or unsubstituted benzene ring.
본 발명의 일 실시상태에 따르면, R1은 치환 또는 비치환된 피리딜, 치환 또는 비치환된 피리미딜, 치환 또는 비치환된 트리아지닐, 치환 또는 비치환된 안트릴, 치환 또는 비치환된 페난트릴, 치환 또는 비치환된 나프틸, 또는 치환 또는 비치환된 페닐기이다.According to an exemplary embodiment of the present invention, R 1 is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenan Trityl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group.
본 발명의 일 실시상태에 따르면, R1은 치환 또는 비치환된 피리딜, 치환 또는 비치환된 피리미딜, 치환 또는 비치환된 트리아지닐, 치환 또는 비치환된 안트릴, 치환 또는 비치환된 페난트릴, 치환 또는 비치환된 나프틸, 또는 치환 또는 비치환된 페닐기이고, 이들은 페닐, 나프틸, 바이페닐, 안트릴, 페난트릴, 피리딜, 피리미딜, 트리아지닐, 퀴놀릴, 이소퀴놀릴 중 적어도 하나로 더 치환될 수 있으며, 이들은 추가로 페닐, 나프틸, 바이페닐, 안트릴, 페난트릴, 피리딜, 피리미딜, 트리아지닐, 퀴놀릴, 이소퀴놀릴 중 적어도 하나로 더 치환될 수 있다. According to an exemplary embodiment of the present invention, R 1 is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenan Triyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group, which are phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl At least one may be further substituted, and they may further be further substituted with at least one of phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl.
예컨대, R1은 추가로 페닐, 나프틸, 바이페닐, 안트릴, 페난트릴, 피리딜, 피리미딜, 트리아지닐, 퀴놀릴, 이소퀴놀릴, 피리딜 치환 페닐, 피리미딜 치환 페닐, 트리아지닐 치환 페닐, 퀴놀릴 치환 페닐, 이소퀴놀릴 치환 페닐, 나프틸 치환 페닐, 안트릴 치환 페닐, 페난트릴 치환 페닐, 페닐 치환 나프틸, 페닐 치환 안트릴, 페닐 치환 페난트릴, 나프틸 치환 안트릴, 안트릴 치환 나프틸, 페닐 치환 피리딜, 나프틸 치환 피리딜, 안트릴 치환 피리딜 또는 페난트릴 치환 피리딜, 페닐 치환 피리미딜, 나프틸 치환 피리미딜, 안트릴 치환 피리미딜, 페난트릴 치환 피리미딜, 페닐 치환 트리아지닐, 나프틸 치환 트리아지닐, 안트릴 치환 트리아지닐, 또는 페난트릴 치환 트리아지닐 등으로 치환될 수 있다.For example, R 1 is further phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl, pyridyl substituted phenyl, pyrimidyl substituted phenyl, triazinyl substituted Phenyl, quinolyl substituted phenyl, isoquinolyl substituted phenyl, naphthyl substituted phenyl, anthryl substituted phenyl, phenanthryl substituted phenyl, phenyl substituted naphthyl, phenyl substituted anthryl, phenyl substituted phenanthryl, naphthyl substituted anthryl, an Triyl substituted naphthyl, phenyl substituted pyridyl, naphthyl substituted pyridyl, anthryl substituted pyridyl or phenanthryl substituted pyridyl, phenyl substituted pyrimidyl, naphthyl substituted pyrimidyl, anthryl substituted pyrimidyl, phenanthryl substituted pyrimidyl , Phenyl substituted triazinyl, naphthyl substituted triazinyl, anthryl substituted triazinyl, or phenanthryl substituted triazinyl and the like.
본 발명의 일 실시상태에 따르면, R1과 R2는 서로 결합하여 치환 또는 비치환된 벤젠 고리를 형성한다. According to an exemplary embodiment of the present invention, R 1 and R 2 combine with each other to form a substituted or unsubstituted benzene ring.
본 발명의 일 실시상태에 따르면, R2과 R3은 서로 결합하여 치환 또는 비치환된 벤젠 고리를 형성한다. According to an exemplary embodiment of the present invention, R 2 and R 3 combine with each other to form a substituted or unsubstituted benzene ring.
본 발명의 일 실시상태에 따르면, R3과 R4은 서로 결합하여 치환 또는 비치환된 벤젠 고리를 형성한다. According to an exemplary embodiment of the present invention, R 3 and R 4 combine with each other to form a substituted or unsubstituted benzene ring.
본 발명의 일 실시상태에 따르면, R5 내지 R8는 서로 같거나 상이하고, 각각 독립적으로 수소; 할로겐; C1 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알킬; C2 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알케닐; C2 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알키닐; C1 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알콕시; C6 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 아릴옥시; C3 내지 C60의 단환 또는 다환의 치환 또는 비치환된 시클로알킬; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로시클로알킬; C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴; 치환 또는 비치환된 C10 내지 C60의 스피로기; C1 내지 C20의 치환 또는 비치환된 알킬아민; C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴아민; 및 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴아민으로 이루어진 군으로부터 선택된다. According to an exemplary embodiment of the present invention, R 5 to R 8 are the same as or different from each other, and each independently hydrogen; halogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; C 2 Through C 60 A straight or branched chain substituted or unsubstituted alkenyl; C 2 to C 60 straight or branched substituted or unsubstituted alkynyl; C 1 to C 60 straight or branched chain substituted or unsubstituted alkoxy; C 6 to C 60 straight or branched chain substituted or unsubstituted aryloxy; C 3 to C 60 of monocyclic or polycyclic substituted or unsubstituted cycloalkyl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heterocycloalkyl; C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Substituted or unsubstituted C 10 Through C 60 Spiro group; C 1 to C 20 substituted or unsubstituted alkylamines; C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted arylamine; And C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroarylamine.
본 발명의 일 실시상태에 따르면, R5 내지 R8는 서로 같거나 상이하고, 각각 독립적으로 수소; C1 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알킬; C2 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알케닐; C2 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알키닐; C3 내지 C60의 단환 또는 다환의 치환 또는 비치환된 시클로알킬; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로시클로알킬; C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴; 및 치환 또는 비치환된 C10 내지 C60의 스피로기으로 이루어진 군으로부터 선택된다. According to an exemplary embodiment of the present invention, R 5 to R 8 are the same as or different from each other, and each independently hydrogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; C 2 Through C 60 A straight or branched chain substituted or unsubstituted alkenyl; C 2 to C 60 straight or branched substituted or unsubstituted alkynyl; C 3 to C 60 of monocyclic or polycyclic substituted or unsubstituted cycloalkyl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heterocycloalkyl; C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; And substituted or unsubstituted C 10 to C 60 spiro groups.
본 발명의 일 실시상태에 따르면, R5 내지 R8는 서로 같거나 상이하고, 각각 독립적으로 수소; C1 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알킬; 및 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴로 이루어진 군으로부터 선택된다. According to an exemplary embodiment of the present invention, R 5 to R 8 are the same as or different from each other, and each independently hydrogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; And C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl.
본 발명의 일 실시상태에 따르면, R5 내지 R8는 수소이다.According to an exemplary embodiment of the present invention, R 5 to R 8 is hydrogen.
본 발명의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 2 내지 4 중 하나로 표시될 수 있다. According to an exemplary embodiment of the present invention, Chemical Formula 1 may be represented by one of the following Chemical Formulas 2 to 4.
[화학식 2][Formula 2]
Figure PCTKR2013012050-appb-I000003
Figure PCTKR2013012050-appb-I000003
[화학식 3][Formula 3]
Figure PCTKR2013012050-appb-I000004
Figure PCTKR2013012050-appb-I000004
[화학식 4][Formula 4]
Figure PCTKR2013012050-appb-I000005
Figure PCTKR2013012050-appb-I000005
상기 화학식에 있어서, R1 내지 R8은 화학식 1에서 정의한 바와 같고, In the above formula, R 1 to R 8 are the same as defined in Formula 1,
R은 R1 내지 R8의 정의와 같으며, u는 1 내지 4의 정수이고, R is as defined in R 1 to R 8 , u is an integer from 1 to 4,
u가 2 이상인 경우 R은 서로 같거나 상이하다. When u is 2 or more, R is the same as or different from each other.
본 발명의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 5 내지 8 중 하나로 표시될 수 있다. According to an exemplary embodiment of the present invention, Chemical Formula 1 may be represented by one of the following Chemical Formulas 5 to 8.
[화학식 5][Formula 5]
Figure PCTKR2013012050-appb-I000006
Figure PCTKR2013012050-appb-I000006
[화학식 6][Formula 6]
Figure PCTKR2013012050-appb-I000007
Figure PCTKR2013012050-appb-I000007
[화학식 7][Formula 7]
Figure PCTKR2013012050-appb-I000008
Figure PCTKR2013012050-appb-I000008
[화학식 8][Formula 8]
Figure PCTKR2013012050-appb-I000009
Figure PCTKR2013012050-appb-I000009
상기 화학식에 있어서, R5 내지 R8은 화학식 1에서 정의한 바와 같고, In the above formula, R 5 to R 8 are the same as defined in Formula 1,
R은 R1 내지 R4의 정의와 같으며, R is as defined in R 1 to R 4 ,
n은 1 내지 3의 정수이고, v는 1 내지 5의 정수이며, n 또는 v가 2 이상인 경우에는 R은 서로 같거나 상이하고,n is an integer of 1 to 3, v is an integer of 1 to 5, when n or v is 2 or more, R is the same or different from each other,
L은 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴렌; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴렌이고, p 및 x는 각각 0 내지 3의 정수이며, p 또는 x가 2 이상인 경우에는 L은 서로 같거나 상이하고,L is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted arylene; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroarylene, p and x are each an integer of 0 to 3, when p or x is 2 or more, L is the same as or different from each other,
Ar은 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이고, q 및 y는 각각 0 내지 3의 정수이며, q 또는 y가 2 이상인 경우에는 Ar은 서로 같거나 상이하다.Ar is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, q and y are each an integer of 0 to 3, and when q or y is 2 or more, Ar is the same as or different from each other.
본 발명의 일 실시상태에 따르면, 화학식 5 내지 8에 있어서, L은 치환 또는 비치환된 피리딘기, 치환 또는 비치환된 피리미딘기, 치환 또는 비치환된 트리아진기, 치환 또는 비치환된 안트라센기, 치환 또는 비치환된 페난트렌기, 치환 또는 비치환된 나프탈렌기, 또는 치환 또는 비치환된 페닐렌기이다.According to an exemplary embodiment of the present invention, in Formulas 5 to 8, L is a substituted or unsubstituted pyridine group, a substituted or unsubstituted pyrimidine group, a substituted or unsubstituted triazine group, a substituted or unsubstituted anthracene group , A substituted or unsubstituted phenanthrene group, a substituted or unsubstituted naphthalene group, or a substituted or unsubstituted phenylene group.
본 발명의 일 실시상태에 따르면, 화학식 5 내지 8에 있어서, L은 피리딘기, 피리미딘기, 트리아진기, 안트라센기, 페난트렌기, 나프탈렌기, 또는 페닐렌기이다.According to an exemplary embodiment of the present invention, in Chemical Formulas 5 to 8, L is a pyridine group, pyrimidine group, triazine group, anthracene group, phenanthrene group, naphthalene group, or phenylene group.
본 발명의 일 실시상태에 따르면, 화학식 5 내지 8에 있어서, L은 피리딘기, 피리미딘기, 트리아진기, 안트라센기, 또는 페닐렌기이다.According to an exemplary embodiment of the present invention, in Chemical Formulas 5 to 8, L is a pyridine group, pyrimidine group, triazine group, anthracene group, or phenylene group.
본 발명의 일 실시상태에 따르면, 화학식 5 내지 8에 있어서, p 및 x는 각각 0 또는 1이다. According to an exemplary embodiment of the present invention, in the formulas 5 to 8, p and x are each 0 or 1.
본 발명의 일 실시상태에 따르면, 화학식 5 내지 8에 있어서, Ar은 치환 또는 비치환된 피리딜, 치환 또는 비치환된 피리미딜, 치환 또는 비치환된 트리아지닐, 치환 또는 비치환된 안트릴, 치환 또는 비치환된 페난트릴, 치환 또는 비치환된 나프틸, 또는 치환 또는 비치환된 페닐기이다.According to an exemplary embodiment of the present invention, in Formula 5 to 8, Ar is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, Substituted or unsubstituted phenanthryl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group.
본 발명의 일 실시상태에 따르면, 화학식 5 내지 8에 있어서, Ar은 치환 또는 비치환된 피리딜, 치환 또는 비치환된 피리미딜, 치환 또는 비치환된 트리아지닐, 치환 또는 비치환된 안트릴, 치환 또는 비치환된 페난트릴, 치환 또는 비치환된 나프틸, 또는 치환 또는 비치환된 페닐기이고, 이들은 페닐, 나프틸, 바이페닐, 안트릴, 페난트릴, 피리딜, 피리미딜, 트리아지닐, 퀴놀릴, 이소퀴놀릴 중 적어도 하나로 더 치환될 수 있으며, 이들은 추가로 페닐, 나프틸, 바이페닐, 안트릴, 페난트릴, 피리딜, 피리미딜, 트리아지닐, 퀴놀릴, 이소퀴놀릴 중 적어도 하나로 더 치환될 수 있다. According to an exemplary embodiment of the present invention, in Formula 5 to 8, Ar is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, Substituted or unsubstituted phenanthryl, substituted or unsubstituted naphthyl, or substituted or unsubstituted phenyl group, which is phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, qui And further substituted with at least one of isnoquinol and isoquinolyl, which are further further substituted with at least one of phenyl, naphthyl, biphenyl, anthryl, phenanthryl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl Can be substituted.
본 발명의 일 실시상태에 따르면, 화학식 5 내지 8에 있어서, q 및 y는 각각 1 또는 2이다. According to an exemplary embodiment of the present invention, in the formulas 5 to 8, q and y are each 1 or 2.
본 발명의 일 실시상태에 따르면, 화학식 5 내지 8에 있어서, q 및 y는 각각 1이다. According to an exemplary embodiment of the present invention, in the formulas 5 to 8, q and y are each one.
본 발명의 일 실시상태에 따르면, 화학식 5 내지 8에 있어서, R은 수소이다.According to an exemplary embodiment of the present invention, in the formulas 5 to 8, R is hydrogen.
본 발명의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 9 내지 13 중 하나로 표시될 수 있다.According to an exemplary embodiment of the present invention, Chemical Formula 1 may be represented by one of the following Chemical Formulas 9 to 13.
[화학식 9][Formula 9]
Figure PCTKR2013012050-appb-I000010
Figure PCTKR2013012050-appb-I000010
[화학식 10][Formula 10]
Figure PCTKR2013012050-appb-I000011
Figure PCTKR2013012050-appb-I000011
[화학식 11][Formula 11]
Figure PCTKR2013012050-appb-I000012
Figure PCTKR2013012050-appb-I000012
[화학식 12][Formula 12]
Figure PCTKR2013012050-appb-I000013
Figure PCTKR2013012050-appb-I000013
[화학식 13][Formula 13]
Figure PCTKR2013012050-appb-I000014
Figure PCTKR2013012050-appb-I000014
상기 화학식에 있어서, R5 내지 R8은 화학식 1에서 정의한 바와 같고, In the above formula, R 5 to R 8 are the same as defined in Formula 1,
X1 내지 X3은 서로 같거나 상이하고, 각각 독립적으로 N 또는 CY6이고, X1 내지 X3 중 적어도 하나는 N이며,X 1 to X 3 are the same as or different from each other, each independently N or CY 6 , at least one of X 1 to X 3 is N,
R, 및 Y1 내지 Y6은 서로 같거나 상이하고, 각각 독립적으로 R1 내지 R4의 정의와 같으며, R 중 인접하는 적어도 2개의 치환기, 또는 Y1 내지 Y6 중 인접하는 적어도 2개의 치환기는 서로 결합하여 방향족 탄화수소계 고리 또는 헤테로고리를 형성할 수 있고, n은 1 내지 3의 정수이고, n이 2 이상인 경우에는 R은 서로 같거나 상이하며, r은 1 내지 5의 정수이고, r이 2 이상인 경우 Y3는 서로 같거나 상이하며, s는 1 내지 7의 정수이고, s가 2 이상인 경우 Y4는 서로 같거나 상이하며, t는 1 내지 9의 정수이고, t가 2 이상인 경우 Y5는 서로 같거나 상이하며,R, and Y 1 to Y 6 are the same as or different from each other, and each independently, as defined by R 1 to R 4 , at least two adjacent substituents in R, or at least two adjacent ones of Y 1 to Y 6 The substituents may be bonded to each other to form an aromatic hydrocarbon ring or heterocycle, n is an integer of 1 to 3, when n is 2 or more, R is the same as or different from each other, r is an integer of 1 to 5, when r is 2 or more, Y 3 is the same as or different from each other, s is an integer of 1 to 7, and when s is 2 or more, Y 4 is the same or different from each other, t is an integer of 1 to 9, and t is 2 or more Y 5 is the same as or different from each other,
L은 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴렌; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴렌이고, p는 0 내지 3의 정수이며, p가 2 이상인 경우에는 L은 서로 같거나 상이하고,L is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted arylene; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroarylene, p is an integer of 0 to 3, when p is 2 or more, L is the same as or different from each other,
Z1 및 Z2는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 방향족 탄화수소 고리; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 방향족 헤테로 고리이다.Z1 and Z2 are C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aromatic hydrocarbon ring; Or a C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted aromatic hetero ring.
본 발명의 일 실시상태에 따르면, 상기 화학식 9의
Figure PCTKR2013012050-appb-I000015
는 하기와 같이 표시될 수 있다.According to an exemplary embodiment of the present invention, the formula (9)
Figure PCTKR2013012050-appb-I000015
May be represented as follows.
Figure PCTKR2013012050-appb-I000016
Figure PCTKR2013012050-appb-I000016
상기 화학식에 있어서, Y11 내지 Y13은 Y6의 정의와 같다. In the above formula, Y 11 to Y 13 are the same as the definition of Y 6 .
본 발명의 일 실시상태에 따르면, Y11 내지 Y13은 각각 C6 내지 C60의 단환 또는 다환의 아릴 또는 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 C6 내지 C60의 단환 또는 다환의 아릴; 또는 C6 내지 C60의 단환 또는 다환의 아릴 또는 C2 내지 C60의 단환 또는 다환의 헤테로아릴로 치환 또는 비치환된 헤테로아릴이다.According to an exemplary embodiment of the present invention, Y 11 to Y 13 are each C 6 to C 60 monocyclic or polycyclic aryl or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl C 6 to C of the 60 monocyclic or polycyclic aryl; Or heteroaryl unsubstituted or substituted with C 6 to C 60 monocyclic or polycyclic aryl or C 2 to C 60 monocyclic or polycyclic heteroaryl.
본 발명의 일 실시상태에 따르면, 상기 화학식 13의
Figure PCTKR2013012050-appb-I000017
는 하기 구조를 포함한다.According to an exemplary embodiment of the present invention,
Figure PCTKR2013012050-appb-I000017
Contains the following structure.
Figure PCTKR2013012050-appb-I000018
Figure PCTKR2013012050-appb-I000018
상기 구조식들에 있어서, T1 내지 T9는 각각 CRR', NR, S 또는 O이고, In the above structural formula, T 1 to T 9 are each CRR ', NR, S or O,
R 및 R'는 서로 같거나 상이하고, 각각 수소; C1 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알킬; 또는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴이다.R and R 'are the same as or different from each other, and each hydrogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; Or C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl.
본 발명의 일 실시상태에 따르면, T1, T2, T4, T7, T8, T9는 각각 독립적으로 CRR', NR, S 또는 O이고, T3, T5 및 T6는 각각 독립적으로 S 또는 O이다. According to an exemplary embodiment of the present invention, T 1 , T 2 , T 4 , T 7 , T 8 , T 9 are each independently CRR ', NR, S or O, and T 3 , T 5 and T 6 are each Independently S or O.
본 발명의 일 실시상태에 따르면, 상기 T1 내지 T9 중 적어도 하나가 CRR'인 경우, R 및 R'는 서로 같거나 상이하고, 각각 독립적으로 C1 내지 C6의 알킬; 또는 C6 내지 C20의 아릴이다. According to an exemplary embodiment of the present invention, when at least one of T 1 to T 9 is CRR ', R and R' are the same as or different from each other, and each independently C 1 to C 6 alkyl; Or C 6 to C 20 aryl.
본 발명의 일 실시상태에 따르면, 상기 T1 내지 T9 중 적어도 하나가 CRR'인 경우, R 및 R'는 서로 같거나 상이하고, 각각 독립적으로 메틸 또는 페닐이다. According to an exemplary embodiment of the present invention, when at least one of T 1 to T 9 is CRR ', R and R' are the same as or different from each other, and are each independently methyl or phenyl.
본 발명의 일 실시상태에 따르면, 상기 T1 내지 T9 중 적어도 하나가 NR인 경우, R은 C6 내지 C20의 아릴이다.According to an exemplary embodiment of the present invention, when at least one of T 1 to T 9 is NR, R is C 6 to C 20 aryl.
본 발명의 일 실시상태에 따르면, 상기 T1 내지 T9 중 적어도 하나가 NR인 경우, R은 페닐이다.According to an exemplary embodiment of the present invention, when at least one of T 1 to T 9 is NR, R is phenyl.
본 발명의 일 실시상태에 따르면, 상기 화학식 9 내지 13에 있어서, p는 0 내지 2의 정수이고, L은 페닐렌이다. According to an exemplary embodiment of the present invention, in Chemical Formulas 9 to 13, p is an integer of 0 to 2, L is phenylene.
본 발명의 일 실시상태에 따르면, 상기 화학식 1의 화합물은 하기 화합물들 중에서 선택될 수 있다.According to an exemplary embodiment of the present invention, the compound of Formula 1 may be selected from the following compounds.
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-134
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-134
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-135
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-135
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-136
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-136
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-137
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-137
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-138
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-138
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-139
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-139
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-140
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-140
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-141
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-141
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-142
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-142
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-143
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-143
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-144
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-144
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-145
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-145
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-146
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-146
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-147
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-147
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-148
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-148
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-149
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-149
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-150
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-150
[규칙 제91조에 의한 정정 23.01.2014]　
Figure WO-DOC-FIGURE-151
[Revision 23.01.2014 under Rule 91]
Figure WO-DOC-FIGURE-151
Figure PCTKR2013012050-appb-I000037
Figure PCTKR2013012050-appb-I000037
Figure PCTKR2013012050-appb-I000038
Figure PCTKR2013012050-appb-I000038
Figure PCTKR2013012050-appb-I000039
Figure PCTKR2013012050-appb-I000039
Figure PCTKR2013012050-appb-I000040
Figure PCTKR2013012050-appb-I000040
Figure PCTKR2013012050-appb-I000041
Figure PCTKR2013012050-appb-I000041
Figure PCTKR2013012050-appb-I000042
Figure PCTKR2013012050-appb-I000042
Figure PCTKR2013012050-appb-I000043
Figure PCTKR2013012050-appb-I000043
Figure PCTKR2013012050-appb-I000044
Figure PCTKR2013012050-appb-I000044
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 compounds described above may be prepared based on the preparation examples described below. In the following production examples, representative examples are described, but if necessary, a substituent may be added or excluded, and the position of the substituent may be changed. In addition, based on techniques known in the art, it is possible to change starting materials, reactants, reaction conditions and the like. Changing the type or position of substituents at the remaining positions as needed can be performed by those skilled in the art using techniques known in the art.
본 발명의 또 하나의 실시상태는 전술한 화학식 1의 화합물을 포함하는 유기발광소자를 제공한다. 구체적으로, 본 발명에 따른 유기발광소자는 양극, 음극 및 양극과 음극 사이에 구비된 1층 이상의 유기물층을 포함하고, 상기 유기물층 중 1층 이상은 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 invention includes one or more organic material layers provided between the anode, the cathode and the anode and the cathode, one or more of the organic material layer comprises a compound of formula (1).
도 1 내지 3에 본 발명의 실시상태들에 따른 유기발광소자의 전극과 유기물층의 적층 순서를 예시하였다. 그러나, 이들 도면에 의하여 본 발명의 범위가 한정될 것을 의도한 것은 아니며, 당 기술분야에 알려져 있는 유기발광소자의 구조가 본 발명에도 적용될 수 있다. 1 to 3 illustrate the stacking order of electrodes and organic material layers of organic light emitting diodes according to exemplary embodiments of the present invention. However, these drawings are not intended to limit the scope of the present invention, the structure of the organic light emitting device known in the art can be applied to the present invention.
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. Referring to FIG. 1, an organic light emitting device in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is illustrated. However, the present invention is not limited thereto, and as shown in FIG. 2, 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.
도 3은 유기물층이 다층인 경우를 예시한 것이다. 도 3에 따른 유기발광소자는 정공주입층(301), 정공수송층(302), 발광층(303), 전자수송층(304) 및 전자주입층(305)를 포함한다. 그러나, 이와 같은 적층구조에 의하여 본 발명의 범위가 한정되는 것은 아니며, 필요에 따라 발광층을 제외한 나머지 층은 생략될 수도 있고, 필요한 다른 기능층이 더 추가될 수 있다. 3 illustrates a case where the organic material layer is a multilayer. The organic light emitting diode according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, an electron transport layer 304, and an electron injection layer 305. However, the scope of the present invention is not limited by such a laminated structure, and other layers except for the light emitting layer may be omitted, and other functional layers may be added as needed.
본 발명에 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 may be manufactured by materials and methods known in the art, except that the compound of Formula 1 is included in at least one layer of the organic material layer.
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 1 may constitute one or more layers of the organic material layer of the organic light emitting device alone. However, if necessary, the organic material layer may be mixed with other materials.
상기 화학식 1의 화합물은 유기발광소자에서 정공주입재료, 정공수송재료, 발광재료, 전자수송재료, 전자주입재료 등으로 사용될 수 있다. 상기 화학식 1의 화합물을 포함하는 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 또는 전자주입층일 수 있다. 특히, 상기 화학식 1의 화합물은 유기발광소자의 전자 주입 및/또는 수송층 재료로서 사용될 수 있다. The compound of Formula 1 may be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material and the like in the organic light emitting device. The organic material layer including the compound of Formula 1 may be a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer or an electron injection layer. In particular, the compound of Formula 1 may be used as the electron injection and / or transport layer material of the organic light emitting device.
하나의 실시상태에 따르면, 상기 화학식 1의 화합물을 포함하는 유기물층은 전자수송층이다. According to one exemplary embodiment, the organic material layer including the compound of Formula 1 is an electron transport layer.
또 하나의 실시상태에 따르면, 상기 화학식 1의 화합물은 유기발광소자의 발광재료로서 사용될 수 있다. 일 구체예로서, 상기 화학식 1의 화합물을 포함하는 유기물층은 유기발광소자의 발광층일 수 있다. According to another exemplary embodiment, the compound of Formula 1 may be used as a light emitting material of an organic light emitting device. In one embodiment, the organic material layer including the compound of Formula 1 may be a light emitting layer of the organic light emitting device.
상기 화학식 1의 화합물은 인광 호스트 재료로서 사용될 수 있다. 이 경우, 상기 화학식 1의 화합물은 발광 도펀트와 함께 사용된다. 상기 발광 도펀트 재료로는 당기술분야에 알려져 있는 것들을 사용할 수 있다. The compound of Formula 1 may be used as a phosphorescent host material. In this case, the compound of Formula 1 is used together with a light emitting dopant. As the light emitting dopant material, those known in the art may be used.
예컨대, LL'MX, LL'L''M, LMXX', L2MX 및 L3M로 표시되는 인광 도펀트 재료를 사용할 수 있으나, 이들 예에 의하여 본 발명의 범위가 한정되는 것은 아니다.For example, phosphorescent dopant materials represented by LL'MX, LL'L''M, LMXX ', L 2 MX, and L 3 M can be used, but the scope of the present invention is not limited to these examples.
여기서, L, L', L", X 및 X'는 서로 상이한 2좌 배위자이고, M은 8 면상 착체를 형성하는 금속이다. Here, L, L ', L ", X and X' are bidentate ligands different from each other, and M is a metal which forms an 8-sided complex.
M은 이리듐, 백금, 오스뮴 등이 될 수 있다. M may be iridium, platinum, osmium or the like.
L은 sp2 탄소 및 헤테로 원자에 의하여 M에 배위되는 음이온성 2좌 배위자이고, X는 전자 또는 정공을 트랩하는 기능을 할 수 있다. L의 비한정적인 예로는 2-(1-나프틸)벤조옥사졸, (2-페닐벤조옥사졸), (2-페닐벤조티아졸), (2-페닐벤조티아졸), (7,8-벤조퀴놀린), (티에닐피리진), 페닐피리딘, 벤조티에닐피리진, 3-메톡시-2-페닐피리딘, 티에닐피리진, 톨릴피리딘 등이 있다. X의 비한정적인 예로는 아세틸아세토네이트(acac), 헥사플루오로아세틸아세토네이트, 살리실리덴, 피콜리네이트, 8-히드록시퀴놀리네이트 등이 있다. L is an anionic bidentate ligand coordinated to M by sp 2 carbon and hetero atom, and X may function to trap electrons or holes. Non-limiting examples of L include 2- (1-naphthyl) benzoxazole, (2-phenylbenzooxazole), (2-phenylbenzothiazole), (2-phenylbenzothiazole), (7,8 -Benzoquinoline), (thienylpyridin), phenylpyridine, benzothienylpyridin, 3-methoxy-2-phenylpyridine, thienylpyridin, tolylpyridine and the like. Non-limiting examples of X include acetylacetonate (acac), hexafluoroacetylacetonate, salicylidene, picolinate, 8-hydroxyquinolinate, and the like.
더욱 구체적인 예를 하기에 표시하나, 이들 예로만 한정되는 것은 아니다.More specific examples are shown below, but are not limited to these examples.
Figure PCTKR2013012050-appb-I000045
Figure PCTKR2013012050-appb-I000045
본 발명에 따른 유기발광소자에 있어서, 상기 화학식 1의 화합물 이외의 재료를 하기에 예시하지만, 이들은 예시를 위한 것일 뿐 본 발명의 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 invention. 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 anode material, materials having a relatively large work function may be used, and a transparent conductive oxide, a metal, or a conductive polymer may 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 a relatively low work function may be used, and a metal, a metal oxide, or a conductive polymer may 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 TCTA, m-MTDATA, 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 injection material, a well-known hole injection material may be used, for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or described in Advanced Material, 6, p.677 (1994). Starburst-type amine derivatives such as TCTA, m-MTDATA, m-MTDAPB, polyaniline / dodecylbenzenesulfonic acid (polyaniline / dodecylbenzenesulfonic acid) or PEDOT / PSS (Poly (3, 4-ethylenedioxythiophene) / Poly (4-styrenesulfonate): poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate)), Pani / CSA (Polyaniline / Camphor sulfonic acid: polyaniline / camphorsulfonic acid) or PANI / PSS (Polyaniline / Poly (4-styrene-sulfonate): polyaniline / poly (4-styrenesulfonate)) and the like 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, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, and the like may be used, and low molecular or polymer materials 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 transport material include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinomethane and derivatives thereof, and fluorenone Derivatives, diphenyl dicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and the like can be used, as well as high molecular weight materials as well as high molecular materials.
전자주입재료로는 예를 들어, LiF가 당업계 대표적으로 사용되나, 본 발명이 이에 한정되는 것은 아니다. As the electron injection material, for example, LiF is representatively used in the art, but the present invention 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 수 도 있으나, 호스트 재료와 도펀트 재료가 함께 발광에 관여하는 재료들이 사용될 수도 있다. As the light emitting material, a red, green or blue light emitting material may be used, and if necessary, two or more light emitting materials may be mixed. In addition, although a fluorescent material can be used as a light emitting material, it can also be used as a phosphorescent material. As the light emitting material, a material which combines holes and electrons injected from the anode and the cathode, respectively, to emit light may be used, but materials in which both the host material and the dopant material are involved in light emission may be used.
이하에서, 실시예를 통하여 본 발명을 더욱 상세하게 설명하지만, 이들은 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위를 한정하기 위한 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to Examples, but these are merely for illustrating the present invention and are not intended to limit the scope of the present invention.
본 발명의 일 실시상태에 따르면, 하기 반응식 1과 같은 방법으로 코어구조를 형성한 후, 반응식 2 또는 3과 같은 방법으로 치환기를 도입하여 화학식 1의 화합물을 제조할 수 있다.According to an exemplary embodiment of the present invention, after forming the core structure in the same manner as in Scheme 1, the compound of formula 1 may be prepared by introducing a substituent in the same manner as in Scheme 2 or 3.
[반응식 1] Scheme 1
Figure PCTKR2013012050-appb-I000046
Figure PCTKR2013012050-appb-I000046
상기 반응식 1과 같이 화합물 a-1과 화합물 b-1이 함께 제조되는 경우에는 당 기술분야에 알려져 있는 방법, 예컨대 컬럼크로마토그래피로 화합물을 분리할 수 있다. When compound a-1 and compound b-1 are prepared together as in Scheme 1, the compound may be separated by a method known in the art, such as column chromatography.
[반응식 2]Scheme 2
Figure PCTKR2013012050-appb-I000047
Figure PCTKR2013012050-appb-I000047
[반응식 3]Scheme 3
Figure PCTKR2013012050-appb-I000048
Figure PCTKR2013012050-appb-I000048
반응식 2 및 3에 있어서, R은 전술한 화학식 1의 R1 내지 R8의 정의와 같다. In Schemes 2 and 3, R is as defined in R 1 to R 8 of Formula 1 above.
상기 반응식 1 내지 3에서는 R2 또는 R4의 위치에 치환기만을 도입하였으나, 필요에 따라 나머지 위치의 치환기를 도입하는 것은 당업자가 당 기술분야에 알려져 있는 기술을 이용하여 수행할 수 있다. 예컨대 Br의 치환된 위치에 따라 치환기의 위치를 변경할 수 있다. In Schemes 1 to 3, only a substituent is introduced at the position of R 2 or R 4 , but if necessary, introducing a substituent at the remaining position may be performed by those skilled in the art using techniques known in the art. For example, the position of the substituent may be changed depending on the substituted position of Br.
전술한 반응식 1의 과정을 하기와 같이 수행하였다. The procedure of Scheme 1 described above was carried out as follows.
화합물 compound 1-31-3 의 제조Manufacture
N-히드록시프탈이미드 8.05g(49.37m㏖)를 아세톤 160㎖에 녹인 혼합 용액에 트리에틸아민 6.9㎖(49.86m㏖)를 첨가한 후 10분 동안 교반하였다. 그 반응 혼합물에 1-클로로-2,4-디니트로벤젠 10g(49.37m㏖) 넣은 후 상온에서 2시간 더 교반하였다. 반응이 완결되면 얼음물에 붓고 그 때 생성된 고체는 필터하였다. 필터한 고체는 메탄올, 헥산으로 씻어준 뒤 건조하여 목적화합물 1-3 15.05g (93%)를 얻었다.6.9 ml (49.86 mmol) of triethylamine was added to a mixed solution of 8.05 g (49.37 mmol) of N-hydroxyphthalimide in 160 ml of acetone, followed by stirring for 10 minutes. 10 g (49.37 mmol) of 1-chloro-2,4-dinitrobenzene was added to the reaction mixture, followed by further stirring at room temperature for 2 hours. Upon completion of the reaction, the mixture was poured into iced water and the solid produced at that time was filtered. The filtered solid was washed with methanol and hexane and dried to obtain 15.05 g (93%) of the title compound 1-3.
화합물 compound 1-21-2 의 제조Manufacture
2-(2,4-디니트로페녹시)이소인돌린-1,3-디온 17.74g(53.88m㏖)을 디클로로메탄 350㎖에 녹인 다음 0℃로 유지한 상태에서 히드라진 모노하이드레이트 7.6㎖(157.33m㏖)를 첨가한 후 4시간 동안 교반하였다. 반응이 완결되면 0℃에서 1N HCl을 부어 다시 교반하고 그 때 생성된 고체는 필터하였다. 필터한 고체는 MeCN으로 씻어 주고 그 여액을 MC로 추출하고 유기층은 MgSO4로 건조하여 목적화합물 1-2 10.50g (98%)를 얻었다.17.74 g (53.88 mmol) of 2- (2,4-dinitrophenoxy) isoindolin-1,3-dione was dissolved in 350 ml of dichloromethane, and then 7.6 ml (157.33) of hydrazine monohydrate was maintained at 0 ° C. mmol) was added and stirred for 4 hours. Upon completion of the reaction, 1N HCl was poured at 0 ° C. and stirred again, and the resulting solid was filtered. The filtered solid was washed with MeCN, the filtrate was extracted with MC, and the organic layer was dried over MgSO 4 to obtain 10.50 g (98%) of the title compound 1-2.
화합물 compound 1-11-1 의 제조Manufacture
3-브로모피리딘 9.2㎖(94.94m㏖)를 H2O, THF(각 38㎖) 혼합 용액에 O-(2,4-디니트로페닐)히드록실아민 28.36g(142.41m㏖)를 첨가하였다. 반응 혼합물을 40℃에서 12시간 교반한 후 0℃로 유지한 상태에서 2.5N NaOH 475㎖와 THF 152㎖에 녹인 TsCl 36.20g(189.88m㏖)를 첨가한 후 4시간 더 교반하였다. 반응이 완결되면 MC로 추출하고 유기층은 MgSO4로 건조하여 목적화합물 1-1 16g (52%)를 얻었다.9.2 mL (94.94 mmol) of 3-bromopyridine was added 28.36 g (142.41 mmol) of O- (2,4-dinitrophenyl) hydroxylamine to a H 2 O, THF (38 mL each) solution. . The reaction mixture was stirred at 40 ° C. for 12 hours, and then T.Cl 36.20 g (189.88 mmol) dissolved in 475 mL of 2.5N NaOH and 152 mL of THF was maintained at 0 ° C., followed by further stirring for 4 hours. Upon completion of the reaction, the mixture was extracted with MC and the organic layer was dried over MgSO 4 to obtain 16 g (52%) of the title compound 1-1.
화합물 compound a-1 a-1 및And b-1 b-1 의 제조Manufacture
(3-브로모피리딘-1-이움-1-일)(토실)아미드((3-bromopyridin-1-ium-1-yl)(tosyl)amide) 16g(48.90m㏖), 2-(트리메틸실릴)페닐 트리플루오로메탄술포네이트 14.2㎖(58.68m㏖)를 THF에 녹인 후 천천히 교반하다가 세슘 플루오라이드 22.28g(146.7m㏖)를 첨가한 후 70℃에서 24시간 동안 교반하였다. 반응이 완결되면 EA로 추출하고 유기층은 MgSO4로 건조하였다. EA/Hex 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 a-1 2.17g(18%) 및 b-1 4.59g(38%)를 얻었다.(3-bromopyridin-1-ium-1-yl) (tosyl) amide ((3-bromopyridin-1-ium-1-yl) (tosyl) amide) 16 g (48.90 mmol), 2- (trimethylsilyl 14.2 mL (58.68 mmol) of phenyl trifluoromethanesulfonate was dissolved in THF, and stirred slowly. Then, 22.28 g (146.7 mmol) of cesium fluoride was added, followed by stirring at 70 ° C. for 24 hours. After completion of the reaction, the mixture was extracted with EA and the organic layer was dried over MgSO 4 . Column chromatography was performed using EA / Hex developing solvent to obtain 2.17 g (18%) and b-1 4.59 g (38%) of the target compound a-1 .
[제조예 1] 화합물 6의 제조Preparation Example 1 Preparation of Compound 6
Figure PCTKR2013012050-appb-I000049
Figure PCTKR2013012050-appb-I000049
화합물 compound 66 의 제조Manufacture
8-브로모피리도[1,2-b]인다졸 2g(8.09m㏖), 2,4-디([1,1'-비페닐]-4-일)-6-(4,4,5,5-테트라메틸-1,3,2-디옥사보롤란-2-일)-1,3,5-트리아진(화합물 Ar1) 4.97g (9.71m㏖), 테트라키스(트리페닐포스핀)팔라듐 0.94g(0.81m㏖), 포타슘 카보네이트 3.35g(24.27m㏖)를 톨루엔, H2O, 에탄올 혼합 용액 환류하에서 24시간 동안 교반하였다. 반응이 완결되면 EA로 추출하고 유기층은 MgSO4로 건조하였다. EA/Hex 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 6 2.45g (55%)를 얻었다.2 g (8.09 mmol) of 8-bromopyrido [1,2-b] indazol, 2,4-di ([1,1'-biphenyl] -4-yl) -6- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3,5-triazine (Compound Ar 1 ) 4.97 g (9.71 mmol), tetrakis (triphenylphosphine ) 0.94 g (0.81 mmol) of palladium and 3.35 g (24.27 mmol) of potassium carbonate were stirred for 24 hours under reflux of a toluene, H 2 O, and ethanol mixed solution. After completion of the reaction, the mixture was extracted with EA and the organic layer was dried over MgSO 4 . 2.45g (55%) of the title compound 6 was obtained by column chromatography using EA / Hex developing solvent.
[제조예 2 내지 제조예 11] 화합물 Preparation Example 2 to Example 11 Compound 1, One, 화합물 compound 3, 3, 화합물 compound 8, 8, 화합물 compound 12, 12, 화합물 compound 13, 13, 화합물 compound 16, 16, 화합물 compound 18, 18, 화합물 compound 2828 , 화합물 , Compound 35 35 및 화합물And compounds 38 38 의 제조Manufacture
화합물 Ar1로서 하기 표 1의 화합물을 이용한 것을 제외하고는, 상기 제조예 1과 동일한 방법으로 수행하여, 화합물 1, 화합물 3, 화합물 8, 화합물 12, 화합물 13, 화합물 16, 화합물 18, 화합물 28, 화합물 35 및 화합물 38를 제조하였다.A compound 1, a compound 3, a compound 8, a compound 12, a compound 13, a compound 16, a compound 18, a compound 28 was performed in the same manner as in Preparation Example 1, except that the compound of Table 1 was used as the compound Ar 1 . , Compound 35 and compound 38 were prepared.
표 1
Figure PCTKR2013012050-appb-T000001
 Table 1
Figure PCTKR2013012050-appb-T000001
Figure PCTKR2013012050-appb-I000050
Figure PCTKR2013012050-appb-I000050
[제조예 12] 화합물 66의 제조Preparation Example 12 Preparation of Compound 66
Figure PCTKR2013012050-appb-I000051
Figure PCTKR2013012050-appb-I000051
화합물 compound 6666 의 제조Manufacture
10-브로모피리도[1,2-b]인다졸 4.1g(16.59m㏖), 2-(9,10-디(나프탈렌-2-일)안트라센-2-일)-4,4,5,5-테트라메틸-1,3,2-디옥사보롤레인 11.08g(19.91m㏖), 테트라키스(트리페닐포스핀)팔라듐 1.92g(1.66m㏖), 포타슘 카보네이트 6.88g(49.77m㏖)를 톨루엔, H2O, 에탄올 혼합 용액 환류하에서 24시간 동안 교반하였다. 반응이 완결되면 EA로 추출하고 유기층은 MgSO4로 건조하였다. EA/Hex 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 66 5.9g (60%)를 얻었다.4.1 g (16.59 mmol) of 10-bromopyrido [1,2-b] indazol, 2- (9,10-di (naphthalen-2-yl) anthracen-2-yl) -4,4,5, 11.08 g (19.91 mmol) of 5-tetramethyl-1,3,2-dioxaborolane, 1.92 g (1.66 mmol) of tetrakis (triphenylphosphine) palladium, 6.88 g (49.77 mmol) of potassium carbonate Toluene, H 2 O, ethanol mixed solution was stirred for 24 hours under reflux. After completion of the reaction, the mixture was extracted with EA and the organic layer was dried over MgSO 4 . Column chromatography was performed using EA / Hex developing solvent to obtain the title compound 66 (5.9g, 60%).
[제조예 13 내지 제조예 21] 화합물 Preparation Example 13 to Production Example 21 Compound 3939 , 화합물 , Compound 4141 , 화합물 , Compound 4242 , 화합물 , Compound 4444 , 화합물 , Compound 4545 , 화합물 , Compound 4747 , 화합물 , Compound 5151 , 화합물 , Compound 5454 및 화합물  And compounds 7676 의 제조Manufacture
화합물 Ar2로서 하기 표 2의 화합물을 이용하고, 상기 제조예 12와 동일한 방법으로 수행하여, 화합물 39, 화합물 41, 화합물 42, 화합물 44, 화합물 45, 화합물 47, 화합물 51, 화합물 54 및 화합물 76를 제조하였다.Using the compound of the following Table 2 as the compound Ar 2 , and by the same method as in Preparation Example 12, Compound 39, Compound 41, Compound 42, Compound 44, Compound 45, Compound 47, Compound 51, Compound 54 and Compound 76 Was prepared.
표 2
Figure PCTKR2013012050-appb-T000002
 TABLE 2
Figure PCTKR2013012050-appb-T000002
Figure PCTKR2013012050-appb-I000052
Figure PCTKR2013012050-appb-I000052
본 발명의 일 실시상태에 따르면, 하기 반응식 4에 따라 화학식 1의 화합물을 제조할 수 있다. According to one embodiment of the present invention, a compound of Chemical Formula 1 may be prepared according to Scheme 4 below.
[반응식 4] Scheme 4
Figure PCTKR2013012050-appb-I000053
Figure PCTKR2013012050-appb-I000053
반응식 4에 있어서, R은 전술한 화학식 1의 R1 내지 R8의 정의와 같다. Br의 치환된 위치에 따라 치환기의 위치를 변경시킬 수 있는 것은 당업자에게 자명하다. In Scheme 4, R is as defined in R 1 to R 8 of Formula 1 above. It will be apparent to those skilled in the art that the position of the substituent can be changed depending on the substituted position of Br.
화합물 compound 2-32-3 의 제조Manufacture
2-브로모피리딘 3㎖(31.65m㏖)를 H2O, THF(각 13㎖) 혼합 용액에 O-(2,4-디니트로페닐)히드록실아민(화합물 1-2) 9.45g(47.48m㏖)를 첨가하였다. 반응 혼합물을 40℃에서 12시간 교반한 후 0℃로 유지한 상태에서 2.5N NaOH 158㎖와 THF 51㎖에 녹인 TsCl 12.07g(63.30m㏖)를 첨가한 후 4시간 더 교반하였다. 반응이 완결되면 MC로 추출하고 유기층은 MgSO4로 건조하여 목적화합물 2-3 6.01g (58%)를 얻었다.9.45 g (47.48) of O- (2,4-dinitrophenyl) hydroxylamine (Compound 1-2) in 3 ml (31.65 mmol) of 2-bromopyridine was mixed with H 2 O and THF (13 ml each). mmol) was added. The reaction mixture was stirred at 40 ° C. for 12 hours, and then 12.07 g (63.30 mmol) of TsCl dissolved in 158 mL of 2.5N NaOH and 51 mL of THF were added and stirred for 4 hours. After completion of the reaction, the mixture was extracted with MC and the organic layer was dried over MgSO 4 to obtain 6.01 g (58%) of the title compound 2-3 .
화합물 compound a-2a-2 의 제조Manufacture
(2-브로모피리딘-1-이움-1-일)(토실)아미드 ((2-bromopyridin-1-ium-1-yl)(tosyl)amide) 6g(18.34m㏖), 2-(트리메틸실릴)페닐 트리플루오로메탄술포네이트 10.9㎖(36.68m㏖)를 THF에 녹인 후 천천히 교반하다가 세슘 플루오라이드 8.36g(55.02m㏖)를 첨가한 후 70℃에서 24시간 동안 교반하였다. 반응이 완결되면 EA로 추출하고 유기층은 MgSO4로 건조하였다. EA/Hex 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 a-2 3.26g (72%)를 얻었다.(2-bromopyridin-1-ium-1-yl) (tosyl) amide ((2-bromopyridin-1-ium-1-yl) (tosyl) amide) 6 g (18.34 mmol), 2- (trimethylsilyl 10.9 mL (36.68 mmol) of phenyl trifluoromethanesulfonate was dissolved in THF, and stirred slowly, followed by addition of 8.36 g (55.02 mmol) of cesium fluoride, followed by stirring at 70 ° C. for 24 hours. After completion of the reaction, the mixture was extracted with EA and the organic layer was dried over MgSO 4 . Column chromatography was performed using EA / Hex developing solvent to obtain 3.26 g (72%) of the target compound a-2 .
[제조예 22] 화합물 78의 제조Preparation Example 22 Preparation of Compound 78
Figure PCTKR2013012050-appb-I000054
Figure PCTKR2013012050-appb-I000054
화합물 compound 7878 의 제조Manufacture
7-브로모피리도[1,2-b]인다졸 3g(12.14m㏖), 2,4-디(나프탈렌-2-일)-6-(4,4,5,5-테트라메틸-1,3,2-디옥사보롤레인-2-일)-1,3,5-트리아진 6.69g(14.57m㏖), 테트라키스(트리페닐포스핀)팔라듐 1.40g(1.21m㏖), 포타슘 카보네이트 5.03g(36.42m㏖)를 톨루엔, H2O, 에탄올 혼합 용액 환류하에서 24시간 동안 교반하였다. 반응이 완결되면 EA로 추출하고 유기층은 MgSO4로 건조하였다. EA/Hex 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 78 4.91g(81%)를 얻었다.3 g (12.14 mmol) of 7-bromopyrido [1,2-b] indazol, 2,4-di (naphthalen-2-yl) -6- (4,4,5,5-tetramethyl-1, 3,2-dioxaborole-2-yl) -1,3,5-triazine 6.69 g (14.57 mmol), tetrakis (triphenylphosphine) palladium 1.40 g (1.21 mmol), potassium carbonate 5.03 g (36.42 mmol) was stirred for 24 h under reflux of toluene, H 2 O, ethanol mixed solution. After completion of the reaction, the mixture was extracted with EA and the organic layer was dried over MgSO 4 . Column chromatography was performed using EA / Hex developing solvent to obtain 4.91 g (81%) of the title compound 78 .
[제조예 23 내지 제조예 31] 화합물 Preparation Example 23 to Production Example 31 Compound 8686 , 화합물 , Compound 8787 , 화합물 , Compound 9393 , 화합물 , Compound 9999 , 화합물 , Compound 102102 , 화합물 , Compound 104104 , 화합물 , Compound 105105 , 화합물 , Compound 110110 및 화합물  And compounds 114114 의 제조Manufacture
화합물 Ar3로서 하기 표 3의 화합물을 이용한 것을 제외하고는, 상기 제조예 22와 동일한 방법으로 수행하여, 화합물 86, 화합물 87, 화합물 93, 화합물 99, 화합물 102, 화합물 104, 화합물 105, 화합물 110 및 화합물 114를 제조하였다.Compound 86, Compound 87, Compound 93, Compound 99, Compound 102, Compound 104, Compound 105, Compound 110 were carried out in the same manner as in Preparation Example 22, except that Compound 3 was used as Ar 3 . And compound 114 was prepared.
표 3
Figure PCTKR2013012050-appb-T000003
 TABLE 3
Figure PCTKR2013012050-appb-T000003
Figure PCTKR2013012050-appb-I000055
Figure PCTKR2013012050-appb-I000055
본 발명의 일 실시상태에 따르면, 하기 반응식 5에 따라 화학식 1의 화합물을 제조할 수 있다. According to the exemplary embodiment of the present invention, a compound of Chemical Formula 1 may be prepared according to Scheme 5 below.
[반응식 5]Scheme 5
Figure PCTKR2013012050-appb-I000056
Figure PCTKR2013012050-appb-I000056
반응식 5에 있어서, R은 전술한 화학식 1의 R1 내지 R8의 정의와 같다. 출발물질의 Br의 치환된 위치 또는 축합고리의 위치에 따라 치환기의 위치를 변경시킬 수 있는 것은 당업자에게 자명하다. In Scheme 5, R is as defined in R 1 to R 8 of Formula 1 above. It will be apparent to those skilled in the art that the position of the substituents can be varied depending on the substituted position of Br or the position of the condensed ring of the starting material.
화합물 compound 3-33-3 의 제조Manufacture
3-브로모퀴놀린 2㎖(14.42m㏖)를 H2O, THF(각 6㎖) 혼합 용액에 O-(2,4-디니트로페닐)히드록실아민(화합물 1-2) 4.31g(21.63m㏖)를 첨가하였다. 반응 혼합물을 40℃에서 12시간 교반한 후 0℃로 유지한 상태에서 2.5N NaOH 72㎖와 THF 23㎖에 녹인 TsCl 5.50g(28.84m㏖)를 첨가한 후 4시간 더 교반하였다. 반응이 완결되면 MC로 추출하고 유기층은 MgSO4로 건조하여 목적화합물 3-3 2.01g(37%)를 얻었다.4.31 g (21.63) of O- (2,4-dinitrophenyl) hydroxylamine (Compound 1-2) in 2 ml (14.42 mmol) of 3-bromoquinoline in a mixture of H 2 O and THF (6 ml each) mmol) was added. The reaction mixture was stirred at 40 ° C. for 12 hours, and then 5.50 g (28.84 mmol) of TsCl dissolved in 72 mL of 2.5N NaOH and 23 mL of THF was added at a temperature of 0 ° C., followed by further stirring for 4 hours. Upon completion of the reaction, the mixture was extracted with MC and the organic layer was dried over MgSO 4 to obtain 2.01 g (37%) of the title compound 3-3 .
화합물 compound b-3b-3 의 제조Manufacture
(3-브로모퀴놀린-1-이움-1-일)(토실)아미드 ((3-bromoquinolin-1-ium-1-yl)(tosyl)amide) 4.5g(11.93m㏖), 2-(트리메틸실릴)페닐 트리플루오로메탄술포네이트 5.8㎖(23.86m㏖)를 THF에 녹인 후 천천히 교반하다가 세슘 플루오라이드 5.44g(35.79m㏖)를 첨가한 후 70℃에서 24시간 동안 교반하였다. 반응이 완결되면 EA로 추출하고 유기층은 MgSO4로 건조하였다. EA/Hex 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 b-3 3.01g(85%)를 얻었다.(3-bromoquinolin-1-ium-1-yl) (tosyl) amide ((3-bromoquinolin-1-ium-1-yl) (tosyl) amide) 4.5 g (11.93 mmol), 2- (trimethyl After dissolving 5.8 ml (23.86 mmol) of silyl) phenyl trifluoromethanesulfonate in THF and slowly stirring, 5.44 g (35.79 mmol) of cesium fluoride was added, followed by stirring at 70 ° C. for 24 hours. After completion of the reaction, the mixture was extracted with EA and the organic layer was dried over MgSO 4 . Column chromatography was performed using EA / Hex developing solvent to obtain 3.01 g (85%) of the title compound b-3.
[제조예 32] 화합물 152의 제조Preparation Example 32 Preparation of Compound 152
Figure PCTKR2013012050-appb-I000057
Figure PCTKR2013012050-appb-I000057
화합물 compound 152152 의 제조Manufacture
6-브로모인다졸로[2,3-a]퀴놀린 3g(10.10m㏖), 2-(4-(9,10-디(나프탈렌-2-일)안트라센-2-일)페닐)-4,4,5,5-테트라메틸-1,3,2-디옥사보롤레인(Ar4) 7.67g(12.12m㏖), 테트라키스(트리페닐포스핀)팔라듐 1.17g(1.01m㏖), 포타슘 카보네이트 4.19g(30.3m㏖)를 톨루엔, H2O, 에탄올 혼합 용액 환류하에서 24시간 동안 교반하였다. 반응이 완결되면 EA로 추출하고 유기층은 MgSO4로 건조하였다. EA/Hex 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 152 6.21g(85%)를 얻었다.6-bromoindazolo [2,3-a] quinoline 3 g (10.10 mmol), 2- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -4,4 , 5,5-tetramethyl-1,3,2-dioxaborolane (Ar 4 ) 7.67 g (12.12 mmol), tetrakis (triphenylphosphine) palladium 1.17 g (1.01 mmol), potassium carbonate 4.19 g (30.3 mmol) was stirred for 24 h under reflux of toluene, H 2 O, ethanol mixed solution. After completion of the reaction, the mixture was extracted with EA and the organic layer was dried over MgSO 4 . 6.21g (85%) of the target compound 152 was obtained by column chromatography using EA / Hex developing solvent.
[제조예 33 내지 제조예 42] 화합물 Preparation Example 33-42 119119 , 화합물 , Compound 123123 , 화합물 , Compound 128128 , 화합물 , Compound 134134 , 화합물 , Compound 136136 , 화합물 , Compound 139139 , 화합물 , Compound 142142 , 화합물 , Compound 144144 , 화합물 , Compound 146146 및 화합물  And compounds 150150 의 제조Manufacture
화합물 Ar4로서 하기 표 4의 화합물을 이용하고, 상기 제조예 32와 동일한 방법으로 수행하여, 화합물 119, 화합물 123, 화합물 128, 화합물 134, 화합물 136, 화합물 139, 화합물 142, 화합물 144, 화합물 146 및 화합물 150을 제조하였다.Compound 119 , compound 123 , compound 128 , compound 134 , compound 136 , compound 139 , compound 142 , compound 144 , compound 146 by using the compound of Table 4 as compound Ar 4 , in the same manner as in Preparation Example 32 And compound 150 were prepared.
표 4
Figure PCTKR2013012050-appb-T000004
 Table 4
Figure PCTKR2013012050-appb-T000004
Figure PCTKR2013012050-appb-I000058
Figure PCTKR2013012050-appb-I000058
본 발명의 일 실시상태에 따르면, 하기 반응식 6에 따라 화학식 1의 화합물을 제조할 수 있다. According to the exemplary embodiment of the present invention, a compound of Chemical Formula 1 may be prepared according to Scheme 6 below.
[반응식 6]  Scheme 6
Figure PCTKR2013012050-appb-I000059
Figure PCTKR2013012050-appb-I000059
반응식 6에 있어서, R은 전술한 화학식 1의 R1 내지 R8의 정의와 같다. 출발물질의 Br의 치환된 위치 또는 축합고리의 위치에 따라 치환기의 위치를 변경시킬 수 있는 것은 당업자에게 자명하다. In Scheme 6, R is as defined in R 1 to R 8 of Formula 1 above. It will be apparent to those skilled in the art that the position of the substituents can be varied depending on the substituted position of Br or the position of the condensed ring of the starting material.
화합물 compound 4-44-4 의 제조Manufacture
4-브로모아이소퀴놀린 4g (19.23 m㏖)를 H2O, THF (각 8㎖) 혼합 용액에 O-(2,4-디니트로페닐)히드록실아민(화합물 1-2) 5.74g(28.85m㏖)를 첨가하였다. 반응 혼합물을 40℃에서 12시간 교반한 후 0℃로 유지한 상태에서 2.5N NaOH 96㎖와 THF 31㎖에 녹인 TsCl 7.33g(38.46m㏖)를 첨가한 후 4시간 더 교반하였다. 반응이 완결되면 MC로 추출하고 유기층은 MgSO4로 건조하여 목적화합물 4-4 2.4g(33%)를 얻었다.4.74 g (28.85) of O- (2,4-dinitrophenyl) hydroxylamine (Compound 1-2) in 4 g (19.23 mmol) of 4-bromoisoquinoline in a mixture of H 2 O and THF (8 ml each) mmol) was added. The reaction mixture was stirred at 40 ° C. for 12 hours, and then 7.33 g (38.46 mmol) of TsCl dissolved in 96 mL of 2.5N NaOH and 31 mL of THF were added and stirred for 4 hours. Upon completion of the reaction, the mixture was extracted with MC and the organic layer was dried over MgSO 4 to obtain 2.4 g (33%) of the title compound 4-4 .
화합물 compound a-4a-4 의 제조Manufacture
(4-브로모이소퀴놀린-2-이움-2-일)(토실)아미드 ((4-bromoisoquinolin-2-ium-2-yl)(tosyl)amide) 2g(5.30m㏖), 2-(트리메틸실릴)페닐 트리플루오로메탄술포네이트 2.6㎖(10.60m㏖)를 THF에 녹인 후 천천히 교반하다가 세슘 플루오라이드 2.42g(15.90m㏖)를 첨가한 후 70℃에서 24시간 동안 교반하였다. 반응이 완결되면 EA로 추출하고 유기층은 MgSO4로 건조하였다. EA/Hex 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 a-4 1.21g (77%)를 얻었다.(4-bromoisoquinolin-2-ium-2-yl) (tosyl) amide ((4-bromoisoquinolin-2-ium-2-yl) (tosyl) amide) 2 g (5.30 mmol), 2- (trimethyl After dissolving 2.6 ml (10.60 mmol) of silyl) phenyl trifluoromethanesulfonate in THF, the mixture was stirred slowly, followed by addition of 2.42 g (15.90 mmol) of cesium fluoride, followed by stirring at 70 ° C. for 24 hours. After completion of the reaction, the mixture was extracted with EA and the organic layer was dried over MgSO 4 . Column chromatography was performed using EA / Hex developing solvent to obtain 1.21 g (77%) of the target compound a-4 .
[제조예 43] 화합물 173의 제조Preparation Example 43 Preparation of Compound 173
Figure PCTKR2013012050-appb-I000060
Figure PCTKR2013012050-appb-I000060
화합물 compound 173173 의 제조Manufacture
5-브로모인다졸로[3,2-a]이소퀴놀린 1.2g(4.04m㏖), 2,2'-(4-(4,4,5,5-테트라메틸-1,3,2-디옥사보롤레인-2-일)피리딘-2,6-디일)디퀴놀린(Ar5) 2.23g(4.85m㏖), 테트라키스(트리페닐포스핀)팔라듐 0.46g(0.40m㏖), 포타슘 카보네이트 1.68g(12.12m㏖)를 톨루엔, H2O, 에탄올 혼합 용액 환류하에서 24시간 동안 교반하였다. 반응이 완결되면 EA로 추출하고 유기층은 MgSO4로 건조하였다. EA/Hex 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 173 1.73g (78%)를 얻었다.1.2 g (4.04 mmol) of 5-bromoindazolo [3,2-a] isoquinoline, 2,2 '-(4- (4,4,5,5-tetramethyl-1,3,2-dioxa Borolein-2-yl) pyridine-2,6-diyl) diquinoline (Ar 5 ) 2.23 g (4.85 mmol), tetrakis (triphenylphosphine) palladium 0.46 g (0.40 mmol), potassium carbonate 1.68 g (12.12 mmol) was stirred for 24 h under reflux of toluene, H 2 O, ethanol mixed solution. After completion of the reaction, the mixture was extracted with EA and the organic layer was dried over MgSO 4 . Column chromatography was performed using EA / Hex developing solvent to obtain 1.73 g (78%) of the title compound 173 .
[제조예 44 내지 제조예 53] 화합물 Preparation Example 44 to Production Example 53 Compound 161161 , 화합물 , Compound 167167 , 화합물 , Compound 171171 , 화합물 , Compound 176176 , 화합물 , Compound 179179 , 화합물 , Compound 180180 , 화합물 , Compound 183183 , 화합물 , Compound 185185 , 화합물 , Compound 188188 및 화합물  And compounds 190190 의 제조Manufacture
화합물 Ar5로서 하기 표 5의 화합물을 이용하고, 상기 제조예 43와 동일한 방법으로 수행하여, 화합물 161, 화합물 167, 화합물 171, 화합물 176, 화합물 179, 화합물 180, 화합물 183, 화합물 185, 화합물 188 및 화합물 190을 제조하였다.Compound 161 , Compound 167 , Compound 171 , Compound 176 , Compound 179 , Compound 180 , Compound 183 , Compound 185 , Compound 188 , using the compound shown in Table 5 below as Compound Ar 5 and the compound 190 was prepared.
표 5
Figure PCTKR2013012050-appb-T000005
 Table 5
Figure PCTKR2013012050-appb-T000005
Figure PCTKR2013012050-appb-I000061
Figure PCTKR2013012050-appb-I000061
본 발명의 일 실시상태에 따르면, 하기 반응식 7에 따라 화학식 1의 화합물을 제조할 수 있다. According to an exemplary embodiment of the present invention, a compound of Chemical Formula 1 may be prepared according to the following Scheme 7.
[반응식 7]  Scheme 7
Figure PCTKR2013012050-appb-I000062
Figure PCTKR2013012050-appb-I000062
반응식 7에 있어서, R은 전술한 화학식 1의 R1 내지 R8의 정의와 같다. 출발물질의 치환기 종류와 위치에 따라 화학식 1의 화합물의 치환기의 종류와 위치를 변경시킬 수 있는 것은 당업자에게 자명하다. In Scheme 7, R is as defined in R 1 to R 8 of Formula 1 above. It will be apparent to those skilled in the art that the type and position of the substituent of the compound of Formula 1 can be changed according to the type and position of the substituent of the starting material.
화합물 compound 7-37-3 의 제조Manufacture
2-브로모벤즈알데히드 4.4㎖(37.83m㏖), 1-브로모-4-에티닐벤젠 8.22g(45.40m㏖), 트리에틸아민 7.6㎖(54.48m㏖), 비스(트리페닐포스핀)팔라듐 디클로라이드 0.53g(0.76m㏖), 구리 요오드화물(copper iodide) 0.29g(1.51m㏖)를 DMF 용액 100℃에서 4시간 동안 교반하였다. 반응이 완결되면 EA로 추출하고 유기층은 MgSO4로 건조하였다. EA/Hex 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 7-3 7.23g(67%)를 얻었다.4.4 ml (37.83 mmol) of 2-bromobenzaldehyde, 8.22 g (45.40 mmol) of 1-bromo-4-ethynylbenzene, 7.6 ml (54.48 mmol) of triethylamine, bis (triphenylphosphine) palladium 0.53 g (0.76 mmol) of dichloride and 0.29 g (1.51 mmol) of copper iodide were stirred at 100 ° C. for DMF solution for 4 hours. After completion of the reaction, the mixture was extracted with EA and the organic layer was dried over MgSO 4 . 7.23g (67%) of the title compound 7-3 was obtained by column chromatography using EA / Hex developing solvent.
화합물 compound 7-27-2 의 제조Manufacture
2-((4-브로모페닐)에티닐)벤즈알데히드 7g(24.55m㏖), p-톨루엔술포닐 히드라지드 5.03g(27.01m㏖)를 메탄올에 녹인 후 상온에서 4시간 동안 교반하였다. 반응이 완결되면 메탄올로 재결정하여 목적화합물 7-2 8.68g (78%)를 얻었다.7 g (24.55 mmol) of 2-((4-bromophenyl) ethynyl) benzaldehyde and 5.03 g (27.01 mmol) of p-toluenesulfonyl hydrazide were dissolved in methanol and stirred at room temperature for 4 hours. Upon completion of the reaction, 8.68 g (78%) of the title compound 7-2 was obtained by recrystallization from methanol.
화합물 compound 7-17-1 의 제조Manufacture
(E)-N'-(2-((4-브로모페닐)에티닐)벤질리덴)-4-메틸벤젠술포노히드라지드 8g(17.65m㏖), 실버 트리플루오로메탄술포네이트 0.45g(1.77m㏖)를 MeCN에 녹인 후 80℃에서 6시간 동안 교반한 후 상온에서 식혔다. 반응 혼합물에 2-(트리메틸실릴)페닐 트리플루오로메탄술포네이트 5.1㎖(21.18m㏖), 세슘 플루오라이드 8.04g(52.95m㏖)를 첨가한 후 80℃에서 12시간 더 교반하였다. 반응이 완결되면 EA로 추출하고 유기층은 MgSO4로 건조하였다. EA/Hex 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 7-1 4.68g(71%)를 얻었다.8 g (17.65 mmol) of (E) -N '-(2-((4-bromophenyl) ethynyl) benzylidene) -4-methylbenzenesulfonohydrazide, 0.45 g of silver trifluoromethanesulfonate ( 1.77 mmol) was dissolved in MeCN, stirred at 80 ° C. for 6 hours, and cooled at room temperature. 5.1 ml (21.18 mmol) of 2- (trimethylsilyl) phenyl trifluoromethanesulfonate and 8.04 g (52.95 mmol) of cesium fluoride were added to the reaction mixture, followed by further stirring at 80 ° C for 12 hours. After completion of the reaction, the mixture was extracted with EA and the organic layer was dried over MgSO 4 . 4.68 g (71%) of the title compound 7-1 was obtained by column chromatography using EA / Hex developing solvent.
[제조예 54] 화합물 204의 제조Preparation Example 54 Preparation of Compound 204
Figure PCTKR2013012050-appb-I000063
Figure PCTKR2013012050-appb-I000063
화합물 compound 204204 의 제조Manufacture
6-(4-브로모페닐)인다졸로[3,2-a]이소퀴놀린 4g(10.72m㏖), 4,6-디(페난트렌-9-일)-2-(4,4,5,5-테트라메틸-1,3,2-디옥사보롤레인-2-일)피리미딘(Ar6) 7.18g(12.86m㏖), 테트라키스(트리페닐포스핀)팔라듐 1.24g(1.07m㏖), 포타슘 카보네이트 4.44g(32.16m㏖)를 톨루엔, H2O, 에탄올 혼합 용액 환류하에서 24시간 동안 교반하였다. 반응이 완결되면 EA로 추출하고 유기층은 MgSO4로 건조하였다. EA/Hex 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 204 6.68g (86%)를 얻었다.4 g (10.72 mmol) of 6- (4-bromophenyl) indazolo [3,2-a] isoquinoline, 4,6-di (phenanthrene-9-yl) -2- (4,4,5, 7.18 g (12.86 mmol) of 5-tetramethyl-1,3,2-dioxaborole-2-yl) pyrimidine (Ar 6 ), 1.24 g (1.07 mmol) of tetrakis (triphenylphosphine) palladium , 4.44 g (32.16 mmol) of potassium carbonate was stirred for 24 hours under reflux of a toluene, H 2 O, and ethanol mixed solution. After completion of the reaction, the mixture was extracted with EA and the organic layer was dried over MgSO 4 . Column chromatography was performed using EA / Hex developing solvent to obtain 6.68 g (86%) of the title compound ( 204 ).
[제조예 55 내지 제조예 63] 화합물 Preparation Example 55 to Production Example 63 Compound 194194 , 화합물 , Compound 196196 , 화합물 , Compound 198198 , 화합물 , Compound 202202 , 화합물 , Compound 206206 , 화합물 , Compound 208208 , 화합물 , Compound 213213 , 화합물 , Compound 218218 및 화합물  And compounds 228228 의 제조Manufacture
화합물 Ar6로서 하기 표 6의 화합물을 이용하고, 상기 제조예 54와 동일한 방법으로 수행하여, 화합물 194, 화합물 196, 화합물 198, 화합물 202, 화합물 206, 화합물 208, 화합물 213, 화합물 218 및 화합물 228을 제조하였다.Compound 194 , compound 196 , compound 198 , compound 202 , compound 206 , compound 208 , compound 213 , compound 218, and 228 were used as the compound Ar 6 , using the compound of Table 6 below. Was prepared.
표 6
Figure PCTKR2013012050-appb-T000006
 Table 6
Figure PCTKR2013012050-appb-T000006
Figure PCTKR2013012050-appb-I000064
Figure PCTKR2013012050-appb-I000064
[제조예 64] 화합물 231의 제조Preparation Example 64 Preparation of Compound 231
Figure PCTKR2013012050-appb-I000065
Figure PCTKR2013012050-appb-I000065
화합물 compound 231-1231-1 의 제조Manufacture
원 네크 r.b.f(one neck r.b.f)에 (9,9-디메틸-9H-플루오렌-2-일)보론산(25.9g, 108m㏖), 1-브로모-2-니트로벤젠(20g, 99m㏖), Pd(PPh3)4(5.7g, 4.95m㏖), K2CO3(27.3g, 198m㏖), THF (250㎖)/H2O(50㎖)의 혼합물을 110℃에서 24시간 환류하였다. 물층을 제거한 후 유기층을 MgSO4로 건조하였다. 농축 후 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=2:1)로 분리하여 노란색 고체 화합물 231-1을 얻었다(21 g, 61%).(9,9-dimethyl-9H-fluoren-2-yl) boronic acid (25.9 g, 108 mmol), 1-bromo-2-nitrobenzene (20 g, 99 mmol) in one neck rbf , A mixture of Pd (PPh 3 ) 4 (5.7 g, 4.95 mmol), K 2 CO 3 (27.3 g, 198 mmol), THF (250 mL) / H 2 O (50 mL) at reflux at 110 ° C. for 24 hours. It was. After removing the water layer, the organic layer was dried over MgSO 4 . After concentration, the residue was separated by column chromatography (SiO 2 , hexane: dichloromethane = 2: 1) to give a yellow solid compound 231-1 (21 g, 61%).
화합물 compound 231-2231-2 의 제조Manufacture
질소 하에서 원 네크 r.b.f에 상기 화합물 231-1(20g, 63.4m㏖), PPh3 (49.8g, 190m㏖), 1,2-디클로로벤젠(300㎖) 혼합물을 180℃에서 18시간 환류하였다. 1,2-디클로로벤젠을 증류하여 제거한 뒤 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=3:1)로 분리하여 흰색 고체 화합물 231-2 (6.6g, 36%), 화합물 251-2 (7.5g, 41%)을 얻었다.The mixture of Compound 231-1 (20 g, 63.4 mmol), PPh 3 (49.8 g, 190 mmol) and 1,2-dichlorobenzene (300 mL) was refluxed at 180 ° C. in a one neck rbf under nitrogen for 18 hours. 1,2-dichlorobenzene was distilled off and separated by column chromatography (SiO 2 , hexane: dichloromethane = 3: 1) to give white solid Compound 231-2 (6.6g, 36%), Compound 251-2 (7.5 g, 41%).
화합물 compound 231231 의 제조Manufacture
질소 충전하에서 원 네크 r.b.f에 상기 화합물 231-2(4.8g, 16.9m㏖), a-1(4.1g, 16.9m㏖), Cu(1g, 16.9m㏖), 18-크라운-6-에테르(550mg, 1.69m㏖), K2CO3(7g, 50.7 m㏖), o-DCB(130㎖) 혼합물을 180℃에서 60시간 환류하였다. 1,2-디클로로벤젠을 증류하여 제거한 뒤, 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=2:1)로 분리하여 흰색 고체 화합물 231을 얻었다(3.2g, 42%).Compound 231-2 (4.8 g, 16.9 mmol), a-1 (4.1 g, 16.9 mmol), Cu (1 g, 16.9 mmol), 18-crown-6-ether 550 mg, 1.69 mmol), K 2 CO 3 (7 g, 50.7 mmol), o- DCB (130 mL) mixture was refluxed at 180 ° C. for 60 hours. After 1,2-dichlorobenzene was distilled off, the residue was separated by column chromatography (SiO 2 , hexane: dichloromethane = 2: 1) to give a white solid compound 231 (3.2 g, 42%).
[제조예 65] 화합물 Preparation Example 65 Compound 236236 의 제조Manufacture
Figure PCTKR2013012050-appb-I000066
Figure PCTKR2013012050-appb-I000066
화합물 compound 236-1236-1 의 제조Manufacture
질소 하에서 원 네크 r.b.f에 2-브로모-9,9-디메틸-9H-플루오렌(15g, 54.91m㏖), 벤조[b]-티오펜-2-일트리부틸스타난(34.8, 82.3m㏖), Pd(PPh3)4, 톨루엔(350㎖)의 혼합물을 110℃에서 12시간 환류시켰다. 농축 후 실리카겔 필터한 뒤 CH2Cl2/MeOH로 침전을 잡은 화합물을 EtOH로 고온 필터하여 불투명한 흰색 고체 화합물 236-1을 얻었다(15.7g, 87%).2-bromo-9,9-dimethyl-9H-fluorene (15 g, 54.91 mmol), benzo [b] -thiophen-2-yltributylstanan (34.8, 82.3 mmol) in one neck rbf under nitrogen ), Pd (PPh 3 ) 4 and toluene (350 mL) were refluxed at 110 ° C for 12 hours. After concentration and silica gel filter, the compound was precipitated with CH 2 Cl 2 / MeOH high temperature filter with EtOH to give an opaque white solid compound 236-1 (15.7g, 87%).
화합물 compound 236-2236-2 의 제조Manufacture
질소 하에서 원 네크 r.b.f에 상기 화합물 236-1(15.7g, 48m㏖)를 함유하는 AcOH(260㎖) 용액, HNO3(6㎖, 143m㏖)를 함유하는 AcOH(260㎖) 혼합물을 천천히 가한 뒤 60℃로 가열하여 30분 교반하였다. 상온으로 식힌 후 필터한 후 증류수(500㎖)로 씻어주었다. 얻어진 물질을 진공오븐에서 50℃로 12시간 건조 후, 노란색 고체 화합물 236-2를 얻었다(16.1g, 90%).To the original neck rbf was slowly added an AcOH (260 mL) solution containing Compound 236-1 (15.7 g, 48 mmol) and an AcOH (260 mL) mixture containing HNO 3 (6 mL, 143 mmol) under nitrogen. Heated to 60 ° C. and stirred for 30 min. After cooling to room temperature, the filter was washed with distilled water (500 ml). The resulting material was dried in a vacuum oven at 50 ° C. for 12 hours to obtain a yellow solid compound 236-2 (16.1 g, 90%).
화합물 compound 236-3236-3 의 제조Manufacture
질소 하에서 원 네크 r.b.f에 상기 화합물 236-2(16.1g, 43m㏖), PPh3(33.8g, 129m㏖), 1,2-디클로로벤젠(250㎖)의 혼합물을 200℃에서 18시간 환류하였다. 1,2-디클로로벤젠을 증류하여 제거한 뒤 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=2:1)로 분리하여 옅은 고등색 고체 화합물 236-3을 얻었다(3.0 g, 20%).A mixture of compound 236-2 (16.1 g, 43 mmol), PPh 3 (33.8 g, 129 mmol) and 1,2-dichlorobenzene (250 mL) was refluxed at 200 ° C. in a one neck rbf under nitrogen for 18 hours. 1,2-dichlorobenzene was distilled off and separated by column chromatography (SiO 2 , hexane: dichloromethane = 2: 1) to give a pale higher solid compound 236-3 (3.0 g, 20%).
화합물 compound 236236 의 제조Manufacture
질소 충전하에서 원 네크 r.b.f에 상기 화합물 263-3 (2g, 5.85m㏖), a-1 (1.4g, 5.85m㏖), Cu(374mg, 5.85m㏖), 18-크라운-6-에테르(191mg, 0.58m㏖), K2CO3 (1.6g, 11.78m㏖), o-DCB(25㎖) 혼합물을 180℃에서 60시간 환류하였다. 1,2-디클로로벤젠을 증류하여 제거한 뒤 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=3:1)로 분리하여 고체 화합물 236을 얻었다(1.45g, 48%).Compound 263-3 (2 g, 5.85 mmol), a-1 (1.4 g, 5.85 mmol), Cu (374 mg, 5.85 mmol), 18-crown-6-ether (191 mg) in a one neck rbf under nitrogen filling , 0.58 mmol), K 2 CO 3 (1.6 g, 11.78 mmol) and o- DCB (25 mL) were refluxed at 180 ° C. for 60 hours. 1,2-dichlorobenzene was distilled off and then separated by column chromatography (SiO 2 , hexane: dichloromethane = 3: 1) to give a solid compound 236 (1.45g, 48%).
[제조예 66] 화합물 Preparation Example 66 Compound 241241 의 제조Manufacture
Figure PCTKR2013012050-appb-I000067
Figure PCTKR2013012050-appb-I000067
화합물 compound 241-1241-1 의 제조Manufacture
9,9-디메틸-9H-플루오렌-2-일보론산(25.95g, 109m㏖), 3-브로모티아-나프텐(10㎖, 72.5m㏖), Pd(PPh3)4(4.189g, 3.625m㏖), K2CO3(30.06g, 217.5m㏖), 톨루엔(200㎖), 에탄올(40㎖), H2O(40㎖)의 혼합물을 환류시켰다. 리플럭스 온도에서 4시간 동안 교반한 뒤 용매를 농축한 후, MC로 추출하였다. 고체를 메탄로 세척하여 여과하였다. 흰색 고체 화합물 241-1을 얻었다(30g, 87%).9,9-dimethyl-9H-fluoren-2-ylboronic acid (25.95 g, 109 mmol), 3-bromothia-naphthene (10 mL, 72.5 mmol), Pd (PPh 3 ) 4 (4.189 g, 3.625 mmol), a mixture of K 2 CO 3 (30.06 g, 217.5 mmol), toluene (200 mL), ethanol (40 mL), H 2 O (40 mL) was refluxed. After stirring at reflux for 4 hours, the solvent was concentrated and then extracted with MC. The solid was washed with methane and filtered. A white solid compound 241-1 was obtained (30 g, 87%).
화합물 compound 241-2241-2 의 제조Manufacture
질소 하에서 원 네크 r.b.f에 상기 화합물 241-1(21.3g, 65.3m㏖)를 함유하는 AcOH(1,260㎖) 용액에 HNO3(5.9㎖, 130m㏖)를 함유하는 AcOH(12㎖)의 혼합물을 천천히 가한 뒤 60℃로 가열하여 30분 교반하였다. 상온으로 식힌 후 필터한 후 증류수(400㎖)로 씻어주었다. 얻어진 물질을 진공오븐에서 50℃로 12시간 건조 후 밝은 노란색 고체 화합물 241-2를 얻었다(21.0g, 95%).Slowly add a mixture of AcOH (12 mL) containing HNO 3 (5.9 mL, 130 mmol) to an AcOH (1,260 mL) solution containing compound 241-1 (21.3 g, 65.3 mmol) in a one neck rbf under nitrogen. After the addition, the mixture was heated to 60 ° C and stirred for 30 minutes. After cooling to room temperature, the filter was washed with distilled water (400 ml). The resulting material was dried in a vacuum oven at 50 ° C. for 12 hours to obtain a light yellow solid compound 241-2 (21.0 g, 95%).
화합물 compound 241-3241-3 의 제조Manufacture
질소 충전하에서 원 네크 r.b.f에 상기 화합물 241-2(29.5g, 79.4m㏖), PPh3 (54.8g, 198.5 m㏖), 1,2-디클로로벤젠(450㎖)의 혼합물을 180℃에서 4시간 환류하였다. 1,2-디클로로벤젠을 증류하여 제거한 뒤 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=4:1)로 분리하여 노란색 고체화합물 241-3을 얻었다(15g, 55%).A mixture of compound 241-2 (29.5 g, 79.4 mmol), PPh 3 (54.8 g, 198.5 mmol) and 1,2-dichlorobenzene (450 mL) was added to one neck rbf under nitrogen filling at 180 ° C. for 4 hours. It was refluxed. 1,2-dichlorobenzene was distilled off and then separated by column chromatography (SiO 2 , hexane: dichloromethane = 4: 1) to give a yellow solid compound 241-3 (15g, 55%).
화합물 compound 241241 의 제조Manufacture
질소 충전하에서 원 네크 r.b.f에 상기 화합물 241-3(4g, 11.7 m㏖), a-1(2.89g, 11.7m㏖), Cu(748mg, 11.7m㏖), 18-크라운-6-에테르(383mg, 1.17m㏖), K2CO3(3.2g, 23.56m㏖), o-DCB(50㎖) 혼합물을 180℃에서 60시간 환류하였다. 1,2-디클로로벤젠을 증류하여 제거한 뒤 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=3:1)로 분리하여 고체 화합물 241을 얻었다(1.9g, 32%).Compound 241-3 (4 g, 11.7 mmol), a-1 (2.89 g, 11.7 mmol), Cu (748 mg, 11.7 mmol), 18-crown-6-ether (383 mg) in one neck rbf under nitrogen charge , 1.17 mmol), K 2 CO 3 (3.2 g, 23.56 mmol) and o- DCB (50 mL) were refluxed at 180 ° C. for 60 hours. 1,2-dichlorobenzene was distilled off and separated by column chromatography (SiO 2 , hexane: dichloromethane = 3: 1) to give a solid compound 241 (1.9g, 32%).
[제조예 67] 화합물 Preparation Example 67 Compound 247247 의 제조Manufacture
Figure PCTKR2013012050-appb-I000068
Figure PCTKR2013012050-appb-I000068
화합물 compound 247-1247-1 의 제조Manufacture
원 네크 r.b.f에 디벤조[b,d]티오펜-4-일보론산(23g, 107.9m㏖), 3-브로모벤젠[b]티오펜(27g, 118.7m㏖), K2CO3(10g, 10.8m㏖), H2O(90㎖), 1,4-디옥산(360㎖) 용액을 110℃에서 12시간 환류하였다. 농축 후 CH2Cl2(3×300㎖), 증류수(150㎖)로 추출하고 실리카겔 필터하였다. 농축 후 MeOH(400㎖)로 1시간 교반한 뒤 CH2Cl2/MeOH로 침전을 잡아서 필터하여 갈색빛 고체 화합물 247-1을 얻었다(26.5g, 77%).Dibenzo [b, d] thiophen-4-ylboronic acid (23 g, 107.9 mmol), 3-bromobenzene [b] thiophene (27 g, 118.7 mmol), K 2 CO 3 (10 g) in one neck rbf. , 10.8 mmol), H 2 O (90 mL) and 1,4-dioxane (360 mL) were refluxed at 110 ° C. for 12 hours. After concentration, the mixture was extracted with CH 2 Cl 2 (3 × 300 mL), distilled water (150 mL) and filtered through a silica gel. After concentration, the mixture was stirred with MeOH (400 mL) for 1 hour, and the precipitate was filtered with CH 2 Cl 2 / MeOH to obtain a brown solid compound 247-1 (26.5 g, 77%).
화합물 compound 247-2247-2 의 제조Manufacture
질소 하에서 원 네크 r.b.f에 상기 화합물 247-1(26g, 82.1 m㏖)을 함유하는 AcOH(400㎖) 용액에 HNO3(10㎖, 246.4m㏖)를 함유하는 AcOH(400㎖) 용액을 천천히 가한 뒤 60℃로 가열하여 30분 교반하였다. 상온으로 식힌 후 필터한 후 증류수 (800㎖)로 씻어주었다. 얻어진 고체화합물을 CH2Cl2(200㎖)에 녹이고 물층을 제거한 뒤 유기층을 감압 농축하였다. 농축물을 흡착한 뒤 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=3:1)로 분리하여 노란색 고체 화합물 247-2를 얻었다(19.6g, 66%).The original neck rbf under nitrogen the compound 247-1 was added to AcOH (400㎖) solution in AcOH (400㎖) solution containing (26g, 82.1 m㏖) containing HNO 3 (10㎖, 246.4m㏖) slowly Then heated to 60 ℃ and stirred for 30 minutes. After cooling to room temperature, the filter was washed with distilled water (800 ml). The obtained solid compound was dissolved in CH 2 Cl 2 (200 mL), the water layer was removed, and the organic layer was concentrated under reduced pressure. The concentrate was adsorbed and separated by column chromatography (SiO 2 , hexane: dichloromethane = 3: 1) to give a yellow solid compound 247-2 (19.6g, 66%).
화합물 compound 247-3247-3 의 제조Manufacture
질소 충전하에서 원 네크 r.b.f에 상기 화합물 247-2(17.9g, 49.6m㏖), PPh3 (38.7g, 148.4m㏖), 1,2-디클로로벤젠(500㎖) 혼합물을 180℃에서 12시간 환류하였다. 1,2-디클로로벤젠을 증류하여 제거한 뒤, CH2Cl2/MeOH 침전을 잡아 필터한 뒤 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=2:1)로 분리하여 불투명한 흰색 고체 화합물 247-3을 얻었다(10g, 61%).The mixture of Compound 247-2 (17.9 g, 49.6 mmol), PPh 3 (38.7 g, 148.4 mmol) and 1,2-dichlorobenzene (500 mL) was refluxed at 180 ° C. for 12 hours in a one neck rbf under nitrogen filling. It was. After distilling off 1,2-dichlorobenzene, the precipitate was filtered by CH 2 Cl 2 / MeOH precipitation and separated by column chromatography (SiO 2 , hexane: dichloromethane = 2: 1) to obtain an opaque white solid compound . 3 was obtained (10 g, 61%).
화합물 compound 247247 의 제조Manufacture
질소 충전하에서 원 네크 r.b.f에 상기 화합물 247-3(10g, 30.35m㏖), a-1 (7.4g, 30.35m㏖), Cu(1.9mg, 30.35m㏖), 18-크라운-6-에테르(987mg, 3.03m㏖), K2CO3(8.3g, 60.7m㏖), o-DCB(100㎖)의 혼합물을 180℃에서 60시간 환류하였다. 1,2-디클로로벤젠을 증류하여 제거한 뒤 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=3:1)로 분리하여 고체 화합물 247를 얻었다(8.9g, 59%).Compound 247-3 (10 g, 30.35 mmol), a-1 (7.4 g, 30.35 mmol), Cu (1.9 mg, 30.35 mmol), 18-crown-6-ether A mixture of 987 mg, 3.03 mmol), K 2 CO 3 (8.3 g, 60.7 mmol) and o- DCB (100 mL) was refluxed at 180 ° C. for 60 hours. 1,2-dichlorobenzene was distilled off and then separated by column chromatography (SiO 2 , hexane: dichloromethane = 3: 1) to give a solid compound 247 (8.9 g, 59%).
[제조예 68] 화합물 Preparation Example 68 Compound 250250 의제조Manufacturing
Figure PCTKR2013012050-appb-I000069
Figure PCTKR2013012050-appb-I000069
화합물 compound 250-1250-1 의 제조Manufacture
질소 충전하에서 원 네크 r.b.f에 1,2-디클로로헥사논(30.0g, 1.0eq), 페닐하이드라진 하이드로클로라이드(77.37g, 2.0eq), 에탄올(1,000㎖)의 혼합물에 황산(1.4㎖, 0.1eq)를 서서히 적가한 뒤 60℃에서 4시간동안 교반하였다. 실온으로 식힌 용액을 필터하여 황갈색 고체 화합물 250-1을 얻었다(69g, 93%).Sulfuric acid (1.4 mL, 0.1 eq) in a mixture of 1,2-dichlorohexanone (30.0 g, 1.0 eq), phenylhydrazine hydrochloride (77.37 g, 2.0 eq) and ethanol (1,000 mL) in a one neck rbf under nitrogen charge Was slowly added dropwise and stirred at 60 ° C. for 4 hours. The solution cooled to room temperature was filtered to give a tan solid compound 250-1 (69 g, 93%).
화합물 compound 250-2250-2 의 제조Manufacture
원 네크 r.b.f에 상기 화합물 250-1(68.9g, 1.0eq)을 함유하는 아세트산(700㎖) 혼합물에 트리플루오로아세트산(46.5㎖, 2.4eq)을 넣고 100℃에서 15시간 동안 교반하였다. 실온으로 식힌 용액을 아세트산과 헥산으로 세척하며 필터하여 아이보리색 고체 화합물 250-2를 얻었다(27.3g, 42%).Trifluoroacetic acid (46.5 ml, 2.4 eq) was added to an acetic acid (700 ml) mixture containing Compound 250-1 (68.9 g, 1.0 eq) in one neck rbf and stirred at 100 ° C. for 15 hours. The solution cooled to room temperature was washed with acetic acid and hexane and filtered to obtain an ivory solid compound 250-2 (27.3 g, 42%).
화합물 compound 250-3250-3 의 제조Manufacture
질소 충전하에서 원 네크 r.b.f에 상기 화합물 250-2(2.1g, 1.0eq), 아이오도벤젠(2.5g, 1.5eq), Cu(0.312g, 0.6eq), 18-크라운-6-에테르(0.433g, 0.2eq), K2CO3(3.397g, 3.0eq), 1,2-디클로로벤젠(20㎖)의 혼합물을 리플럭스 온도에서 16시간 동안 교반하였다. 실온으로 식힌 용액을 MC/H2O로 추출하여 농축하고 컬럼 크로마토그래피 (SiO2, 헥산:에틸 아세테이트=10:1)로 분리하여 흰색 고체 화합물 250-3를 얻었다(1.76g, 64%).Compound 250-2 (2.1 g, 1.0 eq), iodobenzene (2.5 g, 1.5 eq), Cu (0.312 g, 0.6 eq), 18-crown-6-ether (0.433 g) in one neck rbf under nitrogen charge , 0.2eq), K 2 CO 3 (3.397g, 3.0eq), 1,2-dichlorobenzene (20 mL) was stirred at reflux temperature for 16 hours. The solution cooled to room temperature was extracted with MC / H 2 O, concentrated and separated by column chromatography (SiO 2 , hexane: ethyl acetate = 10: 1) to give a white solid compound 250-3 (1.76 g, 64%).
화합물 compound 250250 의 제조Manufacture
질소 충전하에서 원 네크 r.b.f에 상기 화합물 250-3(1.7g, 5.11m㏖), a-1 (1.2g, 5.11m㏖), Cu(324mg, 5.11 m㏖), 18-크라운-6-에테르(166mg, 0.51m㏖), K2CO3(1.4g, 0.22m㏖), o-DCB(10㎖)의 혼합물을 180℃에서 60시간 환류하였다. 1,2-디클로로벤젠을 증류하여 제거한 뒤 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=2:1)로 분리하여 고체 화합물 250를 얻었다(770mg, 30%).Compound 250-3 (1.7 g, 5.11 mmol), a-1 (1.2 g, 5.11 mmol), Cu (324 mg, 5.11 mmol), 18-crown-6-ether A mixture of 166 mg, 0.51 mmol), K 2 CO 3 (1.4 g, 0.22 mmol) and o- DCB (10 mL) was refluxed at 180 ° C. for 60 hours. 1,2-dichlorobenzene was distilled off and then separated by column chromatography (SiO 2 , hexane: dichloromethane = 2: 1) to give a solid compound 250 (770 mg, 30%).
[제조예 69] 화합물 Preparation Example 69 Compound 251251 의 제조Manufacture
Figure PCTKR2013012050-appb-I000070
Figure PCTKR2013012050-appb-I000070
원 네크 r.b.f에 상기 화합물 251-1(1g, 3.53 m㏖), a-1(872mg, 353m㏖), Pd(OAc)2(80mg, 0.353 m㏖), K3PO4(1.4g, 7.06m㏖), P(t-Bu)3(1.5㎖, 1 m㏖), o-DCB (10㎖)의 혼합물을 100℃에서 24시간 환류하였다. MC추출, MgSO4로 건조 후 컬럼 크로마토그래피 (SiO2, 헥산:디클로로메탄=2:1)로 분리하여 고체 화합물 251을 얻었다(950mg, 60%).Compound 251-1 (1 g, 3.53 mmol), a-1 (872 mg, 353 mmol), Pd (OAc) 2 (80 mg, 0.353 mmol), K 3 PO 4 (1.4 g, 7.06 m) in one neck rbf Mol), P (t-Bu) 3 (1.5 mL, 1 mmol) and o- DCB (10 mL) were refluxed at 100 ° C for 24 hours. MC extraction, drying with MgSO 4 and column chromatography (SiO 2 , hexane: dichloromethane = 2: 1) to give a solid compound 251 (950mg, 60%).
[제조예 70] 화합물 Preparation Example 70 Compound 256256 의 제조Manufacture
Figure PCTKR2013012050-appb-I000071
Figure PCTKR2013012050-appb-I000071
화합물 compound 256-1256-1 의 제조Manufacture
원 네크 r.b.f에 디벤조[b,d]푸란-2-일보론산(20g, 94.33m㏖), 1-브로모-2-나이트로벤젠(19g, 94.33m㏖), K2CO3(26g, 188m㏖), H2O(45㎖), 1,4-디옥산(300㎖) 용액을 110℃ 에서 12시간 환류하였다. 농축 후 CH2Cl2 (3×200㎖), 증류수(120㎖)로 추출하고 실리카겔 필터하였다. 농축 후 컬럼 크로마토그래피 (SiO2, 헥산:디클로로메탄=8:1)로 분리하여 아이보리 고체 화합물 256-1을 얻었다(18.2g, 67%).Dibenzo [b, d] furan-2-ylboronic acid (20 g, 94.33 mmol), 1-bromo-2-nitrobenzene (19 g, 94.33 mmol), K 2 CO 3 (26 g, 188 mmol), H 2 O (45 mL), and 1,4-dioxane (300 mL) were refluxed at 110 ° C. for 12 hours. After concentration, the mixture was extracted with CH 2 Cl 2 (3 × 200 mL), distilled water (120 mL) and filtered through a silica gel. After concentration, the residue was separated by column chromatography (SiO 2 , hexane: dichloromethane = 8: 1) to obtain an ivory solid compound 256-1 (18.2g, 67%).
화합물 compound 256-2256-2 의 제조Manufacture
질소 충전하에서 원 네크 r.b.f에 상기 화합물 256-1(19g, 65.6m㏖), PPh3(51.6g, 197m㏖), 1,2-디클로로벤젠(400㎖)의 혼합물을 180℃에서 12시간 환류하였다. 1,2-디클로로벤젠을 증류하여 제거한 뒤, CH2Cl2/MeOH로 침전을 잡아 필터한 뒤 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=2:1)로 분리하여 흰색 고체 화합물 256-2를 얻었다(6.7g, 39%).A mixture of compound 256-1 (19 g, 65.6 mmol), PPh 3 (51.6 g, 197 mmol) and 1,2-dichlorobenzene (400 mL) was refluxed at 180 ° C. in a one neck rbf under nitrogen charging for 12 hours. . After distilling off 1,2-dichlorobenzene, the precipitate was filtered with CH 2 Cl 2 / MeOH, filtered and separated by column chromatography (SiO 2 , hexane: dichloromethane = 2: 1) to give a white solid compound 256-2. Was obtained (6.7 g, 39%).
화합물 compound 256256 의 제조Manufacture
질소 충전하에서 원 네크 r.b.f에 상기 화합물 256-2(6.7g, 26m㏖), S1 (6.4g, 26m㏖), Cu(1.6g, 26m㏖), 18-크라운-6-에테르(847mg, 2.6m㏖), K2CO3 (7.1g, 52m㏖), o-DCB(100㎖)의 혼합물을 180℃에서 48시간 환류하였다. 1,2-디클로로벤젠을 증류하여 제거한 뒤 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=3:1)로 분리하여 흰색 고체 화합물 256을 얻었다(7.5g, 68%).Compound 256-2 (6.7 g, 26 mmol), S1 (6.4 g, 26 mmol), Cu (1.6 g, 26 mmol), 18-crown-6-ether (847 mg, 2.6 m) in a one neck rbf under nitrogen charge Mol), K 2 CO 3 (7.1 g, 52 mmol) and o- DCB (100 mL) were refluxed at 180 ° C. for 48 hours. 1,2-dichlorobenzene was distilled off and then separated by column chromatography (SiO 2 , hexane: dichloromethane = 3: 1) to give a white solid compound 256 (7.5 g, 68%).
[화합물 a-5, b-5의 제조][Production of compound a-5, b-5 ]
Figure PCTKR2013012050-appb-I000072
Figure PCTKR2013012050-appb-I000072
원 네크 r.b.f에 a-1 또는 b-1(3g, 12.1mmol), (3-브로모페닐)보론산(2.4g, 12.1mmol), Pd(PPh3)4(1.39g, 1.21mmol), K2CO3(3.34g, 24.2mmol), 톨루엔(50㎖)/H2O (10㎖)의 혼합물을 70℃에서 24시간 가열하였다. 물층을 제거한 후 유기층을 MgSO4로 건조하였다. 농축 후 컬럼 크로마토그래피(SiO2, 헥산:디클로로메탄=3:1)로 분리하여 고체 화합물 a-5(2.8g, 71%) 또는 b-5(2.7g, 68%)를 얻었다. In one neck rbf a-1 or b-1 (3 g, 12.1 mmol), (3-bromophenyl) boronic acid (2.4 g, 12.1 mmol), Pd (PPh 3 ) 4 (1.39 g, 1.21 mmol), K A mixture of 2 CO 3 (3.34 g, 24.2 mmol) and toluene (50 mL) / H 2 O (10 mL) was heated at 70 ° C. for 24 h. After removing the water layer, the organic layer was dried over MgSO 4 . After concentration was separated by column chromatography (SiO 2 , hexane: dichloromethane = 3: 1) to give a solid compound a-5 (2.8g, 71%) or b-5 (2.7g, 68%).
[제조예 71] 화합물 Preparation Example 71 Compound 271271 의 제조Manufacture
상기 화합물 a-1 대신 상기 화합물 a-5를 이용한 것을 제외하고는 화합물 236의 제조와 동일한 방법으로 합성하였다.Synthesis was performed in the same manner as in the preparation of Compound 236, except that Compound a-5 was used instead of Compound a-1.
[제조예 72] 화합물 Preparation Example 72 Compound 281281 의 제조Manufacture
상기 화합물 a-1 대신 상기 화합물 b-1를 이용한 것을 제외하고는 화합물 231의 제조와 동일한 방법으로 합성하였다.Synthesis was carried out in the same manner as in the preparation of Compound 231, except that Compound b-1 was used instead of Compound a-1.
[제조예 73] 화합물 Preparation Example 73 Compound 316316 의 제조Manufacture
상기 화합물 a-1 대신 상기 화합물 b-5를 이용한 것을 제외하고는 화합물 231의 제조와 동일한 방법으로 합성하였다.Synthesis was carried out in the same manner as in the preparation of Compound 231, except that Compound b-5 was used instead of Compound a-1.
[제조예 74] 화합물 Preparation Example 74 Compound 321321 의 제조Manufacture
상기 화합물 a-1 대신 상기 화합물 b-5를 이용한 것을 제외하고는 화합물 236의 제조와 동일한 방법으로 합성하였다.Synthesis was performed in the same manner as in the preparation of Compound 236, except that Compound b-5 was used instead of Compound a-1.
상기 합성실험예와 같은 방법으로 화합물을 제조하고, 그 합성확인결과를 표 7에 나타내었다. Compounds were prepared in the same manner as in Synthesis Experimental Example, and the results of synthesis confirmation are shown in Table 7.
표 7
화합물번호 1H NMR Found Calculated
1 8.61(s, 1H), 8.32-8.28(m, 5H), 7.92(d, 1H), 7.62(t, 1H), 7.51-7.41(m, 8H), 7.19(d, 1H) 399.45 399.15
3 8.61(s, 1H), 8.44(d, 2H), 8.32(d, 1H), 8.06-7.92(m, 5H), 7.78(t, 2H), 7.62-7.41(m, 7H), 7.19(d, 1H) 501.54 501.17
6 8.61(s, 1H), 8.32(d, 1H), 7.92(d, 1H), 7.85(d, 4H), 7.62(t, 1H), 7.52-7.48(m, 12H), 7.25-7.19(m, 5H) 551.64 551.21
8 8.83(d, 2H), 8.61(s, 1H), 8.38-8.32(m, 3H), 8.21(d, 2H), 8.02(d, 2H), 7.92-7.85(m, 5H), 7.66-7.48(m, 7H), 7.25-7.19(m, 5H) 653.73 653.23
12 10.51(s, 1H), 8.61(s, 1H), 8.44(d, 2H), 8.32(d, 1H), 8.06-7.92(m, 5H), 7.78(t, 2H), 7.62-7.41(m, 7H), 7.19(d, 1H) 500.55 500.17
13 8.83(d, 2H), 8.61-8.59(d, 2H), 8.38-8.32(m, 5H), 8.02(d, 2H), 7.92(d, 1H), 7.66-7.48(m, 7H), 7.19(d, 1H) 500.55 500.17
16 8.75(d, 4H), 8.61-8.59(d, 2H), 8.32-8.30(m, 5H), 7.99-7.85(m, 9H), 7.62(t, 1H), 7.80-7.48(m, 2H), 7.19(d, 1H) 552.63 552.21
18 8.81(d, 4H), 8.61-8.59(d, 2H), 8.33-8.32(m, 5H), 8.10-7.92(m, 7H), 7.78(t, 2H), 7.62-7.60(m, 3H), 7.50-7.48(m, 2H), 7.35(d, 2H), 7.19(d, 1H) 652.74 652.24
28 8.61(s, 1H), 8.32(d, 1H), 8.13(s, 1H), 8.00-7.91(m, 10H), 7.73(d, 2H), 7.62-7.58(m, 8H), 7.50-7.39(m, 4H), 7.19(d, 1H) 596.72 596.23
35 8.81-8.75(m, 8H), 8.61(s, 1H), 8.32(d, 1H), 8.20(s, 2H), 7.99-7.88(m, 9H), 7.62(t, 1H), 7.50-7.48(m, 2H), 7.25-7.19(m, 5H) 627.73 627.24
38 8.98(s, 1H), 8.15(t, 3H), 8.09-8.03(m, 6H), 7.96(d, 2H), 7.89-7.82(m, 2H), 7.78-7.54(m, 16H), 7.34-7.32(m, 2H) 672.83 672.26
39 8.35-8.28(m, 6H), 7.92(d, 1H), 7.62(t, 1H), 7.51-7.41(m, 7H), 7.19(d, 1H), 6.68(t, 1H) 399.45 399.15
41 8.44-8.32(m, 4H), 8.06-7.92(m, 5H), 7.78(t, 2H), 7.62-7.60(m, 3H), 7.48(t, 1H), 7.41(d, 2H), 7.19(d, 1H), 6.68(t, 1H) 501.54 501.17
42 8.83(d, 2H), 8.35-8.32(m, 4H), 8.21(d, 2H), 8.02(d, 2H), 7.92(d, 1H), 7.66-7.48(m, 6H), 7.19(d, 1H), 6.68(t, 1H) 501.54 501.17
44 8.35-8.32(m, 2H), 7.92-7.85(m, 5H), 7.62(t, 1H), 7.52-7.48(m, 11H), 7.25-7.19(m, 5H), 6.68(t, 1H) 551.64 551.21
45 8.75(d, 4H), 8.35-8.32(m, 2H), 7.99-7.85(m, 9H), 7.62(t, 1H), 7.48(t, 1H), 7.25-7.19(m, 5H), 6.68(t, 1H) 553.61 553.20
47 8.71-8.69(m, 6H), 8.49(d, 1H), 8.32(d, 1H), 8.06(d, 2H), 7.96-7.92(m, 7H), 7.85(t, 2H), 7.65(t, 1H), 7.54(t, 2H), 7.45(t, 1H), 7.31-7.29(m, 3H), 6.81(t, 1H) 653.75 653.23
51 8.94(d, 2H), 8.73(s, 1H), 8.63(d, 2H), 8.50-8.49(m, 3H), 8.32(d, 1H), 8.21(d, 2H), 7.92-7.87(m, 3H), 7.65-7.62(m, 3H), 7.45(t, 1H), 7.31(d, 1H), 6.81(t, 1H) 500.57 500.17
54 8.73-8.71(m, 5H), 8.49(d, 1H), 8.32-8.30(m, 5H), 8.00(d, 4H), 7.92(d, 1H), 7.85(d, 4H), 7.65(t, 1H), 7.46(t, 1H), 7.31(d, 1H), 6.81(t, 1H) 552.64 552.21
66 8.72(d, 1H), 8.15(d, 1H), 8.11(s, 1H), 8.06-8.05(m, 1H), 8.02(s, 2H), 7.98-7.94(m, 3H), 7.93-7.91(m, 1H), 7.83-7.75(m, 5H), 7.66-7.63(m, 3H), 7.59-7.45(m, 5H), 7.37(t, 2H), 7.18-7.12(m, 2H), 6.98(t, 1H) 596.73 596.23
76 8.78(d, 1H), 8.14-8.10(m, 3H), 8.08-8.05(m, 4H), 7.96-7.95(m, 2H), 7.90(d, 1H), 7.82-7.67(m, 8H), 7.62-7.61(m, 6H), 7.51-7.45(m, 2H), 7.34-7.32(m, 2H), 7.22-7.17(m, 2H), 6.94(t, 1H) 672.83 672.26
78 9.09(s, 2H), 8.49(d, 2H), 8.32(d, 1H), 8.18-8.16(m, 2H), 8.08(d, 2H), 8.02-8.00(m, 2H), 7.92(d, 1H), 7.65-7.54(m, 6H), 7.45(t, 1H), 7.16(t, 1H), 6.96(d, 1H) 499.58 499.18
86 8.37(s, 1H), 8.32(d, 1H), 7.94-7.92(m, 5H), 7.65(t, 1H), 7.55-7.45(m, 8H), 7.16(t, 1H), 6.96(d, 1H) 398.47 398.15
87 8.46(s, 2H), 8.37(s, 1H), 8.32(d, 1H), 8.08-8.06(m, 4H), 8.00-7.98(m, 4H), 7.92(d, 1H), 7.65-7.59(m, 5H), 7.54(d, 1H), 7.45(t, 1H), 7.16(t, 1H), 6.96(d, 1H) 498.59 498.18
93 8.87(d, 2H), 8.55(d, 2H), 8.37(s, 1H), 8.32-8.30(m, 5H), 8.05(d, 2H), 7.96-7.92(m, 3H), 7.65-7.64(m, 3H), 7.54-7.45(m, 4H), 7.25(d, 4H), 7.16(t, 1H), 6.96(d, 1H) 652.76 652.24
99 9.08(d, 2H), 8.84(d, 2H), 8.44-8.43(m, 4H), 8.32(d, 1H), 8.17(d, 2H), 7.92-7.90(m, 3H), 7.70-7.62(m, 9H), 7.54(d, 1H), 7.45(t, 1H), 7.16(t, 1H), 6.96(d, 1H) 597.72 597.22
102 8.87(d, 2H), 8.69(d, 4H), 8.55(d, 2H), 8.43(s, 2H), 8.32(d, 1H), 8.05(d, 2H), 7.96-7.92(m, 3H), 7.65-7.64(m, 3H), 7.54-7.45(m, 4H), 7.25(d, 4H), 7.16(t, 1H), 6.96(d, 1H) 651.77 651.24
104 8.78(s, 1H), 8.35-8.32(m, 3H), 8.25-8.23(m, 2H), 8.09-8.06(m, 4H), 7.99(d, 2H), 7.92(d, 1H), 7.65-7.60(m, 5H), 7.55(s, 2H), 7.45(t, 1H), 7.38(d, 2H), 7.29-7.27(m, 2H), 7.04(d, 1H), 6.78(d, 1H), 6.69(t, 1H) 596.73 596.23
105 8.69(d, 2H), 8.32-8.29(m, 5H), 8.20(s, 2H), 7.92(d, 1H), 7.85(d, 2H), 7.65(t, 1H), 7.55-7.45(m, 7H), 7.04(d, 1H), 6.78(d, 1H), 6.69(t, 1H) 473.58 473.19
110 8.69(d, 6H), 8.32(d, 1H), 8.20(s, 2H), 7.92(d, 1H), 7.85(d, 6H), 7.75(d, 4H), 7.65(t, 1H), 7.49-7.41(m, 7H), 7.04(d, 1H), 6.78(d, 1H), 6.69(t, 1H) 625.77 625.25
114 8.96(s, 1H), 8.69(d, 2H), 8.39(d, 1H), 8.32(d, 1H), 8.25-8.23(m, 2H), 8.09-8.06(m, 4H), 7.99(d, 2H), 7.92(d, 1H), 7.85(d, 2H), 7.65-7.60(m, 6H), 7.55(s, 2H), 7.45(t, 1H), 7.38(d, 2H), 7.29-7.27(m, 2H), 7.04(d, 1H), 6.78(d, 1H), 6.69(t, 1H) 672.83 672.26
119 9.08(d, 2H), 8.84(d, 2H), 8.34-8.32(m, 2H), 8.17(d, 2H), 8.11-8.05(m, 4H), 7.92-7.90(m, 3H), 7.84(t, 1H), 7.70-7.62(m, 10H), 7.45(t, 1H) 649.76 649.23
123 8.71-8.69(m, 6H), 8.34-8.32(m, 2H), 8.11-8.06(m, 4H), 7.96-7.92(m, 7H), 7.85-7.84(m, 3H), 7.69-7.65(m, 2H), 7.54(t, 2H), 7.45(t, 1H), 7.29(d, 2H) 703.81 703.25
128 9.08(d, 2H), 8.84(d, 2H), 8.73(s, 1H), 8.34-8.32(m, 2H), 8.17(d, 2H), 8.11-8.05(m, 4H), 7.92-7.90(m, 3H), 7.84(t, 1H), 7.70-7.62(m, 10H), 7.45(t, 1H) 648.77 648.23
134 8.85(s, 2H), 8.37-8.32(m, 4H), 8.20(s, 2H), 8.11-8.06(m, 6H), 8.02-8.00(m, 2H), 7.92(d, 1H), 7.84(t, 1H), 7.69-7.59(m, 6H), 7.45(t, 1H) 547.66 547.20
136 9.02(d, 2H), 8.94(d, 2H), 8.50(d, 2H), 8.34-8.32(m, 2H), 8.21-8.20(m, 4H), 8.11-8.08(m, 2H), 7.92(d, 1H), 7.87-7.84(m, 3H), 7.69-7.65(m, 2H), 7.62(t, 2H), 7.45(t, 1H) 549.64 549.20
139 8.71-8.69(m, 8H), 8.34-8.32(m, 2H), 8.20(s, 2H), 8.11-8.08(m, 2H), 8.00(d, 4H), 7.92(d, 1H), 7.85-7.84(m, 5H), 7.69-7.65(m, 2H), 7.45(t, 1H) 601.71 601.23
142 9.10(s, 1H), 8.33-8.32(m, 2H), 8.23-8.20(m, 3H), 8.14(d, 1H), 8.09-8.06(m, 5H), 7.99(d, 2H), 7.96-7.92(m, 2H), 7.85(t, 1H), 7.71(d, 1H), 7.65-7.60(m, 5H), 7.55(s, 2H), 7.45(t, 1H), 7.38(d, 2H), 7.29-7.27(m, 2H) 646.79 646.24
144 8.85(s, 2H), 8.37(d, 2H), 8.32(d, 1H), 8.20(s, 3H), 8.14(d, 1H), 8.09-8.00(m, 7H), 7.92(d, 1H), 7.85(t, 1H), 7.71(t, 1H), 7.65-7.59(m, 5H), 7.45(t, 1H), 7.25(s, 4H) 623.76 623.24
146 9.02(d, 2H), 8.94(d, 2H), 8.50(d, 2H), 8.32(d, 1H), 8.21-8.20(m, 5H), 8.14(d, 1H), 8.09(d, 1H), 7.92-7.85(m, 4H), 7.71-7.65(m, 2H), 7.62(t, 2H), 7.45(t, 1H), 7.25(s, 4H) 625.73 625.23
150 8.87(d, 2H), 8.69(d, 4H), 8.55(d, 2H), 8.32(d, 1H), 8.20(s, 3H), 8.14(d, 1H), 8.09-8.05(m, 3H), 7.96-7.92(m, 3H), 7.85(t, 1H), 7.71(d, 1H), 7.65-7.64(m, 3H), 7.49-7.45(m, 3H), 7.27-7.25(m, 8H) 777.93 777.29
152 8.96(s, 1H), 8.39(d, 1H), 8.32(d, 1H), 8.23-8.20(m, 3H), 8.14(d, 1H), 8.09-8.06(m, 5H), 7.99(d, 2H), 7.92(d, 1H), 7.85(t, 1H), 7.71(d, 1H), 7.65-7.60(m, 6H), 7.55(s, 2H), 7.45(t, 1H), 7.38(d, 2H), 7.27-7.25(m, 6H) 722.89 722.27
161 8.79(s, 1H), 8.71-8.69(m, 6H), 8.32(d, 1H), 8.06(d, 2H), 7.99-7.92(m, 8H), 7.85-7.83(m, 3H), 7.68-7.61(m, 3H), 7.54(t, 2H), 7.45(t, 1H), 7.29(d, 2H) 703.81 703.25
167 8.79(s, 1H), 8.73(s, 1H), 8.32-8.30(m, 5H), 7.99(d, 1H), 7.92(d, 1H), 7.85-7.83(m, 5H), 7.75(d, 4H), 7.68-7.61(m, 3H), 7.49-7.41(m, 7H) 600.73 600.23
171 8.79(s, 1H), 8.32-8.29(m, 5H), 8.20(s, 2H), 7.99(d, 1H), 7.92(d, 1H), 7.83(d, 1H), 7.68-7.61(m, 3H), 7.55-7.45(m, 7H) 447.54 447.17
173 9.14(s, 2H), 8.79(s, 1H), 8.41-8.32(m, 5H), 8.00-7.96(m, 5H), 7.92(d, 1H), 7.85-7.83(m, 3H), 7.68-7.61(m, 3H), 7.53(t, 2H), 7.45(t, 1H) 549.64 549.20
176 8.79(s, 1H), 8.69(d, 4H), 8.32(d, 1H), 8.20(d, 2H), 7.99(d, 1H), 7.92(d, 1H), 7.85-7.83(m, 5H), 7.75(d, 4H), 7.68-7.61(m, 3H), 7.49-7.41(m, 7H) 599.74 599.24
179 8.79(s, 1H), 8.71-8.69(m, 10H), 8.32(d, 1H), 8.20(s, 2H), 8.06(d, 2H), 7.99(d, 1H), 7.94-7.92(m, 3H), 7.85-7.83(m, 3H), 7.68-7.61(m, 3H), 7.54(t, 2H), 7.45(t, 1H), 7.29(d, 2H) 701.83 701.26
180 9.10(s, 1H), 8.34-8.32(m, 3H), 8.25-8.23(m, 2H), 8.09-7.92(m, 9H), 7.81(d, 1H), 7.65-7.60(m, 6H), 7.55(s, 2H), 7.48-7.45(m, 2H), 7.38(d, 2H), 7.29-7.27(m, 2H) 646.79 646.24
183 9.14(s, 2H), 8.41-8.32(m, 6H), 8.04-7.92(m, 6H), 7.83-7.81(m, 3H), 7.65-7.61(m, 2H), 7.53-7.45(m, 4H), 7.25(s, 4H) 625.73 625.23
185 9.08(d, 2H), 8.84(d, 2H), 8.44(s, 2H), 8.34-8.32(m, 2H), 8.20-8.17(m, 4H), 8.04(d, 1H), 7.92-7.90(m, 3H), 7.81(d, 1H), 7.70-7.61(m, 10H), 7.48-7.45(m, 2H), 7.25(s, 4H) 723.88 723.27
188 8.87(d, 2H), 8.69(d, 4H), 8.55(d, 2H), 8.34-8.32(m, 2H), 8.20(s, 2H), 8.05-8.04(m, 3H), 7.96-7.92(m, 3H), 7.81(d, 1H), 7.65-7.61(m, 4H), 7.49-7.45(m, 4H), 7.27-7.25(m, 8H) 777.93 777.29
190 8.96(s, 1H), 8.39(d, 1H), 8.34-8.32(m, 2H), 8.25-8.23(m, 2H), 8.09-8.04(m, 5H), 7.99(d, 2H), 7.92(d, 1H), 7.81(d, 1H), 7.65-7.60(m, 7H), 7.55(s, 2H), 7.48-7.45(m, 2H), 7.38(d, 2H), 7.27-7.25(m, 6H) 722.89 722.27
194 8.94(d, 2H), 8.69(d, 2H), 8.50(d, 2H), 8.41(d, 2H), 8.32(d, 1H), 8.21(d, 2H), 8.05(d, 1H), 7.96-7.87(m, 5H), 7.70-7.62(m, 7H), 7.45(t, 1H) 627.71 627.22
196 8.69(d, 2H), 8.32(d, 1H), 8.05(d, 1H), 7.96-7.92(m, 7H), 7.75(d, 4H), 7.70-7.62(m, 5H), 7.49-7.41(m, 7H), 7.25(d, 4H) 677.81 677.26
198 8.87(d, 2H), 8.69(d, 2H), 8.55(d, 2H), 8.32(d, 1H), 8.05(d, 3H), 7.96-7.92(m, 9H), 7.70-7.62(m, 7H), 7.49-7.45(m, 3H), 7.25(d, 4H) 779.91 779.28
202 10.15(s, 1H), 8.69-8.65(m, 4H), 8.32(d, 1H), 8.05-7.92(m, 8H), 7.83(t, 2H), 7.70-7.62(m, 7H), 7.53(t, 2H), 7.45(t, 1H) 626.72 626.22
204 9.08(d, 2H), 8.84(d, 2H), 8.69(d, 2H), 8.32(d, 1H), 8.23(s, 1H), 8.17(d, 2H), 8.07-8.05(m, 3H), 7.96-7.90(m, 5H), 7.70-7.62(m, 13H), 7.45(t, 1H) 724.87 724.26
206 8.71-8.69(m, 6H), 8.32-8.30(m, 5H), 8.23(s, 1H), 8.05-7.92(m, 8H), 7.85(d, 4H), 7.70-7.62(m, 5H), 7.45(t, 1H) 678.80 678.25
208 8.71-8.69(m, 8H), 8.32-8.30(m, 5H), 8.23(s, 1H), 8.06-8.05(m, 3H), 7.96-7.92(m, 5H), 7.85(t, 2H), 7.70-7.62(m, 5H), 7.54(t, 2H), 7.45(t, 1H), 7.29(d, 2H) 778.92 778.28
213 9.08(d, 2H), 8.84(d, 2H), 8.69(d, 2H), 8.44(s, 2H), 8.32(d, 1H), 8.20-8.17(m, 4H), 8.05(d, 1H), 7.92-7.85(m, 5H), 7.70-7.62(m, 13H), 7.45(t, 1H) 723.88 723.27
218 8.96(s, 1H), 8.69(d, 2H), 8.39(d, 1H), 8.32(d, 1H), 8.25-8.23(m, 2H), 8.09-8.05(m, 5H), 7.99(d, 2H), 7.92(d, 1H), 7.85(d, 2H), 7.70-7.55(m, 12H), 7.45(t, 1H), 7.38(d, 2H), 7.29-7.27(m, 2H) 722.89 722.27
228 8.96(s, 1H), 8.69(d, 2H), 8.39(d, 1H), 8.32(d, 1H), 8.25-8.23(m, 2H), 8.09-8.05(m, 5H), 7.99(d, 2H), 7.92(d, 1H), 7.85(d, 2H), 7.70-7.60(m, 10H), 7.55(s, 2H), 7.45(t, 1H), 7.38(d, 2H), 7.27-7.25(m, 6H) 798.99 798.30
231 8.85 (1H, s), 8.4 (1H, s), 8.32 (1H, d), 8.12~8.09 (2H, t), 7.92 (1H ,d), 7.63~7.61 (3H, t), 8.12~8.09 (2H, t), 7.92 (1H, d), 7.63~7.61 (3H, t), 7.54~7.4 (5H, m), 7.29~7.24 (2H, m), 7.0 (1H, d), 1.72 (6H, s) 449.55 449.19
236 8.85 (1H, S), 8.4 (1H, s), 8.32 (1H, d), 8.09~7.92 (4H, m), 7.62~7.4 (8H, m), 7.24 (1H, t), 7.0 (1H, d), 1.72 (6H, s) 505.63 505.16
241 8.85 (1H, s), 8.45 (1H, m), 8.4 (1H, s), 8.32 (1H, d), 8.09 (1H, d), 7.98~7.92 (2H, m), 7.62~7.4 (8H, m), 7.24 (1H, t), 7.0 (1H, d) 505.63 505.16
247 8.45 (2H, m), 8.4 (1H, s), 8.32 (1H, d), 8.05~7.92 (4H, m), 7.62~7.4 (7H, m), 7.33 (1H, d), 7.0 (1H, d) 495.09 495.62
250 8.55 (2H, d), 8.4 (1H, s), 8.32 (1H, m), 8.12 (1H, d), 7.94~7.92 (3H, m), 7.62~7.45 (9H, m), 7.33~7.25 (4H, m), 7.62~7.45 (9H, m), 7.33~7.25 (4H, m), 7.0 (1H, d) 498.58 498.18
251 8.55 (1H, d), 8.4 (1H, s), 8.32 (1H, d), 8.09 (1H, d), 8.00~7.92 (3H, m), 7.71 (1H, d), 7.62~7.61 (2H, m), 7.48~7.4 (3H, m), 7.33~7.24 (3H, m), 7.0 (1H, d), 1.72 (6H, s) 449.55 449.19
256 8.4 (1H, s), 8.32 (1H, d), 8.12 (1H, d), 8.92~7.89 (2H, t), 7.66~7.62 (3H, m), 7.50~7.4 (8H, m), 7.0 (1H, d) 423.46 423.14
271 8.85 (1H, s), 8.61 (1H, s), 8.32 (1H, d), 8.09~7.92 (5H, m), 7.62~7.48 (11H, m), 7.24~7.19 (2H, m), 1.72 (6H, s) 581.73 581.19
281 8.85 (1H, s), 8.4 (1H, d), 8.32 (1H, s), 8.12~8.09 (2H, t), 7.92 (1H, d), 7.63~7.61 (3H, t), 7.54~7.44 (4H, m), 7.29~7.24 (2H, m), 7.0 (1H, d), 6.6 (1H, t), 1.72 (6H, s) 449.55 449.19
316 8.85 (1H, s), 8.35~8.32 (2H, t), 8.12~8.09 (2H, t), 7.92 (1H, d), 7.79 (2H, d), 7.68~7.61 (5H, m), 7.54~7.44 (4H, m), 7.29~7.19 (3H, m), 6.68 (1H, m), 1.72 (6H, s) 525.64 525.22
321 8.85 (1H, s), 8.35~8.32 (2H, t), 8.09~7.92 (5H, m), 7.62~7.44 (10H, m), 7.24~7.19 (2H, m), 6.68 (1H, t), 1.72 (6H, s) 581.73 581.19
TABLE 7
Compound number 1 H NMR Found Calculated
One 8.61 (s, 1H), 8.32-8.28 (m, 5H), 7.92 (d, 1H), 7.62 (t, 1H), 7.51-7.41 (m, 8H), 7.19 (d, 1H) 399.45 399.15
3 8.61 (s, 1H), 8.44 (d, 2H), 8.32 (d, 1H), 8.06-7.92 (m, 5H), 7.78 (t, 2H), 7.62-7.41 (m, 7H), 7.19 (d, 1H) 501.54 501.17
6 8.61 (s, 1H), 8.32 (d, 1H), 7.92 (d, 1H), 7.85 (d, 4H), 7.62 (t, 1H), 7.52-7.48 (m, 12H), 7.25-7.19 (m, 5H) 551.64 551.21
8 8.83 (d, 2H), 8.61 (s, 1H), 8.38-8.32 (m, 3H), 8.21 (d, 2H), 8.02 (d, 2H), 7.92-7.85 (m, 5H), 7.66-7.48 ( m, 7H), 7.25-7.19 (m, 5H) 653.73 653.23
12 10.51 (s, 1H), 8.61 (s, 1H), 8.44 (d, 2H), 8.32 (d, 1H), 8.06-7.92 (m, 5H), 7.78 (t, 2H), 7.62-7.41 (m, 7H), 7.19 (d, 1H) 500.55 500.17
13 8.83 (d, 2H), 8.61-8.59 (d, 2H), 8.38-8.32 (m, 5H), 8.02 (d, 2H), 7.92 (d, 1H), 7.66-7.48 (m, 7H), 7.19 ( d, 1H) 500.55 500.17
16 8.75 (d, 4H), 8.61-8.59 (d, 2H), 8.32-8.30 (m, 5H), 7.99-7.85 (m, 9H), 7.62 (t, 1H), 7.80-7.48 (m, 2H), 7.19 (d, 1 H) 552.63 552.21
18 8.81 (d, 4H), 8.61-8.59 (d, 2H), 8.33-8.32 (m, 5H), 8.10-7.92 (m, 7H), 7.78 (t, 2H), 7.62-7.60 (m, 3H), 7.50-7.48 (m, 2H), 7.35 (d, 2H), 7.19 (d, 1H) 652.74 652.24
28 8.61 (s, 1H), 8.32 (d, 1H), 8.13 (s, 1H), 8.00-7.91 (m, 10H), 7.73 (d, 2H), 7.62-7.58 (m, 8H), 7.50-7.39 ( m, 4H), 7.19 (d, 1H) 596.72 596.23
35 8.81-8.75 (m, 8H), 8.61 (s, 1H), 8.32 (d, 1H), 8.20 (s, 2H), 7.99-7.88 (m, 9H), 7.62 (t, 1H), 7.50-7.48 ( m, 2H), 7.25-7.19 (m, 5H) 627.73 627.24
38 8.98 (s, 1H), 8.15 (t, 3H), 8.09-8.03 (m, 6H), 7.96 (d, 2H), 7.89-7.82 (m, 2H), 7.78-7.54 (m, 16H), 7.34- 7.32 (m, 2 H) 672.83 672.26
39 8.35-8.28 (m, 6H), 7.92 (d, 1H), 7.62 (t, 1H), 7.51-7.41 (m, 7H), 7.19 (d, 1H), 6.68 (t, 1H) 399.45 399.15
41 8.44-8.32 (m, 4H), 8.06-7.92 (m, 5H), 7.78 (t, 2H), 7.62-7.60 (m, 3H), 7.48 (t, 1H), 7.41 (d, 2H), 7.19 ( d, 1H), 6.68 (t, 1H) 501.54 501.17
42 8.83 (d, 2H), 8.35-8.32 (m, 4H), 8.21 (d, 2H), 8.02 (d, 2H), 7.92 (d, 1H), 7.66-7.48 (m, 6H), 7.19 (d, 1H), 6.68 (t, 1H) 501.54 501.17
44 8.35-8.32 (m, 2H), 7.92-7.85 (m, 5H), 7.62 (t, 1H), 7.52-7.48 (m, 11H), 7.25-7.19 (m, 5H), 6.68 (t, 1H) 551.64 551.21
45 8.75 (d, 4H), 8.35-8.32 (m, 2H), 7.99-7.85 (m, 9H), 7.62 (t, 1H), 7.48 (t, 1H), 7.25-7.19 (m, 5H), 6.68 ( t, 1H) 553.61 553.20
47 8.71-8.69 (m, 6H), 8.49 (d, 1H), 8.32 (d, 1H), 8.06 (d, 2H), 7.96-7.92 (m, 7H), 7.85 (t, 2H), 7.65 (t, 1H), 7.54 (t, 2H), 7.45 (t, 1H), 7.31-7.29 (m, 3H), 6.81 (t, 1H) 653.75 653.23
51 8.94 (d, 2H), 8.73 (s, 1H), 8.63 (d, 2H), 8.50-8.49 (m, 3H), 8.32 (d, 1H), 8.21 (d, 2H), 7.92-7.87 (m, 3H), 7.65-7.62 (m, 3H), 7.45 (t, 1H), 7.31 (d, 1H), 6.81 (t, 1H) 500.57 500.17
54 8.73-8.71 (m, 5H), 8.49 (d, 1H), 8.32-8.30 (m, 5H), 8.00 (d, 4H), 7.92 (d, 1H), 7.85 (d, 4H), 7.65 (t, 1H), 7.46 (t, 1H), 7.31 (d, 1H), 6.81 (t, 1H) 552.64 552.21
66 8.72 (d, 1H), 8.15 (d, 1H), 8.11 (s, 1H), 8.06-8.05 (m, 1H), 8.02 (s, 2H), 7.98-7.94 (m, 3H), 7.93-7.91 ( m, 1H), 7.83-7.75 (m, 5H), 7.66-7.63 (m, 3H), 7.59-7.45 (m, 5H), 7.37 (t, 2H), 7.18-7.12 (m, 2H), 6.98 ( t, 1H) 596.73 596.23
76 8.78 (d, 1H), 8.14-8.10 (m, 3H), 8.08-8.05 (m, 4H), 7.96-7.95 (m, 2H), 7.90 (d, 1H), 7.82-7.67 (m, 8H), 7.62-7.61 (m, 6H), 7.51-7.45 (m, 2H), 7.34-7.32 (m, 2H), 7.22-7.17 (m, 2H), 6.94 (t, 1H) 672.83 672.26
78 9.09 (s, 2H), 8.49 (d, 2H), 8.32 (d, 1H), 8.18-8.16 (m, 2H), 8.08 (d, 2H), 8.02-8.00 (m, 2H), 7.92 (d, 1H), 7.65-7.54 (m, 6H), 7.45 (t, 1H), 7.16 (t, 1H), 6.96 (d, 1H) 499.58 499.18
86 8.37 (s, 1H), 8.32 (d, 1H), 7.94-7.92 (m, 5H), 7.65 (t, 1H), 7.55-7.45 (m, 8H), 7.16 (t, 1H), 6.96 (d, 1H) 398.47 398.15
87 8.46 (s, 2H), 8.37 (s, 1H), 8.32 (d, 1H), 8.08-8.06 (m, 4H), 8.00-7.98 (m, 4H), 7.92 (d, 1H), 7.65-7.59 ( m, 5H), 7.54 (d, 1H), 7.45 (t, 1H), 7.16 (t, 1H), 6.96 (d, 1H) 498.59 498.18
93 8.87 (d, 2H), 8.55 (d, 2H), 8.37 (s, 1H), 8.32-8.30 (m, 5H), 8.05 (d, 2H), 7.96-7.92 (m, 3H), 7.65-7.64 ( m, 3H), 7.54-7.45 (m, 4H), 7.25 (d, 4H), 7.16 (t, 1H), 6.96 (d, 1H) 652.76 652.24
99 9.08 (d, 2H), 8.84 (d, 2H), 8.44-8.43 (m, 4H), 8.32 (d, 1H), 8.17 (d, 2H), 7.92-7.90 (m, 3H), 7.70-7.62 ( m, 9H), 7.54 (d, 1H), 7.45 (t, 1H), 7.16 (t, 1H), 6.96 (d, 1H) 597.72 597.22
102 8.87 (d, 2H), 8.69 (d, 4H), 8.55 (d, 2H), 8.43 (s, 2H), 8.32 (d, 1H), 8.05 (d, 2H), 7.96-7.92 (m, 3H) , 7.65-7.64 (m, 3H), 7.54-7.45 (m, 4H), 7.25 (d, 4H), 7.16 (t, 1H), 6.96 (d, 1H) 651.77 651.24
104 8.78 (s, 1H), 8.35-8.32 (m, 3H), 8.25-8.23 (m, 2H), 8.09-8.06 (m, 4H), 7.99 (d, 2H), 7.92 (d, 1H), 7.65- 7.60 (m, 5H), 7.55 (s, 2H), 7.45 (t, 1H), 7.38 (d, 2H), 7.29-7.27 (m, 2H), 7.04 (d, 1H), 6.78 (d, 1H) , 6.69 (t, 1 H) 596.73 596.23
105 8.69 (d, 2H), 8.32-8.29 (m, 5H), 8.20 (s, 2H), 7.92 (d, 1H), 7.85 (d, 2H), 7.65 (t, 1H), 7.55-7.45 (m, 7H), 7.04 (d, 1H), 6.78 (d, 1H), 6.69 (t, 1H) 473.58 473.19
110 8.69 (d, 6H), 8.32 (d, 1H), 8.20 (s, 2H), 7.92 (d, 1H), 7.85 (d, 6H), 7.75 (d, 4H), 7.65 (t, 1H), 7.49 -7.41 (m, 7H), 7.04 (d, 1H), 6.78 (d, 1H), 6.69 (t, 1H) 625.77 625.25
114 8.96 (s, 1H), 8.69 (d, 2H), 8.39 (d, 1H), 8.32 (d, 1H), 8.25-8.23 (m, 2H), 8.09-8.06 (m, 4H), 7.99 (d, 2H), 7.92 (d, 1H), 7.85 (d, 2H), 7.65-7.60 (m, 6H), 7.55 (s, 2H), 7.45 (t, 1H), 7.38 (d, 2H), 7.29-7.27 (m, 2H), 7.04 (d, 1H), 6.78 (d, 1H), 6.69 (t, 1H) 672.83 672.26
119 9.08 (d, 2H), 8.84 (d, 2H), 8.34-8.32 (m, 2H), 8.17 (d, 2H), 8.11-8.05 (m, 4H), 7.92-7.90 (m, 3H), 7.84 ( t, 1H), 7.70-7.62 (m, 10H), 7.45 (t, 1H) 649.76 649.23
123 8.71-8.69 (m, 6H), 8.34-8.32 (m, 2H), 8.11-8.06 (m, 4H), 7.96-7.92 (m, 7H), 7.85-7.84 (m, 3H), 7.69-7.65 (m , 2H), 7.54 (t, 2H), 7.45 (t, 1H), 7.29 (d, 2H) 703.81 703.25
128 9.08 (d, 2H), 8.84 (d, 2H), 8.73 (s, 1H), 8.34-8.32 (m, 2H), 8.17 (d, 2H), 8.11-8.05 (m, 4H), 7.92-7.90 ( m, 3H), 7.84 (t, 1H), 7.70-7.62 (m, 10H), 7.45 (t, 1H) 648.77 648.23
134 8.85 (s, 2H), 8.37-8.32 (m, 4H), 8.20 (s, 2H), 8.11-8.06 (m, 6H), 8.02-8.00 (m, 2H), 7.92 (d, 1H), 7.84 ( t, 1H), 7.69-7.59 (m, 6H), 7.45 (t, 1H) 547.66 547.20
136 9.02 (d, 2H), 8.94 (d, 2H), 8.50 (d, 2H), 8.34-8.32 (m, 2H), 8.21-8.20 (m, 4H), 8.11-8.08 (m, 2H), 7.92 ( d, 1H), 7.87-7.84 (m, 3H), 7.69-7.65 (m, 2H), 7.62 (t, 2H), 7.45 (t, 1H) 549.64 549.20
139 8.71-8.69 (m, 8H), 8.34-8.32 (m, 2H), 8.20 (s, 2H), 8.11-8.08 (m, 2H), 8.00 (d, 4H), 7.92 (d, 1H), 7.85- 7.84 (m, 5H), 7.69-7.65 (m, 2H), 7.45 (t, 1H) 601.71 601.23
142 9.10 (s, 1H), 8.33-8.32 (m, 2H), 8.23-8.20 (m, 3H), 8.14 (d, 1H), 8.09-8.06 (m, 5H), 7.99 (d, 2H), 7.96- 7.92 (m, 2H), 7.85 (t, 1H), 7.71 (d, 1H), 7.65-7.60 (m, 5H), 7.55 (s, 2H), 7.45 (t, 1H), 7.38 (d, 2H) , 7.29-7.27 (m, 2H) 646.79 646.24
144 8.85 (s, 2H), 8.37 (d, 2H), 8.32 (d, 1H), 8.20 (s, 3H), 8.14 (d, 1H), 8.09-8.00 (m, 7H), 7.92 (d, 1H) , 7.85 (t, 1H), 7.71 (t, 1H), 7.65-7.59 (m, 5H), 7.45 (t, 1H), 7.25 (s, 4H) 623.76 623.24
146 9.02 (d, 2H), 8.94 (d, 2H), 8.50 (d, 2H), 8.32 (d, 1H), 8.21-8.20 (m, 5H), 8.14 (d, 1H), 8.09 (d, 1H) , 7.92-7.85 (m, 4H), 7.71-7.65 (m, 2H), 7.62 (t, 2H), 7.45 (t, 1H), 7.25 (s, 4H) 625.73 625.23
150 8.87 (d, 2H), 8.69 (d, 4H), 8.55 (d, 2H), 8.32 (d, 1H), 8.20 (s, 3H), 8.14 (d, 1H), 8.09-8.05 (m, 3H) , 7.96-7.92 (m, 3H), 7.85 (t, 1H), 7.71 (d, 1H), 7.65-7.64 (m, 3H), 7.49-7.45 (m, 3H), 7.27-7.25 (m, 8H) 777.93 777.29
152 8.96 (s, 1H), 8.39 (d, 1H), 8.32 (d, 1H), 8.23-8.20 (m, 3H), 8.14 (d, 1H), 8.09-8.06 (m, 5H), 7.99 (d, 2H), 7.92 (d, 1H), 7.85 (t, 1H), 7.71 (d, 1H), 7.65-7.60 (m, 6H), 7.55 (s, 2H), 7.45 (t, 1H), 7.38 (d , 2H), 7.27-7.25 (m, 6H) 722.89 722.27
161 8.79 (s, 1H), 8.71-8.69 (m, 6H), 8.32 (d, 1H), 8.06 (d, 2H), 7.99-7.92 (m, 8H), 7.85-7.83 (m, 3H), 7.68- 7.61 (m, 3H), 7.54 (t, 2H), 7.45 (t, 1H), 7.29 (d, 2H) 703.81 703.25
167 8.79 (s, 1H), 8.73 (s, 1H), 8.32-8.30 (m, 5H), 7.99 (d, 1H), 7.92 (d, 1H), 7.85-7.83 (m, 5H), 7.75 (d, 4H), 7.68-7.61 (m, 3H), 7.49-7.41 (m, 7H) 600.73 600.23
171 8.79 (s, 1H), 8.32-8.29 (m, 5H), 8.20 (s, 2H), 7.99 (d, 1H), 7.92 (d, 1H), 7.83 (d, 1H), 7.68-7.61 (m, 3H), 7.55-7.45 (m, 7H) 447.54 447.17
173 9.14 (s, 2H), 8.79 (s, 1H), 8.41-8.32 (m, 5H), 8.00-7.96 (m, 5H), 7.92 (d, 1H), 7.85-7.83 (m, 3H), 7.68- 7.61 (m, 3H), 7.53 (t, 2H), 7.45 (t, 1H) 549.64 549.20
176 8.79 (s, 1H), 8.69 (d, 4H), 8.32 (d, 1H), 8.20 (d, 2H), 7.99 (d, 1H), 7.92 (d, 1H), 7.85-7.83 (m, 5H) , 7.75 (d, 4H), 7.68-7.61 (m, 3H), 7.49-7.41 (m, 7H) 599.74 599.24
179 8.79 (s, 1H), 8.71-8.69 (m, 10H), 8.32 (d, 1H), 8.20 (s, 2H), 8.06 (d, 2H), 7.99 (d, 1H), 7.94-7.92 (m, 3H), 7.85-7.83 (m, 3H), 7.68-7.61 (m, 3H), 7.54 (t, 2H), 7.45 (t, 1H), 7.29 (d, 2H) 701.83 701.26
180 9.10 (s, 1H), 8.34-8.32 (m, 3H), 8.25-8.23 (m, 2H), 8.09-7.92 (m, 9H), 7.81 (d, 1H), 7.65-7.60 (m, 6H), 7.55 (s, 2H), 7.48-7.45 (m, 2H), 7.38 (d, 2H), 7.29-7.27 (m, 2H) 646.79 646.24
183 9.14 (s, 2H), 8.41-8.32 (m, 6H), 8.04-7.92 (m, 6H), 7.83-7.81 (m, 3H), 7.65-7.61 (m, 2H), 7.53-7.45 (m, 4H ), 7.25 (s, 4H) 625.73 625.23
185 9.08 (d, 2H), 8.84 (d, 2H), 8.44 (s, 2H), 8.34-8.32 (m, 2H), 8.20-8.17 (m, 4H), 8.04 (d, 1H), 7.92-7.90 ( m, 3H), 7.81 (d, 1H), 7.70-7.61 (m, 10H), 7.48-7.45 (m, 2H), 7.25 (s, 4H) 723.88 723.27
188 8.87 (d, 2H), 8.69 (d, 4H), 8.55 (d, 2H), 8.34-8.32 (m, 2H), 8.20 (s, 2H), 8.05-8.04 (m, 3H), 7.96-7.92 ( m, 3H), 7.81 (d, 1H), 7.65-7.61 (m, 4H), 7.49-7.45 (m, 4H), 7.27-7.25 (m, 8H) 777.93 777.29
190 8.96 (s, 1H), 8.39 (d, 1H), 8.34-8.32 (m, 2H), 8.25-8.23 (m, 2H), 8.09-8.04 (m, 5H), 7.99 (d, 2H), 7.92 ( d, 1H), 7.81 (d, 1H), 7.65-7.60 (m, 7H), 7.55 (s, 2H), 7.48-7.45 (m, 2H), 7.38 (d, 2H), 7.27-7.25 (m, 6H) 722.89 722.27
194 8.94 (d, 2H), 8.69 (d, 2H), 8.50 (d, 2H), 8.41 (d, 2H), 8.32 (d, 1H), 8.21 (d, 2H), 8.05 (d, 1H), 7.96 -7.87 (m, 5H), 7.70-7.62 (m, 7H), 7.45 (t, 1H) 627.71 627.22
196 8.69 (d, 2H), 8.32 (d, 1H), 8.05 (d, 1H), 7.96-7.92 (m, 7H), 7.75 (d, 4H), 7.70-7.62 (m, 5H), 7.49-7.41 ( m, 7H), 7.25 (d, 4H) 677.81 677.26
198 8.87 (d, 2H), 8.69 (d, 2H), 8.55 (d, 2H), 8.32 (d, 1H), 8.05 (d, 3H), 7.96-7.92 (m, 9H), 7.70-7.62 (m, 7H), 7.49-7.45 (m, 3H), 7.25 (d, 4H) 779.91 779.28
202 10.15 (s, 1H), 8.69-8.65 (m, 4H), 8.32 (d, 1H), 8.05-7.92 (m, 8H), 7.83 (t, 2H), 7.70-7.62 (m, 7H), 7.53 ( t, 2H), 7.45 (t, 1H) 626.72 626.22
204 9.08 (d, 2H), 8.84 (d, 2H), 8.69 (d, 2H), 8.32 (d, 1H), 8.23 (s, 1H), 8.17 (d, 2H), 8.07-8.05 (m, 3H) , 7.96-7.90 (m, 5H), 7.70-7.62 (m, 13H), 7.45 (t, 1H) 724.87 724.26
206 8.71-8.69 (m, 6H), 8.32-8.30 (m, 5H), 8.23 (s, 1H), 8.05-7.92 (m, 8H), 7.85 (d, 4H), 7.70-7.62 (m, 5H), 7.45 (t, 1 H) 678.80 678.25
208 8.71-8.69 (m, 8H), 8.32-8.30 (m, 5H), 8.23 (s, 1H), 8.06-8.05 (m, 3H), 7.96-7.92 (m, 5H), 7.85 (t, 2H), 7.70-7.62 (m, 5H), 7.54 (t, 2H), 7.45 (t, 1H), 7.29 (d, 2H) 778.92 778.28
213 9.08 (d, 2H), 8.84 (d, 2H), 8.69 (d, 2H), 8.44 (s, 2H), 8.32 (d, 1H), 8.20-8.17 (m, 4H), 8.05 (d, 1H) , 7.92-7.85 (m, 5H), 7.70-7.62 (m, 13H), 7.45 (t, 1H) 723.88 723.27
218 8.96 (s, 1H), 8.69 (d, 2H), 8.39 (d, 1H), 8.32 (d, 1H), 8.25-8.23 (m, 2H), 8.09-8.05 (m, 5H), 7.99 (d, 2H), 7.92 (d, 1H), 7.85 (d, 2H), 7.70-7.55 (m, 12H), 7.45 (t, 1H), 7.38 (d, 2H), 7.29-7.27 (m, 2H) 722.89 722.27
228 8.96 (s, 1H), 8.69 (d, 2H), 8.39 (d, 1H), 8.32 (d, 1H), 8.25-8.23 (m, 2H), 8.09-8.05 (m, 5H), 7.99 (d, 2H), 7.92 (d, 1H), 7.85 (d, 2H), 7.70-7.60 (m, 10H), 7.55 (s, 2H), 7.45 (t, 1H), 7.38 (d, 2H), 7.27-7.25 (m, 6H) 798.99 798.30
231 8.85 (1H, s), 8.4 (1H, s), 8.32 (1H, d), 8.12-8.09 (2H, t), 7.92 (1H, d), 7.63-7.61 (3H, t), 8.12-8.09 ( 2H, t), 7.92 (1H, d), 7.63-7.61 (3H, t), 7.54-7.4 (5H, m), 7.29-7.42 (2H, m), 7.0 (1H, d), 1.72 (6H, s) 449.55 449.19
236 8.85 (1H, S), 8.4 (1H, s), 8.32 (1H, d), 8.09-7.82 (4H, m), 7.62-7.4 (8H, m), 7.24 (1H, t), 7.0 (1H, d), 1.72 (6H, s) 505.63 505.16
241 8.85 (1H, s), 8.45 (1H, m), 8.4 (1H, s), 8.32 (1H, d), 8.09 (1H, d), 7.98-7.82 (2H, m), 7.62-7.4 (8H, m), 7.24 (1 H, t), 7.0 (1 H, d) 505.63 505.16
247 8.45 (2H, m), 8.4 (1H, s), 8.32 (1H, d), 8.05-7.92 (4H, m), 7.62-7.4 (7H, m), 7.33 (1H, d), 7.0 (1H, d) 495.09 495.62
250 8.55 (2H, d), 8.4 (1H, s), 8.32 (1H, m), 8.12 (1H, d), 7.94-7.72 (3H, m), 7.62-7.45 (9H, m), 7.33-7.45 ( 4H, m), 7.62 ~ 7.45 (9H, m), 7.33 ~ 7.25 (4H, m), 7.0 (1H, d) 498.58 498.18
251 8.55 (1H, d), 8.4 (1H, s), 8.32 (1H, d), 8.09 (1H, d), 8.00-7.72 (3H, m), 7.71 (1H, d), 7.62-7.61 (2H, m), 7.48 ~ 7.4 (3H, m), 7.33 ~ 7.24 (3H, m), 7.0 (1H, d), 1.72 (6H, s) 449.55 449.19
256 8.4 (1H, s), 8.32 (1H, d), 8.12 (1H, d), 8.92-7.89 (2H, t), 7.66-7.62 (3H, m), 7.50-7.4 (8H, m), 7.0 ( 1H, d) 423.46 423.14
271 8.85 (1H, s), 8.61 (1H, s), 8.32 (1H, d), 8.09-7.92 (5H, m), 7.62-7.48 (11H, m), 7.24-7.19 (2H, m), 1.72 ( 6H, s) 581.73 581.19
281 8.85 (1H, s), 8.4 (1H, d), 8.32 (1H, s), 8.12-8.09 (2H, t), 7.92 (1H, d), 7.63-7.61 (3H, t), 7.54-7.44 ( 4H, m), 7.29 ~ 7.24 (2H, m), 7.0 (1H, d), 6.6 (1H, t), 1.72 (6H, s) 449.55 449.19
316 8.85 (1H, s), 8.35-8.32 (2H, t), 8.12-8.09 (2H, t), 7.92 (1H, d), 7.79 (2H, d), 7.68-7.61 (5H, m), 7.54- 7.44 (4H, m), 7.29-7.19 (3H, m), 6.68 (1H, m), 1.72 (6H, s) 525.64 525.22
321 8.85 (1H, s), 8.35-8.32 (2H, t), 8.09-7.72 (5H, m), 7.62-7.44 (10H, m), 7.24-7.19 (2H, m), 6.68 (1H, t), 1.72 (6H, s) 581.73 581.19
시험예 1Test Example 1
화합물 38, 화합물 66 및 화합물 76의 호모(HOMO), 루모(LUMO), 밴드갭(BAND GAP)을 CV 측정기기(제조사: princeton appied research, 모델명: Parstat2273)를 이용하여 하기 방법으로 측정하였고, 결과를 하기 표 9 내지 표 11에 나타내었다.HOMO, LUMO, and BAND GAP of Compound 38, Compound 66, and Compound 76 were measured using a CV measuring instrument (princeton appied research, model name: Parstat2273) using the following method. Are shown in Tables 9 to 11 below.
1. 전해질액, 표준액, 검액의 제조1. Preparation of electrolyte solution, standard solution and sample solution
1)전해질액: 테트라부틸암모늄 테트라플루오로보레이트(Tetrabutylammonium tetrafluoroborate) 3.3g을 정밀히 달아 100㎖ 용량플라스크에 넣고, 메틸렌 클로라이드(methylene chloride)를 넣어 100㎖로 하여 제조하였다. 1) Electrolyte solution: 3.3 g of tetrabutylammonium tetrafluoroborate was precisely weighed and placed in a 100 ml volumetric flask, and methylene chloride was added to make 100 ml.
2) 표준액: NPB 약 1mg을 정밀히 달아 10㎖ 용량플라스크에 넣고, 전해질액을 넣어 10㎖로 한 후 표준액으로 사용하였다. 2) Standard solution: Approximately 1 mg of NPB was precisely weighed, placed in a 10 ml volumetric flask, and the electrolyte was added to make 10 ml.
3) 검액: 화합물을 시료로 하여 약 1mg을 정밀히 달아 10㎖ 용량플라스크에 넣고, 전해질액을 넣어 10㎖로 한 후 검액으로 사용하였다. 3) Sample solution: About 1 mg of the compound was accurately weighed and placed in a 10 ml volumetric flask, and the electrolyte solution was added to 10 ml before being used as a sample solution.
2. 분석 조건2. Analysis condition
표 8
파라미터(Parameter) Value
레퍼런스 전극 타입(Reference Electrode type) Ag.AgCl / NaCl (sat'd)
초기 전위(Initial Potential, E0) 0.00 Volts
정점 전위(Vertex Potential, E1) 1.5~2.5 Volts
최종 전위(Final Potential, E2) 0.00 Volts
스캔 속도(Scan rate) 50~100 Volts
Table 8
Parameter Value
Reference Electrode Type Ag.AgCl / NaCl (sat'd)
Initial Potential (E0) 0.00 Volts
Vertex Potential (E1) 1.5 ~ 2.5 Volts
Final Potential (E2) 0.00 Volts
Scan rate
50 ~ 100 Volts
3. CV 측정방법3. CV measurement method
1) NPB과 전해질액을 사용하여 6㎖의 표준액을 제조하였다.1) 6 ml of standard solution was prepared using NPB and electrolyte solution.
2) 작업전극, 기준전극, 보조전극을 설치하였다.2) Working electrode, reference electrode and auxiliary electrode were installed.
3) 약 30초 정도 질소 버블링을 시행한 후 측정을 시작하였다.3) Nitrogen bubbling was performed for about 30 seconds and the measurement was started.
4) 측정이 끝나면 MC, 아세톤을 이용하여 깨끗하게 씻은 후, 측정할 화합물의 검액 제조하여 상술한 바와 같은 방법으로 측정하였다.4) After the end of the measurement was washed clean using MC, acetone, and then prepared by the test solution of the compound to be measured by the method described above.
4. 계산식4. Formula
호모 = -5.5-(Eox(측정 대상 화합물) - Eox (NPB))eVHomo = -5.5- (E ox (compound to measure)-E ox (NPB)) eV
밴드갭 (호모-루모)= 1240/UV 흡수한계(UV absorption edge)Bandgap (Homo-Lumo) = 1240 / UV absorption edge
표 9
호모 = -5.5-(Eox(화합물 38)-Eox(NPB))(eV)
밴드갭 =1240/ UV 흡수한계 (430㎚)(eV)
Eox 호모 밴드갭 루모
NPB 0.72eV
화합물 38 1.10eV -5.87eV 2.88eV -2.99eV
Table 9
Homo = -5.5- (E ox (Compound 38) -E ox (NPB)) (eV)
Bandgap = 1240 / UV Absorption Limit (430nm) (eV)
E ox homo Band gap Lumo
NPB 0.72 eV
Compound 38 1.10 eV -5.87 eV 2.88 eV -2.99 eV
표 10
호모 = -5.5-(Eox(화합물 66)-Eox(NPB))(eV)
밴드갭 =1240/ UV 흡수한계 (430㎚)(eV)
Eox 호모 밴드갭 루모
NPB 0.77eV
화합물 66 1.17eV -5.90eV 2.88eV -3.02eV
Table 10
Homo = -5.5- (E ox (Compound 66) -E ox (NPB)) (eV)
Bandgap = 1240 / UV Absorption Limit (430nm) (eV)
E ox homo Band gap Lumo
NPB 0.77eV
Compound 66 1.17 eV -5.90eV 2.88 eV -3.02eV
표 11
호모 = -5.5-(Eox(화합물 76)-Eox(NPB))(eV)
밴드갭 =1240/ UV 흡수한계 (428㎚)(eV)
Eox 호모 밴드갭 루모
NPB 0.79eV
화합물 76 1.17eV -5.88eV 2.90eV -2.98eV
Table 11
Homo = -5.5- (E ox (Compound 76) -E ox (NPB)) (eV)
Bandgap = 1240 / UV Absorption Limit (428nm) (eV)
E ox homo Band gap Lumo
NPB 0.79 eV
Compound 76 1.17 eV -5.88 eV 2.90eV -2.98eV
도 4 및 도 5는 화합물 38의 CV 측정 결과 도출된 Eox값을 나타낸 것이다.4 and 5 show the E ox value derived from the CV measurement of compound 38.
도 6 및 도 7은 화합물 66의 CV 측정 결과 도출된 Eox값을 나타낸 것이다.6 and 7 show E ox values derived as a result of CV measurement of Compound 66.
도 8 및 도 9는 화합물 76의 CV 측정 결과 도출된 Eox값을 나타낸 것이다.8 and 9 show E ox values derived as a result of CV measurement of Compound 76.
도 4 내지 도 9에서, y축은 전류(current, 단위: A), x축은 전위(Potential, 단위: V)를 나타낸다.4 to 9, the y axis represents current (unit: A), and the x axis represents potential (unit: V).
한편, 도 10는 화합물 38의 UV 측정 그래프를 나타낸 것이다.On the other hand, Figure 10 shows a UV measurement graph of the compound 38.
도 11은 화합물 38의 320㎚에 대한 PL 측정 그래프를 나타낸 것이다.11 shows a PL measurement graph for 320 nm of compound 38. FIG.
도 12는 화합물 66의 UV 측정 그래프를 나타낸 것이다.12 shows the UV measurement graph of compound 66.
도 13은 화합물 66의 260㎚에 대한 PL 측정 그래프를 나타낸 것이다.FIG. 13 shows a PL measurement graph for 260 nm of Compound 66.
도 14는 화합물 76의 UV 측정 그래프를 나타낸 것이다.FIG. 14 shows a UV measurement graph of compound 76. FIG.
도 15는 화합물 76의 303㎚에 대한 PL 측정 그래프를 나타낸 것이다.15 shows a PL measurement graph for 303 nm of compound 76. FIG.
도 10 내지 도 15의 y축은 각각 강도(intensity)이고, x축은 파장(단위: ㎚)이다.The y-axis of FIGS. 10 to 15 are intensity, respectively, and the x-axis is wavelength (unit: nm).
비교예 1: OLED 소자 제작Comparative Example 1: OLED Device Fabrication
우선, OLED용 글래스(삼성-코닝사 제조)로부터 얻어진 투명전극 ITO 박막을, 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 초음파 세척을 실시하고, 이소프로필알코올에 세척 후 사용하였다.First, the transparent electrode ITO thin film obtained from the glass for OLED (manufactured by Samsung Corning Corporation) was subjected to ultrasonic washing using trichloroethylene, acetone, ethanol and distilled water in sequence, and used after washing in isopropyl alcohol.
다음으로, 진공 증착 장비의 기판 폴더에 ITO 기판을 설치하고, 진공 증착 장비 내의 진공도가 10-7 torr에 도달할 때까지 배기시킨 후, 하기 4,4',4"-트리스(N,N-(2-나프틸)-페닐아미노)트리페닐아민(4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 이하 2-TNATA라 한다)를 기상 증착시켜 ITO 기판 상에 600Å 두께의 정공 주입층을 증착하였다. Next, an ITO substrate is placed in the substrate folder of the vacuum deposition equipment, and evacuated until the vacuum degree in the vacuum deposition equipment reaches 10 -7 torr, and then the following 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine (4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenyl amine: hereinafter referred to as 2-TNATA) by vapor deposition A 600 μm thick hole injection layer was deposited on the ITO substrate.
이어서, 진공 증착 장비 내의 다른 셀에 하기 N,N'-비스(α-나프틸)-N,N'-디페닐-4,4'-디아민(N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine: 이하, NPB라 한다)을 넣고, 셀에 전류를 인가하여 증발시켜 정공주입층 위에 250Å 두께의 정공수송층을 증착하였다.Subsequently, the following N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine (N, N'-bis (α-naphthyl)- N, N'-diphenyl-4,4'-diamine (hereinafter referred to as NPB)) was added thereto, and a 250 증발 thick hole transport layer was deposited on the hole injection layer by evaporation by applying a current to the cell.
상기 정공주입층, 정공수송층을 형성시킨 후, 그 위에 발광층을 다음과 같이 증착시켰다. 진공 증착 장비 내의 한쪽 셀에 발광 재료로 호스트로 하기 α-ADN를 넣고, 다른 셀에는 도펀트로 하기 BD1을 넣었다.After the hole injection layer and the hole transport layer were formed, a light emitting layer was deposited thereon as follows. The following α-ADN was used as a host as a light emitting material in one cell in the vacuum deposition equipment, and the following BD1 was added as a dopant in the other cell.
Figure PCTKR2013012050-appb-I000073
Figure PCTKR2013012050-appb-I000073
이어서, 두 셀을 같이 가열, 상기 도펀트의 증착속도 비율을 5 중량%(호스트:도펀트= 95:5)로 증착함으로써 상기 정공 전달층 위에 200Å의 두께로 발광층을 증착하였다. 이어서, 전자수송층으로서 하기 트리스(8-히드록시퀴놀린)알루미늄(Ⅲ)(이하 Alq3라 한다)를 200Å 두께로 증착하였다. Subsequently, the two cells were heated together, and the light emitting layer was deposited on the hole transport layer to a thickness of 200 kV by depositing the deposition rate ratio of the dopant at 5 wt% (host: dopant = 95: 5). Subsequently, the following tris (8-hydroxyquinoline) aluminum (III) (hereinafter referred to as Alq 3 ) was deposited to an thickness of 200 kPa as the electron transporting layer.
그 후, 전자주입층으로 리튬 플루오라이드(lithium fluoride: LiF)를 10Å 두께로 증착하였다. 그리고, Al 음극을 1200Å의 두께로 증착하여 OLED를 제작하였다.Subsequently, lithium fluoride (LiF) was deposited to a thickness of 10 으로 with an electron injection layer. An Al cathode was deposited to a thickness of 1200 Å to produce an OLED.
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 was vacuum sublimation purification under 10 -6 ~ 10 -8 torr each material was used in the OLED production.
실시예 1: OLED 소자 제작Example 1 OLED Device Fabrication
전자수송층 재료로서 비교예의 트리스(8-히드록시퀴놀린)알루미늄(Ⅲ)(Alq3) 대신 하기 표 12의 화합물을 이용한 것을 제외하고는 비교예와 같은 방식으로 OLED를 제작하였다. An OLED was manufactured in the same manner as in the comparative example, except that the compound of Table 12 was used instead of the tris (8-hydroxyquinoline) aluminum (III) (Alq 3 ) of the comparative example as the electron transport layer material.
시험예 2: OLED의 특성 평가Test Example 2: Characterization of OLED
전술한 바와 같이 제작한 OLED소자의 구동전압(V), 전력효율(cd/A) 및 구동 수명을 1,000cd/m2 에서 그리고, 효율이 50%까지 떨어질 때까지의 시간을 하기 표 12에 기재하였다.The driving voltage (V), power efficiency (cd / A) and driving life of the OLED device fabricated as described above at 1,000 cd / m 2 and the time until the efficiency drops to 50% are described in Table 12 below. It was.
표 12
전자수송층 재료 Op.V Cd/A T50 (Hour)
Alq3(비교예) 4.72 3.82 180
화합물 1 4.31 4.54 260
화합물 3 4.31 4.45 290
화합물 6 4.32 4.45 250
화합물 8 4.23 4.51 290
화합물 12 4.3 4.56 310
화합물 13 4.3 4.55 300
화합물 16 4.35 4.49 280
화합물 18 4.22 4.5 300
화합물 28 4.15 5.14 350
화합물 35 4.31 4.44 300
화합물 38 4.22 5.25 320
화합물 39 4.31 4.54 280
화합물 41 4.3 4.55 270
화합물 42 4.33 4.43 300
화합물 44 4.31 4.42 290
화합물 45 4.23 4.51 300
화합물 47 4.31 4.56 310
화합물 51 4.34 4.45 290
화합물 54 4.12 4.62 380
화합물 66 4.31 4.49 260
화합물 76 4.24 4.84 350
화합물 78 4.3 4.55 260
화합물 86 4.31 4.54 260
화합물 87 4.29 4.56 270
화합물 93 4.23 4.51 270
화합물 99 4.32 4.5 280
화합물 102 4.3 4.51 290
화합물 104 4.22 4.53 300
화합물 105 4.31 4.54 270
화합물 110 4.29 4.56 280
화합물 114 4.24 4.59 290
화합물 119 4.23 4.51 320
화합물 123 4.32 4.5 320
화합물 128 4.24 4.51 320
화합물 134 4.25 4.63 340
화합물 136 4.39 4.55 320
화합물 139 4.01 4.68 420
화합물 142 4.35 4.48 300
화합물 144 4.38 4.51 320
화합물 146 4.35 4.53 330
화합물 150 4.11 4.73 380
화합물 152 4.32 4.54 300
화합물 161 4.33 4.43 300
화합물 167 4.32 4.49 280
화합물 171 4.3 4.51 290
화합물 173 4.23 4.51 300
화합물 176 4.32 4.45 310
화합물 179 4.3 4.57 310
화합물 180 4.03 4.63 360
화합물 183 4.32 4.61 280
화합물 185 4.31 4.6 300
화합물 188 4.35 4.51 290
화합물 190 4.2 4.69 340
화합물 194 4.31 4.45 290
화합물 196 4.23 4.51 290
화합물 198 4.3 4.56 310
화합물 202 4.32 4.5 300
화합물 204 4.3 4.55 270
화합물 206 4.35 4.49 270
화합물 208 4.22 4.5 290
화합물 213 4.32 4.5 300
화합물 218 4.23 4.72 310
화합물 228 4.35 4.75 300
Table 12
Electron transport layer material Op.V Cd / A T 50 (Hour)
Alq 3 (Comparative) 4.72 3.82 180
Compound 1 4.31 4.54 260
Compound 3 4.31 4.45 290
Compound 6 4.32 4.45 250
Compound 8 4.23 4.51 290
Compound 12 4.3 4.56 310
Compound 13 4.3 4.55 300
Compound 16 4.35 4.49 280
Compound 18 4.22 4.5 300
Compound 28 4.15 5.14 350
Compound 35 4.31 4.44 300
Compound 38 4.22 5.25 320
Compound 39 4.31 4.54 280
Compound 41 4.3 4.55 270
Compound 42 4.33 4.43 300
Compound 44 4.31 4.42 290
Compound 45 4.23 4.51 300
Compound 47 4.31 4.56 310
Compound 51 4.34 4.45 290
Compound 54 4.12 4.62 380
Compound 66 4.31 4.49 260
Compound 76 4.24 4.84 350
Compound 78 4.3 4.55 260
Compound 86 4.31 4.54 260
Compound 87 4.29 4.56 270
Compound 93 4.23 4.51 270
Compound 99 4.32 4.5 280
Compound 102 4.3 4.51 290
Compound 104 4.22 4.53 300
Compound 105 4.31 4.54 270
Compound 110 4.29 4.56 280
Compound 114 4.24 4.59 290
Compound 119 4.23 4.51 320
Compound 123 4.32 4.5 320
Compound 128 4.24 4.51 320
Compound 134 4.25 4.63 340
Compound 136 4.39 4.55 320
Compound 139 4.01 4.68 420
Compound 142 4.35 4.48 300
Compound 144 4.38 4.51 320
Compound 146 4.35 4.53 330
Compound 150 4.11 4.73 380
Compound 152 4.32 4.54 300
Compound 161 4.33 4.43 300
Compound 167 4.32 4.49 280
Compound 171 4.3 4.51 290
Compound 173 4.23 4.51 300
Compound 176 4.32 4.45 310
Compound 179 4.3 4.57 310
Compound 180 4.03 4.63 360
Compound 183 4.32 4.61 280
Compound 185 4.31 4.6 300
Compound 188 4.35 4.51 290
Compound 190 4.2 4.69 340
Compound 194 4.31 4.45 290
Compound 196 4.23 4.51 290
Compound 198 4.3 4.56 310
Compound 202 4.32 4.5 300
Compound 204 4.3 4.55 270
Compound 206 4.35 4.49 270
Compound 208 4.22 4.5 290
Compound 213 4.32 4.5 300
Compound 218 4.23 4.72 310
Compound 228 4.35 4.75 300
상기 표 12의 결과로부터 본 발명 제조예의 화합물을 전자수송층 재료로 이용하여 제작한 유기발광소자의 경우, 비교예에서 트리스(8-히드록시퀴놀린)알루미늄(Ⅲ)(Alq3)를 사용한 유기발광소자 대비 구동전압, 효율 및 수명 등에서 우수한 특성을 확인하였다. 이에 본 발명 화학식 1로 표시되는 피라졸 함유 다환고리 유도체는 유기발광소자 제작시 전자수송층의 재료로서 유용함을 확인하였다.In the case of the organic light emitting device manufactured by using the compound of Preparation Example of the present invention as an electron transporting material from the results of Table 12, the organic light emitting device using tris (8-hydroxyquinoline) aluminum (III) (Alq 3 ) in the Comparative Example Excellent characteristics in driving voltage, efficiency and lifespan were confirmed. Accordingly, it was confirmed that the pyrazole-containing polycyclic derivative represented by Chemical Formula 1 of the present invention was useful as a material of the electron transport layer when manufacturing an organic light emitting device.
비교예 2: OLED 소자 제작Comparative Example 2: OLED Device Fabrication
OLED용 글래스(삼성-코닝사 제조)로부터 얻어진 투명전극 ITO 박막을, 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 초음파 세척을 실시한 후, 이소프로판올에 넣어 보관한 후 사용하였다. 다음으로, 진공 증착 장비의 기판 폴더에 ITO 기판을 설치하고, 진공 증착 장비 내의 셀에 2-TNATA를 넣었다.The transparent electrode ITO thin film obtained from the glass for OLED (manufactured by Samsung-Corning) was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol, and distilled water in sequence, and then stored in isopropanol and used. Next, the ITO board | substrate was installed in the board | substrate folder of a vacuum deposition apparatus, and 2-TNATA was put into the cell in a vacuum deposition apparatus.
이어서, 챔버 내의 진공도가 10-6torr에 도달할 때까지 배기시킨 후, 셀에 전류를 인가하여 2-TNATA를 증발시켜 ITO 기판 상에 600Å 두께의 정공주입층을 증착하였다. 진공 증착 장비 내의 다른 셀에 NPB를 넣고, 셀에 전류를 인가하여 증발시켜 정공주입층 위에 300Å 두께의 정공수송층을 증착하였다.Subsequently, after evacuating until the vacuum in the chamber reached 10 −6 torr, a current was applied to the cell to evaporate 2-TNATA to deposit a 600 kW hole injection layer on the ITO substrate. NPB was placed in another cell in the vacuum deposition equipment, and a 300 증발 thick hole transport layer was deposited on the hole injection layer by applying an electric current to the cell.
이와 같이 정공주입층 및 정공수송층을 형성시킨 후, 그 위에 발광층을 다음과 같은 구조의 인광 녹색 발광재료를 증착시켰다. 진공 증착 장비 내의 한쪽 셀에 녹색 발광 호스트 재료인 CBP(4,4'-bis(carbazol-9-yl)biphenyl)를 350Å 두께로 진공 증착시키고 이와 함께 녹색 발광 도판트 재료인 Ir(ppy)3(Tris(2-phenylpyridine)iridium(Ⅲ))를 호스트 재료 대비 10% 진공 증착시켰다.After the hole injection layer and the hole transport layer were formed in this way, the phosphorescent green light emitting material having the following structure was deposited on the light emitting layer. CBP (4,4'-bis (carbazol-9-yl) biphenyl), a green light emitting host material, was vacuum deposited to a thickness of 350 에 in one cell of the vacuum deposition equipment, and Ir (ppy) 3 (green light emitting dopant material) was vacuum deposited. Tris (2-phenylpyridine) iridium (III)) was 10% vacuum deposited relative to the host material.
이어서, 정공저지층으로 하기와 같은 정공저지층 재료인 BCP(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)를 50Å 두께로 증착을 하고, 전자수송층으로서 Alq3를 200Å 두께로 증착하였다. 그 후, 전자주입층으로 리튬 플루오라이드를 10Å 두께로 증착하였다. 그리고, Al 음극을 1000Å의 두께로 증착하여 OLED를 제작하였다.Subsequently, as a hole blocking layer, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), which is a hole blocking layer material as described below, was deposited to a thickness of 50 GPa, and Alq 3 as an electron transport layer was 200 GPa thick. Was deposited. Thereafter, lithium fluoride was deposited to a thickness of 10 kPa with an electron injection layer. And an Al cathode was deposited to a thickness of 1000 Å to produce an OLED.
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 was vacuum sublimation purification under 10 -6 ~ 10 -8 torr each material was used in the OLED production.
시험예 3: OLED 소자 제작Test Example 3: OLED device fabrication
상기 비교예에서의 녹색 발광층에 해당하는 표 13의 재료들을 CBP를 대신하여 사용한 것 외에 나머지 재료는 비교예 2와 동일하게 사용하여 소자를 제작하였다. A device was fabricated using the same materials as in Comparative Example 2 except for using the materials shown in Table 13 corresponding to the green light emitting layer in Comparative Example instead of CBP.
시험예 4: OLED의 특성 평가Test Example 4: Characterization of OLED
전술한 바와 같이 제작한 OLED소자의 구동전압(Op.V), 전력효율(cd/A)을 1,000cd/m2 에서, 효율이 50%까지 떨어질 때까지의 시간을 하기 표 13에 기재하였다.The drive voltage (Op.V) and power efficiency (cd / A) of the OLED device manufactured as described above are described in Table 13 below until the efficiency drops to 50% at 1,000 cd / m 2 .
표 13
발광층의 호스트 Op.V Cd/A T50 (Hour)
비교예 2(CBP) 6.71 35.3 260
화합물 231 4.63 43.1 400
화합물 236 4.69 45.2 400
화합물 241 4.62 43.1 380
화합물 247 4.64 42.2 410
화합물 250 4.59 42.2 380
화합물 251 4.60 42.8 370
화합물 256 4.61 43.0 370
화합물 271 4.58 42.7 350
화합물 281 4.61 43.0 370
화합물 316 4.58 42.7 350
화합물 321 4.65 42.4 430
Table 13
Host of emitting layer Op.V Cd / A T 50 (Hour)
Comparative Example 2 (CBP) 6.71 35.3 260
Compound 231 4.63 43.1 400
Compound 236 4.69 45.2 400
Compound 241 4.62 43.1 380
Compound 247 4.64 42.2 410
Compound 250 4.59 42.2 380
Compound 251 4.60 42.8 370
Compound 256 4.61 43.0 370
Compound 271 4.58 42.7 350
Compound 281 4.61 43.0 370
Compound 316 4.58 42.7 350
Compound 321 4.65 42.4 430
상기 표 13의 결과로부터 본 발명 제조예의 화합물을 인광 발광층 재료로 이용하여 제작한 유기발광소자의 경우, 비교예에서 CBP를 사용한 유기발광소자 대비 구동전압, 효율 및 수명 등에서 우수한 특성을 확인하였다. 이에 본 발명 화학식 1로 표시되는 피라졸 함유 다환고리 유도체는 유기발광소자 제작시 인광 발광층의 재료로서 유용함을 확인하였다.From the results of Table 13, the organic light emitting device manufactured by using the compound of Preparation Example of the present invention as a phosphorescent light emitting layer material, compared to the organic light emitting device using the CBP in the comparative example was confirmed excellent characteristics in driving voltage, efficiency and life. Accordingly, it was confirmed that the pyrazole-containing polycyclic derivative represented by Chemical Formula 1 of the present invention is useful as a material of the phosphorescent light emitting layer in fabricating an organic light emitting device.
[부호의 설명][Description of the code]
100: 기판100: substrate
200: 양극200: anode
300: 유기물층300: organic material layer
301: 정공주입층301: hole injection layer
302: 정공수송층302: hole transport layer
303: 발광층303: light emitting layer
304: 전자수송층304: electron transport layer
305: 전자주입층305: electron injection layer
400: 음극400: cathode

Claims (17)

  1. 하기 화학식 1의 화합물:A compound of formula
    [화학식 1][Formula 1]
    Figure PCTKR2013012050-appb-I000074
    Figure PCTKR2013012050-appb-I000074
    상기 화학식 1에 있어서, In Chemical Formula 1,
    R1 내지 R8은 서로 같거나 상이하고, 각각 독립적으로 수소; 할로겐; C1 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알킬; C2 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알케닐; C2 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알키닐; C1 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 알콕시; C6 내지 C60의 직쇄 또는 분지쇄의 치환 또는 비치환된 아릴옥시; C3 내지 C60의 단환 또는 다환의 치환 또는 비치환된 시클로알킬; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로시클로알킬; C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴; 치환 또는 비치환된 C10 내지 C60의 스피로기; C1 내지 C20의 치환 또는 비치환된 알킬아민; C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴아민; 및 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴아민으로 이루어진 군으로부터 선택되거나, R1 내지 R8 중 인접하는 적어도 2개의 치환기는 서로 결합하여 방향족 탄화수소계 고리 또는 헤테로고리를 형성한다. R 1 to R 8 are the same as or different from each other, and each independently hydrogen; halogen; C 1 to C 60 straight or branched chain substituted or unsubstituted alkyl; C 2 Through C 60 A straight or branched chain substituted or unsubstituted alkenyl; C 2 to C 60 straight or branched substituted or unsubstituted alkynyl; C 1 to C 60 straight or branched chain substituted or unsubstituted alkoxy; C 6 to C 60 straight or branched chain substituted or unsubstituted aryloxy; C 3 to C 60 of monocyclic or polycyclic substituted or unsubstituted cycloalkyl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heterocycloalkyl; C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Substituted or unsubstituted C 10 Through C 60 Spiro group; C 1 to C 20 substituted or unsubstituted alkylamines; C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted arylamine; And C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroarylamine, or at least two adjacent substituents of R 1 to R 8 are bonded to each other to form an aromatic hydrocarbon ring or heterocyclic ring. Form.
  2. 청구항 1에 있어서, R1 내지 R4 중 적어도 하나는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴; 또는 치환 또는 비치환된 C10 내지 C60의 스피로기인 것인 화합물.The compound of claim 1, wherein at least one of R 1 to R 4 is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Or a substituted or unsubstituted C 10 to C 60 spiro group.
  3. 청구항 1에 있어서, R1 내지 R4 중 적어도 하나는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴; 또는 치환 또는 비치환된 C10 내지 C60의 스피로기이고, R1 내지 R4 중 나머지는 수소이거나, 인접한 치환기와 결합하여 방향족 탄화수소계 고리 또는 헤테로고리를 형성하는 것인 화합물. The compound of claim 1, wherein at least one of R 1 to R 4 is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; C 2 Through C 60 Monocyclic or polycyclic substituted or unsubstituted heteroaryl; Or a substituted or unsubstituted C 10 to C 60 spiro group, and the remainder of R 1 to R 4 is hydrogen, or combines with an adjacent substituent to form an aromatic hydrocarbon ring or heterocycle.
  4. 청구항 1에 있어서, R1과 R2; R2과 R3; 또는 R3과 R4은 서로 결합하여 치환 또는 비치환된 벤젠 고리를 형성하는 것인 화합물.The compound according to claim 1, wherein R 1 and R 2 ; R 2 and R 3 ; Or R 3 and R 4 combine with each other to form a substituted or unsubstituted benzene ring.
  5. 청구항 1에 있어서, R2는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이고, R1, R3 및 R4는 수소이거나, R1는 수소이고, R3 및 R4는 서로 결합하여 치환 또는 비치환된 벤젠 고리를 형성하는 것인 화합물.The compound of claim 1, wherein R 2 is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, R 1 , R 3 and R 4 are hydrogen, R 1 is hydrogen, and R 3 and R 4 are bonded to each other to form a substituted or unsubstituted To form a ringed benzene ring.
  6. 청구항 1에 있어서, R4는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이고, R1 내지 R3는 수소이거나, R3는 수소이고, R1 및 R2는 서로 결합하여 치환 또는 비치환된 벤젠 고리를 형성하는 것인 화합물. The compound according to claim 1, R 4 is C 6 Through C 60 Monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, R 1 to R 3 are hydrogen, R 3 is hydrogen, and R 1 and R 2 are bonded to each other to form a substituted or unsubstituted benzene. To form a ring.
  7. 청구항 1에 있어서, R1은 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이고, R2 내지 R4는 수소이거나, R2는 수소이고, R3 및 R4는 서로 결합하여 치환 또는 비치환된 벤젠 고리를 형성하는 것인 화합물. The compound of claim 1, wherein R 1 is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, R 2 to R 4 are hydrogen, R 2 is hydrogen, R 3 and R 4 are combined with each other to form a substituted or unsubstituted benzene To form a ring.
  8. 청구항 1에 있어서, 상기 화학식 1은 하기 화학식 5 내지 8 중에서 선택되는 것인 화합물:The compound of claim 1, wherein Formula 1 is selected from Formulas 5 to 8:
    [화학식 5][Formula 5]
    Figure PCTKR2013012050-appb-I000075
    Figure PCTKR2013012050-appb-I000075
    [화학식 6][Formula 6]
    Figure PCTKR2013012050-appb-I000076
    Figure PCTKR2013012050-appb-I000076
    [화학식 7][Formula 7]
    Figure PCTKR2013012050-appb-I000077
    Figure PCTKR2013012050-appb-I000077
    [화학식 8][Formula 8]
    Figure PCTKR2013012050-appb-I000078
    Figure PCTKR2013012050-appb-I000078
    상기 화학식에 있어서, R5 내지 R8은 화학식 1에서 정의한 바와 같고, In the above formula, R 5 to R 8 are the same as defined in Formula 1,
    R은 R1 내지 R4의 정의와 같으며, R is as defined in R 1 to R 4 ,
    n은 1 내지 3의 정수이고, v는 1 내지 5의 정수이며, n 또는 v가 2 이상인 경우에는 R은 서로 같거나 상이하고,n is an integer of 1 to 3, v is an integer of 1 to 5, when n or v is 2 or more, R is the same or different from each other,
    L은 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴렌; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴렌이고, p 및 x는 각각 0 내지 3의 정수이며, p 또는 x가 2 이상인 경우에는 L은 서로 같거나 상이하고,L is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted arylene; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroarylene, p and x are each an integer of 0 to 3, when p or x is 2 or more, L is the same as or different from each other,
    Ar은 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴이고, q 및 y는 각각 0 내지 3의 정수이며, q 또는 y가 2 이상인 경우에는 Ar은 서로 같거나 상이하다.Ar is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aryl; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroaryl, q and y are each an integer of 0 to 3, and when q or y is 2 or more, Ar is the same as or different from each other.
  9. 청구항 8에 있어서, L은 치환 또는 비치환된 피리딘기, 치환 또는 비치환된 피리미딘기, 치환 또는 비치환된 트리아진기, 치환 또는 비치환된 안트라센기, 치환 또는 비치환된 페난트렌기, 치환 또는 비치환된 나프탈렌기, 또는 치환 또는 비치환된 페닐렌기인 것인 화합물. The substituted or unsubstituted pyridine group, substituted or unsubstituted pyrimidine group, substituted or unsubstituted triazine group, substituted or unsubstituted anthracene group, substituted or unsubstituted phenanthrene group, substituted Or an unsubstituted naphthalene group, or a substituted or unsubstituted phenylene group.
  10. 청구항 8에 있어서, Ar은 치환 또는 비치환된 피리딜, 치환 또는 비치환된 피리미딜, 치환 또는 비치환된 트리아지닐, 치환 또는 비치환된 안트릴, 치환 또는 비치환된 페난트릴, 치환 또는 비치환된 나프틸, 또는 치환 또는 비치환된 페닐기인 것인 화합물. The compound of claim 8, wherein Ar is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted It is a substituted naphthyl, or a substituted or unsubstituted phenyl group.
  11. 청구항 1에 있어서, 상기 화학식 1의 화합물은 하기 화학식 9 내지 13 중 어느 하나로 표시되는 것인 화합물:The compound of claim 1, wherein the compound of Formula 1 is represented by any one of Formulas 9 to 13:
    [화학식 9][Formula 9]
    Figure PCTKR2013012050-appb-I000079
    Figure PCTKR2013012050-appb-I000079
    [화학식 10][Formula 10]
    Figure PCTKR2013012050-appb-I000080
    Figure PCTKR2013012050-appb-I000080
    [화학식 11] [Formula 11]
    Figure PCTKR2013012050-appb-I000081
    Figure PCTKR2013012050-appb-I000081
    [화학식 12][Formula 12]
    Figure PCTKR2013012050-appb-I000082
    Figure PCTKR2013012050-appb-I000082
    [화학식 13][Formula 13]
    Figure PCTKR2013012050-appb-I000083
    Figure PCTKR2013012050-appb-I000083
    상기 화학식에 있어서, R5 내지 R8은 화학식 1에서 정의한 바와 같고, In the above formula, R 5 to R 8 are the same as defined in Formula 1,
    X1 내지 X3은 서로 같거나 상이하고, 각각 독립적으로 N 또는 CY6이고, X1 내지 X3 중 적어도 하나는 N이며,X 1 to X 3 are the same as or different from each other, each independently N or CY 6 , at least one of X 1 to X 3 is N,
    R, 및 Y1 내지 Y6은 서로 같거나 상이하고, 각각 독립적으로 R1 내지 R4의 정의와 같으며, R 중 인접하는 적어도 2개의 치환기, 또는 Y1 내지 Y6 중 인접하는 적어도 2개의 치환기는 서로 결합하여 방향족 탄화수소계 고리 또는 헤테로고리를 형성할 수 있고, n은 1 내지 3의 정수이고, n이 2 이상인 경우에는 R은 서로 같거나 상이하며, r은 1 내지 5의 정수이고, r이 2 이상인 경우 Y3는 서로 같거나 상이하며, s는 1 내지 7의 정수이고, s가 2 이상인 경우 Y4는 서로 같거나 상이하며, t는 1 내지 9의 정수이고, t가 2 이상인 경우 Y5는 서로 같거나 상이하며,R, and Y 1 to Y 6 are the same as or different from each other, and each independently, as defined by R 1 to R 4 , at least two adjacent substituents in R, or at least two adjacent ones of Y 1 to Y 6 The substituents may be bonded to each other to form an aromatic hydrocarbon ring or heterocycle, n is an integer of 1 to 3, when n is 2 or more, R is the same as or different from each other, r is an integer of 1 to 5, when r is 2 or more, Y 3 is the same as or different from each other, s is an integer of 1 to 7, and when s is 2 or more, Y 4 is the same or different from each other, t is an integer of 1 to 9, and t is 2 or more Y 5 is the same as or different from each other,
    L은 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 아릴렌; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 헤테로아릴렌이고, p는 0 내지 3의 정수이며, p가 2 이상인 경우에는 L은 서로 같거나 상이하고,L is C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted arylene; Or C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted heteroarylene, p is an integer of 0 to 3, when p is 2 or more, L is the same as or different from each other,
    Z1 및 Z2는 C6 내지 C60의 단환 또는 다환의 치환 또는 비치환된 방향족 탄화수소 고리; 또는 C2 내지 C60의 단환 또는 다환의 치환 또는 비치환된 방향족 헤테로 고리이다.Z1 and Z2 are C 6 to C 60 monocyclic or polycyclic substituted or unsubstituted aromatic hydrocarbon ring; Or a C 2 to C 60 monocyclic or polycyclic substituted or unsubstituted aromatic hetero ring.
  12. [규칙 제91조에 의한 정정 23.01.2014]
    청구항 1에 있어서, 상기 화학식 1의 화합물은 하기 화학식들로부터 선택되는 것인 화합물:
    Figure WO-DOC-FIGURE-12-1
    Figure WO-DOC-FIGURE-12-2
    Figure WO-DOC-FIGURE-3
    Figure WO-DOC-FIGURE-4
    Figure WO-DOC-FIGURE-5
    Figure WO-DOC-FIGURE-6
    Figure WO-DOC-FIGURE-7
    Figure WO-DOC-FIGURE-8
    Figure WO-DOC-FIGURE-9
    Figure WO-DOC-FIGURE-10
    Figure WO-DOC-FIGURE-11
    Figure WO-DOC-FIGURE-12
    Figure WO-DOC-FIGURE-13
    Figure WO-DOC-FIGURE-14
    Figure WO-DOC-FIGURE-15
    Figure PCTKR2013012050-appb-I000099
    Figure PCTKR2013012050-appb-I000100
    Figure PCTKR2013012050-appb-I000101
    Figure PCTKR2013012050-appb-I000102
    Figure PCTKR2013012050-appb-I000103
    Figure PCTKR2013012050-appb-I000104
    [Revision 23.01.2014 under Rule 91]
    The compound of claim 1, wherein the compound of Formula 1 is selected from the following formulas:
    Figure WO-DOC-FIGURE-12-1
    Figure WO-DOC-FIGURE-12-2
    Figure WO-DOC-FIGURE-3
    Figure WO-DOC-FIGURE-4
    Figure WO-DOC-FIGURE-5
    Figure WO-DOC-FIGURE-6
    Figure WO-DOC-FIGURE-7
    Figure WO-DOC-FIGURE-8
    Figure WO-DOC-FIGURE-9
    Figure WO-DOC-FIGURE-10
    Figure WO-DOC-FIGURE-11
    Figure WO-DOC-FIGURE-12
    Figure WO-DOC-FIGURE-13
    Figure WO-DOC-FIGURE-14
    Figure WO-DOC-FIGURE-15
    Figure PCTKR2013012050-appb-I000099
    Figure PCTKR2013012050-appb-I000100
    Figure PCTKR2013012050-appb-I000101
    Figure PCTKR2013012050-appb-I000102
    Figure PCTKR2013012050-appb-I000103
    Figure PCTKR2013012050-appb-I000104
  13. 양극, 음극 및 상기 양극과 음극 사이에 구비된 1층 이상의 유기물층을 포함하고, 상기 유기물층 중 1층 이상이 청구항 1 내지 12 중 어느 하나의 항에 따른 화학식 1의 화합물을 포함하는 유기발광소자. An organic light emitting device comprising an anode, a cathode and at least one organic material layer provided between the anode and the cathode, at least one of the organic material layer comprises a compound of formula 1 according to any one of claims 1 to 12.
  14. 청구항 13에 있어서, 상기 화학식 1의 화합물을 포함하는 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 또는 전자주입층인 것인 유기발광소자. The organic light emitting device of claim 13, wherein the organic material layer including the compound of Formula 1 is a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, or an electron injection layer.
  15. 청구항 13에 있어서, 상기 화학식 1의 화합물을 포함하는 유기물층은 전자수송층인 것인 유기발광소자. The organic light emitting device of claim 13, wherein the organic material layer including the compound of Formula 1 is an electron transport layer.
  16. 청구항 13에 있어서, 상기 화학식 1의 화합물을 포함하는 유기물층은 발광층인 것인 유기발광소자. The organic light emitting device of claim 13, wherein the organic material layer including the compound of Formula 1 is a light emitting layer.
  17. 청구항 13에 있어서, 상기 화학식 1의 화합물은 인광 호스트 재료인 것인 유기발광소자. The organic light emitting device of claim 13, wherein the compound of Formula 1 is a phosphorescent host material.
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