WO2020218680A1 - Organic compound and organic electroluminescent diode using same - Google Patents

Organic compound and organic electroluminescent diode using same Download PDF

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WO2020218680A1
WO2020218680A1 PCT/KR2019/009280 KR2019009280W WO2020218680A1 WO 2020218680 A1 WO2020218680 A1 WO 2020218680A1 KR 2019009280 W KR2019009280 W KR 2019009280W WO 2020218680 A1 WO2020218680 A1 WO 2020218680A1
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group
mmol
formula
aryl
compound
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French (fr)
Korean (ko)
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이용환
박호철
엄민식
심재의
박정근
김영모
박우재
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두산솔루스 주식회사
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to a novel organic light-emitting compound and an organic electroluminescent device using the same, and more particularly, a compound having excellent thermal stability, electrochemical stability, and hole transport ability, and by including the same in one or more organic material layers, luminous efficiency, driving voltage, and lifetime It relates to an organic electroluminescent device having improved properties such as.
  • organic electroluminescent device In an organic electroluminescent device (hereinafter, referred to as “organic EL device”), when a voltage is applied between two electrodes, holes are injected into the organic material layer from the anode, and electrons are injected into the organic material layer from the cathode. When injected holes and electrons meet, excitons are formed, and when these excitons fall to the ground state, light is emitted.
  • the material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like according to their function.
  • the light-emitting materials of the organic EL device may be classified into blue, green, and red light-emitting materials, and yellow and orange light-emitting materials for realizing better natural colors according to light emission colors.
  • a host/dopant system may be used as a light emitting material.
  • the dopant material can be classified into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt.
  • a metal complex compound containing heavy atoms such as Ir and Pt.
  • NPB hole blocking layer
  • BCP hole blocking layer
  • Alq 3 materials for the hole blocking layer and the electron transport layer
  • anthracene derivatives have been reported as materials for the light emitting layer.
  • metal complex compounds containing Ir such as Firpic, Ir(ppy) 3 and (acac)Ir(btp) 2 , which have advantages in terms of efficiency improvement, among the light emitting layer materials are blue, green, and red. (red) is used as a phosphorescent dopant material, and 4,4-dicarbazolybiphenyl (CBP) is used as a phosphorescent host material.
  • Ir such as Firpic, Ir(ppy) 3 and (acac)Ir(btp) 2
  • red is used as a phosphorescent dopant material
  • CBP 4,4-dicarbazolybiphenyl
  • An object of the present invention is to provide a novel organic compound that can be applied to an organic electroluminescent device and is excellent in thermal stability, electrochemical stability, and hole transport capability, and thus can be used as a material for a hole transport layer.
  • another object of the present invention is to provide an organic electroluminescent device including the novel organic compound, exhibiting a low driving voltage and high luminous efficiency, and improving lifespan.
  • X is O or S
  • a, b, c, and d are each an integer of 0 to 3
  • L 1 , L 2 , L 3 and L 4 are the same as or different from each other, and each independently a single bond, or is selected from the group consisting of an arylene group of C 6 to C 60 and a heteroarylene group having 5 to 60 nuclear atoms ,
  • Ar 1 to Ar 6 are the same as or different from each other, and are each independently selected from the group consisting of an aryl group of C 6 to C 60 and a heteroaryl group having 5 to 60 nuclear atoms,
  • e and f are each an integer of 0 to 4,
  • R 1 and R 2 are the same as or different from each other, and each independently hydrogen, deuterium, halogen group, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 to C 40 cycloalkyl group, 3 to 40 nuclear atom heterocycloalkyl group, C 6 to C 60 aryl group, 5 to 60 nuclear atom heteroaryl group, C 1 to C 40 alkyloxy group, C 6 ⁇ C 60 aryloxy group, C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ C Selected from the group consisting of an aryl boron group of 60 , an arylphosphine group of C 6 to C 60 , and an aryl phosphine oxide group of C 6 to C 60 , or con
  • the present invention is a positive electrode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers comprises a compound represented by Formula 1 do.
  • the compound of the present invention has excellent thermal stability, electrochemical stability, and hole transport ability, it can be usefully applied as an organic material layer material of an organic electroluminescent device.
  • the organic electroluminescent device including the compound of the present invention in the organic material layer can be effectively applied to a full-color display panel or the like because the light emitting performance, driving voltage, lifespan, and efficiency are greatly improved.
  • FIG. 1 is a schematic cross-sectional view of an organic electroluminescent device according to an exemplary embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of an organic electroluminescent device according to another example of the present invention.
  • 300 organic material layer
  • 310 hole injection layer
  • the present invention provides a novel organic compound that is excellent in electrochemical stability, thermal stability, and carrier transport capability (especially, hole transport capability) and can be used as a material for a high-efficiency hole transport layer.
  • the compound represented by Formula 1 according to the present invention is either a spiro [fluorene-xanthene] moiety or a spyro [fluorene-thioxathene] moiety It includes a core structure formed by introducing a substituent of an amine group-linker group-amine group structure directly or through a linker at the benzene site of
  • the compound of Formula 1 includes a spiro[fluorene-xanthene] moiety or a spiro[fluorene-thioxanthene] moiety, and thus has high hole mobility and excellent hole transporting ability. This is between the HOMO and LUMO energy levels of the hole injection layer and the emission layer, and hole injection and transfer are smooth. Accordingly, when the compound of the present invention is used as a material for the hole transport layer and the organic electroluminescent device is included, not only the luminous efficiency of the organic electroluminescent device is improved, but the driving voltage is lowered to increase the lifespan.
  • the compound of Formula 1 has an amine group-linker group-amine group structure substituent introduced at any one of the benzene moieties in the above-described moiety, due to physicochemical properties such as amorphous properties and high refractive index properties. The luminous efficiency can be further improved.
  • the compound of Formula 1 since the compound of Formula 1 has a high glass transition temperature (Tg), it is not only excellent in stability, but also excellent in electrochemical stability.
  • the compound represented by Formula 1 according to the present invention has excellent thermal stability, electrochemical stability, and hole transport properties. Accordingly, the compound represented by Formula 1 of the present invention may be used as an organic material layer material of an organic electroluminescent device, preferably a hole transport layer material or a hole transport auxiliary layer material, more preferably a hole transport layer material.
  • the performance and lifetime characteristics of the organic electroluminescent device including the compound of the present invention can be greatly improved, and the performance of a full-color organic light-emitting panel to which such an organic electroluminescent device is applied can also be maximized.
  • X is O or S.
  • the compound of Formula 1 has excellent amphoteric properties of electrons and holes, and thus has excellent carrier transport capability. Therefore, when the compound of Formula 1 according to the present invention is used as a material for a hole transport layer, an effect of improving efficiency and driving voltage may be improved by improving hole transport capability.
  • the compound represented by Formula 1 is a compound represented by Formula 2 or 3 below.
  • X, L 1 to L 4 , Ar 1 to Ar 6 , R 1 , R 2 , a, b, c, d, e and f are the same as defined in Formula 1, respectively.
  • These compounds of Formulas 2 and 3 are Moiety or It may be a compound represented by any one of the following Formulas 4 to 10 depending on the position of the moiety introduced (bonded).
  • X, L 1 to L 4 , Ar 1 to Ar 6 , R 1 , R 2 , a, b, c, d, e and f are the same as defined in Formula 1, respectively.
  • a, b, c, and d are each an integer of 0 to 3, preferably 0 or 1.
  • each of L 1 to L 4 is a divalent linker, the same or different from each other, and each independently C 6 to C It is selected from the group consisting of an arylene group of 60 and a heteroarylene group having 5 to 60 nuclear atoms, and specifically selected from the group consisting of an arylene group of C 6 to C 30 and a heteroarylene group having 5 to 30 nuclear atoms have.
  • b and d are each an integer of 1 to 3
  • L 2 and L 4 are the same as or different from each other, and each independently an arylene group of C 6 to C 60 and the number of nuclear atoms from 5 to It may be selected from the group consisting of 60 heteroarylene groups.
  • L 1 and L 3 are the same as or different from each other, and each independently may be a single bond, or may be selected from the group consisting of an arylene group of C 6 to C 60 and a heteroarylene group having 5 to 60 nuclear atoms.
  • L 1 , L 2 , L 3 and L 4 are the same as or different from each other, and each independently may be a single bond or may be selected from the group consisting of the linker groups Link1 to Link7 below, but is not limited thereto.
  • Y 1 is selected from the group consisting of O, S, C(R 4 )(R 5 ), and Si(R 6 )(R 7 ),
  • g, h, i, j, k, l are each an integer of 0 to 4
  • m is an integer of 0 to 6
  • n is an integer of 0 to 8
  • o is an integer of 0 to 6
  • p is 0
  • q and r are each an integer of 0 to 3
  • At least one R 3 is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alky Nyl group, C 3 to C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyl jade of C 1 to C 40 Group, C 6 ⁇ C 60 aryloxy group, C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ C 60 aryl boron group, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ C 60 aryl phosphine oxide group, and a C 6 ⁇ , or selected from the group consisting of an
  • R 4 to R 7 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 Alkynyl group, C 3 to C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyl of C 1 to C 40 Oxy group, C 6 ⁇ C 60 aryloxy group, C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ C 60 aryl boron group, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ C 60 aryl phosphine oxide group, and a C 6 ⁇ selected from the group consisting of C 60
  • the condensed ring may be a C 6 ⁇ C 20 condensed aromatic ring, or a 5 to 20 membered condensed heteroaromatic ring, and the heterocycloalkyl group, heteroaryl group and condensed heteroaromatic ring are each N, S , O and Se may contain at least one hetero atom selected from the group consisting of.
  • Ar 1 to Ar 6 are the same as or different from each other, and each independently selected from the group consisting of an aryl group of C 6 to C 60 and a heteroaryl group having 5 to 60 nuclear atoms
  • each independently C 6 ⁇ C 30 may be selected from the group consisting of an aryl group and a heteroaryl group having 5 to 30 nuclear atoms.
  • Ar 1 to Ar 6 may be the same as or different from each other, and each independently may be selected from the group consisting of substituents S1 to S13, but is not limited thereto.
  • Y 1 is selected from the group consisting of O, S, C(R 4 )(R 5 ), and Si(R 6 )(R 7 ),
  • g, i, l are each an integer of 0 to 5
  • h, j, k, p, r, s are each an integer of 0 to 4
  • m is an integer of 0 to 7
  • n is an integer of 0 to 9
  • o is an integer of 0 to 7
  • q, t, u, and v are integers of 0 to 3
  • w and x are each an integer of 0 to 2
  • At least one R 3 is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alky Nyl group, C 3 to C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyl jade of C 1 to C 40 Group, C 6 ⁇ C 60 aryloxy group, C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ C 60 aryl boron group, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ C 60 aryl phosphine oxide group, and a C 6 ⁇ , or selected from the group consisting of an
  • R 4 to R 7 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 Alkynyl group, C 3 to C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyl of C 1 to C 40 Oxy group, C 6 ⁇ C 60 aryloxy group, C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ C 60 aryl boron group, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ C 60 aryl phosphine oxide group, and a C 6 ⁇ selected from the group consisting of C 60
  • the condensed ring may be a C 6 ⁇ C 20 condensed aromatic ring, or a 5 to 20 membered condensed heteroaromatic ring, and the heterocycloalkyl group, heteroaryl group and condensed heteroaromatic ring are each N, S , O and Se may contain at least one hetero atom selected from the group consisting of.
  • e and f are each an integer of 0 to 4.
  • R 1 and 1 or more R 2 are The same or different from each other, and each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 ⁇ C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 ⁇ C 60 aryl group, 5 to 60 nuclear atoms heteroaryl group, C 1 ⁇ C 40 alkyloxy group, C 6 ⁇ C 60 aryloxy group, C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ C 60 aryl
  • the heterocycloalkyl group and the heteroaryl group each include at least one heteroatom selected from the group consisting of N, S, O and Se.
  • e and f are each 0, and R 1 and R 2 are hydrogen.
  • e and f may be 1, and R 1 and R 2 may each be a phenyl group or a biphenyl group.
  • the boron group, arylphosphine group, arylphosphine oxide group and condensed ring are each independently deuterium, halogen, cyano group, nitro group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 to C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms,
  • the heterocycloalkyl group and the heteroaryl group may each include one or more heteroatoms selected from the group consisting of N, S, O, and Se.
  • the compound represented by Formula 1 according to the present invention may be embodied as a compound represented by any one of the following Formulas 11 to 24, but is not limited thereto.
  • Each X is as defined in Formula 1;
  • R 1 and R 2 are each as defined in Formula 1, specifically the same or different from each other, and each independently may be selected from the group consisting of hydrogen, a phenyl group and a biphenyl group, and more specifically, of R 1 and R 2 One of them may be hydrogen and the rest may be a phenyl group or a biphenyl group;
  • Y 1 is selected from the group consisting of O, S, C(R 4 )(R 5 ), and Si(R 6 )(R 7 );
  • a plurality of Y 2 may be the same as or different from each other, N or CR 8 , specifically, all of the plurality of Y 2 may be CH, or one of the plurality of Y 2 may be N and the rest may be CH;
  • g is an integer of 0 to 4, specifically an integer of 0 to 2;
  • At least one R 3 and R 4 to R 8 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 to C 60 aryl group, 5 to 60 nuclear atoms heteroaryl group, C 1 ⁇ C 40 alkyloxy group, C 6 ⁇ C 60 aryloxy group, C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ C group 60 arylboronic of, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ C 60 aryl phosphine oxide group, and a C 6 ⁇ , or selected from the group consisting
  • R 3 -It can be condensed with another R 3 ) to form a condensed ring, specifically each independently hydrogen, phenyl group, naphthyl group, monovalent dibenzothiophene group, monovalent dibenzofuran group, monovalent fluorene It may be selected from the group consisting of a group, a monovalent pyridine group, a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the compound represented by Formula 1 according to the present invention described above may be further specified as Compound 1 to Compound 270, but is not limited thereto.
  • alkyl refers to a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.
  • alkenyl refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms having one or more carbon-carbon double bonds. Examples thereof include vinyl (vinyl), allyl (allyl), isopropenyl (isopropenyl), 2-butenyl (2-butenyl), and the like, but is not limited thereto.
  • alkynyl refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.
  • cycloalkyl refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms.
  • examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.
  • heterocycloalkyl refers to a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S Or a hetero atom such as Se.
  • heterocycloalkyl include morpholine and piperazine, but are not limited thereto.
  • aryl refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined.
  • a form in which two or more rings are simply attached to each other or condensed may be included. Examples of such aryl include phenyl, naphthyl, phenanthryl, and anthryl, but are not limited thereto.
  • heteroaryl refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. At this time, one or more carbons, preferably 1 to 3 carbons in the ring are substituted with heteroatoms such as N, O, S or Se.
  • heteroatoms such as N, O, S or Se.
  • a form in which two or more rings are simply attached to each other or condensed may be included, and further, a form condensed with an aryl group may be included.
  • heteroaryl examples include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl, phenoxathienyl, indolizinyl, indolyl ( indolyl), purinyl, quinolyl, benzothiazole, polycyclic rings such as carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.
  • alkyloxy is a monovalent substituent represented by R'O-, wherein R'refers to alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure It may include. Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, and the like.
  • aryloxy is a monovalent substituent represented by RO-, and R means an aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, and diphenyloxy.
  • alkylsilyl refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and includes mono- as well as di- and tri-alkylsilyl.
  • arylsilyl refers to silyl substituted with aryl having 5 to 60 carbon atoms, and includes polyarylsilyl such as di- and tri-arylsilyl as well as mono-.
  • alkyl boron group refers to a boron group substituted with an alkyl having 1 to 40 carbon atoms
  • aryl boron group refers to a boron group substituted with an aryl having 6 to 60 carbon atoms.
  • alkylphosfinyl group refers to a phosphine group substituted with an alkyl having 1 to 40 carbon atoms, and includes not only mono- but also di-alkylphosfinyl groups.
  • arylphosphinyl group refers to a phosphine group substituted with a monoaryl or diaryl having 6 to 60 carbon atoms, and includes not only mono- but also di-arylphosfinyl groups.
  • arylamine refers to an amine substituted with an aryl having 6 to 40 carbon atoms, and includes mono- as well as di-arylamine.
  • organic electroluminescent device (hereinafter, referred to as “organic EL device”) including the compound represented by Formula 1 above.
  • the organic electroluminescent device includes an anode, a cathode, and one or more organic material layers interposed between the anode and the cathode, and at least one of the one or more organic material layers is It includes a compound represented by Formula 1.
  • the compound may be used alone, or two or more may be used in combination.
  • the one or more organic material layers may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and at least one of the organic material layers includes the compound represented by Formula 1.
  • the organic material layer including the compound of Formula 1 may be a hole transport layer.
  • the one or more organic material layers may include a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, and an electron injection layer, and the hole transport layer may be a compound represented by Formula 1 above.
  • the compound represented by Formula 1 may be included in an organic electroluminescent device as a hole transport layer material.
  • the compound of Formula 1 has a high glass transition temperature, high hole mobility, high hole transport capability, and hole injection from the hole injection layer to the emission layer due to an appropriate HOMO and LUMO energy level between the hole injection layer and the emission layer. Transfer is smooth, and has amorphous crystallinity and high refractive index characteristics. Accordingly, the organic electroluminescent device including the compound of Formula 1 may improve efficiency (luminescence efficiency and power efficiency), lifespan, luminance, driving voltage, thermal stability, and the like.
  • the structure of the organic electroluminescent device of the present invention is not particularly limited, but, for example, an anode 100, one or more organic material layers 300, and a cathode 200 may be sequentially stacked on a substrate (FIGS. 1 and 2 Reference). In addition, it may have a structure in which an insulating layer or an adhesive layer is inserted at the interface between the electrode and the organic material layer.
  • the organic electroluminescent device includes an anode 100, a hole injection layer 310, a hole transport layer 320, a light emitting layer 330, an electron transport layer 340, and
  • the cathode 200 may have a sequentially stacked structure.
  • an electron injection layer 350 may be positioned between the electron transport layer 340 and the cathode 200.
  • a hole blocking layer (not shown) may be positioned between the emission layer 330 and the electron transport layer 340.
  • the organic electroluminescent device of the present invention materials and methods known in the art, except that at least one of the organic material layers 300 (eg, hole transport layer 320) includes a compound represented by Formula 1 It can be prepared by forming an organic material layer and an electrode.
  • the organic material layers 300 eg, hole transport layer 320
  • a compound represented by Formula 1 It can be prepared by forming an organic material layer and an electrode.
  • the organic material layer may be formed by a vacuum deposition method or a solution coating method.
  • the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer method.
  • the substrate usable in the present invention is not particularly limited, and non-limiting examples include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets.
  • examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb; Conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole or polyaniline; And carbon black, but are not limited thereto.
  • metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof
  • Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb
  • Conductive polymers such as polythiophene, poly
  • examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead, or alloys thereof; And a multilayered material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
  • the hole injection layer, the light emitting layer, the electron transport layer and the electron injection layer are not particularly limited, and conventional materials known in the art may be used.
  • N-phenylspiro[fluorene-9,9'-xanthen]-3-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-1 (3.86 g, yield 59%) was obtained by column chromatography.
  • N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (4.23 g, 10 mmol), 1-bromo-4-iodobenzene (2.82 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-2 (3.29 g, yield 57%) was obtained by column chromatography.
  • N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-4-amine (4.99 g, 10 mmol), 3-bromo-7-iododibenzo[b,d ]furan (3.72 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and 110 Stirred at °C for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-3 (4.09 g, yield 55%) was obtained by column chromatography.
  • the target compound N-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-1-amine (2.91) was used by column chromatography. g, yield 54%) was obtained.
  • N-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-1-amine (5.39 g, 10 mmol), 1-bromo-4-iodonaphthalene (3.32 g , 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene at 110° C. for 12 hours. Stirred. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-4 (3.94 g, yield 53%) was obtained by column chromatography.
  • the target compound N-(phenanthren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine (2.72 g, yield 52%) was prepared by column chromatography. Got it.
  • N-(phenanthren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine (5.23 g, 10 mmol), 1-bromo-8-iododibenzo[b,d]thiophene (3.89 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours I did. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-5 (4.00 g, yield 51%) was obtained by column chromatography.
  • the target compound N-([1,1':2',1''-terphenyl]-4-yl)spiro[fluorene-9,9'-xanthen] was used by column chromatography. -3'-amine (2.87 g, yield 50%) was obtained.
  • N-([1,1':2',1''-terphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3'-amine (5.75 g, 10 mmol), 5-bromo -2-iodo-9,9-dimethyl-9H-fluorene (3.99 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-6 (4.14 g, yield 49%) was obtained by column chromatography.
  • the target compound N-(4-(pyridin-3-yl)phenyl)spiro[fluorene-9,9'-xanthen]-2'-amine (2.40 g,) was used by column chromatography. Yield 48%).
  • N-(4-(pyridin-3-yl)phenyl)spiro[fluorene-9,9'-xanthen]-2'-amine (5.00 g, 10 mmol), 3-bromo-4'-iodo-1,1 '-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene. The mixture was stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-7 (3.43 g, yield 47%) was obtained by column chromatography.
  • Step 1 4-phenyl-N- (triphenylen-2-yl)spiro [ fluorene -9,9'- xanthen ]-2'-amine synthesis
  • the target compound 4-phenyl-N-(triphenylen-2-yl)spiro[fluorene-9,9'-xanthen]-2'-amine (2.98 g, yield) was performed using column chromatography. 46%).
  • the target compound N-([1,1'-biphenyl]-3-yl)-2-phenylspiro[fluorene-9,9'-xanthen]-2'- was used by column chromatography. An amine (2.53 g, yield 44%) was obtained.
  • the target compound 4-(tert-butyl)-N-(4-(spiro[fluorene-9,9'-xanthen]-3-yl)phenyl)aniline ( 2.33 g, yield 42%) was obtained.
  • the target compound N-([1,1':3',1''-terphenyl]-5'-yl)-6-phenylspiro[fluorene-9,9] was used by column chromatography. '-xanthen]-3-amine (2.67 g, yield 41%) was obtained.
  • the target compound 2-([1,1'-biphenyl]-3-yl)-7-chlorospiro[fluorene-9,9'-xanthene] (2.23 g), was used by column chromatography. , Yield 43%).
  • the target compound 2-([1,1'-biphenyl]-3-yl)-N-(5,5-dimethyl-5H-dibenzo[b,d] was used by column chromatography.
  • silol-3-yl)spiro[fluorene-9,9'-xanthen]-7-amine (3.11 g, yield 44%) was obtained.
  • the target compound was 2'-([1,1'-biphenyl]-4-yl)-7'-chlorospiro[fluorene-9,9'-xanthene] ( 2.38 g, yield 46%) was obtained.
  • the target compound 2'-([1,1'-biphenyl]-4-yl)-N-mesitylspiro[fluorene-9,9'-xanthen]-7' was used by column chromatography. -amine (2.90 g, yield 47%) was obtained.
  • the target compound 4'-chloro-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthene] was used by column chromatography. (2.73 g, yield 49%) was obtained.
  • the target compound N-(9,9'-spirobi[fluoren]-2-yl)-2-(9,9-dimethyl-9H-fluoren-2-yl) was used by column chromatography. )spiro[fluorene-9,9'-xanthen]-4'-amine (4.27 g, yield 50%) was obtained.
  • N-(9,9'-spirobi[fluoren]-2-yl)-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-4'- amine (8.54 g, 10 mmol), 1-bromo-3-iodobenzene (2.82 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-14 (4.94 g, yield 49%) was obtained by column chromatography.
  • the target compound N-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-3 was used by column chromatography. -amine (2.95 g, yield 48%) was obtained.
  • N-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-3-amine (6.15 g, 10 mmol), 1-bromo-5- Add iodonaphthalene (3.32 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) to 100 ml of Toluene and 110°C The mixture was stirred for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-15 (3.85 g, yield 47%) was obtained by column chromatography.
  • the target compound N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3-amine (2.29 g) was used by column chromatography. , Yield 46%) was obtained.
  • N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3-amine (4.99 g, 10 mmol), 4-bromo-4'-iodo-1, 1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) in 100 ml of Toluene And stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-16 (3.28 g, yield 45%) was obtained by column chromatography.
  • N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-17 (2.81 g, yield 43%) was obtained by column chromatography.
  • N-phenylspiro[fluorene-9,9'-xanthen]-4-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-18 (2.68 g, yield 41%) was obtained by column chromatography.
  • N-phenylspiro[fluorene-9,9'-xanthen]-4'-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-19 (2.68 g, yield 41%) was obtained by column chromatography.
  • N-phenylspiro[fluorene-9,9'-thioxanthen]-3'-amine (4.39 g, 10 mmol), 2-bromo-2'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-20 (2.88 g, yield 43%) was obtained by column chromatography.
  • ITO Indium tin oxide
  • a solvent such as isopropyl alcohol, acetone, methanol, etc.
  • UV OZONE cleaner Power Sonic 405, Hwashin Tech
  • m-MTDATA 60nm
  • Compound 1 80nm
  • DS-H522 + 5% DS-501 300nm
  • BCP 10nm
  • Alq 3 30nm
  • LiF (1nm) LiF
  • Al 200nm
  • the DS-H522 and DS-501 used at this time are products of Doosan Electronics Co., Ltd. BG
  • the structures of m-MTDATA and BCP are as follows.
  • Example 1 when forming the hole transport layer, a green organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compounds shown in Table 1 were respectively used instead of the compound 1 used as the hole transport layer material.
  • Example 1 when forming the hole transport layer, a green organic electroluminescent device was manufactured in the same manner as in Example 1, except that NPB was used instead of Compound 1 as a material for the hole transport layer.
  • the structure of the NPB used at this time is as follows.
  • Example 1 when forming the hole transport layer, a green organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound S-1 was used instead of Compound 1 as a material for the hole transport layer.
  • the structure of S-1 used at this time is as follows.
  • Example 1 One 4.1 25.1 Example 2 2 4.0 23.9 Example 3 3 4.2 25.2 Example 4 4 4.1 22.9 Example 5 5 3.9 24.5 Example 6 6 4.1 24.8 Example 7 7 4.2 23.5 Example 8 8 4.1 23.7 Example 9 9 4.5 22.9 Example 10 10 4.4 24.0 Example 11 11 3.8 22.8 Example 12 12 4.5 22.4 Example 13 13 3.7 25.1 Example 14 14 4.4 24.7 Example 15 15 4.1 24.1 Example 16 16 4.2 24.8 Example 17 17 4.1 20.3 Example 18 18 3.8 19.4 Example 19 19 19 3.9 21.5 Example 20 20 4.4 24.9 Comparative Example 1 NPB 5.2 18.2 Comparative Example 2 S-1 5.0 19.0
  • the organic electroluminescent devices of Examples 1 to 20 in which the compound according to the present invention is applied as a hole transport layer material are Comparative Example 1 in which NPB is applied as a hole transport layer material, and a material in which an amine group is not continuously substituted. It was confirmed that the driving voltage and current efficiency were superior to the applied organic electroluminescent device of Comparative Example 2.

Abstract

The present invention relates to a novel organic light emitting compound and an organic electroluminescent diode using same and, more specifically, to: a compound having excellent thermal stability, electrochemical stability, light emitting ability, and hole/electron transport ability; and an organic electroluminescent diode which contains the compound in one or more organic layers thereof and thereby has improved characteristics in terms of luminous efficiency, driving voltage, service life, and the like.

Description

유기 화합물 및 이를 이용한 유기 전계 발광 소자 Organic compound and organic electroluminescent device using the same
본 발명은 신규한 유기 발광 화합물 및 이를 이용한 유기 전계 발광 소자에 관한 것으로, 보다 상세하게는 열적 안정성, 전기화학적 안정성, 정공 수송능이 우수한 화합물 및 이를 하나 이상의 유기물층에 포함함으로써 발광효율, 구동 전압, 수명 등의 특성이 향상된 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel organic light-emitting compound and an organic electroluminescent device using the same, and more particularly, a compound having excellent thermal stability, electrochemical stability, and hole transport ability, and by including the same in one or more organic material layers, luminous efficiency, driving voltage, and lifetime It relates to an organic electroluminescent device having improved properties such as.
유기 전계 발광 소자(이하, '유기 EL 소자'라 함)는 두 전극 사이에 전압을 걸어주면 양극에서는 정공이 유기물층으로 주입되고, 음극에서는 전자가 유기물층으로 주입된다. 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다. 이때, 유기물층으로 사용되는 물질은 그 기능에 따라, 발광물질, 정공주입 물질, 정공수송 물질, 전자수송 물질, 전자주입 물질 등으로 분류될 수 있다.In an organic electroluminescent device (hereinafter, referred to as “organic EL device”), when a voltage is applied between two electrodes, holes are injected into the organic material layer from the anode, and electrons are injected into the organic material layer from the cathode. When injected holes and electrons meet, excitons are formed, and when these excitons fall to the ground state, light is emitted. In this case, the material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like according to their function.
유기 EL 소자의 발광 물질은 발광색에 따라 청색, 녹색, 적색 발광 물질과, 보다 나은 천연색을 구현하기 위한 노란색 및 주황색 발광 물질로 구분될 수 있다. 또한, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여, 발광 물질로서 호스트/도펀트 계를 사용할 수 있다.The light-emitting materials of the organic EL device may be classified into blue, green, and red light-emitting materials, and yellow and orange light-emitting materials for realizing better natural colors according to light emission colors. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material.
도펀트 물질은 유기 물질을 사용하는 형광 도펀트와 Ir, Pt 등의 중원자(heavy atoms)가 포함된 금속 착체 화합물을 사용하는 인광 도펀트로 나눌 수 있다. 이때, 인광 재료는 이론적으로 형광 재료에 비해 4배까지 발광 효율이 높기 때문에, 인광 도펀트 뿐만 아니라 인광 호스트 재료들에 대한 연구도 많이 진행되고 있다.The dopant material can be classified into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. At this time, since the phosphorescent material theoretically has a luminous efficiency up to four times higher than that of the fluorescent material, many studies on phosphorescent host materials as well as phosphorescent dopants are being conducted.
현재까지 정공주입층, 정공수송층. 정공 차단층, 전자수송층 재료로는 NPB, BCP, Alq3 등이 널리 알려져 있으며, 발광층 재료로는 안트라센 유도체들이 보고되고 있다. 특히, 발광층 재료 중 효율 향상 측면에서 장점을 가지고 있는 Firpic, Ir(ppy)3, (acac)Ir(btp)2 등과 같은 Ir을 포함하는 금속 착체 화합물이 청색(blue), 녹색(green), 적색(red)의 인광 도판트 재료로 사용되고 있으며, 4,4-디카바졸리비페닐(4,4-dicarbazolybiphenyl, CBP)은 인광 호스트 재료로 사용되고 있다.Until now, the hole injection layer and the hole transport layer. As materials for the hole blocking layer and the electron transport layer, NPB, BCP, and Alq 3 are widely known, and anthracene derivatives have been reported as materials for the light emitting layer. In particular, metal complex compounds containing Ir such as Firpic, Ir(ppy) 3 and (acac)Ir(btp) 2 , which have advantages in terms of efficiency improvement, among the light emitting layer materials are blue, green, and red. (red) is used as a phosphorescent dopant material, and 4,4-dicarbazolybiphenyl (CBP) is used as a phosphorescent host material.
그러나 종래의 유기물층 재료들은 발광 특성 측면에서는 유리한 면이 있으나, 유리전이온도가 낮아 열적 안정성이 매우 좋지 않기 때문에, 유기 전계 발광 소자의 수명 측면에서 만족할 만한 수준이 되지 못하고 있다. 따라서, 성능이 뛰어난 유기물층 재료의 개발이 요구되고 있다.However, conventional organic material layer materials have an advantage in terms of light emission characteristics, but their thermal stability is not very good due to a low glass transition temperature, and thus, they are not at a satisfactory level in terms of the lifespan of an organic electroluminescent device. Therefore, there is a demand for the development of an organic material layer material having excellent performance.
본 발명은 유기 전계 발광 소자에 적용할 수 있으며, 열적 안정성, 전기화학적 안정성, 정공 수송능이 우수하여 정공 수송층 재료로 사용될 수 있는 신규 유기 화합물을 제공하는 것을 목적으로 한다. An object of the present invention is to provide a novel organic compound that can be applied to an organic electroluminescent device and is excellent in thermal stability, electrochemical stability, and hole transport capability, and thus can be used as a material for a hole transport layer.
또한, 본 발명은 상기 신규 유기 화합물을 포함하여 낮은 구동 전압과 높은 발광 효율을 나타내며 수명이 향상되는 유기 전계 발광 소자를 제공하는 것을 또 다른 목적으로 한다.In addition, another object of the present invention is to provide an organic electroluminescent device including the novel organic compound, exhibiting a low driving voltage and high luminous efficiency, and improving lifespan.
상기한 목적을 달성하기 위해, 본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다:In order to achieve the above object, the present invention provides a compound represented by the following formula 1:
Figure PCTKR2019009280-appb-C000001
Figure PCTKR2019009280-appb-C000001
(상기 화학식 1에서, (In Formula 1,
X는 O 또는 S이고, X is O or S,
A1 및 A2는 각각 0 또는 1이고, 단 A1+A2=1이며,A1 and A2 are each 0 or 1, provided that A1+A2=1,
a, b, c, 및 d는 각각 0 내지 3의 정수이고, a, b, c, and d are each an integer of 0 to 3,
L1, L2, L3 및 L4는 서로 동일하거나 상이하고, 각각 독립적으로 단일결합이거나, C6 내지 C60의 아릴렌기 및 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택되고,L 1 , L 2 , L 3 and L 4 are the same as or different from each other, and each independently a single bond, or is selected from the group consisting of an arylene group of C 6 to C 60 and a heteroarylene group having 5 to 60 nuclear atoms ,
Ar1 내지 Ar6는 서로 동일하거나 상이하고, 각각 독립적으로 C6~C60의 아릴기, 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되고,Ar 1 to Ar 6 are the same as or different from each other, and are each independently selected from the group consisting of an aryl group of C 6 to C 60 and a heteroaryl group having 5 to 60 nuclear atoms,
e 및 f는 각각 0 내지 4의 정수이고, e and f are each an integer of 0 to 4,
R1 및 R2는 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, 및 C6~C60의 아릴포스핀옥사이드기로 이루어진 군에서 선택되거나, 또는 인접한 기와 축합하여 축합고리를 형성하고,R 1 and R 2 are the same as or different from each other, and each independently hydrogen, deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 to C 40 cycloalkyl group, 3 to 40 nuclear atom heterocycloalkyl group, C 6 to C 60 aryl group, 5 to 60 nuclear atom heteroaryl group, C 1 to C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C Selected from the group consisting of an aryl boron group of 60 , an arylphosphine group of C 6 to C 60 , and an aryl phosphine oxide group of C 6 to C 60 , or condensed with an adjacent group to form a condensed ring,
L1, L2, L3 및 L4의 아릴렌기 및 헤테로아릴렌기, Ar1 내지 Ar6의 아릴기 및 헤테로아릴기, 및 R1 및 R2의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 축합고리는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환되거나, 또는 상기 치환기들이 서로 축합하여 축합고리를 형성할 수 있으며, 이때 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이함).Arylene and heteroarylene groups of L 1 , L 2 , L 3 and L 4 , aryl and heteroaryl groups of Ar 1 to Ar 6 , and alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups of R 1 and R 2 , Heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylborone group, arylborone group, arylphosphine group, arylphosphine oxide group and condensed ring are each independently Deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, nuclear atom number 3 To 40 heterocycloalkyl group, C 6 to C 60 aryl group, heteroaryl group of 5 to 60 nuclear atoms, C 1 to C 40 alkyloxy group, C 6 to C 60 aryloxy group, C 1 to C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 arylphosphine group, C 6 ~ to C aryl phosphine oxide 60 group and a C 6 ~ C 60 aryl amine groups the group 1 or the unsubstituted or substituted with a substituent at least one selected from the consisting of, or the substituent are fused to each other may form a fused ring, in which the When there are multiple substituents, they are the same or different from each other).
또한, 본 발명은 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, 상기 1층 이상의 유기물층 중에서 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자를 제공한다.In addition, the present invention is a positive electrode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers comprises a compound represented by Formula 1 do.
본 발명의 화합물은 열적 안정성, 전기화학적 안정성, 정공 수송능이 우수하기 때문에 유기 전계 발광 소자의 유기물층 재료로 유용하게 적용될 수 있다.Since the compound of the present invention has excellent thermal stability, electrochemical stability, and hole transport ability, it can be usefully applied as an organic material layer material of an organic electroluminescent device.
또한, 본 발명의 화합물을 유기물층에 포함하는 유기 전계 발광 소자는 발광성능, 구동전압, 수명, 효율 등의 측면이 크게 향상되어 풀 칼라 디스플레이 패널 등에 효과적으로 적용될 수 있다.In addition, the organic electroluminescent device including the compound of the present invention in the organic material layer can be effectively applied to a full-color display panel or the like because the light emitting performance, driving voltage, lifespan, and efficiency are greatly improved.
도 1은 본 발명의 일례에 따른 유기 전계 발광 소자를 개략적으로 나타낸 단면도이다.1 is a schematic cross-sectional view of an organic electroluminescent device according to an exemplary embodiment of the present invention.
도 2는 본 발명의 다른 일례에 따른 유기 전계 발광 소자를 개략적으로 나타낸 단면도이다.2 is a schematic cross-sectional view of an organic electroluminescent device according to another example of the present invention.
** 도면 부호 **** Reference number **
100: 양극, 200: 음극,100: anode, 200: cathode,
300: 유기물층, 310: 정공주입층,300: organic material layer, 310: hole injection layer,
320: 정공수송층, 330: 발광층,320: hole transport layer, 330: light emitting layer,
340: 전자수송층, 350: 전자주입층340: electron transport layer, 350: electron injection layer
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
<신규 화합물><New compound>
본 발명은 전기화학적 안정성, 열적 안정성, 캐리어 수송능(특히, 정공 수송능)이 우수하여 고효율의 정공수송층 재료로 사용될 수 있는 신규 유기 화합물을 제공한다.The present invention provides a novel organic compound that is excellent in electrochemical stability, thermal stability, and carrier transport capability (especially, hole transport capability) and can be used as a material for a high-efficiency hole transport layer.
구체적으로, 본 발명에 따른 화학식 1로 표시되는 화합물은 스파이로[플루오렌(fluorene)-크산텐(xanthene)] 모이어티 또는 스파이로[플루오렌-티옥산텐(thioxathene)] 모이어티 내 어느 하나의 벤젠 부위에, 직접 또는 링커(linker)를 통해 아민기-링커기-아민기 구조의 치환체가 도입되어 이루어진 코어 구조를 포함한다.Specifically, the compound represented by Formula 1 according to the present invention is either a spiro [fluorene-xanthene] moiety or a spyro [fluorene-thioxathene] moiety It includes a core structure formed by introducing a substituent of an amine group-linker group-amine group structure directly or through a linker at the benzene site of
상기 화학식 1의 화합물은 스파이로[플루오렌-크산텐] 모이어티 또는 스파이로[플루오렌-티옥산텐] 모이어티를 포함함으로써, 정공 이동도가 높아 정공 수송능이 우수하다. 이는 정공 주입층과 발광층의 HOMO 및 LUMO 에너지 레벨 사이로, 정공 주입 및 전달이 원활하다. 따라서, 본 발명의 화합물을 정공 수송층 물질로 유기 전계 발광 소자가 포함할 경우, 유기 전계 발광 소자의 발광 효율이 향상될 뿐만 아니라, 구동 전압이 낮아져 수명이 상승할 수 있다. The compound of Formula 1 includes a spiro[fluorene-xanthene] moiety or a spiro[fluorene-thioxanthene] moiety, and thus has high hole mobility and excellent hole transporting ability. This is between the HOMO and LUMO energy levels of the hole injection layer and the emission layer, and hole injection and transfer are smooth. Accordingly, when the compound of the present invention is used as a material for the hole transport layer and the organic electroluminescent device is included, not only the luminous efficiency of the organic electroluminescent device is improved, but the driving voltage is lowered to increase the lifespan.
또한, 상기 화학식 1의 화합물은 전술한 모이어티 내 어느 하나의 벤젠 부위에 아민기-링커기-아민기 구조의 치환체가 도입됨으로써, 무정형(amorphous) 특성 및 고굴절률 특성과 같은 물리화학적 특성으로 인해 발광 효율이 더 향상될 수 있다. 게다가, 상기 화학식 1의 화합물은 유리전이온도(Tg)가 높기 때문에, 안정성이 우수할 뿐만 아니라, 전기화학적 안정성이 우수하다. In addition, the compound of Formula 1 has an amine group-linker group-amine group structure substituent introduced at any one of the benzene moieties in the above-described moiety, due to physicochemical properties such as amorphous properties and high refractive index properties. The luminous efficiency can be further improved. In addition, since the compound of Formula 1 has a high glass transition temperature (Tg), it is not only excellent in stability, but also excellent in electrochemical stability.
전술한 바와 같이, 본 발명에 따른 화학식 1로 표시되는 화합물은 열적 안정성, 전기화학적 안정성, 정공 수송성이 우수하다. 따라서, 본 발명의 화학식 1로 표시되는 화합물은 유기 전계 발광 소자의 유기물층 재료, 바람직하게는 정공수송층 재료 또는 정공수송 보조층 재료, 더 바람직하게 정공수송층 재료로 사용될 수 있다. 이러한 본 발명의 화합물을 포함하는 유기 전계 발광소자는 성능 및 수명 특성이 크게 향상될 수 있고, 이러한 유기 전계 발광 소자가 적용된 풀 칼라 유기 발광 패널도 성능이 극대화될 수 있다.As described above, the compound represented by Formula 1 according to the present invention has excellent thermal stability, electrochemical stability, and hole transport properties. Accordingly, the compound represented by Formula 1 of the present invention may be used as an organic material layer material of an organic electroluminescent device, preferably a hole transport layer material or a hole transport auxiliary layer material, more preferably a hole transport layer material. The performance and lifetime characteristics of the organic electroluminescent device including the compound of the present invention can be greatly improved, and the performance of a full-color organic light-emitting panel to which such an organic electroluminescent device is applied can also be maximized.
상기 화학식 1로 표시되는 화합물에서, X는 O 또는 S이다. 이러한 화학식 1의 화합물은 X가 N 또는 C인 경우에 비해, 전자 및 정공의 양쪽성 성질이 우수하여 캐리어(carrier) 수송 능력이 우수하다. 따라서, 본 발명에 따른 화학식 1의 화합물을 정공수송층 재료로 사용할 경우, 정공 수송 능력 향상으로 효율 및 구동 전압 개선 효과가 향상될 수 있다.In the compound represented by Formula 1, X is O or S. Compared to the case where X is N or C, the compound of Formula 1 has excellent amphoteric properties of electrons and holes, and thus has excellent carrier transport capability. Therefore, when the compound of Formula 1 according to the present invention is used as a material for a hole transport layer, an effect of improving efficiency and driving voltage may be improved by improving hole transport capability.
또, 상기 화학식 1로 표시되는 화합물에서, A1 및 A2는 각각 0 또는 1이고, 다만 A1+A2=1이다. 따라서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2 또는 3으로 표시되는 화합물이다.Further, in the compound represented by Chemical Formula 1, A1 and A2 are each 0 or 1, but A1+A2=1. Therefore, the compound represented by Formula 1 is a compound represented by Formula 2 or 3 below.
Figure PCTKR2019009280-appb-C000002
Figure PCTKR2019009280-appb-C000002
Figure PCTKR2019009280-appb-C000003
Figure PCTKR2019009280-appb-C000003
상기 화학식 2 및 3에서,In Formulas 2 and 3,
X, L1 내지 L4, Ar1 내지 Ar6, R1, R2, a, b, c, d, e 및 f는 각각 상기 화학식 1에서 정의한 같다.X, L 1 to L 4 , Ar 1 to Ar 6 , R 1 , R 2 , a, b, c, d, e and f are the same as defined in Formula 1, respectively.
이러한 화학식 2 및 3의 화합물은
Figure PCTKR2019009280-appb-I000001
모이어티 또는
Figure PCTKR2019009280-appb-I000002
모이어티의 도입(결합) 위치에 따라 하기 화학식 4 내지 10 중 어느 하나로 표시되는 화합물일 수 있다.These compounds of Formulas 2 and 3 are
Figure PCTKR2019009280-appb-I000001
Moiety or
Figure PCTKR2019009280-appb-I000002
It may be a compound represented by any one of the following Formulas 4 to 10 depending on the position of the moiety introduced (bonded).
Figure PCTKR2019009280-appb-C000004
Figure PCTKR2019009280-appb-C000004
Figure PCTKR2019009280-appb-C000005
Figure PCTKR2019009280-appb-C000005
Figure PCTKR2019009280-appb-C000006
Figure PCTKR2019009280-appb-C000006
Figure PCTKR2019009280-appb-C000007
Figure PCTKR2019009280-appb-C000007
Figure PCTKR2019009280-appb-C000008
Figure PCTKR2019009280-appb-C000008
Figure PCTKR2019009280-appb-C000009
Figure PCTKR2019009280-appb-C000009
Figure PCTKR2019009280-appb-C000010
Figure PCTKR2019009280-appb-C000010
상기 화학식 4 내지 10에서,In Formulas 4 to 10,
X, L1 내지 L4, Ar1 내지 Ar6, R1, R2, a, b, c, d, e 및 f는 각각 상기 화학식 1에서 정의한 바와 같다.X, L 1 to L 4 , Ar 1 to Ar 6 , R 1 , R 2 , a, b, c, d, e and f are the same as defined in Formula 1, respectively.
또, 상기 화학식 1로 표시되는 화합물에서, a, b, c 및 d는 각각 0 내지 3의 정수이고, 바람직하게 0 또는 1이다.Further, in the compound represented by Formula 1, a, b, c, and d are each an integer of 0 to 3, preferably 0 or 1.
여기서, a, b, c 및 d가 각각 0인 경우, L1 내지 L4가 각각 단일결합인 경우를 의미한다. 한편, a, b, c 및 d가 각각 1 내지 3의 정수인 경우, L1 내지 L4가 각각 2가(divalent)의 연결기(linker)로서, 서로 동일하거나 상이하고, 각각 독립적으로 C6 내지 C60의 아릴렌기 및 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택되고, 구체적으로 C6 내지 C30의 아릴렌기 및 핵원자수 5 내지 30의 헤테로아릴렌기로 이루어진 군에서 선택될 수 있다. Here, when a, b, c, and d are each 0, it means that L 1 to L 4 are each a single bond. On the other hand, when a, b, c and d are each an integer of 1 to 3, each of L 1 to L 4 is a divalent linker, the same or different from each other, and each independently C 6 to C It is selected from the group consisting of an arylene group of 60 and a heteroarylene group having 5 to 60 nuclear atoms, and specifically selected from the group consisting of an arylene group of C 6 to C 30 and a heteroarylene group having 5 to 30 nuclear atoms have.
일례에 따르면, 상기 화학식 1에서, b 및 d는 각각 1 내지 3의 정수이고, L2 및 L4는 서로 동일하거나 상이하고, 각각 독립적으로 C6 내지 C60의 아릴렌기 및 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택될 수 있다. 이때, L1 및 L3은 서로 동일하거나 상이하고, 각각 독립적으로 단일결합이거나, 또는 C6 내지 C60의 아릴렌기 및 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택될 수 있다.According to an example, in Formula 1, b and d are each an integer of 1 to 3, L 2 and L 4 are the same as or different from each other, and each independently an arylene group of C 6 to C 60 and the number of nuclear atoms from 5 to It may be selected from the group consisting of 60 heteroarylene groups. At this time, L 1 and L 3 are the same as or different from each other, and each independently may be a single bond, or may be selected from the group consisting of an arylene group of C 6 to C 60 and a heteroarylene group having 5 to 60 nuclear atoms.
구체적으로, L1, L2, L3 및 L4는 서로 동일하거나 상이하고, 각각 독립적으로 단일결합이거나, 또는 하기 링커기 Link1 내지 Link7로 이루어진 군에서 선택된 것일 수 있는데, 이에 한정되지 않는다.Specifically, L 1 , L 2 , L 3 and L 4 are the same as or different from each other, and each independently may be a single bond or may be selected from the group consisting of the linker groups Link1 to Link7 below, but is not limited thereto.
Figure PCTKR2019009280-appb-I000003
Figure PCTKR2019009280-appb-I000003
상기 Link1 내지 Link7에서,In the Link1 to Link7,
Y1은 O, S, C(R4)(R5), 및 Si(R6)(R7)로 이루어진 군에서 선택되며,Y 1 is selected from the group consisting of O, S, C(R 4 )(R 5 ), and Si(R 6 )(R 7 ),
g, h, i, j, k, l는 각각 0 내지 4의 정수이고, m은 0 내지 6의 정수이고, n은 0 내지 8의 정수이며, o는 0 내지 6의 정수이고, p는 0 내지 4의 정수이며, q 및 r은 각각 0 내지 3의 정수이고, g, h, i, j, k, l are each an integer of 0 to 4, m is an integer of 0 to 6, n is an integer of 0 to 8, o is an integer of 0 to 6, p is 0 Is an integer of 4, q and r are each an integer of 0 to 3,
하나 이상의 R3은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 또는 인접한 기(예, 다른 R3)와 축합하여 축합 고리를 형성할 수 있고,At least one R 3 is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alky Nyl group, C 3 to C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyl jade of C 1 to C 40 Group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60 of, or adjacent groups (e.g., other R 3) and Condensation to form a condensed ring,
R4 내지 R7은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 또는 인접한 기들(예, R4-R5, R6-R7 등)이 서로 축합하여 축합 고리를 형성할 수 있다. 여기서, 축합 고리는 C6~C20의 축합 방향족 고리이거나, 또는 5원~20원의 축합 헤테로방향족고리일 수 있고, 또 상기 헤테로시클로알킬기, 헤테로아릴기 및 축합 헤테로방향족고리는 각각 N, S, O 및 Se로 이루어진 군에서 선택된 1개 이상의 헤테로 원자를 포함할 수 있다. R 4 to R 7 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 Alkynyl group, C 3 to C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyl of C 1 to C 40 Oxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ selected from the group consisting of C 60 aryl amine, or of, or adjacent groups (e.g., R 4 -R 5 , R 6 -R 7, etc.) may condense with each other to form a condensed ring. Here, the condensed ring may be a C 6 ~ C 20 condensed aromatic ring, or a 5 to 20 membered condensed heteroaromatic ring, and the heterocycloalkyl group, heteroaryl group and condensed heteroaromatic ring are each N, S , O and Se may contain at least one hetero atom selected from the group consisting of.
또, 상기 화학식 1로 표시되는 화합물에서, Ar1 내지 Ar6는 서로 동일하거나 상이하고, 각각 독립적으로 C6~C60의 아릴기, 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되고, 구체적으로 각각 독립적으로 C6~C30의 아릴기, 및 핵원자수 5 내지 30개의 헤테로아릴기로 이루어진 군에서 선택될 수 있다. 예들 들어, Ar1 내지 Ar6는 서로 동일하거나 상이하고, 각각 독립적으로 치환체 S1 내지 S13으로 이루어진 군에서 선택된 것일 수 있는데, 이에 한정되지 않는다.In addition, in the compound represented by Formula 1, Ar 1 to Ar 6 are the same as or different from each other, and each independently selected from the group consisting of an aryl group of C 6 to C 60 and a heteroaryl group having 5 to 60 nuclear atoms And, specifically, each independently C 6 ~ C 30 may be selected from the group consisting of an aryl group and a heteroaryl group having 5 to 30 nuclear atoms. For example, Ar 1 to Ar 6 may be the same as or different from each other, and each independently may be selected from the group consisting of substituents S1 to S13, but is not limited thereto.
Figure PCTKR2019009280-appb-I000004
Figure PCTKR2019009280-appb-I000004
상기 S1 내지 S13에서,In the above S1 to S13,
Y1은 O, S, C(R4)(R5), 및 Si(R6)(R7)로 이루어진 군에서 선택되며,Y 1 is selected from the group consisting of O, S, C(R 4 )(R 5 ), and Si(R 6 )(R 7 ),
g, i, l는 각각 0 내지 5의 정수이고, h, j, k, p, r, s는 각각 0 내지 4의 정수이고, m은 0 내지 7의 정수이고, n은 0 내지 9의 정수이며, o는 0 내지 7의 정수이고, q, t, u, v는 0 내지 3의 정수이며, w 및 x는 각각 0 내지 2의 정수이고,g, i, l are each an integer of 0 to 5, h, j, k, p, r, s are each an integer of 0 to 4, m is an integer of 0 to 7, n is an integer of 0 to 9 And o is an integer of 0 to 7, q, t, u, and v are integers of 0 to 3, w and x are each an integer of 0 to 2,
하나 이상의 R3은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 또는 인접한 기(예, 다른 R3)와 축합하여 축합 고리를 형성할 수 있고,At least one R 3 is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alky Nyl group, C 3 to C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyl jade of C 1 to C 40 Group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60 of, or adjacent groups (e.g., other R 3) and Condensation to form a condensed ring,
R4 내지 R7은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 또는 인접한 기들(예, R4-R5, R6-R7 등)이 서로 축합하여 축합 고리를 형성할 수 있다. 여기서, 축합 고리는 C6~C20의 축합 방향족 고리이거나, 또는 5원~20원의 축합 헤테로방향족고리일 수 있고, 또 상기 헤테로시클로알킬기, 헤테로아릴기 및 축합 헤테로방향족고리는 각각 N, S, O 및 Se로 이루어진 군에서 선택된 1개 이상의 헤테로 원자를 포함할 수 있다. R 4 to R 7 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 Alkynyl group, C 3 to C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyl of C 1 to C 40 Oxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ selected from the group consisting of C 60 aryl amine, or of, or adjacent groups (e.g., R 4 -R 5 , R 6 -R 7, etc.) may condense with each other to form a condensed ring. Here, the condensed ring may be a C 6 ~ C 20 condensed aromatic ring, or a 5 to 20 membered condensed heteroaromatic ring, and the heterocycloalkyl group, heteroaryl group and condensed heteroaromatic ring are each N, S , O and Se may contain at least one hetero atom selected from the group consisting of.
또, 상기 화학식 1로 표시되는 화합물에서, e 및 f는 각각 0 내지 4의 정수이다.In addition, in the compound represented by Formula 1, e and f are each an integer of 0 to 4.
여기서, e 및 f가 각각 0인 경우, 수소가 각각 치환기 R1 및 R2로 치환되지 않는 것을 의미하고, e 및 f가 각각 1 내지 4의 정수인 경우, 1 이상의 R1 및 1 이상의 R2가 서로 동일하거나 상이하고, 각각 독립적으로 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기 및 C6~C60의 아릴포스핀옥사이드기로 이루어진 군에서 선택된다. 이때, 상기 헤테로시클로알킬기 및 헤테로아릴기는 각각 N, S, O 및 Se로 이루어진 군에서 선택된 1개 이상의 헤테로원자를 포함한다. 일례에 따르면, e 및 f가 각각 0으로, R1 및 R2는 수소이다. 다른 일례에 따르면, e 및 f가 각각 1로, R1 및 R2가 각각 페닐기 또는 비페닐기(biphenyl group)일 수 있다.Here, when e and f are each 0, it means that hydrogen is not substituted with substituents R 1 and R 2 , respectively, and when e and f are each an integer of 1 to 4, 1 or more R 1 and 1 or more R 2 are The same or different from each other, and each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 ~ C 60 aryl group, 5 to 60 nuclear atoms heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 It is selected from the group consisting of an arylphosphine group of ~C 60 and an arylphosphine oxide group of C 6 ~C 60 . At this time, the heterocycloalkyl group and the heteroaryl group each include at least one heteroatom selected from the group consisting of N, S, O and Se. According to an example, e and f are each 0, and R 1 and R 2 are hydrogen. According to another example, e and f may be 1, and R 1 and R 2 may each be a phenyl group or a biphenyl group.
또, 상기 화학식 1에서, L1, L2, L3 및 L4의 아릴렌기 및 헤테로아릴렌기; Ar1 내지 Ar6의 아릴기 및 헤테로아릴기; 및 R1 및 R2의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 축합고리는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환되고, 바람직하게 중수소, 할로겐, 시아노기, 니트로기, C1~C20의 알킬기, C6~C30의 아릴기, 핵원자수 5 내지 30개의 헤테로아릴기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환될 수 있다. 이때, 상기 치환기가 복수인 경우, 복수의 치환기는 서로 동일하거나 상이하다. 여기서, 상기 헤테로시클로알킬기 및 헤테로아릴기는 각각 N, S, O 및 Se로 이루어진 군에서 선택된 1개 이상의 헤테로원자를 포함할 수 있다.In addition, in Formula 1, an arylene group and a heteroarylene group of L 1 , L 2 , L 3 and L 4 ; Ar 1 to Ar 6 aryl group and heteroaryl group; And an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl of R 1 and R 2 The boron group, arylphosphine group, arylphosphine oxide group and condensed ring are each independently deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 to C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, C 1 to C 40 Alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 the arylboronic group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ C to 1 substituent at least one selected from the 60 group consisting of aryl amines, and substituted or unsubstituted , Preferably substituted with one or more substituents selected from the group consisting of deuterium, halogen, cyano group, nitro group, C 1 ~ C 20 alkyl group, C 6 ~ C 30 aryl group, heteroaryl group having 5 to 30 nuclear atoms Or can be unsubstituted. In this case, when there are a plurality of substituents, the plurality of substituents are the same or different from each other. Here, the heterocycloalkyl group and the heteroaryl group may each include one or more heteroatoms selected from the group consisting of N, S, O, and Se.
본 발명에 따른 화학식 1로 표시되는 화합물은 하기 화학식 11 내지 24 중 어느 하나로 표시되는 화합물로 구체화될 수 있는데, 이에 한정되지 않는다. The compound represented by Formula 1 according to the present invention may be embodied as a compound represented by any one of the following Formulas 11 to 24, but is not limited thereto.
Figure PCTKR2019009280-appb-C000011
Figure PCTKR2019009280-appb-C000011
Figure PCTKR2019009280-appb-C000012
Figure PCTKR2019009280-appb-C000012
Figure PCTKR2019009280-appb-C000013
Figure PCTKR2019009280-appb-C000013
Figure PCTKR2019009280-appb-C000014
Figure PCTKR2019009280-appb-C000014
Figure PCTKR2019009280-appb-C000015
Figure PCTKR2019009280-appb-C000015
Figure PCTKR2019009280-appb-C000016
Figure PCTKR2019009280-appb-C000016
Figure PCTKR2019009280-appb-C000017
Figure PCTKR2019009280-appb-C000017
Figure PCTKR2019009280-appb-C000018
Figure PCTKR2019009280-appb-C000018
Figure PCTKR2019009280-appb-C000019
Figure PCTKR2019009280-appb-C000019
Figure PCTKR2019009280-appb-C000020
Figure PCTKR2019009280-appb-C000020
Figure PCTKR2019009280-appb-C000021
Figure PCTKR2019009280-appb-C000021
Figure PCTKR2019009280-appb-C000022
Figure PCTKR2019009280-appb-C000022
Figure PCTKR2019009280-appb-C000023
Figure PCTKR2019009280-appb-C000023
Figure PCTKR2019009280-appb-C000024
Figure PCTKR2019009280-appb-C000024
상기 화학식 11 내지 24에서, In Formulas 11 to 24,
X는 각각 상기 화학식 1에서 정의한 바와 같고;Each X is as defined in Formula 1;
R1 및 R2는 각각 상기 화학식 1에서 정의한 바와 같고, 구체적으로 서로 동일하거나 상이하고, 각각 독립적으로 수소, 페닐기 및 비페닐기로 이루어진 군에서 선택될 수 있고, 더 구체적으로 R1 및 R2 중 어느 하나는 수소이고, 나머지는 페닐기 또는 비페닐기일 수 있으며;R 1 and R 2 are each as defined in Formula 1, specifically the same or different from each other, and each independently may be selected from the group consisting of hydrogen, a phenyl group and a biphenyl group, and more specifically, of R 1 and R 2 One of them may be hydrogen and the rest may be a phenyl group or a biphenyl group;
Y1은 O, S, C(R4)(R5), 및 Si(R6)(R7)로 이루어진 군에서 선택되며;Y 1 is selected from the group consisting of O, S, C(R 4 )(R 5 ), and Si(R 6 )(R 7 );
복수의 Y2는 서로 동일하거나 상이하고, N 또는 CR8이고, 구체적으로 복수의 Y2가 모두 CH이거나, 또는 복수의 Y2 중 하나는 N이고 나머지는 CH일 수 있고;A plurality of Y 2 may be the same as or different from each other, N or CR 8 , specifically, all of the plurality of Y 2 may be CH, or one of the plurality of Y 2 may be N and the rest may be CH;
g는 0 내지 4의 정수이고, 구체적으로 0 내지 2의 정수이며;g is an integer of 0 to 4, specifically an integer of 0 to 2;
하나 이상의 R3 및 R4 내지 R8은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 또는 인접한 기들(예, R3-다른 R3)와 축합하여 축합 고리를 형성할 수 있고, 구체적으로 각각 독립적으로 수소, 페닐기, 나프틸기, 1가의 디벤조티오펜기, 1가의 디벤조퓨란기, 1가의 플루오렌기, 1가의 피리딘기, 메틸기, 에틸기, 프로필기 및 부틸기로 이루어진 군에서 선택될 수 있다.At least one R 3 and R 4 to R 8 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 to C 60 aryl group, 5 to 60 nuclear atoms heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60 of, or adjacent groups (e.g. , R 3 -It can be condensed with another R 3 ) to form a condensed ring, specifically each independently hydrogen, phenyl group, naphthyl group, monovalent dibenzothiophene group, monovalent dibenzofuran group, monovalent fluorene It may be selected from the group consisting of a group, a monovalent pyridine group, a methyl group, an ethyl group, a propyl group, and a butyl group.
상기에서 설명한 본 발명에 따른 화학식 1로 표시되는 화합물은 화합물 1 내지 화합물 270으로 보다 구체화될 수 있는데, 이에 의해 한정되는 것은 아니다.The compound represented by Formula 1 according to the present invention described above may be further specified as Compound 1 to Compound 270, but is not limited thereto.
Figure PCTKR2019009280-appb-I000005
Figure PCTKR2019009280-appb-I000005
Figure PCTKR2019009280-appb-I000006
Figure PCTKR2019009280-appb-I000006
Figure PCTKR2019009280-appb-I000007
Figure PCTKR2019009280-appb-I000007
Figure PCTKR2019009280-appb-I000008
Figure PCTKR2019009280-appb-I000008
Figure PCTKR2019009280-appb-I000009
Figure PCTKR2019009280-appb-I000009
Figure PCTKR2019009280-appb-I000010
Figure PCTKR2019009280-appb-I000010
Figure PCTKR2019009280-appb-I000011
Figure PCTKR2019009280-appb-I000011
Figure PCTKR2019009280-appb-I000012
Figure PCTKR2019009280-appb-I000012
Figure PCTKR2019009280-appb-I000013
Figure PCTKR2019009280-appb-I000013
Figure PCTKR2019009280-appb-I000014
Figure PCTKR2019009280-appb-I000014
Figure PCTKR2019009280-appb-I000015
Figure PCTKR2019009280-appb-I000015
Figure PCTKR2019009280-appb-I000016
Figure PCTKR2019009280-appb-I000016
Figure PCTKR2019009280-appb-I000017
Figure PCTKR2019009280-appb-I000017
Figure PCTKR2019009280-appb-I000018
Figure PCTKR2019009280-appb-I000018
Figure PCTKR2019009280-appb-I000019
Figure PCTKR2019009280-appb-I000019
Figure PCTKR2019009280-appb-I000020
Figure PCTKR2019009280-appb-I000020
Figure PCTKR2019009280-appb-I000021
Figure PCTKR2019009280-appb-I000021
Figure PCTKR2019009280-appb-I000022
Figure PCTKR2019009280-appb-I000022
본 발명에서 "알킬"은 탄소수 1 내지 40의 직쇄 또는 측쇄의 포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등이 있는데, 이에 한정되지는 않는다.In the present invention, "alkyl" refers to a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.
본 발명에서 "알케닐(alkenyl)"은 탄소-탄소 이중 결합을 1개 이상 가진 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등이 있는데, 이에 한정되지는 않는다.In the present invention, "alkenyl" refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms having one or more carbon-carbon double bonds. Examples thereof include vinyl (vinyl), allyl (allyl), isopropenyl (isopropenyl), 2-butenyl (2-butenyl), and the like, but is not limited thereto.
본 발명에서"알키닐(alkynyl)"은 탄소-탄소 삼중 결합을 1개 이상 가진 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 에티닐(ethynyl), 2-프로파닐(2-propynyl) 등이 있는데, 이에 한정되지는 않는다.In the present invention, "alkynyl" refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.
본 발명에서 "시클로알킬"은 탄소수 3 내지 40의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이러한 사이클로알킬의 예로는 사이클로프로필, 사이클로펜틸, 사이클로헥실, 노르보닐(norbornyl), 아다만틴(adamantine) 등이 있는데, 이에 한정되지는 않는다.In the present invention, "cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.
본 발명에서 "헤테로시클로알킬"은 핵원자수 3 내지 40의 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로 원자로 치환된다. 이러한 헤테로시클로알킬의 예로는 모르폴린, 피페라진 등이 있는데, 이에 한정되지는 않는다.In the present invention, "heterocycloalkyl" refers to a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S Or a hetero atom such as Se. Examples of such heterocycloalkyl include morpholine and piperazine, but are not limited thereto.
본 발명에서 "아릴"은 단독 고리 또는 2이상의 고리가 조합된 탄소수 6 내지 60의 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있다. 이러한 아릴의 예로는 페닐, 나프틸, 페난트릴, 안트릴 등이 있는데, 이에 한정되지는 않는다.In the present invention, "aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined. In addition, a form in which two or more rings are simply attached to each other or condensed may be included. Examples of such aryl include phenyl, naphthyl, phenanthryl, and anthryl, but are not limited thereto.
본 발명에서 "헤테로아릴"은 핵원자수 5 내지 60의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이때, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로원자로 치환된다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있고, 나아가 아릴기와의 축합된 형태도 포함될 수 있다. 이러한 헤테로아릴의 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6-원 모노사이클릭 고리, 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(benzothiazole), 카바졸릴(carbazolyl)과 같은 폴리사이클릭 고리 및 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등이 있는데, 이에 한정되지는 않는다.In the present invention, "heteroaryl" refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. At this time, one or more carbons, preferably 1 to 3 carbons in the ring are substituted with heteroatoms such as N, O, S or Se. In addition, a form in which two or more rings are simply attached to each other or condensed may be included, and further, a form condensed with an aryl group may be included. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl, phenoxathienyl, indolizinyl, indolyl ( indolyl), purinyl, quinolyl, benzothiazole, polycyclic rings such as carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.
본 발명에서 "알킬옥시"는 R'O-로 표시되는 1가의 치환기로, 상기 R'는 탄소수 1 내지 40의 알킬을 의미하며, 직쇄(linear), 측쇄(branched) 또는 사이클릭(cyclic) 구조를 포함할 수 있다. 이러한 알킬옥시의 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등이 있는데, 이에 한정되지는 않는다.In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R'refers to alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure It may include. Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, and the like.
본 발명에서 "아릴옥시"는 RO-로 표시되는 1가의 치환기로, 상기 R은 탄소수 5 내지 40의 아릴을 의미한다. 이러한 아릴옥시의 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등이 있는데, 이에 한정되지는 않는다.In the present invention, "aryloxy" is a monovalent substituent represented by RO-, and R means an aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, and diphenyloxy.
본 발명에서 "알킬실릴"은 탄소수 1 내지 40의 알킬로 치환된 실릴을 의미하며, 모노-뿐만 아니라 디-, 트리-알킬실릴을 포함한다. 또, "아릴실릴"은 탄소수 5 내지 60의 아릴로 치환된 실릴을 의미하고, 모노-뿐만 아니라 디-, 트리-아릴실릴 등의 폴리아릴실릴을 포함한다.In the present invention, "alkylsilyl" refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and includes mono- as well as di- and tri-alkylsilyl. In addition, "arylsilyl" refers to silyl substituted with aryl having 5 to 60 carbon atoms, and includes polyarylsilyl such as di- and tri-arylsilyl as well as mono-.
본 발명에서 "알킬보론기"는 탄소수 1 내지 40의 알킬로 치환된 보론기를 의미하며, "아릴보론기"는 탄소수 6 내지 60의 아릴로 치환된 보론기를 의미한다.In the present invention, "alkyl boron group" refers to a boron group substituted with an alkyl having 1 to 40 carbon atoms, and "aryl boron group" refers to a boron group substituted with an aryl having 6 to 60 carbon atoms.
본 발명에서 "알킬포스피닐기"는 탄소수 1 내지 40의 알킬로 치환된 포스핀기를 의미하고, 모노- 뿐만 아니라 디-알킬포스피닐기를 포함한다. 또, 본 발명에서 "아릴포스피닐기"는 탄소수 6 내지 60의 모노아릴 또는 디아릴로 치환된 포스핀기를 의미하고, 모노- 뿐만 아니라 디-아릴포스피닐기를 포함한다. In the present invention, the "alkylphosfinyl group" refers to a phosphine group substituted with an alkyl having 1 to 40 carbon atoms, and includes not only mono- but also di-alkylphosfinyl groups. In addition, in the present invention, "arylphosphinyl group" refers to a phosphine group substituted with a monoaryl or diaryl having 6 to 60 carbon atoms, and includes not only mono- but also di-arylphosfinyl groups.
본 발명에서 "아릴아민"은 탄소수 6 내지 40의 아릴로 치환된 아민을 의미하며, 모노-뿐만 아니라 디-아릴아민를 포함한다.In the present invention, "arylamine" refers to an amine substituted with an aryl having 6 to 40 carbon atoms, and includes mono- as well as di-arylamine.
<유기 전계 발광 소자><Organic EL device>
한편, 본 발명의 다른 측면은 전술한 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자(이하, '유기 EL 소자')에 관한 것이다.Meanwhile, another aspect of the present invention relates to an organic electroluminescent device (hereinafter, referred to as “organic EL device”) including the compound represented by Formula 1 above.
구체적으로, 본 발명에 따른 유기 전계 발광 소자는 양극(anode), 음극(cathode) 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함한다. 이때, 상기 화합물은 단독으로 사용되거나, 또는 2 이상이 혼합되어 사용될 수 있다.Specifically, the organic electroluminescent device according to the present invention includes an anode, a cathode, and one or more organic material layers interposed between the anode and the cathode, and at least one of the one or more organic material layers is It includes a compound represented by Formula 1. In this case, the compound may be used alone, or two or more may be used in combination.
상기 1층 이상의 유기물층은 정공 주입층, 정공 수송층, 발광층, 정공 저지층, 전자 수송층 및 전자 주입층 중 어느 하나 이상일 수 있고, 이 중에서 적어도 하나의 유기물층은 상기 화학식 1로 표시되는 화합물을 포함한다. 바람직하게, 상기 화학식 1의 화합물을 포함하는 유기물층은 정공 수송층일 수 있다.The one or more organic material layers may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and at least one of the organic material layers includes the compound represented by Formula 1. Preferably, the organic material layer including the compound of Formula 1 may be a hole transport layer.
일례에 따르면, 상기 1층 이상의 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층, 및 전자주입층을 포함하고, 상기 정공 수송층은 상기 화학식 1로 표시되는 화합물일 수 있다. According to an example, the one or more organic material layers may include a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, and an electron injection layer, and the hole transport layer may be a compound represented by Formula 1 above.
상기 화학식 1로 표시되는 화합물은 정공 수송층 물질로 유기 전계 발광 소자에 포함될 수 있다. 이 경우, 상기 화학식 1의 화합물은 유리전이온도가 높고, 정공 이동도가 높아 정공 수송능이 높으며, 정공 주입층과 발광층 사이의 적절한 HOMO 및 LUMO 에너지 레벨로 인해 정공 주입층에서 발광층 측으로의 정공 주입 및 전달이 원활하며, 무정형의 결정성과 고굴절률 특성을 갖는다. 따라서, 상기 화학식 1의 화합물을 포함하는 유기 전계 발광 소자는 효율(발광효율 및 전력효율), 수명, 휘도, 구동 전압, 열적 안정성 등이 향상될 수 있다. The compound represented by Formula 1 may be included in an organic electroluminescent device as a hole transport layer material. In this case, the compound of Formula 1 has a high glass transition temperature, high hole mobility, high hole transport capability, and hole injection from the hole injection layer to the emission layer due to an appropriate HOMO and LUMO energy level between the hole injection layer and the emission layer. Transfer is smooth, and has amorphous crystallinity and high refractive index characteristics. Accordingly, the organic electroluminescent device including the compound of Formula 1 may improve efficiency (luminescence efficiency and power efficiency), lifespan, luminance, driving voltage, thermal stability, and the like.
이러한 본 발명의 유기 전계 발광 소자의 구조는 특별히 한정되지 않으나, 예컨대 기판 위에, 양극(100), 1층 이상의 유기물층(300) 및 음극(200)이 순차적으로 적층될 수 있다(도 1 및 도 2참조). 뿐만 아니라, 전극과 유기물층 계면에 절연층 또는 접착층이 삽입된 구조일 수 있다.The structure of the organic electroluminescent device of the present invention is not particularly limited, but, for example, an anode 100, one or more organic material layers 300, and a cathode 200 may be sequentially stacked on a substrate (FIGS. 1 and 2 Reference). In addition, it may have a structure in which an insulating layer or an adhesive layer is inserted at the interface between the electrode and the organic material layer.
일례에 따르면, 상기 유기 전계 발광 소자는 도 1에 도시된 바와 같이, 기판 위에, 양극(100), 정공주입층(310), 정공수송층(320), 발광층(330), 전자수송층(340) 및 음극(200)이 순차적으로 적층된 구조를 가질 수 있다. 선택적으로, 도 2에 도시된 바와 같이, 상기 전자수송층(340)과 음극(200) 사이에 전자주입층(350)이 위치할 수 있다. 또한, 상기 발광층(330)과 전자수송층(340) 사이에 정공저지층(미도시됨)이 위치할 수 있다. 본 발명의 유기 전계 발광 소자는 상기 유기물층(300) 중 적어도 하나[예컨대, 정공수송층(320)]가 상기 화학식 1로 표시되는 화합물을 포함하는 것을 제외하고는, 당 기술 분야에 알려져 있는 재료 및 방법으로 유기물층 및 전극을 형성하여 제조할 수 있다.According to an example, as shown in FIG. 1, the organic electroluminescent device includes an anode 100, a hole injection layer 310, a hole transport layer 320, a light emitting layer 330, an electron transport layer 340, and The cathode 200 may have a sequentially stacked structure. Optionally, as shown in FIG. 2, an electron injection layer 350 may be positioned between the electron transport layer 340 and the cathode 200. In addition, a hole blocking layer (not shown) may be positioned between the emission layer 330 and the electron transport layer 340. In the organic electroluminescent device of the present invention, materials and methods known in the art, except that at least one of the organic material layers 300 (eg, hole transport layer 320) includes a compound represented by Formula 1 It can be prepared by forming an organic material layer and an electrode.
상기 유기물층은 진공 증착법이나 용액 도포법에 의하여 형성될 수 있다. 상기 용액 도포법의 예로는 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅 또는 열 전사법 등이 있으나, 이에 한정되지는 않는다.The organic material layer may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer method.
본 발명에서 사용 가능한 기판은 특별히 한정되지 않으며, 비제한적인 예로는 실리콘 웨이퍼, 석영, 유리판, 금속판, 플라스틱 필름 및 시트 등이 있다.The substrate usable in the present invention is not particularly limited, and non-limiting examples include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets.
또, 양극 물질의 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리티오펜, 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 또는 폴리아닐린과 같은 전도성 고분자; 및 카본블랙 등이 있는데, 이에 한정되지는 않는다.Further, examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb; Conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole or polyaniline; And carbon black, but are not limited thereto.
또, 음극 물질의 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석, 또는 납과 같은 금속 또는 이들의 합금; 및 LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있는데, 이에 한정되지는 않는다.Further, examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead, or alloys thereof; And a multilayered material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
또한, 정공주입층, 발광층, 전자수송층 및 전자주입층은 특별히 한정되는 것은 아니며, 당 업계에 알려진 통상의 물질을 사용할 수 있다.Further, the hole injection layer, the light emitting layer, the electron transport layer and the electron injection layer are not particularly limited, and conventional materials known in the art may be used.
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail through examples. However, the following examples are only illustrative of the present invention, and the present invention is not limited by the following examples.
[[ 준비예Preparation example 1] 화합물 C-1의 합성 1] Synthesis of Compound C-1
<단계 1> N-<Step 1> N- phenylspirophenylspiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-3-amine의 합성]-3-amine synthesis
Figure PCTKR2019009280-appb-I000023
Figure PCTKR2019009280-appb-I000023
3-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Tris(dibenzylideneacetone)dipalladium(0)(Pd2(dba)3) (0.91 g, 1 mmol), 1,1'-bis(diphenylphosphino)ferrocene(dppf) (1.10 g, 2 mmol), Sodium tert-butoxide(NaOt-Bu) (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후, 메틸렌클로라이드로 유기층을 추출하고, MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후, 컬럼크로마토그래피를 이용하여 목적 화합물 N-phenylspiro[fluorene-9,9'-xanthen]-3-amine (2.54 g, 수율 60 %)을 얻었다.3-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Tris(dibenzylideneacetone)dipalladium(0)(Pd 2 (dba) 3 ) (0.91 g, 1 mmol), 1,1'-bis(diphenylphosphino)ferrocene(dppf) (1.10 g, 2 mmol), Sodium tert-butoxide(NaOt-Bu) (1.9 g, 20 mmol) was added to 100 ml of Toluene at 110℃. Stir for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-phenylspiro[fluorene-9,9'-xanthen]-3-amine (2.54 g, yield 60%) was obtained by column chromatography.
<단계 2> 화합물 C-1의 합성<Step 2> Synthesis of Compound C-1
Figure PCTKR2019009280-appb-I000024
Figure PCTKR2019009280-appb-I000024
N-phenylspiro[fluorene-9,9'-xanthen]-3-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-1 (3.86 g, 수율 59 %)을 얻었다.N-phenylspiro[fluorene-9,9'-xanthen]-3-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-1 (3.86 g, yield 59%) was obtained by column chromatography.
[[ 준비예Preparation example 2] 화합물 C-2의 합성 2] Synthesis of Compound C-2
<단계 1> N-<Step 1> N- phenylspirophenylspiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-2-amine의 합성Synthesis of ]-2-amine
Figure PCTKR2019009280-appb-I000025
Figure PCTKR2019009280-appb-I000025
2-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (2.45 g, 수율 58 %)을 얻었다.2-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (2.45 g, yield 58%) was obtained by column chromatography.
<단계 2> 화합물 C-2의 합성<Step 2> Synthesis of Compound C-2
Figure PCTKR2019009280-appb-I000026
Figure PCTKR2019009280-appb-I000026
N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (4.23 g, 10 mmol), 1-bromo-4-iodobenzene (2.82 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-2 (3.29 g, 수율 57 %)을 얻었다.N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (4.23 g, 10 mmol), 1-bromo-4-iodobenzene (2.82 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-2 (3.29 g, yield 57%) was obtained by column chromatography.
[[ 준비예Preparation example 3] 화합물 C-3의 합성 3] Synthesis of Compound C-3
<단계 1> N-<Step 1> N- ([1,1'-biphenyl]-4-yl)spiro([1,1'-biphenyl]-4-yl)spiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-4-amine의 합성]-4-amine synthesis
Figure PCTKR2019009280-appb-I000027
Figure PCTKR2019009280-appb-I000027
4-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), [1,1'-biphenyl]-4-amine (1.69 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-4-amine (2.79 g, 수율 56 %)을 얻었다.4-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), [1,1'-biphenyl]-4-amine (1.69 g, 10 mmol), Pd 2 (dba) 3 (0.91 g , 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-4-amine (2.79 g) was used by column chromatography. , Yield 56%) was obtained.
<단계 2> 화합물 C-3의 합성<Step 2> Synthesis of Compound C-3
Figure PCTKR2019009280-appb-I000028
Figure PCTKR2019009280-appb-I000028
N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-4-amine (4.99 g, 10 mmol), 3-bromo-7-iododibenzo[b,d]furan (3.72 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-3 (4.09 g, 수율 55 %)을 얻었다.N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-4-amine (4.99 g, 10 mmol), 3-bromo-7-iododibenzo[b,d ]furan (3.72 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and 110 Stirred at °C for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-3 (4.09 g, yield 55%) was obtained by column chromatography.
[[ 준비예Preparation example 4] 화합물 C-4의 합성 4] Synthesis of Compound C-4
<단계 1> N-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-1-amine의 합성<Step 1> Synthesis of N-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-1-amine
Figure PCTKR2019009280-appb-I000029
Figure PCTKR2019009280-appb-I000029
1-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), 9,9-dimethyl-9H-fluoren-2-amine (2.09 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-1-amine (2.91 g, 수율 54 %)을 얻었다.1-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), 9,9-dimethyl-9H-fluoren-2-amine (2.09 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-1-amine (2.91) was used by column chromatography. g, yield 54%) was obtained.
<단계 2> 화합물 C-4의 합성<Step 2> Synthesis of Compound C-4
Figure PCTKR2019009280-appb-I000030
Figure PCTKR2019009280-appb-I000030
N-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-1-amine (5.39 g, 10 mmol), 1-bromo-4-iodonaphthalene (3.32 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) 를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-4 (3.94 g, 수율 53 %)을 얻었다.N-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-1-amine (5.39 g, 10 mmol), 1-bromo-4-iodonaphthalene (3.32 g , 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene at 110° C. for 12 hours. Stirred. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-4 (3.94 g, yield 53%) was obtained by column chromatography.
[[ 준비예Preparation example 5] 화합물 C-5의 합성 5] Synthesis of Compound C-5
<단계 1> N-<Step 1> N- (phenanthren-2-yl)spiro(phenanthren-2-yl)spiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-4'-amine의 합성]-4'-amine synthesis
Figure PCTKR2019009280-appb-I000031
Figure PCTKR2019009280-appb-I000031
4'-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), phenanthren-2-amine (1.93 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-(phenanthren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine (2.72 g, 수율 52 %)을 얻었다.4'-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), phenanthren-2-amine (1.93 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-(phenanthren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine (2.72 g, yield 52%) was prepared by column chromatography. Got it.
<단계 2> 화합물 C-5의 합성<Step 2> Synthesis of Compound C-5
Figure PCTKR2019009280-appb-I000032
Figure PCTKR2019009280-appb-I000032
N-(phenanthren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine (5.23 g, 10 mmol), 1-bromo-8-iododibenzo[b,d]thiophene (3.89 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-5 (4.00 g, 수율 51 %)을 얻었다.N-(phenanthren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine (5.23 g, 10 mmol), 1-bromo-8-iododibenzo[b,d]thiophene (3.89 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours I did. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-5 (4.00 g, yield 51%) was obtained by column chromatography.
[[ 준비예Preparation example 6] 화합물 C-6의 합성 6] Synthesis of Compound C-6
<단계 1> N-<Step 1> N- ([1,1':2',1''-terphenyl]([1,1':2',1''-terphenyl] -4--4- ylyl )) spirospiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-3'-amine의 합성]-3'-amine synthesis
Figure PCTKR2019009280-appb-I000033
Figure PCTKR2019009280-appb-I000033
3'-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), [1,1':2',1''-terphenyl]-4-amine (2.45 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-([1,1':2',1''-terphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3'-amine (2.87 g, 수율 50 %)을 얻었다.3'-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), [1,1':2',1''-terphenyl]-4-amine (2.45 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-([1,1':2',1''-terphenyl]-4-yl)spiro[fluorene-9,9'-xanthen] was used by column chromatography. -3'-amine (2.87 g, yield 50%) was obtained.
<단계 2> 화합물 C-6의 합성<Step 2> Synthesis of Compound C-6
Figure PCTKR2019009280-appb-I000034
Figure PCTKR2019009280-appb-I000034
N-([1,1':2',1''-terphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3'-amine (5.75 g, 10 mmol), 5-bromo-2-iodo-9,9-dimethyl-9H-fluorene (3.99 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-6 (4.14 g, 수율 49 %)을 얻었다.N-([1,1':2',1''-terphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3'-amine (5.75 g, 10 mmol), 5-bromo -2-iodo-9,9-dimethyl-9H-fluorene (3.99 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-6 (4.14 g, yield 49%) was obtained by column chromatography.
[[ 준비예Preparation example 7] 화합물 C-7의 합성 7] Synthesis of Compound C-7
<단계 1> N-<Step 1> N- (4-(pyridin-3-yl)phenyl)spiro(4-(pyridin-3-yl)phenyl)spiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-2'-amine의 합성]-2'-amine synthesis
Figure PCTKR2019009280-appb-I000035
Figure PCTKR2019009280-appb-I000035
2'-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), 4-(pyridin-3-yl)aniline (1.70 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-(4-(pyridin-3-yl)phenyl)spiro[fluorene-9,9'-xanthen]-2'-amine (2.40 g, 수율 48 %)을 얻었다.2'-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), 4-(pyridin-3-yl)aniline (1.70 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-(4-(pyridin-3-yl)phenyl)spiro[fluorene-9,9'-xanthen]-2'-amine (2.40 g,) was used by column chromatography. Yield 48%).
<단계 2> 화합물 C-7의 합성<Step 2> Synthesis of Compound C-7
Figure PCTKR2019009280-appb-I000036
Figure PCTKR2019009280-appb-I000036
N-(4-(pyridin-3-yl)phenyl)spiro[fluorene-9,9'-xanthen]-2'-amine (5.00 g, 10 mmol), 3-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-7 (3.43 g, 수율 47 %)을 얻었다.N-(4-(pyridin-3-yl)phenyl)spiro[fluorene-9,9'-xanthen]-2'-amine (5.00 g, 10 mmol), 3-bromo-4'-iodo-1,1 '-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene. The mixture was stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-7 (3.43 g, yield 47%) was obtained by column chromatography.
[[ 준비예Preparation example 8] 화합물 C-8의 합성 8] Synthesis of Compound C-8
<단계 1> 4-phenyl-N-<Step 1> 4-phenyl-N- (triphenylen-2-yl)spiro(triphenylen-2-yl)spiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-2'-amine의 합성]-2'-amine synthesis
Figure PCTKR2019009280-appb-I000037
Figure PCTKR2019009280-appb-I000037
2'-bromo-4-phenylspiro[fluorene-9,9'-xanthene] (4.87 g, 10 mmol), triphenylen-2-amine (2.43 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 4-phenyl-N-(triphenylen-2-yl)spiro[fluorene-9,9'-xanthen]-2'-amine (2.98 g, 수율 46 %)을 얻었다.2'-bromo-4-phenylspiro[fluorene-9,9'-xanthene] (4.87 g, 10 mmol), triphenylen-2-amine (2.43 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 4-phenyl-N-(triphenylen-2-yl)spiro[fluorene-9,9'-xanthen]-2'-amine (2.98 g, yield) was performed using column chromatography. 46%).
<단계 2> 화합물 C-8의 합성<Step 2> Synthesis of Compound C-8
Figure PCTKR2019009280-appb-I000038
Figure PCTKR2019009280-appb-I000038
4-phenyl-N-(triphenylen-2-yl)spiro[fluorene-9,9'-xanthen]-2'-amine (6.49 g, 10 mmol), 3-bromo-3'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-8 (3.96 g, 수율 45 %)을 얻었다.4-phenyl-N-(triphenylen-2-yl)spiro[fluorene-9,9'-xanthen]-2'-amine (6.49 g, 10 mmol), 3-bromo-3'-iodo-1,1' -biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and 110 Stirred at °C for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-8 (3.96 g, yield 45%) was obtained by column chromatography.
[[ 준비예Preparation example 9] 화합물 C-9의 합성 9] Synthesis of Compound C-9
<단계 1> N-([1,1'-biphenyl]-3-<Step 1> N-([1,1'-biphenyl]-3- ylyl )-2-)-2- phenylspirophenylspiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-2'-amine의 합성]-2'-amine synthesis
Figure PCTKR2019009280-appb-I000039
Figure PCTKR2019009280-appb-I000039
2'-bromo-2-phenylspiro[fluorene-9,9'-xanthene] (4.87 g, 10 mmol), [1,1'-biphenyl]-3-amine (1.69 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-([1,1'-biphenyl]-3-yl)-2-phenylspiro[fluorene-9,9'-xanthen]-2'-amine (2.53 g, 수율 44 %)을 얻었다.2'-bromo-2-phenylspiro[fluorene-9,9'-xanthene] (4.87 g, 10 mmol), [1,1'-biphenyl]-3-amine (1.69 g, 10 mmol), Pd 2 (dba ) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-([1,1'-biphenyl]-3-yl)-2-phenylspiro[fluorene-9,9'-xanthen]-2'- was used by column chromatography. An amine (2.53 g, yield 44%) was obtained.
<단계 2> 화합물 C-9의 합성<Step 2> Synthesis of Compound C-9
Figure PCTKR2019009280-appb-I000040
Figure PCTKR2019009280-appb-I000040
N-([1,1'-biphenyl]-3-yl)-2-phenylspiro[fluorene-9,9'-xanthen]-2'-amine (5.75 g, 10 mmol), 4'-bromo-2-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-9 (3.46 g, 수율 43 %)을 얻었다.N-([1,1'-biphenyl]-3-yl)-2-phenylspiro[fluorene-9,9'-xanthen]-2'-amine (5.75 g, 10 mmol), 4'-bromo-2- iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) Put in 100 ml of Toluene and stirred at 110 ℃ for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-9 (3.46 g, yield 43%) was obtained by column chromatography.
[[ 준비예Preparation example 10] 화합물 C-10의 합성 10] Synthesis of Compound C-10
<단계 1> 4-(<Step 1> 4-( terttert -butyl)-N-(4-(-butyl)-N-(4-( spirospiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-3-yl)phenyl)aniline의 합성Synthesis of ]-3-yl)phenyl)aniline
Figure PCTKR2019009280-appb-I000041
Figure PCTKR2019009280-appb-I000041
3-(4-bromophenyl)spiro[fluorene-9,9'-xanthene] (4.87 g, 10 mmol), 4-(tert-butyl)aniline (1.49 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 4-(tert-butyl)-N-(4-(spiro[fluorene-9,9'-xanthen]-3-yl)phenyl)aniline (2.33 g, 수율 42 %)을 얻었다.3-(4-bromophenyl)spiro[fluorene-9,9'-xanthene] (4.87 g, 10 mmol), 4-(tert-butyl)aniline (1.49 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 4-(tert-butyl)-N-(4-(spiro[fluorene-9,9'-xanthen]-3-yl)phenyl)aniline ( 2.33 g, yield 42%) was obtained.
<단계 2> 화합물 C-10의 합성<Step 2> Synthesis of Compound C-10
Figure PCTKR2019009280-appb-I000042
Figure PCTKR2019009280-appb-I000042
4-(tert-butyl)-N-(4-(spiro[fluorene-9,9'-xanthen]-3-yl)phenyl)aniline (5.55 g, 10 mmol), 3-bromo-3''-iodo-1,1':2',1''-terphenyl (4.35 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-10 (3.53 g, 수율 41 %)을 얻었다.4-(tert-butyl)-N-(4-(spiro[fluorene-9,9'-xanthen]-3-yl)phenyl)aniline (5.55 g, 10 mmol), 3-bromo-3''-iodo -1,1':2',1''-terphenyl (4.35 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-10 (3.53 g, yield 41%) was obtained by column chromatography.
[[ 준비예Preparation example 11] 화합물 C-11의 합성 11] Synthesis of Compound C-11
<단계 1> 3-<Step 1> 3- chlorochloro -6--6- phenylspirophenylspiro [[ fluorenefluorene -9,9'--9,9'- xanthenexanthene ]의 합성Synthesis of]
Figure PCTKR2019009280-appb-I000043
Figure PCTKR2019009280-appb-I000043
3-bromo-6-chlorospiro[fluorene-9,9'-xanthene] (4.45 g, 10 mmol), phenylboronic acid (1.21 g, 10 mmol), Pd(PPh3)4 (0.34 g, 0.3 mmol), K2CO3 (2.76 g, 20 mmol)를 1,4-Dioxane 100 ml/ H2O 25 ml에 넣고 100℃에서 8시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 3-chloro-6-phenylspiro[fluorene-9,9'-xanthene] (1.77 g, 수율 40 %)을 얻었다.3-bromo-6-chlorospiro[fluorene-9,9'-xanthene] (4.45 g, 10 mmol), phenylboronic acid (1.21 g, 10 mmol), Pd(PPh 3 ) 4 (0.34 g, 0.3 mmol), K 2 CO 3 (2.76 g, 20 mmol) was added to 100 ml of 1,4-Dioxane/ 25 ml of H 2 O and stirred at 100° C. for 8 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound, 3-chloro-6-phenylspiro[fluorene-9,9'-xanthene] (1.77 g, yield 40%) was obtained by column chromatography.
<단계 2> N-([1,1':3',1''-<Step 2> N-([1,1':3',1''- terphenylterphenyl ]-5'-]-5'- ylyl )-6-)-6- phenylspirophenylspiro [[ fluorenefluorene -9,9'-xanthen]-3-amine의 합성Synthesis of -9,9'-xanthen]-3-amine
Figure PCTKR2019009280-appb-I000044
Figure PCTKR2019009280-appb-I000044
3-chloro-6-phenylspiro[fluorene-9,9'-xanthene] (4.42 g, 10 mmol), [1,1':3',1''-terphenyl]-5'-amine (2.45 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-([1,1':3',1''-terphenyl]-5'-yl)-6-phenylspiro[fluorene-9,9'-xanthen]-3-amine (2.67 g, 수율 41 %)을 얻었다.3-chloro-6-phenylspiro[fluorene-9,9'-xanthene] (4.42 g, 10 mmol), [1,1':3',1''-terphenyl]-5'-amine (2.45 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-([1,1':3',1''-terphenyl]-5'-yl)-6-phenylspiro[fluorene-9,9] was used by column chromatography. '-xanthen]-3-amine (2.67 g, yield 41%) was obtained.
<단계 3> 화합물 C-11의 합성<Step 3> Synthesis of Compound C-11
Figure PCTKR2019009280-appb-I000045
Figure PCTKR2019009280-appb-I000045
N-([1,1':3',1''-terphenyl]-5'-yl)-6-phenylspiro[fluorene-9,9'-xanthen]-3-amine (6.51 g, 10 mmol), 4-bromo-4'-iodo-2,2'-dimethyl-1,1'-biphenyl (3.87 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-11 (3.82 g, 수율 42 %)을 얻었다.N-([1,1':3',1''-terphenyl]-5'-yl)-6-phenylspiro[fluorene-9,9'-xanthen]-3-amine (6.51 g, 10 mmol), 4-bromo-4'-iodo-2,2'-dimethyl-1,1'-biphenyl (3.87 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-11 (3.82 g, yield 42%) was obtained by column chromatography.
[[ 준비예Preparation example 12] 화합물 C-12의 합성 12] Synthesis of Compound C-12
<단계 1> 2-([1,1'-biphenyl]-3-<Step 1> 2-([1,1'-biphenyl]-3- ylyl )-7-)-7- chlorospirochlorospiro [[ fluorenefluorene -9,9'--9,9'- xanthenexanthene ]의 합성Synthesis of]
Figure PCTKR2019009280-appb-I000046
Figure PCTKR2019009280-appb-I000046
2-bromo-7-chlorospiro[fluorene-9,9'-xanthene] (4.45 g, 10 mmol), [1,1'-biphenyl]-3-ylboronic acid (1.98 g, 10 mmol), Pd(PPh3)4 (0.34 g, 0.3 mmol), K2CO3 (2.76 g, 20 mmol)를 1,4-Dioxane 100 ml/ H2O 25 ml에 넣고 100℃에서 8시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 2-([1,1'-biphenyl]-3-yl)-7-chlorospiro[fluorene-9,9'-xanthene] (2.23 g, 수율 43 %)을 얻었다.2-bromo-7-chlorospiro[fluorene-9,9'-xanthene] (4.45 g, 10 mmol), [1,1'-biphenyl]-3-ylboronic acid (1.98 g, 10 mmol), Pd(PPh 3 ) 4 (0.34 g, 0.3 mmol), K 2 CO 3 (2.76 g, 20 mmol) was added to 1,4-Dioxane 100 ml/H 2 O 25 ml and stirred at 100° C. for 8 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound, 2-([1,1'-biphenyl]-3-yl)-7-chlorospiro[fluorene-9,9'-xanthene] (2.23 g), was used by column chromatography. , Yield 43%).
<단계 2> 2-([1,1'-biphenyl]-3-<Step 2> 2-([1,1'-biphenyl]-3- ylyl )-N-)-N- (5,5-dimethyl-5H-dibenzo(5,5-dimethyl-5H-dibenzo [[ b,db,d ]] silolsilol -3-yl)spiro[fluorene-9,9'-xanthen]-7-amine의 합성Synthesis of -3-yl)spiro[fluorene-9,9'-xanthen]-7-amine
Figure PCTKR2019009280-appb-I000047
Figure PCTKR2019009280-appb-I000047
2-([1,1'-biphenyl]-3-yl)-7-chlorospiro[fluorene-9,9'-xanthene] (5.19 g, 10 mmol), 5,5-dimethyl-5H-dibenzo[b,d]silol-3-amine (2.25 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) 를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 2-([1,1'-biphenyl]-3-yl)-N-(5,5-dimethyl-5H-dibenzo[b,d]silol-3-yl)spiro[fluorene-9,9'-xanthen]-7-amine (3.11 g, 수율 44 %)을 얻었다.2-([1,1'-biphenyl]-3-yl)-7-chlorospiro[fluorene-9,9'-xanthene] (5.19 g, 10 mmol), 5,5-dimethyl-5H-dibenzo[b, d]silol-3-amine (2.25 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) toluene Put in 100 ml and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 2-([1,1'-biphenyl]-3-yl)-N-(5,5-dimethyl-5H-dibenzo[b,d] was used by column chromatography. silol-3-yl)spiro[fluorene-9,9'-xanthen]-7-amine (3.11 g, yield 44%) was obtained.
<단계 3> 화합물 C-12의 합성<Step 3> Synthesis of Compound C-12
Figure PCTKR2019009280-appb-I000048
Figure PCTKR2019009280-appb-I000048
2-([1,1'-biphenyl]-3-yl)-N-(5,5-dimethyl-5H-dibenzo[b,d]silol-3-yl)spiro[fluorene-9,9'-xanthen]-7-amine (7.07 g, 10 mmol), 2-bromo-7-iodophenanthrene (3.83 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-12 (4.33 g, 수율 45 %)을 얻었다.2-([1,1'-biphenyl]-3-yl)-N-(5,5-dimethyl-5H-dibenzo[b,d]silol-3-yl)spiro[fluorene-9,9'-xanthen ]-7-amine (7.07 g, 10 mmol), 2-bromo-7-iodophenanthrene (3.83 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) , NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-12 (4.33 g, yield 45%) was obtained by column chromatography.
[[ 준비예Preparation example 13] 화합물 C-13의 합성 13] Synthesis of Compound C-13
<단계 1> 2'-([1,1'-biphenyl]-4-<Step 1> 2'-([1,1'-biphenyl]-4- ylyl )-7'-)-7'- chlorospirochlorospiro [[ fluorenefluorene -9,9'-xanthene]의 합성-9,9'-xanthene] synthesis
Figure PCTKR2019009280-appb-I000049
Figure PCTKR2019009280-appb-I000049
2'-bromo-7'-chlorospiro[fluorene-9,9'-xanthene] (4.45 g, 10 mmol), [1,1'-biphenyl]-4-ylboronic acid (1.98 g, 10 mmol), Pd(PPh3)4 (0.34 g, 0.3 mmol), K2CO3 (2.76 g, 20 mmol)를 1,4-Dioxane 100 ml/ H2O 25 ml에 넣고 100℃에서 8시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 2'-([1,1'-biphenyl]-4-yl)-7'-chlorospiro[fluorene-9,9'-xanthene] (2.38 g, 수율 46 %)을 얻었다.2'-bromo-7'-chlorospiro[fluorene-9,9'-xanthene] (4.45 g, 10 mmol), [1,1'-biphenyl]-4-ylboronic acid (1.98 g, 10 mmol), Pd( PPh 3 ) 4 (0.34 g, 0.3 mmol), K 2 CO 3 (2.76 g, 20 mmol) was added to 1,4-Dioxane 100 ml/H 2 O 25 ml and stirred at 100° C. for 8 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound was 2'-([1,1'-biphenyl]-4-yl)-7'-chlorospiro[fluorene-9,9'-xanthene] ( 2.38 g, yield 46%) was obtained.
<단계 2> 2'-([1,1'-biphenyl]-4-<Step 2> 2'-([1,1'-biphenyl]-4- ylyl )-N-)-N- mesitylspiromesitylspiro [[ fluorenefluorene -9,9'-xanthen]-7'-amine의 합성Synthesis of -9,9'-xanthen]-7'-amine
Figure PCTKR2019009280-appb-I000050
Figure PCTKR2019009280-appb-I000050
2'-([1,1'-biphenyl]-4-yl)-7'-chlorospiro[fluorene-9,9'-xanthene] (5.19 g, 10 mmol), 2,4,6-trimethylaniline (1.35 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 2'-([1,1'-biphenyl]-4-yl)-N-mesitylspiro[fluorene-9,9'-xanthen]-7'-amine (2.90 g, 수율 47 %)을 얻었다.2'-([1,1'-biphenyl]-4-yl)-7'-chlorospiro[fluorene-9,9'-xanthene] (5.19 g, 10 mmol), 2,4,6-trimethylaniline (1.35 g , 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene at 110° C. for 12 hours. Stirred. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 2'-([1,1'-biphenyl]-4-yl)-N-mesitylspiro[fluorene-9,9'-xanthen]-7' was used by column chromatography. -amine (2.90 g, yield 47%) was obtained.
<단계 3> 화합물 C-13의 합성<Step 3> Synthesis of Compound C-13
Figure PCTKR2019009280-appb-I000051
Figure PCTKR2019009280-appb-I000051
2'-([1,1'-biphenyl]-4-yl)-N-mesitylspiro[fluorene-9,9'-xanthen]-7'-amine (6.17 g, 10 mmol), 2-bromo-7-iodotriphenylene (4.33 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-13 (4.43 g, 수율 48 %)을 얻었다.2'-([1,1'-biphenyl]-4-yl)-N-mesitylspiro[fluorene-9,9'-xanthen]-7'-amine (6.17 g, 10 mmol), 2-bromo-7- Add iodotriphenylene (4.33 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) to 100 ml of Toluene and 110℃ The mixture was stirred for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-13 (4.43 g, yield 48%) was obtained by column chromatography.
[[ 준비예Preparation example 14] 화합물 C-14의 합성 14] Synthesis of Compound C-14
<단계 1> 4'-<Step 1> 4'- chlorochloro -2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthene]의 합성Synthesis of -2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthene]
Figure PCTKR2019009280-appb-I000052
Figure PCTKR2019009280-appb-I000052
2-bromo-4'-chlorospiro[fluorene-9,9'-xanthene] (4.45 g, 10 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (2.38 g, 10 mmol), Pd(PPh3)4 (0.34 g, 0.3 mmol), K2CO3 (2.76 g, 20 mmol)를 1,4-Dioxane 100 ml/ H2O 25 ml에 넣고 100℃에서 8시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 4'-chloro-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthene] (2.73 g, 수율 49 %)을 얻었다.2-bromo-4'-chlorospiro[fluorene-9,9'-xanthene] (4.45 g, 10 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (2.38 g, 10 mmol) , Pd(PPh 3 ) 4 (0.34 g, 0.3 mmol), K 2 CO 3 (2.76 g, 20 mmol) was added to 1,4-Dioxane 100 ml/ H 2 O 25 ml and stirred at 100° C. for 8 hours . After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 4'-chloro-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthene] was used by column chromatography. (2.73 g, yield 49%) was obtained.
<단계 2> N-(9,9'-<Step 2> N-(9,9'- spirobispirobi [[ fluorenfluoren ]-2-]-2- ylyl )-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine의 합성Synthesis of )-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine
Figure PCTKR2019009280-appb-I000053
Figure PCTKR2019009280-appb-I000053
4'-chloro-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthene] (5.59 g, 10 mmol), 9,9'-spirobi[fluoren]-2-amine (3.31 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) 를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-(9,9'-spirobi[fluoren]-2-yl)-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine (4.27 g, 수율 50 %)을 얻었다.4'-chloro-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthene] (5.59 g, 10 mmol), 9,9'-spirobi[fluoren] -2-amine (3.31 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) in 100 ml of Toluene And stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-(9,9'-spirobi[fluoren]-2-yl)-2-(9,9-dimethyl-9H-fluoren-2-yl) was used by column chromatography. )spiro[fluorene-9,9'-xanthen]-4'-amine (4.27 g, yield 50%) was obtained.
<단계 3> 화합물 C-14의 합성<Step 3> Synthesis of Compound C-14
Figure PCTKR2019009280-appb-I000054
Figure PCTKR2019009280-appb-I000054
N-(9,9'-spirobi[fluoren]-2-yl)-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine (8.54 g, 10 mmol), 1-bromo-3-iodobenzene (2.82 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-14 (4.94 g, 수율 49 %)을 얻었다.N-(9,9'-spirobi[fluoren]-2-yl)-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-4'- amine (8.54 g, 10 mmol), 1-bromo-3-iodobenzene (2.82 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-14 (4.94 g, yield 49%) was obtained by column chromatography.
[[ 준비예Preparation example 15] 화합물 C-15의 합성 15] Synthesis of Compound C-15
<단계 1> N-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-3-amine의 합성<Step 1> Synthesis of N-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-3-amine
Figure PCTKR2019009280-appb-I000055
Figure PCTKR2019009280-appb-I000055
3-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), 9,9-dimethyl-7-phenyl-9H-fluoren-2-amine (2.85 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-3-amine (2.95 g, 수율 48 %)을 얻었다.3-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), 9,9-dimethyl-7-phenyl-9H-fluoren-2-amine (2.85 g, 10 mmol), Pd 2 (dba ) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-3 was used by column chromatography. -amine (2.95 g, yield 48%) was obtained.
<단계 2> 화합물 C-15의 합성<Step 2> Synthesis of Compound C-15
Figure PCTKR2019009280-appb-I000056
Figure PCTKR2019009280-appb-I000056
N-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-3-amine (6.15 g, 10 mmol), 1-bromo-5-iodonaphthalene (3.32 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-15 (3.85 g, 수율 47 %)을 얻었다.N-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-3-amine (6.15 g, 10 mmol), 1-bromo-5- Add iodonaphthalene (3.32 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) to 100 ml of Toluene and 110℃ The mixture was stirred for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-15 (3.85 g, yield 47%) was obtained by column chromatography.
[[ 준비예Preparation example 16] 화합물 C-16의 합성 16] Synthesis of Compound C-16
<단계 1> N-<Step 1> N- ([1,1'-biphenyl]-4-yl)spiro([1,1'-biphenyl]-4-yl)spiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-3-amine의 합성]-3-amine synthesis
Figure PCTKR2019009280-appb-I000057
Figure PCTKR2019009280-appb-I000057
3-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), [1,1'-biphenyl]-4-amine (1.69 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3-amine (2.29 g, 수율 46 %)을 얻었다.3-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), [1,1'-biphenyl]-4-amine (1.69 g, 10 mmol), Pd 2 (dba) 3 (0.91 g , 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3-amine (2.29 g) was used by column chromatography. , Yield 46%) was obtained.
<단계 2> 화합물 C-16의 합성<Step 2> Synthesis of Compound C-16
Figure PCTKR2019009280-appb-I000058
Figure PCTKR2019009280-appb-I000058
N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3-amine (4.99 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) 를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-16 (3.28 g, 수율 45 %)을 얻었다.N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3-amine (4.99 g, 10 mmol), 4-bromo-4'-iodo-1, 1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) in 100 ml of Toluene And stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-16 (3.28 g, yield 45%) was obtained by column chromatography.
[[ 준비예Preparation example 17] 화합물 C-17의 합성 17] Synthesis of Compound C-17
<단계 1> N-<Step 1> N- phenylspirophenylspiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-2-amine의 합성Synthesis of ]-2-amine
Figure PCTKR2019009280-appb-I000059
Figure PCTKR2019009280-appb-I000059
2-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) 를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (1.86 g, 수율 44 %)을 얻었다.2-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (1.86 g, yield 44%) was obtained by column chromatography.
<단계 2> 화합물 C-17의 합성<Step 2> Synthesis of Compound C-17
Figure PCTKR2019009280-appb-I000060
Figure PCTKR2019009280-appb-I000060
N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-17 (2.81 g, 수율 43 %)을 얻었다.N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-17 (2.81 g, yield 43%) was obtained by column chromatography.
[[ 준비예Preparation example 18] 화합물 C-18의 합성 18] Synthesis of Compound C-18
<단계 1> N-<Step 1> N- phenylspirophenylspiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-4-amine의 합성]-4-amine synthesis
Figure PCTKR2019009280-appb-I000061
Figure PCTKR2019009280-appb-I000061
4-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-phenylspiro[fluorene-9,9'-xanthen]-4-amine (1.77 g, 수율 42 %)을 얻었다.4-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-phenylspiro[fluorene-9,9'-xanthen]-4-amine (1.77 g, yield 42%) was obtained by column chromatography.
<단계 2> 화합물 C-18의 합성<Step 2> Synthesis of Compound C-18
Figure PCTKR2019009280-appb-I000062
Figure PCTKR2019009280-appb-I000062
N-phenylspiro[fluorene-9,9'-xanthen]-4-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-18 (2.68 g, 수율 41 %)을 얻었다.N-phenylspiro[fluorene-9,9'-xanthen]-4-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-18 (2.68 g, yield 41%) was obtained by column chromatography.
[[ 준비예Preparation example 19] 화합물 C-19의 합성 19] Synthesis of Compound C-19
<단계 1> N-<Step 1> N- phenylspirophenylspiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-4'-amine의 합성]-4'-amine synthesis
Figure PCTKR2019009280-appb-I000063
Figure PCTKR2019009280-appb-I000063
4'-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-phenylspiro[fluorene-9,9'-xanthen]-4'-amine (1.69 g, 수율 40 %)을 얻었다.4'-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-phenylspiro[fluorene-9,9'-xanthen]-4'-amine (1.69 g, yield 40%) was obtained by column chromatography.
<단계 2> 화합물 C-19의 합성<Step 2> Synthesis of Compound C-19
Figure PCTKR2019009280-appb-I000064
Figure PCTKR2019009280-appb-I000064
N-phenylspiro[fluorene-9,9'-xanthen]-4'-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-19 (2.68 g, 수율 41 %)을 얻었다.N-phenylspiro[fluorene-9,9'-xanthen]-4'-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-19 (2.68 g, yield 41%) was obtained by column chromatography.
[[ 준비예Preparation example 20] 화합물 C-20의 합성 20] Synthesis of Compound C-20
<단계 1> N-<Step 1> N- phenylspirophenylspiro [[ fluorenefluorene -9,9'--9,9'- xanthenxanthen ]-3'-amine의 합성]-3'-amine synthesis
Figure PCTKR2019009280-appb-I000065
Figure PCTKR2019009280-appb-I000065
3'-bromospiro[fluorene-9,9'-thioxanthene] (4.27 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 N-phenylspiro[fluorene-9,9'-thioxanthen]-3'-amine (1.84 g, 수율 42 %)을 얻었다.3'-bromospiro[fluorene-9,9'-thioxanthene] (4.27 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-phenylspiro[fluorene-9,9'-thioxanthen]-3'-amine (1.84 g, yield 42%) was obtained by column chromatography.
<단계 2> 화합물 C-20의 합성<Step 2> Synthesis of Compound C-20
Figure PCTKR2019009280-appb-I000066
Figure PCTKR2019009280-appb-I000066
N-phenylspiro[fluorene-9,9'-thioxanthen]-3'-amine (4.39 g, 10 mmol), 2-bromo-2'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 C-20 (2.88 g, 수율 43 %)을 얻었다.N-phenylspiro[fluorene-9,9'-thioxanthen]-3'-amine (4.39 g, 10 mmol), 2-bromo-2'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-20 (2.88 g, yield 43%) was obtained by column chromatography.
[[ 합성예Synthesis example 1] 화합물 1의 합성 1] Synthesis of Compound 1
Figure PCTKR2019009280-appb-I000067
Figure PCTKR2019009280-appb-I000067
화합물 C-1 (6.54 g, 10 mmol), N-phenyl-[1,1'-biphenyl]-4-amine (2.45 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 1 (3.60 g, 수율 44 %)을 얻었다.Compound C-1 (6.54 g, 10 mmol), N-phenyl-[1,1'-biphenyl]-4-amine (2.45 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 1 (3.60 g, yield 44%) was obtained by column chromatography.
Mass : [(M+H)+] : 819Mass: [(M+H) + ]: 819
[[ 합성예Synthesis example 2] 화합물 2의 합성 2] Synthesis of Compound 2
Figure PCTKR2019009280-appb-I000068
Figure PCTKR2019009280-appb-I000068
화합물 C-2 (5.78 g, 10 mmol), N-phenyl-[1,1'-biphenyl]-3-amine (2.45 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 2 (3.34 g, 수율 45 %)을 얻었다.Compound C-2 (5.78 g, 10 mmol), N-phenyl-[1,1'-biphenyl]-3-amine (2.45 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 2 (3.34 g, yield 45%) was obtained by column chromatography.
Mass : [(M+H)+] : 742Mass: [(M+H) + ]: 742
[[ 합성예Synthesis example 3] 화합물 3의 합성 3] Synthesis of compound 3
Figure PCTKR2019009280-appb-I000069
Figure PCTKR2019009280-appb-I000069
화합물 C-3 (7.44 g, 10 mmol), N-phenyl-[1,1'-biphenyl]-2-amine (2.45 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 3 (4.18 g, 수율 46 %)을 얻었다.Compound C-3 (7.44 g, 10 mmol), N-phenyl-[1,1'-biphenyl]-2-amine (2.45 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 3 (4.18 g, yield 46%) was obtained by column chromatography.
Mass : [(M+H)+] : 909Mass: [(M+H) + ]: 909
[[ 합성예Synthesis example 4] 화합물 4의 합성 4] Synthesis of compound 4
Figure PCTKR2019009280-appb-I000070
Figure PCTKR2019009280-appb-I000070
화합물 C-4 (7.44 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 4 (3.91 g, 수율 47 %)을 얻었다.Compound C-4 (7.44 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g , 20 mmol) was added to 100 ml of Toluene and stirred at 110°C for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 4 (3.91 g, yield 47%) was obtained by column chromatography.
Mass : [(M+H)+] : 833Mass: [(M+H) + ]: 833
[[ 합성예Synthesis example 5] 화합물 5의 합성 5] Synthesis of compound 5
Figure PCTKR2019009280-appb-I000071
Figure PCTKR2019009280-appb-I000071
화합물 C-5 (7.84 g, 10 mmol), N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-3-amine (3.21 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 5 (4.92 g, 수율 48 %)을 얻었다.Compound C-5 (7.84 g, 10 mmol), N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-3-amine (3.21 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 5 (4.92 g, yield 48%) was obtained by column chromatography.
Mass : [(M+H)+] : 1025Mass: [(M+H) + ]: 1025
[[ 합성예Synthesis example 6] 화합물 6의 합성 6] Synthesis of compound 6
Figure PCTKR2019009280-appb-I000072
Figure PCTKR2019009280-appb-I000072
화합물 C-6 (8.46 g, 10 mmol), N-phenylnaphthalen-1-amine (2.19 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 6 (4.82 g, 수율 49 %)을 얻었다.Compound C-6 (8.46 g, 10 mmol), N-phenylnaphthalen-1-amine (2.19 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 6 (4.82 g, yield 49%) was obtained by column chromatography.
Mass : [(M+H)+] : 985Mass: [(M+H) + ]: 985
[[ 합성예Synthesis example 7] 화합물 7의 합성 7] Synthesis of compound 7
Figure PCTKR2019009280-appb-I000073
Figure PCTKR2019009280-appb-I000073
화합물 C-7 (7.31 g, 10 mmol), N-phenyldibenzo[b,d]thiophen-3-amine (2.75 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 7 (4.63 g, 수율 50 %)을 얻었다.Compound C-7 (7.31 g, 10 mmol), N-phenyldibenzo[b,d]thiophen-3-amine (2.75 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 7 (4.63 g, yield 50%) was obtained by column chromatography.
Mass : [(M+H)+] : 926Mass: [(M+H) + ]: 926
[[ 합성예Synthesis example 8] 화합물 8의 합성 8] Synthesis of compound 8
Figure PCTKR2019009280-appb-I000074
Figure PCTKR2019009280-appb-I000074
화합물 C-8 (8.80 g, 10 mmol), di([1,1'-biphenyl]-3-yl)amine (3.21 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 8 (5.49 g, 수율 49 %)을 얻었다.Compound C-8 (8.80 g, 10 mmol), di([1,1'-biphenyl]-3-yl)amine (3.21 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 8 (5.49 g, yield 49%) was obtained by column chromatography.
Mass : [(M+H)+] : 1121Mass: [(M+H) + ]: 1121
[[ 합성예Synthesis example 9] 화합물 9의 합성 9] Synthesis of compound 9
Figure PCTKR2019009280-appb-I000075
Figure PCTKR2019009280-appb-I000075
화합물 C-9 (8.06 g, 10 mmol), N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (3.61 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 9 (5.21 g, 수율 48 %)을 얻었다.Compound C-9 (8.06 g, 10 mmol), N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (3.61 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 9 (5.21 g, yield 48%) was obtained by column chromatography.
Mass : [(M+H)+] : 1087Mass: [(M+H) + ]: 1087
[[ 합성예Synthesis example 10] 화합물 10의 합성 10] Synthesis of compound 10
Figure PCTKR2019009280-appb-I000076
Figure PCTKR2019009280-appb-I000076
화합물 C-10 (8.62 g, 10 mmol), N,6-diphenylpyridin-3-amine (2.46 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 10 (4.83 g, 수율 47 %)을 얻었다.Compound C-10 (8.62 g, 10 mmol), N,6-diphenylpyridin-3-amine (2.46 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) ), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 10 (4.83 g, yield 47%) was obtained by column chromatography.
Mass : [(M+H)+] : 1028Mass: [(M+H) + ]: 1028
[[ 합성예Synthesis example 11] 화합물 11의 합성 11] Synthesis of compound 11
Figure PCTKR2019009280-appb-I000077
Figure PCTKR2019009280-appb-I000077
화합물 C-11 (9.10 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 11 (4.59 g, 수율 46 %)을 얻었다.Compound C-11 (9.10 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g , 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 11 (4.59 g, yield 46%) was obtained by column chromatography.
Mass : [(M+H)+] : 999Mass: [(M+H) + ]: 999
[[ 합성예Synthesis example 12] 화합물 12의 합성 12] Synthesis of Compound 12
Figure PCTKR2019009280-appb-I000078
Figure PCTKR2019009280-appb-I000078
화합물 C-12 (9.63 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 12 (4.73 g, 수율 45 %)을 얻었다.Compound C-12 (9.63 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g , 20 mmol) was added to 100 ml of Toluene and stirred at 110°C for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 12 (4.73 g, yield 45%) was obtained by column chromatography.
Mass : [(M+H)+] : 1051Mass: [(M+H) + ]: 1051
[[ 합성예Synthesis example 13] 화합물 13의 합성 13] Synthesis of compound 13
Figure PCTKR2019009280-appb-I000079
Figure PCTKR2019009280-appb-I000079
화합물 C-13 (9.22 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 13 (4.44 g, 수율 44 %)을 얻었다.Compound C-13 (9.22 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g , 20 mmol) was added to 100 ml of Toluene and stirred at 110°C for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 13 (4.44 g, yield 44%) was obtained by column chromatography.
Mass : [(M+H)+] : 1011Mass: [(M+H) + ]: 1011
[[ 합성예Synthesis example 14] 화합물 14의 합성 14] Synthesis of compound 14
Figure PCTKR2019009280-appb-I000080
Figure PCTKR2019009280-appb-I000080
화합물 C-14 (10.09 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 14 (4.71 g, 수율 43 %)을 얻었다.Compound C-14 (10.09 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g , 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 14 (4.71 g, yield 43%) was obtained by column chromatography.
Mass : [(M+H)+] : 1097Mass: [(M+H) + ]: 1097
[[ 합성예Synthesis example 15] 화합물 15의 합성 15] Synthesis of compound 15
Figure PCTKR2019009280-appb-I000081
Figure PCTKR2019009280-appb-I000081
화합물 C-15 (8.20 g, 10 mmol), N-phenylphenanthren-9-amine (2.69 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 15 (4.23 g, 수율 42 %)을 얻었다.Compound C-15 (8.20 g, 10 mmol), N-phenylphenanthren-9-amine (2.69 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 15 (4.23 g, yield 42%) was obtained by column chromatography.
Mass : [(M+H)+] : 1009Mass: [(M+H) + ]: 1009
[[ 합성예Synthesis example 16] 화합물 16의 합성 16] Synthesis of compound 16
Figure PCTKR2019009280-appb-I000082
Figure PCTKR2019009280-appb-I000082
화합물 C-16 (7.30 g, 10 mmol), N-phenyl-[1,1':2',1''-terphenyl]-4'-amine (3.21 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 16 (3.98 g, 수율 41 %)을 얻었다.Compound C-16 (7.30 g, 10 mmol), N-phenyl-[1,1':2',1''-terphenyl]-4'-amine (3.21 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 16 (3.98 g, yield 41%) was obtained by column chromatography.
Mass : [(M+H)+] : 971Mass: [(M+H) + ]: 971
[[ 합성예Synthesis example 17] 화합물 17의 합성 17] Synthesis of compound 17
Figure PCTKR2019009280-appb-I000083
Figure PCTKR2019009280-appb-I000083
화합물 C-17 (6.54 g, 10 mmol), N-phenyldibenzo[b,d]furan-3-amine (2.59 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 17 (3.33 g, 수율 40 %)을 얻었다.Compound C-17 (6.54 g, 10 mmol), N-phenyldibenzo[b,d]furan-3-amine (2.59 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 17 (3.33 g, yield 40%) was obtained by column chromatography.
Mass : [(M+H)+] : 833Mass: [(M+H) + ]: 833
[[ 합성예Synthesis example 18] 화합물 18의 합성 18] Synthesis of compound 18
Figure PCTKR2019009280-appb-I000084
Figure PCTKR2019009280-appb-I000084
화합물 C-18 (6.54 g, 10 mmol), bis(9,9-dimethyl-9H-fluoren-2-yl)amine (4.01 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 18 (3.99 g, 수율 41 %)을 얻었다.Compound C-18 (6.54 g, 10 mmol), bis(9,9-dimethyl-9H-fluoren-2-yl)amine (4.01 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol) , dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 18 (3.99 g, yield 41%) was obtained by column chromatography.
Mass : [(M+H)+] : 975Mass: [(M+H) + ]: 975
[[ 합성예Synthesis example 19] 화합물 19의 합성 19] Synthesis of compound 19
Figure PCTKR2019009280-appb-I000085
Figure PCTKR2019009280-appb-I000085
화합물 C-19 (6.54 g, 10 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (2.85 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 19 (3.60 g, 수율 42 %)을 얻었다.Compound C-19 (6.54 g, 10 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (2.85 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol) , dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 19 (3.60 g, yield 42%) was obtained by column chromatography.
Mass : [(M+H)+] : 859Mass: [(M+H) + ]: 859
[[ 합성예Synthesis example 20] 화합물 20의 합성 20] Synthesis of Compound 20
Figure PCTKR2019009280-appb-I000086
Figure PCTKR2019009280-appb-I000086
화합물 C-20 (6.70 g, 10 mmol), di([1,1'-biphenyl]-4-yl)amine (3.21 g, 10 mmol), Pd2(dba)3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol)를 Toluene 100 ml에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 유기층을 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층에서 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물 20 (3.91 g, 수율 43 %)을 얻었다.Compound C-20 (6.70 g, 10 mmol), di([1,1'-biphenyl]-4-yl)amine (3.21 g, 10 mmol), Pd 2 (dba) 3 (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the filtered organic layer, the target compound 20 (3.91 g, yield 43%) was obtained by column chromatography.
Mass : [(M+H)+] : 911Mass: [(M+H) + ]: 911
[[ 실시예Example 1] 녹색 유기 1] green organic 전계Electric field 발광 소자의 제작 Fabrication of light emitting device
상기 합성예 1에서 합성한 화합물 1을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후, 아래의 과정에 따라 녹색 유기 전계 발광 소자를 제작하였다.After compound 1 synthesized in Synthesis Example 1 was subjected to high-purity sublimation purification by a conventionally known method, a green organic electroluminescent device was manufactured according to the following procedure.
먼저, ITO(Indium tin oxide)가 1500 Å 두께로 박막 코팅된 유리 기판을 증류수로 초음파 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척하고 건조시킨 후 UV OZONE 세정기(Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 5분간 세정하고 진공 증착기로 코팅된 유리 기판을 이송하였다.First, ITO (Indium tin oxide) was ultrasonically cleaned with distilled water on a glass substrate coated with a thin film with a thickness of 1500 Å. After washing with distilled water, ultrasonically clean with a solvent such as isopropyl alcohol, acetone, methanol, etc., dry, transfer to a UV OZONE cleaner (Power Sonic 405, Hwashin Tech), wash for 5 minutes using UV, and coat glass with a vacuum evaporator The substrate was transferred.
이렇게 준비된 ITO 투명 유리 기판(전극) 위에 m-MTDATA (60nm)/ 화합물 1(80nm) / DS-H522 + 5% DS-501(300nm) / BCP(10nm) / Alq3(30nm) / LiF(1nm) / Al(200nm) 순으로 적층하여 유기 EL 소자를 제작하였다. 이때 사용된 DS-H522 및 DS-501은 ㈜두산전자 BG 제품이며, m-MTDATA, BCP의 구조는 각각 하기와 같다.On the prepared ITO transparent glass substrate (electrode), m-MTDATA (60nm) / Compound 1 (80nm) / DS-H522 + 5% DS-501 (300nm) / BCP (10nm) / Alq 3 (30nm) / LiF (1nm) ) / Al (200nm) was stacked in order to fabricate an organic EL device. The DS-H522 and DS-501 used at this time are products of Doosan Electronics Co., Ltd. BG, and the structures of m-MTDATA and BCP are as follows.
Figure PCTKR2019009280-appb-I000087
Figure PCTKR2019009280-appb-I000087
[[ 실시예Example 2~20] 녹색 유기 2~20] green organic 전계Electric field 발광 소자의 제작 Fabrication of light emitting device
실시예 1에서 정공 수송층의 형성시 정공 수송층 재료로 사용된 화합물 1 대신 하기 표 1에 기재된 화합물을 각각 사용하는 것을 제외하고는, 실시예 1과 동일하게 수행하여 녹색 유기 전계 발광 소자를 제작하였다.In Example 1, when forming the hole transport layer, a green organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compounds shown in Table 1 were respectively used instead of the compound 1 used as the hole transport layer material.
[[ 비교예Comparative example 1] 녹색 유기 1] green organic 전계Electric field 발광 소자의 제조 Manufacturing of light emitting devices
실시예 1에서 정공 수송층의 형성시 정공 수송층 재료로서 화합물 1 대신 NPB를 사용하는 것을 제외하고는, 상기 실시예 1과 동일하게 수행하여 녹색 유기 전계 발광 소자를 제작하였다. 이때 사용된 NPB의 구조는 하기와 같다.In Example 1, when forming the hole transport layer, a green organic electroluminescent device was manufactured in the same manner as in Example 1, except that NPB was used instead of Compound 1 as a material for the hole transport layer. The structure of the NPB used at this time is as follows.
Figure PCTKR2019009280-appb-I000088
Figure PCTKR2019009280-appb-I000088
[[ 비교예Comparative example 2] 녹색 유기 2] green organic 전계Electric field 발광 소자의 제조 Manufacturing of light emitting devices
실시예 1에서 정공 수송층의 형성시 정공 수송층 재료로서 화합물 1 대신 하기 화합물 S-1를 사용하는 것을 제외하고는, 상기 실시예 1과 동일하게 수행하여 녹색 유기 전계 발광 소자를 제작하였다. 이때 사용된 S-1의 구조는 하기와 같다.In Example 1, when forming the hole transport layer, a green organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound S-1 was used instead of Compound 1 as a material for the hole transport layer. The structure of S-1 used at this time is as follows.
Figure PCTKR2019009280-appb-I000089
Figure PCTKR2019009280-appb-I000089
[[ 평가예Evaluation example 1] One]
실시예 1 내지 20 및 비교예 1 내지 2에서 각각 제조된 유기 전계 발광 소자에 대하여, 전류밀도 10 mA/㎠에서의 구동전압, 전류효율을 측정하였고, 그 결과를 하기 표 1에 나타내었다.For the organic electroluminescent devices prepared in Examples 1 to 20 and Comparative Examples 1 to 2, respectively, the driving voltage and current efficiency at a current density of 10 mA/cm 2 were measured, and the results are shown in Table 1 below.
샘플Sample 정공 수송층 재료Hole transport layer material 구동 전압(V)Driving voltage (V) 전류효율(cd/A)Current efficiency (cd/A)
실시예 1Example 1 1One 4.14.1 25.125.1
실시예 2Example 2 22 4.04.0 23.923.9
실시예 3Example 3 33 4.24.2 25.225.2
실시예 4Example 4 44 4.14.1 22.922.9
실시예 5Example 5 55 3.93.9 24.524.5
실시예 6Example 6 66 4.14.1 24.824.8
실시예 7Example 7 77 4.24.2 23.523.5
실시예 8Example 8 88 4.14.1 23.723.7
실시예 9Example 9 99 4.54.5 22.922.9
실시예 10Example 10 1010 4.44.4 24.024.0
실시예 11Example 11 1111 3.83.8 22.822.8
실시예 12Example 12 1212 4.54.5 22.422.4
실시예 13Example 13 1313 3.73.7 25.125.1
실시예 14Example 14 1414 4.44.4 24.724.7
실시예 15Example 15 1515 4.14.1 24.124.1
실시예 16Example 16 1616 4.24.2 24.824.8
실시예 17Example 17 1717 4.14.1 20.320.3
실시예 18Example 18 1818 3.83.8 19.419.4
실시예 19Example 19 1919 3.93.9 21.521.5
실시예 20Example 20 2020 4.44.4 24.924.9
비교예 1Comparative Example 1 NPBNPB 5.25.2 18.218.2
비교예 2Comparative Example 2 S-1S-1 5.05.0 19.019.0
상기 표 1에 나타낸 바와 같이, 본 발명에 따른 화합물을 정공수송층 재료로 적용한 실시예 1 내지 20의 유기 전계 발광 소자는 종래 NPB를 정공수송층 재료로 적용한 비교예 1 및 아민기가 연속 치환되지 않은 물질을 적용한 비교예 2의 유기 전계 발광 소자보다 구동전압 및 전류효율이 우수하다는 것을 확인할 수 있었다.As shown in Table 1 above, the organic electroluminescent devices of Examples 1 to 20 in which the compound according to the present invention is applied as a hole transport layer material are Comparative Example 1 in which NPB is applied as a hole transport layer material, and a material in which an amine group is not continuously substituted. It was confirmed that the driving voltage and current efficiency were superior to the applied organic electroluminescent device of Comparative Example 2.

Claims (10)

  1. 하기 화학식 1로 표시되는 화합물:Compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2019009280-appb-I000090
    Figure PCTKR2019009280-appb-I000090
    (상기 화학식 1에서, (In Formula 1,
    X는 O 또는 S이고, X is O or S,
    A1 및 A2는 각각 0 또는 1이고, 단 A1+A2=1이며,A1 and A2 are each 0 or 1, provided that A1+A2=1,
    a, b, c, 및 d는 각각 0 내지 3의 정수이고, a, b, c, and d are each an integer of 0 to 3,
    L1, L2, L3 및 L4는 서로 동일하거나 상이하고, 각각 독립적으로 단일결합이거나, C6 내지 C60의 아릴렌기 및 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택되고,L 1 , L 2 , L 3 and L 4 are the same as or different from each other, and each independently a single bond, or is selected from the group consisting of an arylene group of C 6 to C 60 and a heteroarylene group having 5 to 60 nuclear atoms ,
    Ar1 내지 Ar6는 서로 동일하거나 상이하고, 각각 독립적으로 C6~C60의 아릴기, 및 핵원자수 5 내지 60개의 헤테로아릴기로 이루어진 군에서 선택되고,Ar 1 to Ar 6 are the same as or different from each other, and are each independently selected from the group consisting of an aryl group of C 6 to C 60 and a heteroaryl group having 5 to 60 nuclear atoms,
    e 및 f는 각각 0 내지 4의 정수이고, e and f are each an integer of 0 to 4,
    R1 및 R2는 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, 및 C6~C60의 아릴포스핀옥사이드기로 이루어진 군에서 선택되거나, 또는 인접한 기와 축합하여 축합고리를 형성하고,R 1 and R 2 are the same as or different from each other, and each independently hydrogen, deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 to C 40 cycloalkyl group, 3 to 40 nuclear atom heterocycloalkyl group, C 6 to C 60 aryl group, 5 to 60 nuclear atom heteroaryl group, C 1 to C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C Selected from the group consisting of an aryl boron group of 60 , an arylphosphine group of C 6 to C 60 , and an aryl phosphine oxide group of C 6 to C 60 , or condensed with an adjacent group to form a condensed ring,
    L1, L2, L3 및 L4의 아릴렌기 및 헤테로아릴렌기, Ar1 내지 Ar6의 아릴기 및 헤테로아릴기, 및 R1 및 R2의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 축합고리는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환되거나, 또는 상기 인접한 치환기들이 서로 축합하여 축합 고리를 형성할 수 있으며, 이때 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이함).Arylene and heteroarylene groups of L 1 , L 2 , L 3 and L 4 , aryl and heteroaryl groups of Ar 1 to Ar 6 , and alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups of R 1 and R 2 , Heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylborone group, arylborone group, arylphosphine group, arylphosphine oxide group and condensed ring are each independently Deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, nuclear atom number 3 To 40 heterocycloalkyl group, C 6 to C 60 aryl group, heteroaryl group of 5 to 60 nuclear atoms, C 1 to C 40 alkyloxy group, C 6 to C 60 aryloxy group, C 1 to C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 arylphosphine group, C 6 ~ to C 60 aryl phosphine oxide group, and a C 6 ~ substituted or unsubstituted with substituents at least one selected from the group consisting of an aryl amine of the C 60 in, or are condensed with each other the neighboring substituents may form a condensed ring, wherein When the above substituents are plural, they are the same or different from each other).
  2. 제1항에 있어서,The method of claim 1,
    상기 화학식 1로 표시되는 화합물은 하기 화학식 2 또는 3으로 표시되는 화합물:The compound represented by Formula 1 is a compound represented by the following Formula 2 or 3:
    [화학식 2][Formula 2]
    Figure PCTKR2019009280-appb-I000091
    Figure PCTKR2019009280-appb-I000091
    [화학식 3][Formula 3]
    Figure PCTKR2019009280-appb-I000092
    Figure PCTKR2019009280-appb-I000092
    (상기 화학식 2 및 3에서,(In Formulas 2 and 3,
    X, L1 내지 L4, Ar1 내지 Ar6, R1, R2, a, b, c, d, e 및 f는 각각 제1항에서 정의한 바와 같음).X, L 1 to L 4 , Ar 1 to Ar 6 , R 1 , R 2 , a, b, c, d, e and f are each as defined in claim 1).
  3. 제1항에 있어서,The method of claim 1,
    상기 화학식 1로 표시되는 화합물은 하기 화학식 4 내지 10 중 어느 하나로 표시되는 화합물:The compound represented by Formula 1 is a compound represented by any one of the following Formulas 4 to 10:
    [화학식 4][Formula 4]
    Figure PCTKR2019009280-appb-I000093
    Figure PCTKR2019009280-appb-I000093
    [화학식 5][Formula 5]
    Figure PCTKR2019009280-appb-I000094
    Figure PCTKR2019009280-appb-I000094
    [화학식 6][Formula 6]
    Figure PCTKR2019009280-appb-I000095
    Figure PCTKR2019009280-appb-I000095
    [화학식 7][Formula 7]
    Figure PCTKR2019009280-appb-I000096
    Figure PCTKR2019009280-appb-I000096
    [화학식 8][Formula 8]
    Figure PCTKR2019009280-appb-I000097
    Figure PCTKR2019009280-appb-I000097
    [화학식 9][Formula 9]
    Figure PCTKR2019009280-appb-I000098
    Figure PCTKR2019009280-appb-I000098
    [화학식 10][Formula 10]
    Figure PCTKR2019009280-appb-I000099
    Figure PCTKR2019009280-appb-I000099
    (상기 화학식 4 내지 10에서,(In Chemical Formulas 4 to 10,
    X, L1 내지 L4, Ar1 내지 Ar6, R1, R2, a, b, c, d, e 및 f는 각각 제1항에서 정의한 바와 같음).X, L 1 to L 4 , Ar 1 to Ar 6 , R 1 , R 2 , a, b, c, d, e and f are each as defined in claim 1).
  4. 제1항에 있어서,The method of claim 1,
    b 및 d는 각각 1 내지 3의 정수이고,b and d are each an integer of 1 to 3,
    L2 및 L4는 각각 독립적으로 C6 내지 C60의 아릴렌기 및 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택되고,L 2 and L 4 are each independently selected from the group consisting of an arylene group of C 6 to C 60 and a heteroarylene group of 5 to 60 nuclear atoms,
    L1, L2, L3 및 L4의 아릴렌기 및 헤테로아릴렌기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환되며, 이때 상기 치환기가 복수인 경우, 이들은 서로 동일하거나 상이한, 화합물.The arylene and heteroarylene groups of L 1 , L 2 , L 3 and L 4 are each independently deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 6 ~ C 60 aryl group, nucleus Heteroaryl group having 5 to 60 atoms, C 1 to C 40 alkyloxy group, C 6 to C 60 aryloxy group, C 1 to C 40 alkylsilyl group, C 6 to C 60 arylsilyl group, C group of 1 to alkylboronic of C 40, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ C 60 aryl amine Unsubstituted or substituted with one or more substituents selected from the group consisting of groups, wherein when the substituents are plural, they are the same or different from each other.
  5. 제1항에 있어서,The method of claim 1,
    L1, L2, L3 및 L4는 서로 동일하거나 상이하고, 각각 독립적으로 단일결합이거나, 또는 하기 링커기 Link1 내지 Link7로 이루어진 군에서 선택된 것인, 화합물:L 1 , L 2 , L 3 and L 4 are the same as or different from each other, and each independently a single bond, or a linker group selected from the group consisting of Link1 to Link7, a compound:
    Figure PCTKR2019009280-appb-I000100
    Figure PCTKR2019009280-appb-I000100
    (상기 Link1 내지 Link7에서,(In Link1 to Link7 above,
    Y1은 O, S, CR4R5, 및 SiR6R7로 이루어진 군에서 선택되며,Y 1 is selected from the group consisting of O, S, CR 4 R 5 , and SiR 6 R 7 ,
    g, h, i, j, k, l는 각각 0 내지 4의 정수이고, m은 0 내지 6의 정수이고, n은 0 내지 8의 정수이며, o는 0 내지 6의 정수이고, p는 0 내지 4의 정수이며, q 및 r은 각각 0 내지 3의 정수이고, g, h, i, j, k, l are each an integer of 0 to 4, m is an integer of 0 to 6, n is an integer of 0 to 8, o is an integer of 0 to 6, p is 0 Is an integer of 4, q and r are each an integer of 0 to 3,
    하나 이상의 R3, R4 내지 R7은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 또는 인접한 기와 축합하여 축합 고리를 형성함).One or more R 3 , R 4 to R 7 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 to C 60 aryl group, 5 to 60 nuclear atoms heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60 of, or by an adjacent group condensed Forming a condensed ring).
  6. 제1항에 있어서,The method of claim 1,
    Ar1 내지 Ar6는 서로 동일하거나 상이하고, 각각 독립적으로 치환체 S1 내지 S13으로 이루어진 군에서 선택된 것인, 화합물:Ar 1 to Ar 6 are the same as or different from each other, and each independently selected from the group consisting of substituents S1 to S13, a compound:
    Figure PCTKR2019009280-appb-I000101
    Figure PCTKR2019009280-appb-I000101
    (상기 S1 내지 S13에서,(In the above S1 to S13,
    Y1은 O, S, CR4R5, 및 SiR6R7로 이루어진 군에서 선택되며,Y 1 is selected from the group consisting of O, S, CR 4 R 5 , and SiR 6 R 7 ,
    g, i, l는 각각 0 내지 5의 정수이고, h, j, k, p, r, s는 각각 0 내지 4의 정수이고, m은 0 내지 7의 정수이고, n은 0 내지 9의 정수이며, o는 0 내지 7의 정수이고, q, t, u, v는 0 내지 3의 정수이며, w 및 x는 각각 0 내지 2의 정수이고,g, i, l are each an integer of 0 to 5, h, j, k, p, r, s are each an integer of 0 to 4, m is an integer of 0 to 7, n is an integer of 0 to 9 And o is an integer of 0 to 7, q, t, u, and v are integers of 0 to 3, w and x are each an integer of 0 to 2,
    복수의 R3, R4 내지 R7은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 또는 인접한 기와 축합하여 축합 고리를 형성함).A plurality of R 3 , R 4 to R 7 are the same or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 to C 60 aryl group, 5 to 60 nuclear atoms heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60 of, or by an adjacent group condensed Forming a condensed ring).
  7. 제1항에 있어서,The method of claim 1,
    상기 화학식 1로 표시되는 화합물은 하기 화학식 11 내지 24 중 어느 하나로 표시되는 화합물:The compound represented by Formula 1 is a compound represented by any one of the following Formulas 11 to 24:
    [화학식 11][Formula 11]
    Figure PCTKR2019009280-appb-I000102
    Figure PCTKR2019009280-appb-I000102
    [화학식 12][Formula 12]
    Figure PCTKR2019009280-appb-I000103
    Figure PCTKR2019009280-appb-I000103
    [화학식 13][Formula 13]
    Figure PCTKR2019009280-appb-I000104
    Figure PCTKR2019009280-appb-I000104
    [화학식 14][Formula 14]
    Figure PCTKR2019009280-appb-I000105
    Figure PCTKR2019009280-appb-I000105
    [화학식 15][Formula 15]
    Figure PCTKR2019009280-appb-I000106
    Figure PCTKR2019009280-appb-I000106
    [화학식 16][Formula 16]
    Figure PCTKR2019009280-appb-I000107
    Figure PCTKR2019009280-appb-I000107
    [화학식 17][Formula 17]
    Figure PCTKR2019009280-appb-I000108
    Figure PCTKR2019009280-appb-I000108
    [화학식 18][Formula 18]
    Figure PCTKR2019009280-appb-I000109
    Figure PCTKR2019009280-appb-I000109
    [화학식 19][Formula 19]
    Figure PCTKR2019009280-appb-I000110
    Figure PCTKR2019009280-appb-I000110
    [화학식 20][Formula 20]
    Figure PCTKR2019009280-appb-I000111
    Figure PCTKR2019009280-appb-I000111
    [화학식 21][Formula 21]
    Figure PCTKR2019009280-appb-I000112
    Figure PCTKR2019009280-appb-I000112
    [화학식 22][Formula 22]
    Figure PCTKR2019009280-appb-I000113
    Figure PCTKR2019009280-appb-I000113
    [화학식 23][Formula 23]
    Figure PCTKR2019009280-appb-I000114
    Figure PCTKR2019009280-appb-I000114
    [화학식 24][Formula 24]
    Figure PCTKR2019009280-appb-I000115
    Figure PCTKR2019009280-appb-I000115
    (상기 화학식 11 내지 24에서, (In Formulas 11 to 24,
    X, R1 및 R2는 각각 제1항에서 정의한 바와 같고, X, R 1 and R 2 are each as defined in claim 1,
    Y1은 O, S, C(R4)(R5), 및 Si(R6)(R7)로 이루어진 군에서 선택되며,Y 1 is selected from the group consisting of O, S, C(R 4 )(R 5 ), and Si(R 6 )(R 7 ),
    복수의 Y2는 서로 동일하거나 상이하고, N 또는 CR8이고, A plurality of Y 2 is the same as or different from each other, and is N or CR 8 ,
    g는 0 내지 4의 정수이고, g is an integer from 0 to 4,
    하나 이상의 R3 및 R4 내지 R8은 서로 동일하거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 또는 인접한 기들이 서로 축합하여 축합 고리를 형성할 수 있음).At least one R 3 and R 4 to R 8 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 to C 60 aryl group, 5 to 60 nuclear atoms heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60 of, or adjacent groups together are Condensation can form a condensed ring).
  8. 제1항에 있어서,The method of claim 1,
    상기 화학식 1로 표시되는 화합물은 하기 화합물 1 내지 화합물 270 중 어느 하나인 화합물:The compound represented by Formula 1 is a compound of any one of the following compounds 1 to 270:
    Figure PCTKR2019009280-appb-I000116
    Figure PCTKR2019009280-appb-I000116
    Figure PCTKR2019009280-appb-I000117
    Figure PCTKR2019009280-appb-I000117
    Figure PCTKR2019009280-appb-I000118
    Figure PCTKR2019009280-appb-I000118
    Figure PCTKR2019009280-appb-I000119
    Figure PCTKR2019009280-appb-I000119
    Figure PCTKR2019009280-appb-I000120
    Figure PCTKR2019009280-appb-I000120
    Figure PCTKR2019009280-appb-I000121
    Figure PCTKR2019009280-appb-I000121
    Figure PCTKR2019009280-appb-I000122
    Figure PCTKR2019009280-appb-I000122
    Figure PCTKR2019009280-appb-I000123
    Figure PCTKR2019009280-appb-I000123
    Figure PCTKR2019009280-appb-I000124
    Figure PCTKR2019009280-appb-I000124
    Figure PCTKR2019009280-appb-I000125
    Figure PCTKR2019009280-appb-I000125
    Figure PCTKR2019009280-appb-I000126
    Figure PCTKR2019009280-appb-I000126
    Figure PCTKR2019009280-appb-I000127
    Figure PCTKR2019009280-appb-I000127
    Figure PCTKR2019009280-appb-I000128
    Figure PCTKR2019009280-appb-I000128
    Figure PCTKR2019009280-appb-I000129
    Figure PCTKR2019009280-appb-I000129
    Figure PCTKR2019009280-appb-I000130
    Figure PCTKR2019009280-appb-I000130
    Figure PCTKR2019009280-appb-I000131
    Figure PCTKR2019009280-appb-I000131
    Figure PCTKR2019009280-appb-I000132
    Figure PCTKR2019009280-appb-I000132
    Figure PCTKR2019009280-appb-I000133
    .
    Figure PCTKR2019009280-appb-I000133
    .
  9. 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, anode; cathode; And As an organic electroluminescent device comprising at least one organic material layer interposed between the anode and the cathode,
    상기 1층 이상의 유기물층 중에서 적어도 하나는 제1항 내지 제8항 중 어느 한 항에 기재된 유기 화합물을 포함하는 유기 전계 발광 소자. An organic electroluminescent device containing the organic compound according to any one of claims 1 to 8, wherein at least one of the one or more organic material layers.
  10. 제9항에 있어서,The method of claim 9,
    상기 유기 화합물을 포함하는 유기물층은 정공수송층인 유기 전계 발광 소자.An organic electroluminescent device wherein the organic material layer including the organic compound is a hole transport layer.
PCT/KR2019/009280 2019-04-25 2019-07-25 Organic compound and organic electroluminescent diode using same WO2020218680A1 (en)

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