WO2017217676A1 - Organic luminescent compound and organic electroluminescent element including same - Google Patents

Organic luminescent compound and organic electroluminescent element including same Download PDF

Info

Publication number
WO2017217676A1
WO2017217676A1 PCT/KR2017/005670 KR2017005670W WO2017217676A1 WO 2017217676 A1 WO2017217676 A1 WO 2017217676A1 KR 2017005670 W KR2017005670 W KR 2017005670W WO 2017217676 A1 WO2017217676 A1 WO 2017217676A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
aryl
compound
formula
mmol
Prior art date
Application number
PCT/KR2017/005670
Other languages
French (fr)
Korean (ko)
Inventor
박우재
김영배
김회문
Original Assignee
주식회사 두산
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 두산 filed Critical 주식회사 두산
Publication of WO2017217676A1 publication Critical patent/WO2017217676A1/en

Links

Classifications

    • 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
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Definitions

  • the present invention relates to a novel organic compound and an organic electroluminescent device comprising the same, and more particularly to a compound used in the organic material layer of the organic electroluminescent device.
  • 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 its function.
  • the light emitting layer forming material of the organic EL device may be classified into blue, green, and red light emitting materials according to light emission colors. In addition, yellow and orange light emitting materials are also used as light emitting materials for realizing a better natural color.
  • a host / dopant system may be used as the light emitting material in order to increase the light emission efficiency through increase in color purity and energy transfer.
  • the dopant material may be divided 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, the development of the phosphorescent material can theoretically improve the luminous efficiency up to 4 times compared to the fluorescence, so attention is focused on phosphorescent dopants as well as phosphorescent host materials.
  • NPB hole blocking layer
  • BCP hole blocking layer
  • Alq 3 hole blocking layer
  • anthracene derivatives have been reported as fluorescent dopant / host materials in the light emitting material.
  • phosphorescent materials having advantages in terms of efficiency improvement among the light emitting materials include metal complex compounds containing Ir such as Firpic, Ir (ppy) 3 , and (acac) Ir (btp) 2 . Is being used.
  • CBP 4,4-dicarbazolybiphenyl
  • CBP 4,4-dicarbazolybiphenyl
  • the present invention can be applied to an organic electroluminescent device, and an object of the present invention is to provide a novel compound excellent in thermal stability and luminescent properties.
  • Another object of the present invention is to provide an organic electroluminescent device including the novel compound, which exhibits low driving voltage and high luminous efficiency and has an improved lifetime.
  • the present invention provides a compound represented by the following formula (1).
  • a ring is a monocyclic or polycyclic aromatic ring
  • X is -O-, -S-, or -C (R 5 R 6 )-;
  • L 1 and L 2 are a single bond or selected from the group consisting of C 6 to C 18 arylene groups and heteroarylene groups having 5 to 18 nuclear atoms,
  • Ar 1 is represented by any one of the following Chemical Formulas 2 to 4,
  • Y 1 to Y 17 are the same as or different from each other, and each independently selected from N or C (R 7 ), wherein when R 7 is plural, a plurality of R 7 are the same as or different from each other,
  • any one of Y 6 to Y 9 bonded to L 1 is C (R 7 ),
  • Z 1 is N or C (R 7 ),
  • R 1 to R 4 and R 7 are each independently hydrogen, deuterium, halogen, cyano group, C 1 to C 40 alkyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C Aryl group of 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C 1 to C 40 , aryloxy group of C 6 to C 60 , alkylsilyl group of C 3 to C 40 , C 6 ⁇ C 60 aryl silyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ C of the group 60 arylboronic of, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ aryl phosphine oxide of the C 60 group And it is selected from the group consisting of C 6 ⁇ C 60 arylamine group,
  • R 5 and R 6 are hydrogen, deuterium, halogen, cyano group, C 1 -C 40 alkyl group, C 3 -C 40 cycloalkyl group, nuclear atom 3-40 heterocycloalkyl group, C 6 -C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, C 1 ⁇ C 40 alkyloxy group of, C 6 ⁇ C 60 aryloxy group, C group 3 ⁇ C 40 alkylsilyl, C 6 ⁇ aryl of C 60 silyl group, C 1 ⁇ C 40 group of an alkyl boron, C 6 ⁇ C group 60 arylboronic of, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ aryl phosphine oxide of a C 60 group, and a C 6 ⁇ C 60 Is selected from the group consisting of arylamine groups, or combine with each other to form a condensed ring,
  • the arylphosphine oxide group and the arylamine group are each independently deuterium, halogen, cyano group, C 1 ⁇ C 40 alkyl group, C 3 ⁇ C 40 cycloalkyl group, 3 to 40 heterocycloalkyl group, C 6 ⁇ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C 1 ⁇ C 40 alkyloxy group of, C 6 ⁇ aryloxy C 60, C 3 ⁇ C 40 alkyl silyl group, C 6 ⁇ C 60 aryl si
  • a to d are each an integer of 1 to 4.
  • the present invention is an organic electroluminescent device comprising an anode, a cathode, and at least one organic layer interposed between the anode and the cathode, at least one of the at least one organic layer is represented by the formula (1)
  • An organic electroluminescent device comprising a compound is provided.
  • the compound represented by Chemical Formula 1 of the present invention may be used as a material of the organic material layer of the organic electroluminescent device because of its excellent thermal stability and luminescence properties.
  • the compound represented by Chemical Formula 1 of the present invention when used as a phosphorescent host material, an organic electroluminescent device having thermal stability, excellent light emission performance, low driving voltage, high efficiency, and long life compared to a conventional host material can be manufactured.
  • the present invention is a compound in which a carbazole and a dibenzo moiety are combined to form a basic skeleton, and an electron-withdrawing group (EWG) having high electron hygroscopicity is introduced into the basic skeleton.
  • EWG electron-withdrawing group
  • the compound represented by the formula (1) of the present invention is substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group (for example, triazine group, pyridine group, tri-substituted with nitrogen (N) of carbazole) Since the electron attractor (EWG) having high electron hygroscopicity (such as a solo pyridine group) is introduced and the whole molecule has a bipolar characteristic, when applied to the organic material layer of the organic electroluminescent device, the binding force between the hole and the electron is increased. Can be.
  • EWG electron attractor
  • the compound represented by Chemical Formula 1 is not only excellent in electron mobility but also high in glass transition temperature (Tg) and thermal stability.
  • the compound represented by the formula (1) of the present invention has excellent electron transport ability and light emission characteristics, and thus, any one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer, which are the organic material layers of the organic EL device.
  • it may be used as a material of any one of an electron transport auxiliary layer further laminated on the light emitting layer, the electron transport layer, and the electron transport layer.
  • the exciton generated in the light emitting layer may be prevented from being diffused into the electron transport layer or the hole transport layer adjacent to the light emitting layer.
  • the number of excitons contributing to light emission in the light emitting layer may be improved, and thus the luminous efficiency of the device may be improved, and the durability and stability of the device may be improved, and thus the life of the device may be efficiently increased.
  • Most of the materials developed show physical characteristics that can be driven at low voltages, thereby improving their lifetime.
  • a ring is a monocyclic or polycyclic aromatic ring
  • X is -O-, -S-, or -C (R 5 R 6 )-
  • L 1 and L 2 is a single Or a C 6 to C 18 arylene group and a heteroarylene group having 5 to 18 nuclear atoms.
  • Ar 1 is represented by any one of the following formulas (2) to (4).
  • Y 1 to Y 17 are the same as or different from each other, and each independently selected from N or C (R 7 ), wherein when R 7 is plural, a plurality of R 7 may be the same or different from each other.
  • any one of Y 6 to Y 9 bonded to L 1 is preferably C (R 7 ).
  • Z 1 may be N or C (R 7 ).
  • R 1 to R 4 and R 7 are each independently hydrogen, deuterium, halogen, cyano group, C 1 to C 40 alkyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C Aryl group of 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C 1 to C 40 , aryloxy group of C 6 to C 60 , alkylsilyl group of C 3 to C 40 , C 6 ⁇ C 60 aryl silyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ C of the group 60 arylboronic of, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ aryl phosphine oxide of the C 60 group And it is selected from the group consisting of C 6 ⁇ C 60 arylamine group.
  • R 1 to R 4 are all hydrogen.
  • R 5 and R 6 are hydrogen, deuterium, halogen, cyano group, C 1 -C 40 alkyl group, C 3 -C 40 cycloalkyl group, nuclear atom 3-40 heterocycloalkyl group, C 6 -C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, C 1 ⁇ C 40 alkyloxy group of, C 6 ⁇ C 60 aryloxy group, C group 3 ⁇ C 40 alkylsilyl, C 6 ⁇ aryl of C 60 silyl group, C 1 ⁇ C 40 group of an alkyl boron, C 6 ⁇ C group 60 arylboronic of, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ aryl phosphine oxide of a C 60 group, and a C 6 ⁇ C 60 It may be selected from the group consisting of arylamine groups, or may be combined with each other to form a condensed ring.
  • R 5
  • the arylphosphine oxide group and the arylamine group are each independently deuterium, halogen, cyano group, C 1 ⁇ C 40 alkyl group, C 3 ⁇ C 40 cycloalkyl group, 3 to 40 heterocycloalkyl group, C 6 ⁇ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C 1 ⁇ C 40 alkyloxy group of, C 6 ⁇ aryloxy C 60, C 3 ⁇ C 40 alkyl silyl group, C 6 ⁇ C 60 aryl si
  • a to d are each an integer of 1 to 4.
  • L 2 is an aryl group containing phenyl, biphenyl and the like
  • L 2 is an aryl group containing phenyl, biphenyl and the like
  • L 1 may be a single bond or arylene selected from the following structures, and n is an integer of 0 to 2.
  • L 1 is a single bond
  • Ar 1 is represented by Chemical Formula 2 or 3, wherein at least two of Y 1 to Y 5 and Y 6 to Y 9 are N , wherein L 2 is preferably an arylene group of C 6 ⁇ C 18.
  • the substituents represented by Formulas 2 and 3 are preferably selected from the group consisting of substituents represented by Formulas S1 to S5.
  • the compound represented by Formula 1 of the present invention may be embodied by the following Compound 1 to 330, but is not limited thereto.
  • Alkyl in the present invention means a monovalent substituent derived from a straight or branched chain 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 chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.
  • alkynyl refers to a monovalent substituent derived from a straight or branched chain 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, 2-propynyl, and the like.
  • Aryl in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms combined with a single ring or two or more rings.
  • a form in which two or more rings are attached to each other (pendant) or condensed may also be included.
  • Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.
  • Heteroaryl as used herein means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. At least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O, S or Se.
  • a form in which two or more rings are pendant or condensed with each other may be included, and may also include a form in which the two or more rings are condensed with an aryl group.
  • heteroaryl examples include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.
  • 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carb
  • aryloxy is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 40 carbon atoms.
  • R means aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.
  • alkyloxy is a monovalent substituent represented by R'O-, wherein R 'means an alkyl having 1 to 40 carbon atoms, linear, branched or cyclic structure It may include.
  • alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
  • Arylamine in the present invention means an amine substituted with aryl having 6 to 40 carbon atoms.
  • Cycloalkyl as used herein means monovalent substituents derived from monocyclic or polycyclic non-aromatic hydrocarbons having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
  • heterocycloalkyl monovalent substituents derived from non-aromatic hydrocarbons having 3 to 40 nuclear atoms, wherein 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, but are not limited to, morpholine, piperazine, and the like.
  • alkylsilyl means silyl substituted with alkyl having 1 to 40 carbon atoms
  • arylsilyl means silyl substituted with aryl having 5 to 40 carbon atoms
  • condensed ring means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
  • the present invention provides an organic electroluminescent device (organic EL device) comprising the compound represented by the formula (1).
  • the organic electroluminescent device of the present invention comprises an anode, a cathode and at least one organic layer interposed between the anode and the cathode, at least one of the at least one organic layer It includes a compound represented by the formula (1).
  • the compound may be used alone, or two or more may be used in combination.
  • the at least one organic material layer may be any one or more of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, a life improvement layer, an electron transport layer and an electron injection layer, wherein at least one organic material layer is a compound represented by Formula 1 It may include.
  • the organic material layer including the compound of Formula 1 may be selected from the group consisting of an emission layer, an electron transport layer and an electron transport auxiliary layer further stacked on the electron transport layer, it is preferable that the light emitting layer.
  • the light emitting layer of the organic electroluminescent device of the present invention may include a host, wherein the host may include a compound represented by Formula 1 alone or another compound together with the compound represented by Formula 1 as a host. .
  • the compound represented by Chemical Formula 1 is included as a light emitting layer material of the organic electroluminescent device, preferably a blue, green, or red phosphorescent host material, the binding force between the holes and the electrons in the light emitting layer increases, so that the efficiency of the organic electroluminescent device (Luminescence efficiency and power efficiency), lifetime, brightness and driving voltage can be improved.
  • the compound represented by Chemical Formula 1 is preferably included in the organic electroluminescent device as a green and / or red phosphorescent host, fluorescent host, or dopant material.
  • the compound represented by Formula 1 of the present invention is preferably a phosphorescent host, a fluorescent host or a dopant material of the light emitting layer, and more preferably a red phosphorescent host of the light emitting layer.
  • the structure of the organic EL device of the present invention is not particularly limited, but may be a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer, and a cathode are sequentially stacked.
  • At least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer may include a compound represented by the formula (1), preferably in addition to the light emitting layer, the electron transport layer and the electron transport layer
  • the electron transport auxiliary layer to be laminated may include a compound represented by Chemical Formula 1.
  • the structure of the organic EL device of the present invention may be a structure in which an insulating layer or an adhesive layer is inserted at the interface between the electrode (cathode or anode) and the organic material layer.
  • the organic electroluminescent device of the present invention can be manufactured by forming an organic material layer and an electrode by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Chemical Formula 1.
  • 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.
  • the substrate used in the manufacture of the organic EL device of the present invention is not particularly limited, but silicon wafers, quartz, glass plates, metal plates, plastic films, sheets, and the like may be used.
  • 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), 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), 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
  • the negative electrode material may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or an alloy thereof; And multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.
  • the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer is not particularly limited, and conventional materials known in the art may be used.
  • CD1 (10 g, 22.9 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (6.8 g, 22.9 mmol) and Pd 2 (dba) 3 (1.1 g, 1.15 mmol), P (t-Bu) 3 (0.9 g, 4.6 mmol) and sodium tert-butoxide (4.4 g, 45.9 mmol) were added to 150 ml toluene and stirred at 110 ° C. for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer was purified by column chromatography to give the target compound 1 (11.6 g, yield 75%).
  • a target compound 60 (12.1 g, yield 76%) was obtained in the same manner as Synthesis Example 12 except for using CD8 (10 g, 21.7 mmol) instead of CD1.
  • a glass substrate coated with ITO Indium tin oxide
  • ITO Indium tin oxide
  • a solvent such as isopropyl alcohol, acetone, methanol, etc.
  • UV OZONE cleaner Power sonic 405, Hwasin Tech
  • M-MTDATA 60 nm) / TCTA (80 nm) / 90% of compound 1 + 10% of Ir (ppy) 3 (30nm) / BCP (10 nm) / Alq 3 on the prepared ITO transparent glass substrate (electrode) (30 nm) / LiF (1 nm) / Al (200 nm) were stacked in order to prepare a green organic EL device.
  • a green organic EL device was manufactured in the same manner as in Example 1, except that each compound synthesized in Synthesis Examples 2 to 11 was used instead of Compound 1 as the green light-emitting host material.
  • a green organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound 1 as the green light-emitting host material.
  • Example 1 Compound 1 6.61 515 41.3
  • Example 2 Compound 6 6.72 516 42.6
  • Example 3 Compound 171 6.43 517 44.5
  • Example 4 Compound 191 6.63 517 42.3
  • Example 5 Compound 51 6.53 518 44.1
  • Example 6 Compound 56 6.34 515 43.6
  • Example 7 Compound 231 6.34 514 48.2
  • Example 8 Compound 251 6.54 515 47.4
  • Example 9 Compound 106 6.56 516 43.2
  • Example 10 Compound 296 6.45 517 42.4
  • Example 11 Compound 316 6.74 515 43.5 Comparative Example 1 CBP 6.93 516 38.2
  • the green organic electroluminescent devices of Examples 1 to 11 using the compound according to the present invention as the material of the light emitting layer compared to the green organic electroluminescent device of Comparative Example 1, in which the conventional CBP was used as the light emitting layer. It can be seen that the efficiency and the driving voltage are excellent.
  • a glass substrate coated with ITO Indium tin oxide
  • ITO Indium tin oxide
  • a solvent such as isopropyl alcohol, acetone, methanol, etc.
  • UV OZONE cleaner Power sonic 405, Hwasin Tech
  • a red organic electroluminescent device was manufactured in the same manner as in Example 12, except that each compound synthesized in Synthesis Examples 13 to 22 was used instead of the compound 5 as a red light emitting host material.
  • a red organic electroluminescent device was manufactured in the same manner as in Example 12, except that CBP was used instead of compound 5 as a red light emitting host material.
  • the red organic electroluminescent devices of Examples 12 to 22 using the compound according to the present invention in the light emitting layer compared to the red organic electroluminescent device of Comparative Example 2 using the conventional CBP in the light emitting layer, It can be seen that the driving voltage is excellent.
  • the compound represented by Chemical Formula 1 of the present invention may be used as a material of the organic material layer of the organic electroluminescent device because of its excellent thermal stability and luminescence properties.
  • the compound represented by Chemical Formula 1 of the present invention when used as a phosphorescent host material, an organic electroluminescent device having thermal stability, excellent light emission performance, low driving voltage, high efficiency, and long life compared to a conventional host material can be manufactured.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Luminescent Compositions (AREA)
  • Indole Compounds (AREA)

Abstract

The present invention relates to a novel compound having excellent thermal stability and luminescent ability, and an organic electroluminescent element having enhanced characteristics such as luminous efficiency, driving voltage, and lifespan by incorporating the novel compound into one organic layer or more.

Description

유기 발광 화합물 및 이를 포함하는 유기 전계 발광 소자Organic light emitting compound and organic electroluminescent device comprising the same
본 발명은 신규한 유기 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것으로, 보다 구체적으로는 유기 전계 발광 소자의 유기물층에 사용되는 화합물에 관한 것이다.The present invention relates to a novel organic compound and an organic electroluminescent device comprising the same, and more particularly to a compound used in the organic material layer of the organic electroluminescent device.
1950년대 베르나소스(Bernanose)의 유기 박막 발광 관측을 시점으로 1965년 안트라센 단결정을 이용한 청색 전기발광으로 이어진 유기 전계 발광(electroluminescent, EL) 소자에 대한 연구는 1987년 탕(Tang)에 의하여 정공층과 발광층의 기능층으로 나눈 적층구조의 유기 전계 발광 소자가 제시되었다. 이후, 고효율, 고수명의 유기 전계 발광 소자를 만들기 위하여, 소자 내 각각의 특징적인 유기물 층을 도입하는 형태로 발전하여 왔으며, 이에 사용되는 특화된 물질의 개발로 이어졌다.From the observation of Bernanose organic thin film emission in the 1950s, the study of organic electroluminescent (EL) devices, which led to blue electroluminescence using anthracene single crystal in 1965, was developed by Tang in 1987. An organic electroluminescent device having a laminated structure divided by a functional layer of a light emitting layer has been proposed. Since then, in order to make a high efficiency, high-life organic electroluminescent device, it has been developed in the form of introducing each characteristic organic material layer in the device, leading to the development of specialized materials used therein.
유기 전계 발광 소자는 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 the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground, they shine. 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 its function.
유기 전계 발광 소자의 발광층 형성 재료는 발광색에 따라 청색, 녹색, 적색 발광 재료로 구분될 수 있다. 그 밖에, 보다 나은 천연색을 구현하기 위한 발광 재료로 노란색 및 주황색 발광 재료도 사용된다. 또한, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여, 발광 재료로서 호스트/도펀트 계를 사용할 수 있다. 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 재료의 개발은 이론적으로 형광에 비해 4배까지 발광 효율을 향상시킬 수 있어 인광 도펀트 뿐만 아니라 인광 호스트 재료들에 대해 관심이 집중되고 있다.The light emitting layer forming material of the organic EL device may be classified into blue, green, and red light emitting materials according to light emission colors. In addition, yellow and orange light emitting materials are also used as light emitting materials for realizing a better natural color. In addition, a host / dopant system may be used as the light emitting material in order to increase the light emission efficiency through increase in color purity and energy transfer. The dopant material may be divided 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, the development of the phosphorescent material can theoretically improve the luminous efficiency up to 4 times compared to the fluorescence, so attention is focused on phosphorescent dopants as well as phosphorescent host materials.
현재까지 정공 주입층, 정공 수송층. 정공 차단층, 전자 수송층 재료로는, 하기 화학식으로 표현된 NPB, BCP, Alq3 등이 널리 알려져 있고, 발광 재료는 안트라센 유도체들이 형광 도펀트/호스트 재료로서 보고되고 있다. 특히, 발광 재료 중 효율 향상 측면에서 장점을 가지고 있는 인광 재료로서는 Firpic, Ir(ppy)3, (acac)Ir(btp)2 등과 같은 Ir을 포함하는 금속 착체 화합물이 청색, 녹색, 적색의 도펀트 재료로 사용되고 있다. 현재까지는 CBP(4,4-dicarbazolybiphenyl)가 인광 호스트 재료로 우수한 특성을 나타내고 있다.Hole injection layer, hole transport layer to date. As the hole blocking layer and the electron transporting layer material, NPB, BCP, Alq 3 and the like represented by the following general formulas are widely known, and anthracene derivatives have been reported as fluorescent dopant / host materials in the light emitting material. In particular, phosphorescent materials having advantages in terms of efficiency improvement among the light emitting materials include metal complex compounds containing Ir such as Firpic, Ir (ppy) 3 , and (acac) Ir (btp) 2 . Is being used. To date, CBP (4,4-dicarbazolybiphenyl) has excellent properties as a phosphorescent host material.
Figure PCTKR2017005670-appb-I000001
Figure PCTKR2017005670-appb-I000001
Figure PCTKR2017005670-appb-I000002
Figure PCTKR2017005670-appb-I000002
그러나 기존의 재료들은 발광 특성 측면에서는 유리한 면이 있으나, 유리전이온도가 낮고 열적 안정성이 좋지 않아 유기 전계 발광 소자의 수명 측면에서 만족할 만한 수준이 되지 못하고 있다.However, existing materials have advantages in terms of luminescence properties, but are not satisfactory in terms of lifespan of organic electroluminescent devices due to low glass transition temperature and poor thermal stability.
상기한 문제점을 해결하기 위해, 본 발명은 유기 전계 발광 소자에 적용할 수 있으며, 열적 안적성 및 발광 특성 등이 우수한 신규 화합물을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention can be applied to an organic electroluminescent device, and an object of the present invention is to provide a novel compound excellent in thermal stability and luminescent properties.
또한 본 발명은 상기 신규 화합물을 포함하여 낮은 구동 전압과 높은 발광 효율을 나타내며 수명이 향상된 유기 전계 발광 소자를 제공하는 것을 목적으로 한다.Another object of the present invention is to provide an organic electroluminescent device including the novel compound, which exhibits low driving voltage and high luminous efficiency and has an improved lifetime.
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).
[화학식 1][Formula 1]
Figure PCTKR2017005670-appb-I000003
Figure PCTKR2017005670-appb-I000003
상기 화학식 1에서,In Chemical Formula 1,
A 고리는 단일환 또는 다환의 방향족 고리이고;A ring is a monocyclic or polycyclic aromatic ring;
X는 -O-, -S-, 또는 -C(R5R6)- 이며;X is -O-, -S-, or -C (R 5 R 6 )-;
L1 및 L2는 단일결합이거나, 또는 C6~C18의 아릴렌기 및 핵원자수 5 내지 18의 헤테로아릴렌기로 이루어진 군에서 선택되고,L 1 and L 2 are a single bond or selected from the group consisting of C 6 to C 18 arylene groups and heteroarylene groups having 5 to 18 nuclear atoms,
Ar1은 하기 화학식 2 내지 화학식 4 중 어느 하나로 표시되고,Ar 1 is represented by any one of the following Chemical Formulas 2 to 4,
[화학식 2][Formula 2]
Figure PCTKR2017005670-appb-I000004
Figure PCTKR2017005670-appb-I000004
[화학식 3][Formula 3]
Figure PCTKR2017005670-appb-I000005
Figure PCTKR2017005670-appb-I000005
[화학식 4][Formula 4]
Figure PCTKR2017005670-appb-I000006
Figure PCTKR2017005670-appb-I000006
상기 화학식 2 내지 4에서, *은 결합이 이루어지는 부분을 의미하고,In Chemical Formulas 2 to 4, * means a part in which a bond is formed,
Y1 내지 Y17은 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R7)에서 선택되고, 이때 R7이 복수인 경우, 복수의 R7은 서로 같거나 또는 상이하며,Y 1 to Y 17 are the same as or different from each other, and each independently selected from N or C (R 7 ), wherein when R 7 is plural, a plurality of R 7 are the same as or different from each other,
상기 화학식 3에서 L1에 결합되는 Y6 내지 Y9 중 어느 하나는 C(R7)이고,In Formula 3, any one of Y 6 to Y 9 bonded to L 1 is C (R 7 ),
Z1은 N 또는 C(R7)이며,Z 1 is N or C (R 7 ),
R1 내지 R4 및 R7은 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,R 1 to R 4 and R 7 are each independently hydrogen, deuterium, halogen, cyano group, C 1 to C 40 alkyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C Aryl group of 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C 1 to C 40 , aryloxy group of C 6 to C 60 , alkylsilyl group of C 3 to C 40 , C 6 ~ C 60 aryl silyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C of the group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ aryl phosphine oxide of the C 60 group And it is selected from the group consisting of C 6 ~ C 60 arylamine group,
R5 및 R6는 수소, 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 서로 결합하여 축합 고리를 형성하며,R 5 and R 6 are hydrogen, deuterium, halogen, cyano group, C 1 -C 40 alkyl group, C 3 -C 40 cycloalkyl group, nuclear atom 3-40 heterocycloalkyl group, C 6 -C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, C 1 ~ C 40 alkyloxy group of, C 6 ~ C 60 aryloxy group, C group 3 ~ C 40 alkylsilyl, C 6 ~ aryl of C 60 silyl group, C 1 ~ C 40 group of an alkyl boron, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ aryl phosphine oxide of a C 60 group, and a C 6 ~ C 60 Is selected from the group consisting of arylamine groups, or combine with each other to form a condensed ring,
R1 내지 R7의 알킬기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴아민기는 각각 독립적으로, 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~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,An alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, an arylphosphine group of R 1 to R 7 , The arylphosphine oxide group and the arylamine group are each independently deuterium, halogen, cyano group, C 1 ~ C 40 alkyl group, C 3 ~ C 40 cycloalkyl group, 3 to 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C 1 ~ C 40 alkyloxy group of, C 6 ~ aryloxy C 60, C 3 ~ C 40 alkyl silyl group, C 6 ~ C 60 aryl silyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ aryl phosphine oxide of a C 60 group, and Is substituted or unsubstituted with one or more substituents selected from the group consisting of C 6 ~ C 60 arylamine group,
a 내지 d는 각각 1 내지 4의 정수이다.a to d are each an integer of 1 to 4;
또한, 본 발명은 양극, 음극, 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물 층을 포함하는 유기 전계 발광 소자로서, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자를 제공한다.In addition, the present invention is an organic electroluminescent device comprising an anode, a cathode, and at least one organic layer interposed between the anode and the cathode, at least one of the at least one organic layer is represented by the formula (1) An organic electroluminescent device comprising a compound is provided.
본 발명의 화학식 1로 표시되는 화합물은 열적 안정성 및 발광 특성이 우수하기 때문에 유기 전계 발광 소자의 유기물 층의 재료로 사용될 수 있다. 특히, 본 발명의 화학식 1로 표시되는 화합물을 인광 호스트 재료로 사용할 경우, 종래의 호스트 재료에 비해 열적 안정성, 우수한 발광 성능, 낮은 구동전압, 높은 효율 및 장수명을 갖는 유기 전계 발광 소자를 제조할 수 있고, 나아가 성능 및 수명이 향상된 풀 칼라 디스플레이 패널도 제조할 수 있다.The compound represented by Chemical Formula 1 of the present invention may be used as a material of the organic material layer of the organic electroluminescent device because of its excellent thermal stability and luminescence properties. In particular, when the compound represented by Chemical Formula 1 of the present invention is used as a phosphorescent host material, an organic electroluminescent device having thermal stability, excellent light emission performance, low driving voltage, high efficiency, and long life compared to a conventional host material can be manufactured. In addition, it is possible to manufacture a full color display panel with improved performance and lifespan.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
<신규 유기 화합물><New organic compound>
본 발명은 카바졸과 디벤조 모이어티가 결합되어 기본 골격을 형성하고, 상기 기본 골격에 전자 흡습성이 큰 전자 끌개기(electron-withdrawing group; EWG)가 도입된 화합물로, 상기 화학식 1로 표시된다.The present invention is a compound in which a carbazole and a dibenzo moiety are combined to form a basic skeleton, and an electron-withdrawing group (EWG) having high electron hygroscopicity is introduced into the basic skeleton. .
구체적으로, 본 발명의 화학식 1로 표시되는 화합물은 카바졸의 질소(N)에 치환 또는 비치환된 아릴기, 또는 치환 또는 비치환된 헤테로아릴기(예를 들어, 트리아진기, 피리딘기, 트라이졸로피리딘기 등)와 같은 전자 흡습성이 큰 전자 끌개기(EWG)가 도입되어 분자 전체가 바이폴라(bipolar) 특성을 갖기 때문에, 이를 유기 전계 발광 소자의 유기물층에 적용할 경우 정공과 전자의 결합력을 높일 수 있다.Specifically, the compound represented by the formula (1) of the present invention is substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group (for example, triazine group, pyridine group, tri-substituted with nitrogen (N) of carbazole) Since the electron attractor (EWG) having high electron hygroscopicity (such as a solo pyridine group) is introduced and the whole molecule has a bipolar characteristic, when applied to the organic material layer of the organic electroluminescent device, the binding force between the hole and the electron is increased. Can be.
이와 같이, 상기 화학식 1로 표시되는 화합물은 전자 이동성이 우수할 뿐 아니라 높은 유리 전이온도(Tg) 및 열적 안정이 우수하다. 이로 인해, 본 발명의 화학식 1로 표시되는 화합물은 전자 수송 능력 및 발광 특성이 우수하기 때문에, 유기 전계 발광 소자의 유기물층인 정공 주입층, 정공 수송층, 발광층, 전자 수송층 및 전자 주입층 중 어느 하나의 재료로 사용될 수 있다. 바람직하게는 발광층, 전자 수송층 및 전자 수송층에 추가로 적층되는 전자수송 보조층 중 어느 하나의 재료로 사용될 수 있다.As such, the compound represented by Chemical Formula 1 is not only excellent in electron mobility but also high in glass transition temperature (Tg) and thermal stability. For this reason, the compound represented by the formula (1) of the present invention has excellent electron transport ability and light emission characteristics, and thus, any one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer, which are the organic material layers of the organic EL device. Can be used as a material. Preferably, it may be used as a material of any one of an electron transport auxiliary layer further laminated on the light emitting layer, the electron transport layer, and the electron transport layer.
또한, 발광층에서 생성된 엑시톤이 발광층에 인접하는 전자수송층 또는 정공수송층으로 확산되는 것을 방지할 수 있다. 발광층 내에서 발광에 기여하는 엑시톤의 수가 증가되어 소자의 발광 효율이 개선될 수 있고, 소자의 내구성 및 안정성이 향상되어 소자의 수명이 효율적으로 증가될 수 있다. 개발된 재료들이 대부분 저전압 구동이 가능하여 이로 인한 수명이 개선되는 물리적 특징들을 나타낸다.In addition, the exciton generated in the light emitting layer may be prevented from being diffused into the electron transport layer or the hole transport layer adjacent to the light emitting layer. The number of excitons contributing to light emission in the light emitting layer may be improved, and thus the luminous efficiency of the device may be improved, and the durability and stability of the device may be improved, and thus the life of the device may be efficiently increased. Most of the materials developed show physical characteristics that can be driven at low voltages, thereby improving their lifetime.
상기 화학식 1로 표시되는 화합물에서, A 고리는 단일환 또는 다환의 방향족 고리이고, X는 -O-, -S-, 또는 -C(R5R6)- 이며, L1 및 L2는 단일결합이거나, 또는 C6~C18의 아릴렌기 및 핵원자수 5 내지 18의 헤테로아릴렌기로 이루어진 군에서 선택된다.In the compound represented by Formula 1, A ring is a monocyclic or polycyclic aromatic ring, X is -O-, -S-, or -C (R 5 R 6 )-, L 1 and L 2 is a single Or a C 6 to C 18 arylene group and a heteroarylene group having 5 to 18 nuclear atoms.
본 발명의 바람직한 일례를 들면, Ar1은 하기 화학식 2 내지 화학식 4 중 어느 하나로 표시된다.For one preferred embodiment of the present invention, Ar 1 is represented by any one of the following formulas (2) to (4).
[화학식 2][Formula 2]
Figure PCTKR2017005670-appb-I000007
Figure PCTKR2017005670-appb-I000007
[화학식 3][Formula 3]
Figure PCTKR2017005670-appb-I000008
Figure PCTKR2017005670-appb-I000008
[화학식 4][Formula 4]
Figure PCTKR2017005670-appb-I000009
Figure PCTKR2017005670-appb-I000009
상기 화학식 2 내지 4에서,In Chemical Formulas 2 to 4,
*은 결합이 이루어지는 부분을 의미하고,* Means the part where the coupling is made,
Y1 내지 Y17은 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R7)에서 선택되고, 이때 R7이 복수인 경우, 복수의 R7은 서로 같거나 또는 상이할 수 있다.Y 1 to Y 17 are the same as or different from each other, and each independently selected from N or C (R 7 ), wherein when R 7 is plural, a plurality of R 7 may be the same or different from each other.
상기 화학식 3에서, L1에 결합되는 Y6 내지 Y9 중 어느 하나는 C(R7)인 것이 바람직하다.In Formula 3, any one of Y 6 to Y 9 bonded to L 1 is preferably C (R 7 ).
상기 화학식 4에서, Z1은 N 또는 C(R7)일 수 있다.In Chemical Formula 4, Z 1 may be N or C (R 7 ).
R1 내지 R4 및 R7은 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된다. 바람직하게는 상기 R1 내지 R4는 모두 수소인 경우이다.R 1 to R 4 and R 7 are each independently hydrogen, deuterium, halogen, cyano group, C 1 to C 40 alkyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C Aryl group of 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C 1 to C 40 , aryloxy group of C 6 to C 60 , alkylsilyl group of C 3 to C 40 , C 6 ~ C 60 aryl silyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C of the group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ aryl phosphine oxide of the C 60 group And it is selected from the group consisting of C 6 ~ C 60 arylamine group. Preferably, R 1 to R 4 are all hydrogen.
R5 및 R6는 수소, 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 서로 결합하여 축합 고리를 형성할 수 있다. 바람직하게는, 상기 R5 및 R6는 각각 독립적으로, 수소, C1~C40의 알킬기 및 C6~60의 아릴기로 이루어진 군에서 선택된다.R 5 and R 6 are hydrogen, deuterium, halogen, cyano group, C 1 -C 40 alkyl group, C 3 -C 40 cycloalkyl group, nuclear atom 3-40 heterocycloalkyl group, C 6 -C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, C 1 ~ C 40 alkyloxy group of, C 6 ~ C 60 aryloxy group, C group 3 ~ C 40 alkylsilyl, C 6 ~ aryl of C 60 silyl group, C 1 ~ C 40 group of an alkyl boron, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ aryl phosphine oxide of a C 60 group, and a C 6 ~ C 60 It may be selected from the group consisting of arylamine groups, or may be combined with each other to form a condensed ring. Preferably, R 5 and R 6 are each independently selected from the group consisting of hydrogen, an alkyl group of C 1 ~ C 40 and an aryl group of C 6 ~ 60 .
R1 내지 R7의 알킬기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴아민기는 각각 독립적으로, 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~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 비치환되될 수 있다.An alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, an arylphosphine group of R 1 to R 7 , The arylphosphine oxide group and the arylamine group are each independently deuterium, halogen, cyano group, C 1 ~ C 40 alkyl group, C 3 ~ C 40 cycloalkyl group, 3 to 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C 1 ~ C 40 alkyloxy group of, C 6 ~ aryloxy C 60, C 3 ~ C 40 alkyl silyl group, C 6 ~ C 60 aryl silyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ aryl phosphine oxide of a C 60 group, and It may be unsubstituted or substituted with one or more substituents selected from the group consisting of C 6 to C 60 arylamine groups.
a 내지 d는 각각 1 내지 4의 정수이다.a to d are each an integer of 1 to 4;
본 발명의 화학식 1로 표시되는 화합물은, L2가 페닐 또는 비페닐 등을 포함하는 아릴기인 경우에 하기 화학식 5의 화합물로 보다 구체화될 수 있다.The compound represented by the general formula (1) of the present invention, when L 2 is an aryl group containing phenyl, biphenyl and the like can be more specifically embodied by the compound of the formula (5).
[화학식 5][Formula 5]
Figure PCTKR2017005670-appb-I000010
Figure PCTKR2017005670-appb-I000010
상기 화학식 5에서, L1은 단일결합 또는 하기 구조에서 선택되는 아릴렌일 수 있으며, n은 0 내지 2의 정수이다.In Formula 5, L 1 may be a single bond or arylene selected from the following structures, and n is an integer of 0 to 2.
Figure PCTKR2017005670-appb-I000011
Figure PCTKR2017005670-appb-I000011
한편 본 발명에 따른 화학식 1로 표시되는 화합물에서, L1은 단일결합이고, Ar1은 화학식 2 또는 3으로 표시되며, 여기서 Y1 내지 Y5, 및 Y6 내지 Y9 중에서 2 이상은 N이고, 상기 L2는 C6~C18의 아릴렌기인 것이 바람직하다.Meanwhile, in the compound represented by Chemical Formula 1 according to the present invention, L 1 is a single bond, Ar 1 is represented by Chemical Formula 2 or 3, wherein at least two of Y 1 to Y 5 and Y 6 to Y 9 are N , wherein L 2 is preferably an arylene group of C 6 ~ C 18.
구체적으로, 상기 화학식 2 및 3으로 표시되는 치환체는 하기 화학식 S1 내지 S5로 표시되는 치환체로 이루어진 군에서 선택되는 것이 바람직하다.Specifically, the substituents represented by Formulas 2 and 3 are preferably selected from the group consisting of substituents represented by Formulas S1 to S5.
Figure PCTKR2017005670-appb-I000012
Figure PCTKR2017005670-appb-I000012
이러한 본 발명의 화학식 1로 표시되는 화합물은 하기 화합물 1 내지 330으로 구체화될 수 있으나, 이들로 한정되는 것은 아니다.The compound represented by Formula 1 of the present invention may be embodied by the following Compound 1 to 330, but is not limited thereto.
Figure PCTKR2017005670-appb-I000013
Figure PCTKR2017005670-appb-I000013
Figure PCTKR2017005670-appb-I000014
Figure PCTKR2017005670-appb-I000014
Figure PCTKR2017005670-appb-I000015
Figure PCTKR2017005670-appb-I000015
Figure PCTKR2017005670-appb-I000016
Figure PCTKR2017005670-appb-I000016
Figure PCTKR2017005670-appb-I000017
Figure PCTKR2017005670-appb-I000017
Figure PCTKR2017005670-appb-I000018
Figure PCTKR2017005670-appb-I000018
Figure PCTKR2017005670-appb-I000019
Figure PCTKR2017005670-appb-I000019
Figure PCTKR2017005670-appb-I000020
Figure PCTKR2017005670-appb-I000020
Figure PCTKR2017005670-appb-I000021
Figure PCTKR2017005670-appb-I000021
Figure PCTKR2017005670-appb-I000022
Figure PCTKR2017005670-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 등을 들 수 있으나, 이에 한정되지는 않는다."Alkyl" in the present invention means a monovalent substituent derived from a straight or branched chain 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) 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "alkenyl" refers to a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.
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) 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "alkynyl" refers to a monovalent substituent derived from a straight or branched chain 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, 2-propynyl, and the like.
본 발명에서 "아릴"은 단독 고리 또는 2이상의 고리가 조합된 탄소수 6 내지 40의 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 등을 들 수 있으나, 이에 한정되지는 않는다."Aryl" in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms combined with a single ring or two or more rings. In addition, a form in which two or more rings are attached to each other (pendant) or condensed may also be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.
본 발명에서 "헤테로아릴"은 핵원자수 5 내지 40의 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 등을 들 수 있으나, 이에 한정되지는 않는다."Heteroaryl" as used herein means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. At least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are pendant or condensed with each other may be included, and may also include a form in which the two or more rings are condensed with an aryl group. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.
본 발명에서 "아릴옥시"는 RO-로 표시되는 1가의 치환기로, 상기 R은 탄소수 5 내지 40의 아릴을 의미한다. 이러한 아릴옥시의 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.
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. 알킬옥시의 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R 'means an alkyl having 1 to 40 carbon atoms, linear, branched or cyclic structure It may include. Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
본 발명에서 "아릴아민"은 탄소수 6 내지 40의 아릴로 치환된 아민을 의미한다."Arylamine" in the present invention means an amine substituted with aryl having 6 to 40 carbon atoms.
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) 등을 들 수 있으나, 이에 한정되지는 않는다."Cycloalkyl" as used herein means monovalent substituents derived from monocyclic or polycyclic non-aromatic hydrocarbons having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
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 등을 들 수 있으나, 이에 한정되지는 않는다.By "heterocycloalkyl" is meant monovalent substituents derived from non-aromatic hydrocarbons having 3 to 40 nuclear atoms, wherein 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, but are not limited to, morpholine, piperazine, and the like.
본 발명에서 "알킬실릴"은 탄소수 1 내지 40의 알킬로 치환된 실릴이고, "아릴실릴"은 탄소수 5 내지 40의 아릴로 치환된 실릴을 의미한다.In the present invention, "alkylsilyl" means silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" means silyl substituted with aryl having 5 to 40 carbon atoms.
본 발명에서 "축합고리"는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.As used herein, the term “condensed ring” means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
<유기 전계 발광 소자><Organic EL device>
본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자(유기 EL 소자)를 제공한다.The present invention provides an organic electroluminescent device (organic EL device) comprising the compound represented by the formula (1).
보다 구체적으로, 본 발명의 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.More specifically, the organic electroluminescent device of the present invention comprises an anode, a cathode and at least one organic layer interposed between the anode and the cathode, at least one of the at least one organic layer It includes a compound represented by the 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, 발광 보조층, 발광층, 수명 개선층, 전자 수송층 및 전자 주입층 중 어느 하나 이상일 수 있고, 이 중에서 적어도 하나의 유기물층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. 구체적으로 상기 화학식 1의 화합물을 포함하는 유기물층은 발광층, 전자수송층 및 전자 수송층에 추가로 적층되는 전자수송 보조층으로 구성된 군에서 선택될 수 있으며, 발광층인 것이 바람직하다.The at least one organic material layer may be any one or more of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, a life improvement layer, an electron transport layer and an electron injection layer, wherein at least one organic material layer is a compound represented by Formula 1 It may include. Specifically, the organic material layer including the compound of Formula 1 may be selected from the group consisting of an emission layer, an electron transport layer and an electron transport auxiliary layer further stacked on the electron transport layer, it is preferable that the light emitting layer.
본 발명의 유기 전계 발광 소자의 발광층은 호스트를 포함할 수 있는데, 이때 호스트로서 상기 화학식 1로 표시되는 화합물을 단독으로 포함하거나 상기 화학식 1로 표시되는 화합물과 함께 다른 화합물을 호스트로 포함할 수 있다.The light emitting layer of the organic electroluminescent device of the present invention may include a host, wherein the host may include a compound represented by Formula 1 alone or another compound together with the compound represented by Formula 1 as a host. .
상기 화학식 1로 표시되는 화합물을 유기 전계 발광 소자의 발광층 재료, 바람직하게는 청색, 녹색, 적색의 인광 호스트 재료로 포함할 경우, 발광층에서 정공과 전자의 결합력이 높아지기 때문에, 유기 전계 발광 소자의 효율(발광효율 및 전력효율), 수명, 휘도 및 구동전압 등을 향상시킬 수 있다. 구체적으로 상기 화학식 1로 표시되는 화합물은 녹색 및/또는 적색의 인광 호스트, 형광 호스트, 또는 도펀트 재료로서 유기 전계 발광 소자에 포함되는 것이 바람직하다. 특히, 본 발명의 화학식 1로 표시되는 화합물은 발광층의 인광 호스트, 형광 호스트 또는 도펀트 재료인 것이 바람직하며, 발광층의 적색 인광 호스트인 것이 더욱 바람직하다.When the compound represented by Chemical Formula 1 is included as a light emitting layer material of the organic electroluminescent device, preferably a blue, green, or red phosphorescent host material, the binding force between the holes and the electrons in the light emitting layer increases, so that the efficiency of the organic electroluminescent device (Luminescence efficiency and power efficiency), lifetime, brightness and driving voltage can be improved. Specifically, the compound represented by Chemical Formula 1 is preferably included in the organic electroluminescent device as a green and / or red phosphorescent host, fluorescent host, or dopant material. In particular, the compound represented by Formula 1 of the present invention is preferably a phosphorescent host, a fluorescent host or a dopant material of the light emitting layer, and more preferably a red phosphorescent host of the light emitting layer.
이러한 본 발명의 유기 전계 발광 소자의 구조는 특별히 한정되지 않으나, 기판, 양극, 정공 주입층, 정공 수송층, 발광 보조층, 발광층, 전자 수송층 및 음극이 순차적으로 적층된 구조일 수 있다. 상기 정공주입층, 정공수송층, 발광보조층, 발광층, 전자수송층 및 전자주입층 중 하나 이상은 상기 화학식 1로 표시되는 화합물을 포함할 수 있고, 바람직하게는 발광층, 전자수송층 및 전자 수송층에 추가로 적층되는 전자수송 보조층이 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.The structure of the organic EL device of the present invention is not particularly limited, but may be a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer, and a cathode are sequentially stacked. At least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer may include a compound represented by the formula (1), preferably in addition to the light emitting layer, the electron transport layer and the electron transport layer The electron transport auxiliary layer to be laminated may include a compound represented by Chemical Formula 1.
본 발명의 유기 전계 발광 소자의 구조는 전극(음극, 또는 양극)과 유기물층의 계면에 절연층 또는 접착층이 삽입된 구조일 수 있다.The structure of the organic EL device of the present invention may be a structure in which an insulating layer or an adhesive layer is inserted at the interface between the electrode (cathode or anode) and the organic material layer.
본 발명의 유기 전계 발광 소자는 상기 유기물층 중 1층 이상이 상기 화학식 1로 표시되는 화합물을 포함하는 것을 제외하고는, 당업계에 공지된 재료 및 방법으로 유기물층 및 전극을 형성하여 제조할 수 있다.The organic electroluminescent device of the present invention can be manufactured by forming an organic material layer and an electrode by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Chemical Formula 1.
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.
본 발명의 유기 전계 발광 소자 제조 시 사용되는 기판은 특별히 한정되지 않으나, 실리콘 웨이퍼, 석영, 유리판, 금속판, 플라스틱 필름 및 시트 등을 사용할 수 있다.The substrate used in the manufacture of the organic EL device of the present invention is not particularly limited, but silicon wafers, quartz, glass plates, metal plates, plastic films, sheets, and the like may be used.
또, 양극 물질로는 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 등을 들 수 있으나, 이에 한정되지는 않는다.In addition, 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), 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 물질로는 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 등을 들 수 있으나, 이에 한정되지는 않는다.The negative electrode material may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or an alloy thereof; And multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.
또한, 정공 주입층, 정공 수송층, 전자 주입층 및 전자 수송층은 특별히 한정되는 것은 아니며, 당 업계에 알려진 통상의 물질을 사용할 수 있다.In addition, the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer is 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 with reference to the following Examples. However, the following examples are merely to illustrate the invention, the present invention is not limited by the following examples.
[[ 준비예Preparation 1] CD1의 합성 1] Synthesis of CD1
<단계 1> 10-(3-<Step 1> 10- (3- 클로로페닐Chlorophenyl )-7H-) -7H- 벤조[c]카바졸의Of benzo [c] carbazole 합성 synthesis
Figure PCTKR2017005670-appb-I000023
Figure PCTKR2017005670-appb-I000023
질소 기류 하에서 10-브로모-7H-벤조[c]카바졸 (20 g, 81.3 mmol), (3-클로로페닐)보로닉산 (15.3 g, 97.5 mmol), Pd(PPh3)4 (4.7 g, 5 mol%), NaOH (9.8 g, 243.8 mmol)에 400 ml/100 ml의 THF/H2O를 넣고 80℃에서 12시간 동안 교반하였다.10-Bromo-7H-benzo [c] carbazole (20 g, 81.3 mmol), (3-chlorophenyl) boronic acid (15.3 g, 97.5 mmol), Pd (PPh 3 ) 4 under nitrogen stream (4.7 g, 5 mol%) and NaOH (9.8 g, 243.8 mmol) were added 400 ml / 100 ml of THF / H 2 O and stirred at 80 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 10-(3-클로로페닐)-7H-벤조[c]카바졸 (19.4 g, 수율 86 %)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the organic layer was filtered and purified by column chromatography to give the title compound 10- (3-chlorophenyl) -7H-benzo [c] carbazole (19.4 g, yield 86%).
1H-NMR: δ 7.38 (d, 1H), 7.46 (m, 6H), 7.61 (m, 2H), 7.77 (d, 1H), 8.03 (s, 1H), 8.15 (d, 2H), 10.30 (s, 1H) 1 H-NMR: δ 7.38 (d, 1H), 7.46 (m, 6H), 7.61 (m, 2H), 7.77 (d, 1H), 8.03 (s, 1H), 8.15 (d, 2H), 10.30 ( s, 1 H)
<단계 2> CD1의 합성<Step 2> Synthesis of CD1
Figure PCTKR2017005670-appb-I000024
Figure PCTKR2017005670-appb-I000024
질소 기류 하에서 10-(3-클로로페닐)-7H-벤조[c]카바졸 (15 g, 54.01 mmol), 디벤조[b,d]싸이오페-4-닐보로닉산 (15.4 g, 64.8 mmol), Cs2CO3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd(OAc)2 (0.6 g, 5 mol%) 및 1,4-디옥산/H2O (400 ml/100 ml)를 혼합한 다음 120℃에서 12시간 동안 교반하였다.10- (3-chlorophenyl) -7H-benzo [c] carbazole (15 g, 54.01 mmol), dibenzo [b, d] thiophen-4-ylboronic acid (15.4 g, 64.8 mmol) under a nitrogen stream , Cs 2 CO 3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd (OAc) 2 (0.6 g, 5 mol%) and 1,4-dioxane / H 2 O (400 ml / 100 ml) were mixed and then stirred at 120 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과하여 얻어진 유기층에서 용매를 제거한 후 컬럼크로마토그래피로 정제하여 CD1 (18.4 g, 수율 78%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the organic layer obtained by filtration and purified by column chromatography to obtain CD1 (18.4 g, yield 78%).
1H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.88 (d, 3H), 8.13 (d, 1H), 10.3 (s, 1H) 1 H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.88 (d, 3H), 8.13 (d, 1H), 10.3 (s, 1H)
[준비예 2] CD2의 합성Preparation Example 2 Synthesis of CD2
<단계 1> 9-(3-클로로페닐)-7H-벤조[c]카바졸의 합성Step 1 Synthesis of 9- (3-chlorophenyl) -7H-benzo [c] carbazole
Figure PCTKR2017005670-appb-I000025
Figure PCTKR2017005670-appb-I000025
질소 기류 하에서 9-브로모-7H-벤조[c]카바졸 (20 g, 81.3 mmol), (3-클로로페닐)보로닉산 (15.3 g, 97.5 mmol), Pd(PPh3)4 (4.7 g, 5 mol%), NaOH (9.8 g, 243.8 mmol)에 400 ml/100 ml의 THF/H2O를 넣고 80℃에서 12시간 동안 교반하였다.9-bromo-7H-benzo [c] carbazole (20 g, 81.3 mmol), (3-chlorophenyl) boronic acid (15.3 g, 97.5 mmol), Pd (PPh 3 ) 4 (4.7 g, 5 mol%), 400 mL / 100 ml of THF / H 2 O was added to NaOH (9.8 g, 243.8 mmol), and the mixture was stirred at 80 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층의 용매를 제거한 후 컬럼크로마토그래피로 이용하여 목적 화합물인 9-(3-클로로페닐)-7H-벤조[c]카바졸 (18.4 g, 수율 82 %)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent of the filtered organic layer was removed and then used by column chromatography to obtain 9- (3-chlorophenyl) -7H-benzo [c] carbazole (18.4 g, yield 82%) as a target compound.
1H-NMR: δ 7.40 (d, 1H), 7.44 (m, 5H), 7.48 (d, 1H) 7.60 (m, 2H), 7.74 (d, 1H), 8.01 (s, 1H), 8.12 (d, 2H), 10.11 (s, 1H)1 H-NMR: δ 7.40 (d, 1H), 7.44 (m, 5H), 7.48 (d, 1H) 7.60 (m, 2H), 7.74 (d, 1H), 8.01 (s, 1H), 8.12 (d, 2H), 10.11 (s, 1H)
<단계 2> CD2의 합성<Step 2> Synthesis of CD2
Figure PCTKR2017005670-appb-I000026
Figure PCTKR2017005670-appb-I000026
질소 기류 하에서 9-(3-클로로페닐)-7H-벤조[c]카바졸 (15 g, 54.01 mmol), 디벤조[b,d]싸이오페-4-닐보로닉산 (15.4 g, 64.8 mmol), Cs2CO3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd(OAc)2 (0.6 g, 5 mol%) 및 1,4-디옥산/H2O (400 ml/100 ml)를 혼합한 다음 120℃에서 12시간 동안 교반하였다.9- (3-chlorophenyl) -7H-benzo [c] carbazole (15 g, 54.01 mmol), dibenzo [b, d] thiophen-4-ylboronic acid (15.4 g, 64.8 mmol) under a nitrogen stream , Cs 2 CO 3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd (OAc) 2 (0.6 g, 5 mol%) and 1,4-dioxane / H 2 O (400 ml / 100 ml) were mixed and then stirred at 120 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과하여 얻어진 유기층에서 용매를 제거한 후 컬럼크로마토그래피로 정제하여 CD2 (17.8 g, 수율 76%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the organic layer obtained by filtration and purified by column chromatography to give a CD2 (17.8 g, yield 76%).
1H-NMR: δ 7.01 (t, 3H), 7.44 (d, 2H), 7.60 (m, 10H), 7.75 (s, 1H), 7.88 (d, 3H), 8.13 (d, 1H), 10.22 (s, 1H) 1 H-NMR: δ 7.01 (t, 3H), 7.44 (d, 2H), 7.60 (m, 10H), 7.75 (s, 1H), 7.88 (d, 3H), 8.13 (d, 1H), 10.22 ( s, 1 H)
[준비예 3] CD3의 합성Preparation Example 3 Synthesis of CD3
<단계 1> 8-(3-클로로페닐)-7H-벤조[c]카바졸의 합성<Step 1> Synthesis of 8- (3-chlorophenyl) -7H-benzo [c] carbazole
Figure PCTKR2017005670-appb-I000027
Figure PCTKR2017005670-appb-I000027
질소 기류 하에서 8-브로모-7H-벤조[c]카바졸 (20 g, 81.3 mmol), (3-클로로페닐)보로닉산 (15.3 g, 97.5 mmol), Pd(PPh3)4 (4.7 g, 5 mol%), NaOH (9.8 g, 243.8 mmol)에 400 ml/100 ml의 THF/H2O를 넣고 80℃에서 12시간 동안 교반하였다.8-bromo-7H-benzo [c] carbazole (20 g, 81.3 mmol), (3-chlorophenyl) boronic acid (15.3 g, 97.5 mmol), Pd (PPh 3 ) 4 (4.7 g, 5 mol%), 400 mL / 100 ml of THF / H 2 O was added to NaOH (9.8 g, 243.8 mmol), and the mixture was stirred at 80 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 8-(3-클로로페닐)-7H-벤조[c]카바졸 (15.3 g, 수율 71 %)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the organic layer was filtered and purified by column chromatography to give the title compound 8- (3-chlorophenyl) -7H-benzo [c] carbazole (15.3 g, 71% yield).
1H-NMR: δ 7.33 (d, 1H), 7.41 (m, 5H), 7.48 (d, 1H) 7.60 (m, 2H), 7.74 (d, 1H), 8.01 (s, 1H), 8.31 (d, 1H) 8.42 (d, 1H), 10.76 (s, 1H)1 H-NMR: δ 7.33 (d, 1H), 7.41 (m, 5H), 7.48 (d, 1H) 7.60 (m, 2H), 7.74 (d, 1H), 8.01 (s, 1H), 8.31 (d, 1H) 8.42 (d, 1H), 10.76 (s, 1H)
<단계 2> CD3의 합성<Step 2> Synthesis of CD3
Figure PCTKR2017005670-appb-I000028
Figure PCTKR2017005670-appb-I000028
질소 기류 하에서 8-(3-클로로페닐)-7H-벤조[c]카바졸 (15 g, 54.01 mmol), 디벤조[b,d]싸이오페-4-닐보로닉산 (15.4 g, 64.8 mmol), Cs2CO3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd(OAc)2 (0.6 g, 5 mol%) 및 1,4-디옥산/H2O (400 ml/100 ml)를 혼합한 다음 120℃에서 12시간 동안 교반하였다.8- (3-chlorophenyl) -7H-benzo [c] carbazole (15 g, 54.01 mmol), dibenzo [b, d] thiophen-4-ylboronic acid (15.4 g, 64.8 mmol) under a nitrogen stream , Cs 2 CO 3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd (OAc) 2 (0.6 g, 5 mol%) and 1,4-dioxane / H 2 O (400 ml / 100 ml) were mixed and then stirred at 120 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과하여 얻어진 유기층에서 용매를 제거한 후 컬럼크로마토그래피로 정제하여 CD3 (15.8 g, 수율 70%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the organic layer obtained by filtration and purified by column chromatography to obtain CD3 (15.8 g, yield 70%).
1H-NMR: δ 7.11 (t, 3H), 7.48 (d, 2H), 7.63 (m, 10H), 7.75 (d, 1H), 7.88 (d, 3H), 8.19 (d, 1H), 10.83 (s, 1H) 1 H-NMR: δ 7.11 (t, 3H), 7.48 (d, 2H), 7.63 (m, 10H), 7.75 (d, 1H), 7.88 (d, 3H), 8.19 (d, 1H), 10.83 ( s, 1 H)
[준비예 4] CD4의 합성Preparation Example 4 Synthesis of CD4
Figure PCTKR2017005670-appb-I000029
Figure PCTKR2017005670-appb-I000029
질소 기류 하에서 [준비예 1] <단계 1>에서 합성한, 10-(3-클로로페닐)-7H-벤조[c]카바졸 (15 g, 54.01 mmol), 디벤조[b,d]싸이오페-3-닐보로닉산 (15.4 g, 64.8 mmol), Cs2CO3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd(OAc)2 (0.6 g, 5 mol%) 및 1,4-디옥산/H2O (400 ml/100 ml)를 혼합한 다음 120℃에서 12시간 동안 교반하였다.10- (3-chlorophenyl) -7H-benzo [c] carbazole (15 g, 54.01 mmol) synthesized in <Step 1> under a nitrogen stream, dibenzo [b, d] thiope 3-Nylboronic acid (15.4 g, 64.8 mmol), Cs 2 CO 3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd (OAc) 2 (0.6 g, 5 mol%) and 1,4-dioxane / H 2 O (400 ml / 100 ml) were mixed and then stirred at 120 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과하여 얻어진 유기층에서 용매를 제거한 후 컬럼크로마토그래피로 정제하여 CD4 (17.2 g, 수율 75%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the organic layer obtained by filtration and purified by column chromatography to obtain CD4 (17.2 g, yield 75%).
1H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s, 1H) 1 H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 ( s, 1 H)
[준비예 5] CD5의 합성Preparation Example 5 Synthesis of CD5
Figure PCTKR2017005670-appb-I000030
Figure PCTKR2017005670-appb-I000030
질소 기류 하에서 [준비예 1] <단계 1>에서 합성한, 10-(3-클로로페닐)-7H-벤조[c]카바졸 (15 g, 54.01 mmol), 디벤조[b,d]퓨란-4-닐보로닉산 (15.4 g, 64.6 mmol), Cs2CO3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd(OAc)2 (0.6 g, 5 mol%) 및 1,4-디옥산/H2O (400 ml/100 ml)를 혼합한 다음 120℃에서 12시간 동안 교반하였다.10- (3-chlorophenyl) -7H-benzo [c] carbazole (15 g, 54.01 mmol), dibenzo [b, d] furan-, synthesized in Preparation Example 1 Step 1 under a nitrogen stream. 4-Nylboronic acid (15.4 g, 64.6 mmol), Cs 2 CO 3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd (OAc) 2 (0.6 g, 5 mol%) and 1,4-dioxane / H 2 O (400 ml / 100 ml) was mixed and then stirred at 120 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과하여 얻어진 유기층에서 용매를 제거한 후 컬럼크로마토그래피로 정제하여 CD5 (17.2 g, 수율 75%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the organic layer obtained by filtration and purified by column chromatography to obtain a CD5 (17.2 g, yield 75%).
1H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s, 1H)1 H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s , 1H)
[준비예 6] CD6의 합성Preparation Example 6 Synthesis of CD6
Figure PCTKR2017005670-appb-I000031
Figure PCTKR2017005670-appb-I000031
질소 기류 하에서 [준비예 2] <단계 1>에서 합성한, 9-(3-클로로페닐)-7H-벤조[c]카바졸 (15 g, 54.01 mmol), 디벤조[b,d]퓨란-4-닐보로닉산 (15.4 g, 64.6 mmol), Cs2CO3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd(OAc)2 (0.6 g, 5 mol%) 및 1,4-디옥산/H2O (400 ml/100 ml)를 혼합한 다음 120℃에서 12시간 동안 교반하였다.9- (3-chlorophenyl) -7H-benzo [c] carbazole (15 g, 54.01 mmol), dibenzo [b, d] furan-, synthesized in Preparation Example 2 Step 1 under a nitrogen stream. 4-Nylboronic acid (15.4 g, 64.6 mmol), Cs 2 CO 3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd (OAc) 2 (0.6 g, 5 mol%) and 1,4-dioxane / H 2 O (400 ml / 100 ml) was mixed and then stirred at 120 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과하여 얻어진 유기층에서 용매를 제거한 후 컬럼크로마토그래피로 정제하여 CD6 (18.7 g, 수율 79%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the organic layer obtained by filtration and purified by column chromatography to obtain CD6 (18.7 g, yield 79%).
1H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s, 1H)1 H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s , 1H)
[준비예 7] CD7의 합성Preparation Example 7 Synthesis of CD7
Figure PCTKR2017005670-appb-I000032
Figure PCTKR2017005670-appb-I000032
질소 기류 하에서 [준비예 3] <단계 1>에서 합성한, 8-(3-클로로페닐)-7H-벤조[c]카바졸 (15 g, 54.01 mmol), 디벤조[b,d]퓨란-4-닐보로닉산 (15.4 g, 64.6 mmol), Cs2CO3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd(OAc)2 (0.6 g, 5 mol%) 및 1,4-디옥산/H2O (400 ml/100 ml)를 혼합한 다음 120℃에서 12시간 동안 교반하였다.8- (3-chlorophenyl) -7H-benzo [c] carbazole (15 g, 54.01 mmol), dibenzo [b, d] furan-, synthesized in [Preparation Example 3] <Step 1> under a nitrogen stream. 4-Nylboronic acid (15.4 g, 64.6 mmol), Cs 2 CO 3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd (OAc) 2 (0.6 g, 5 mol%) and 1,4-dioxane / H 2 O (400 ml / 100 ml) was mixed and then stirred at 120 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과하여 얻어진 유기층에서 용매를 제거한 후 컬럼크로마토그래피로 정제하여 CD7 (18.7 g, 수율 79%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the organic layer obtained by filtration and purified by column chromatography to obtain a CD7 (18.7 g, yield 79%).
1H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s, 1H)1 H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s , 1H)
[준비예 8] CD8의 합성Preparation Example 8 Synthesis of CD8
Figure PCTKR2017005670-appb-I000033
Figure PCTKR2017005670-appb-I000033
질소 기류 하에서 [준비예 1] <단계 1>에서 합성한, 10-(3-클로로페닐)-7H-벤조[c]카바졸 (15 g, 54.01 mmol), 디벤조[b,d]퓨란-3-닐보로닉산 (15.4 g, 64.6 mmol), Cs2CO3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd(OAc)2 (0.6 g, 5 mol%) 및 1,4-디옥산/H2O (400 ml/100 ml)를 혼합한 다음 120℃에서 12시간 동안 교반하였다.10- (3-chlorophenyl) -7H-benzo [c] carbazole (15 g, 54.01 mmol), dibenzo [b, d] furan-, synthesized in Preparation Example 1 Step 1 under a nitrogen stream. 3-Nylboronic acid (15.4 g, 64.6 mmol), Cs 2 CO 3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd (OAc) 2 (0.6 g, 5 mol%) and 1,4-dioxane / H 2 O (400 ml / 100 ml) was mixed and then stirred at 120 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과하여 얻어진 유기층에서 용매를 제거한 후 컬럼크로마토그래피로 정제하여 CD8 (18.7 g, 수율 79%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the organic layer obtained by filtration and purified by column chromatography to give a CD8 (18.7 g, yield 79%).
1H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s, 1H)1 H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s , 1H)
[준비예 9] CD9의 합성Preparation Example 9 Synthesis of CD9
Figure PCTKR2017005670-appb-I000034
Figure PCTKR2017005670-appb-I000034
질소 기류 하에서 [준비예 1] <단계 1>에서 합성한, 10-(3-클로로페닐)-7H-벤조[c]카바졸 (15 g, 54.01 mmol), (9,9-디메틸-플루오렌-2-일)보로닉산 (15.4 g, 64.6 mmol), Cs2CO3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd(OAc)2 (0.6 g, 5 mol%) 및 1,4-디옥산/H2O (400 ml/100 ml)를 혼합한 다음 120℃에서 12시간 동안 교반하였다.10- (3-chlorophenyl) -7H-benzo [c] carbazole (15 g, 54.01 mmol), synthesized in <Step 1> under nitrogen stream, (9,9-dimethyl-fluorene -2-yl) boronic acid (15.4 g, 64.6 mmol), Cs 2 CO 3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd (OAc) 2 (0.6 g, 5 mol% ) And 1,4-dioxane / H 2 O (400 ml / 100 ml) were mixed and then stirred at 120 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과하여 얻어진 유기층에서 용매를 제거한 후 컬럼크로마토그래피로 정제하여 CD9 (18.7 g, 수율 79%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the organic layer obtained by filtration and purified by column chromatography to give a CD9 (18.7 g, yield 79%).
1H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s, 1H)1 H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s , 1H)
[준비예 10] CD10의 합성Preparation Example 10 Synthesis of CD10
Figure PCTKR2017005670-appb-I000035
Figure PCTKR2017005670-appb-I000035
질소 기류 하에서 [준비예 2] <단계 1>에서 합성한, 9-(3-클로로페닐)-7H-벤조[c]카바졸 (15 g, 54.01 mmol), 디벤조[b,d]퓨란-3-닐보로닉산 (15.4 g, 64.6 mmol), Cs2CO3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd(OAc)2 (0.6 g, 5 mol%) 및 1,4-디옥산/H2O (400 ml/100 ml)를 혼합한 다음 120℃에서 12시간 동안 교반하였다.9- (3-chlorophenyl) -7H-benzo [c] carbazole (15 g, 54.01 mmol), dibenzo [b, d] furan-, synthesized in Preparation Example 2 Step 1 under a nitrogen stream. 3-Nylboronic acid (15.4 g, 64.6 mmol), Cs 2 CO 3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd (OAc) 2 (0.6 g, 5 mol%) and 1,4-dioxane / H 2 O (400 ml / 100 ml) was mixed and then stirred at 120 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과하여 얻어진 유기층에서 용매를 제거한 후 컬럼크로마토그래피로 정제하여 CD10 (18.7 g, 수율 79%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the organic layer obtained by filtration and purified by column chromatography to obtain CD10 (18.7 g, yield 79%).
1H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s, 1H)1 H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s , 1H)
[준비예 11] CD11의 합성Preparation Example 11 Synthesis of CD11
Figure PCTKR2017005670-appb-I000036
Figure PCTKR2017005670-appb-I000036
질소 기류 하에서 [준비예 3] <단계 1>에서 합성한, 8-(3-클로로페닐)-7H-벤조[c]카바졸 (15 g, 54.01 mmol), 디벤조[b,d]퓨란-3-닐보로닉산 (15.4 g, 64.6 mmol), Cs2CO3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd(OAc)2 (0.6 g, 5 mol%) 및 1,4-디옥산/H2O (400 ml/100 ml)를 혼합한 다음 120℃에서 12시간 동안 교반하였다.8- (3-chlorophenyl) -7H-benzo [c] carbazole (15 g, 54.01 mmol), dibenzo [b, d] furan-, synthesized in [Preparation Example 3] <Step 1> under a nitrogen stream. 3-Nylboronic acid (15.4 g, 64.6 mmol), Cs 2 CO 3 (35.19 g, 108.01 mmol), X-phos (5.2 g, 10.8 mmol), Pd (OAc) 2 (0.6 g, 5 mol%) and 1,4-dioxane / H 2 O (400 ml / 100 ml) was mixed and then stirred at 120 ° C. for 12 hours.
반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼크로마토그래피로 정제하여 CD11 (18.7 g, 수율 79%)을 얻었다.After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. The solvent was removed from the organic layer and purified by column chromatography to obtain CD11 (18.7 g, yield 79%).
1H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s, 1H)1 H-NMR: δ 7.32 (t, 3H), 7.58 (m, 11H), 7.75 (s, 2H), 7.86 (d, 2H), 7.98 (s, 1H), 8.09 (d, 1H), 10.31 (s , 1H)
[[ 합성예Synthesis Example 1] 화합물 1의 합성 1] Synthesis of Compound 1
Figure PCTKR2017005670-appb-I000037
Figure PCTKR2017005670-appb-I000037
CD1 (10 g, 22.9 mmol)와 2-클로로-4,6-디페닐-1,3,5-트리아진 (6.8 g, 22.9 mmol) 및 Pd2(dba)3 (1.1 g, 1.15 mmol), P(t-Bu)3 (0.9 g, 4.6 mmol), 나트륨 tert-부톡사이드 (4.4 g, 45.9 mmol)을 150 ml 톨루엔에 넣고 110℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 여과된 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물 1 (11.6 g, 수율 75%)을 얻었다.CD1 (10 g, 22.9 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (6.8 g, 22.9 mmol) and Pd 2 (dba) 3 (1.1 g, 1.15 mmol), P (t-Bu) 3 (0.9 g, 4.6 mmol) and sodium tert-butoxide (4.4 g, 45.9 mmol) were added to 150 ml toluene and stirred at 110 ° C. for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer was purified by column chromatography to give the target compound 1 (11.6 g, yield 75%).
Mass: [(M+H)+] : 707Mass: [(M + H) + ]: 707
[[ 합성예Synthesis Example 2] 화합물 6의 합성 2] Synthesis of Compound 6
Figure PCTKR2017005670-appb-I000038
Figure PCTKR2017005670-appb-I000038
CD1 대신 CD4(10 g, 22.9 mmol)를 사용하는 것을 제외하고는 합성예 1과 동일한 과정을 수행하여 목적 화합물 6 (11.2 g, 수율 74%)를 얻었다.Except for using CD4 (10 g, 22.9 mmol) instead of CD1 was the same procedure as in Synthesis Example 1 to give the target compound 6 (11.2 g, yield 74%).
Mass: [(M+H)+] : 707Mass: [(M + H) + ]: 707
[[ 합성예Synthesis Example 3] 화합물 171의 합성 3] Synthesis of Compound 171
Figure PCTKR2017005670-appb-I000039
Figure PCTKR2017005670-appb-I000039
CD1 대신 CD2(10 g, 22.9 mmol)를 사용하는 것을 제외하고는 합성예 1과 동일한 과정을 수행하여 목적 화합물 171 (10.8 g, 수율 72%)를 얻었다.Except for using CD2 (10 g, 22.9 mmol) instead of CD1 was carried out in the same manner as in Synthesis Example 1 to obtain the target compound 171 (10.8 g, 72% yield).
Mass: [(M+H)+] : 707Mass: [(M + H) + ]: 707
[[ 합성예Synthesis Example 4] 화합물 191의 합성 4] Synthesis of Compound 191
Figure PCTKR2017005670-appb-I000040
Figure PCTKR2017005670-appb-I000040
CD1 대신 CD3(10 g, 22.9 mmol)를 사용하는 것을 제외하고는 합성예 1과 동일한 과정을 수행하여 목적 화합물 191 (13.3 g, 수율 79%)를 얻었다.Except for using CD3 (10 g, 22.9 mmol) instead of CD1 was carried out in the same manner as in Synthesis Example 1 to obtain the target compound 191 (13.3 g, yield 79%).
Mass: [(M+H)+] : 707Mass: [(M + H) + ]: 707
[[ 합성예Synthesis Example 5] 화합물 51의 합성 5] Synthesis of Compound 51
Figure PCTKR2017005670-appb-I000041
Figure PCTKR2017005670-appb-I000041
CD1 대신 CD5(10 g, 21.7 mmol)를 사용하는 것을 제외하고는 합성예 1과 동일한 과정을 수행하여 목적 화합물 51 (12.1 g, 수율 76%)를 얻었다.Except for using CD5 (10 g, 21.7 mmol) in place of CD1 was carried out in the same manner as in Synthesis Example 1 to obtain the target compound 51 (12.1 g, yield 76%).
Mass: [(M+H)+] : 691Mass: [(M + H) + ] 691
[[ 합성예Synthesis Example 6] 화합물 56의 합성 6] Synthesis of Compound 56
Figure PCTKR2017005670-appb-I000042
Figure PCTKR2017005670-appb-I000042
CD1 대신 CD8(10 g, 21.7 mmol)을 사용하는 것을 제외하고는 합성예 1과 동일한 과정을 수행하여 목적 화합물 56 (13.5 g, 수율 79%)를 얻었다.Except for using CD8 (10 g, 21.7 mmol) instead of CD1 was carried out in the same manner as in Synthesis Example 1 to obtain the target compound 56 (13.5 g, yield 79%).
Mass: [(M+H)+] : 691Mass: [(M + H) + ] 691
[[ 합성예Synthesis Example 7] 화합물 231의 합성 7] Synthesis of Compound 231
Figure PCTKR2017005670-appb-I000043
Figure PCTKR2017005670-appb-I000043
CD1 대신 CD6(10 g, 21.7 mmol)을 사용하는 것을 제외하고는 합성예 1과 동일한 과정을 수행하여 목적 화합물 231 (11.2 g, 수율 74%)를 얻었다.Except for using CD6 (10 g, 21.7 mmol) in place of CD1 was carried out in the same manner as in Synthesis Example 1 to obtain the target compound 231 (11.2 g, yield 74%).
Mass: [(M+H)+] : 691Mass: [(M + H) + ] 691
[[ 합성예Synthesis Example 8] 화합물 251의 합성 8] Synthesis of Compound 251
Figure PCTKR2017005670-appb-I000044
Figure PCTKR2017005670-appb-I000044
CD1 대신 CD7(10 g, 21.7 mmol)을 사용하는 것을 제외하고는 합성예 1과 동일한 과정을 수행하여 목적 화합물 251 (12.9 g, 수율 77%)를 얻었다.Except for using CD7 (10 g, 21.7 mmol) in place of CD1 was carried out in the same manner as in Synthesis Example 1 to obtain the target compound 251 (12.9 g, yield 77%).
Mass: [(M+H)+] : 691Mass: [(M + H) + ] 691
[[ 합성예Synthesis Example 9] 화합물 106의 합성 9] Synthesis of Compound 106
Figure PCTKR2017005670-appb-I000045
Figure PCTKR2017005670-appb-I000045
CD1 대신 CD9(10 g, 20.6 mmol)를 사용하는 것을 제외하고는 합성예 1과 동일한 과정을 수행하여 목적 화합물 106 (12.1 g, 수율 76%)를 얻었다.Except for using CD9 (10 g, 20.6 mmol) instead of CD1 was carried out in the same manner as in Synthesis Example 1 to obtain the target compound 106 (12.1 g, yield 76%).
Mass: [(M+H)+] : 717Mass: [(M + H) + ]: 717
[[ 합성예Synthesis Example 10] 화합물 296의 합성 10] Synthesis of Compound 296
Figure PCTKR2017005670-appb-I000046
Figure PCTKR2017005670-appb-I000046
CD1 대신 CD10(10 g, 20.6 mmol)을 사용하는 것을 제외하고는 합성예 1과 동일한 과정을 수행하여 목적 화합물 296 (13.4 g, 수율 79%)를 얻었다.Except for using CD10 (10 g, 20.6 mmol) instead of CD1 was carried out in the same manner as in Synthesis Example 1 to obtain the target compound 296 (13.4 g, yield 79%).
Mass: [(M+H)+] : 717Mass: [(M + H) + ]: 717
[[ 합성예Synthesis Example 11] 화합물 316의 합성 11] Synthesis of Compound 316
Figure PCTKR2017005670-appb-I000047
Figure PCTKR2017005670-appb-I000047
CD1 대신 CD11(10 g, 20.6 mmol)을 사용하는 것을 제외하고는 합성예 1과 동일한 과정을 수행하여 목적 화합물 316 (11.2 g, 수율 74%)를 얻었다.Except for using CD11 (10 g, 20.6 mmol) in place of CD1 was carried out in the same manner as in Synthesis Example 1 to obtain the target compound 316 (11.2 g, yield 74%).
Mass: [(M+H)+] : 717Mass: [(M + H) + ]: 717
[[ 합성예Synthesis Example 12] 화합물 5의 합성 12] Synthesis of Compound 5
Figure PCTKR2017005670-appb-I000048
Figure PCTKR2017005670-appb-I000048
2-클로로-4,6-디페닐-1,3,5-트리아진 대신 2-클로로-4-페닐퀴나졸린 (6.3 g, 22.9 mmol)을 사용하는 것을 제외하고는 합성예 1과 동일한 과정을 수행하여 목적 화합물 5 (10.9 g, 수율 73%)를 얻었다.The same procedure as in Synthesis Example 1 was repeated except that 2-chloro-4-phenylquinazoline (6.3 g, 22.9 mmol) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. To give the target compound 5 (10.9 g, 73% yield).
Mass: [(M+H)+] : 680Mass: [(M + H) + ]: 680
[[ 합성예Synthesis Example 13] 화합물 10의 합성 13] Synthesis of Compound 10
Figure PCTKR2017005670-appb-I000049
Figure PCTKR2017005670-appb-I000049
CD1 대신 CD4(10 g, 22.9 mmol)를 사용하는 것을 제외하고는 합성예 12와 동일한 과정을 수행하여 목적 화합물 10 (13.5 g, 수율 79%)를 얻었다.Except for using CD4 (10 g, 22.9 mmol) instead of CD1 was carried out in the same manner as in Synthesis Example 12 to obtain the target compound 10 (13.5 g, yield 79%).
Mass: [(M+H)+] : 680Mass: [(M + H) + ]: 680
[[ 합성예Synthesis Example 14] 화합물 175의 합성 14] Synthesis of Compound 175
Figure PCTKR2017005670-appb-I000050
Figure PCTKR2017005670-appb-I000050
CD1 대신 CD2(10 g, 22.9 mmol)을 사용하는 것을 제외하고는 합성예 12와 동일한 과정을 수행하여 목적 화합물 175 (11.2 g, 수율 74%)를 얻었다.Except for using CD2 (10 g, 22.9 mmol) instead of CD1 was carried out in the same manner as in Synthesis Example 12 to obtain the target compound 175 (11.2 g, yield 74%).
Mass: [(M+H)+] : 680Mass: [(M + H) + ]: 680
[[ 합성예Synthesis Example 15] 화합물 195의 합성 15] Synthesis of Compound 195
Figure PCTKR2017005670-appb-I000051
Figure PCTKR2017005670-appb-I000051
CD1 대신 CD3(10 g, 22.9 mmol)을 사용하는 것을 제외하고는 합성예 12와 동일한 과정을 수행하여 목적 화합물 195 (11.2 g, 수율 74%)를 얻었다.Except for using CD3 (10 g, 22.9 mmol) instead of CD1 was carried out in the same manner as in Synthesis Example 12 to obtain the target compound 195 (11.2 g, yield 74%).
Mass: [(M+H)+] : 680Mass: [(M + H) + ]: 680
[[ 합성예Synthesis Example 16] 화합물 55의 합성 16] Synthesis of Compound 55
Figure PCTKR2017005670-appb-I000052
Figure PCTKR2017005670-appb-I000052
CD1 대신 CD5(10 g, 21.7 mmol)를 사용하는 것을 제외하고는 합성예 12와 동일한 과정을 수행하여 목적 화합물 55 (11.2 g, 수율 74%)를 얻었다.Except for using CD5 (10 g, 21.7 mmol) in place of CD1 was carried out in the same manner as in Synthesis Example 12 to obtain the target compound 55 (11.2 g, yield 74%).
Mass: [(M+H)+] : 664Mass: [(M + H) + ]: 664
[[ 합성예Synthesis Example 17] 화합물 60의 합성 17] Synthesis of Compound 60
Figure PCTKR2017005670-appb-I000053
Figure PCTKR2017005670-appb-I000053
CD1 대신 CD8(10 g, 21.7 mmol)을 사용하는 것을 제외하고는 합성예 12와 동일한 과정을 수행하여 목적 화합물 60 (12.1 g, 수율 76%)를 얻었다.A target compound 60 (12.1 g, yield 76%) was obtained in the same manner as Synthesis Example 12 except for using CD8 (10 g, 21.7 mmol) instead of CD1.
Mass: [(M+H)+] : 664Mass: [(M + H) + ]: 664
[[ 합성예Synthesis Example 18] 화합물 235의 합성 18] Synthesis of Compound 235
Figure PCTKR2017005670-appb-I000054
Figure PCTKR2017005670-appb-I000054
CD1 대신 CD6(10 g, 21.7 mmol)을 사용하는 것을 제외하고는 합성예 12와 동일한 과정을 수행하여 목적 화합물 235 (12.6 g, 수율 76%)를 얻었다.Except for using CD6 (10 g, 21.7 mmol) instead of CD1 was carried out in the same manner as in Synthesis Example 12 to obtain the target compound 235 (12.6 g, yield 76%).
Mass: [(M+H)+] : 664Mass: [(M + H) + ]: 664
[[ 합성예Synthesis Example 19] 화합물 255의 합성 19] Synthesis of Compound 255
Figure PCTKR2017005670-appb-I000055
Figure PCTKR2017005670-appb-I000055
CD1 대신 CD7(10 g, 21.7 mmol)를 사용하는 것을 제외하고는 합성예 12와 동일한 과정을 수행하여 목적 화합물 255 (11.2 g, 수율 74%)를 얻었다.Except for using CD7 (10 g, 21.7 mmol) in place of CD1 was carried out in the same manner as in Synthesis Example 12 to obtain the target compound 255 (11.2 g, yield 74%).
Mass: [(M+H)+] : 664Mass: [(M + H) + ]: 664
[[ 합성예Synthesis Example 20] 화합물 110의 합성 20] Synthesis of Compound 110
Figure PCTKR2017005670-appb-I000056
Figure PCTKR2017005670-appb-I000056
CD1 대신 CD9(10 g, 20.6 mmol)을 사용하는 것을 제외하고는 합성예 12와 동일한 과정을 수행하여 목적 화합물 110 (11.4 g, 수율 74%)를 얻었다.Except for using CD9 (10 g, 20.6 mmol) instead of CD1 was carried out in the same manner as in Synthesis Example 12 to obtain the target compound 110 (11.4 g, 74% yield).
Mass: [(M+H)+] : 690Mass: [(M + H) + ]: 690
[[ 합성예Synthesis Example 21] 화합물 300의 합성 21] Synthesis of Compound 300
Figure PCTKR2017005670-appb-I000057
Figure PCTKR2017005670-appb-I000057
CD1 대신 CD10(10 g, 20.6 mmol)을 사용하는 것을 제외하고는 합성예 12와 동일한 과정을 수행하여 목적 화합물 300 (10.9 g, 수율 72%)를 얻었다.Except for using CD10 (10 g, 20.6 mmol) in place of CD1 was carried out in the same manner as in Synthesis Example 12 to obtain the target compound 300 (10.9 g, 72% yield).
Mass: [(M+H)+] : 690Mass: [(M + H) + ]: 690
[[ 합성예Synthesis Example 22] 화합물 320의 합성 22] Synthesis of Compound 320
Figure PCTKR2017005670-appb-I000058
Figure PCTKR2017005670-appb-I000058
CD1 대신 CD11(10 g, 20.6 mmol)을 사용하는 것을 제외하고는 합성예 12와 동일한 과정을 수행하여 목적 화합물 320 (11.4 g, 수율 74%)를 얻었다.Except for using CD11 (10 g, 20.6 mmol) in place of CD1 was carried out in the same manner as in Synthesis Example 12 to obtain the target compound 320 (11.4 g, 74% yield).
Mass: [(M+H)+] : 690Mass: [(M + H) + ]: 690
[실시예 1] 녹색 유기 전계 발광 소자의 제작Example 1 Fabrication of Green Organic Electroluminescent Device
합성예 1에서 합성한 화합물 1을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후, 하기 과정에 따라 녹색 유기 전계 발광 소자를 제작하였다.Compound 1 synthesized in Synthesis Example 1 was subjected to high purity sublimation purification by a conventionally known method, and then a green organic EL device was manufactured according to the following procedure.
먼저, ITO (Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수로 초음파 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV OZONE 세정기 (Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 코팅된 유리 기판을 이송하였다.First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 된 was ultrasonically washed with distilled water. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then the substrate is cleaned for 5 minutes by UV and vacuum evaporator The glass substrate coated with was transferred.
이렇게 준비된 ITO 투명 유리 기판(전극) 위에 m-MTDATA (60 nm)/TCTA (80 nm)/ 90%의 화합물 1 + 10%의 Ir(ppy)3 (30nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 녹색 유기 전계 발광 소자를 제조하였다.M-MTDATA (60 nm) / TCTA (80 nm) / 90% of compound 1 + 10% of Ir (ppy) 3 (30nm) / BCP (10 nm) / Alq 3 on the prepared ITO transparent glass substrate (electrode) (30 nm) / LiF (1 nm) / Al (200 nm) were stacked in order to prepare a green organic EL device.
[실시예 2 내지 11] 녹색 유기 전계 발광 소자의 제작[Examples 2 to 11] Fabrication of Green Organic Electroluminescent Device
녹색 발광 호스트 물질로서 화합물 1 대신 합성예 2~11에서 합성된 각각의 화합물을 사용하는 것을 제외하고는, 상기 실시예 1과 동일하게 수행하여 녹색 유기 전계 발광 소자를 제조하였다.A green organic EL device was manufactured in the same manner as in Example 1, except that each compound synthesized in Synthesis Examples 2 to 11 was used instead of Compound 1 as the green light-emitting host material.
[비교예 1] 녹색 유기 전계 발광 소자의 제작Comparative Example 1 Fabrication of Green Organic Electroluminescent Device
녹색 발광 호스트 물질로서 화합물 1 대신 CBP를 사용하는 것을 제외하고는, 상기 실시예 1과 동일하게 수행하여 녹색 유기 전계 발광 소자를 제조하였다.A green organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound 1 as the green light-emitting host material.
한편 실시예 1 내지 11 및 비교예 1에서 사용된 m-MTDATA, TCTA, Ir(ppy)3, CBP 및 BCP의 구조는 하기와 같다.Meanwhile, the structures of m-MTDATA, TCTA, Ir (ppy) 3 , CBP, and BCP used in Examples 1 to 11 and Comparative Example 1 are as follows.
Figure PCTKR2017005670-appb-I000059
Figure PCTKR2017005670-appb-I000059
Figure PCTKR2017005670-appb-I000060
Figure PCTKR2017005670-appb-I000060
[평가예 1][Evaluation Example 1]
실시예 1 내지 11 및 비교예 1에서 각각 제조된 녹색 유기 전계 발광 소자에 대하여, 전류밀도 10 mA/㎠에서의 구동전압, 전류효율 및 발광 피크를 측정하였고, 그 결과를 하기 표 1에 나타내었다.For green organic electroluminescent devices prepared in Examples 1 to 11 and Comparative Example 1, driving voltage, current efficiency, and emission peak at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below. .
샘플Sample 호스트Host 구동 전압(V)Drive voltage (V) 발광 피크(nm)Emission Peak (nm) 전류효율(cd/A)Current efficiency (cd / A)
실시예 1Example 1 화합물 1Compound 1 6.616.61 515515 41.341.3
실시예 2Example 2 화합물 6Compound 6 6.726.72 516516 42.642.6
실시예 3Example 3 화합물 171Compound 171 6.436.43 517517 44.544.5
실시예 4Example 4 화합물 191Compound 191 6.636.63 517517 42.342.3
실시예 5Example 5 화합물 51Compound 51 6.536.53 518518 44.144.1
실시예 6Example 6 화합물 56Compound 56 6.346.34 515515 43.643.6
실시예 7Example 7 화합물 231Compound 231 6.346.34 514514 48.248.2
실시예 8Example 8 화합물 251Compound 251 6.546.54 515515 47.447.4
실시예 9Example 9 화합물 106Compound 106 6.566.56 516516 43.243.2
실시예 10Example 10 화합물 296Compound 296 6.456.45 517517 42.442.4
실시예 11Example 11 화합물 316Compound 316 6.746.74 515515 43.543.5
비교예 1Comparative Example 1 CBPCBP 6.93 6.93 516 516 38.2 38.2
상기 표 1에 나타낸 바와 같이, 본 발명에 따른 화합물을 발광층의 재료로 사용한 실시예 1 내지 11의 녹색 유기 전계 발광 소자는, 종래 CBP를 발광층에 사용한 비교예 1의 녹색 유기 전계 발광 소자에 비해 전류효율 및 구동전압이 우수하다는 것을 알 수 있다.As shown in Table 1, the green organic electroluminescent devices of Examples 1 to 11 using the compound according to the present invention as the material of the light emitting layer, compared to the green organic electroluminescent device of Comparative Example 1, in which the conventional CBP was used as the light emitting layer. It can be seen that the efficiency and the driving voltage are excellent.
[실시예 12] 적색 유기 전계 발광 소자의 제조Example 12 Fabrication of Red Organic Electroluminescent Device
합성예 12에서 합성한 화합물 5를 통상적으로 알려진 방법으로 고순도 승화정제를 한 후, 하기 과정에 따라 적색 유기 전계 발광 소자를 제조하였다.Compound 5 synthesized in Synthesis Example 12 was subjected to high purity sublimation purification by a conventionally known method, and then a red organic EL device was manufactured according to the following procedure.
먼저, ITO (Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수로 초음파 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV OZONE 세정기 (Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 코팅된 유기 기판을 이송하였다.First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 된 was ultrasonically washed with distilled water. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then the substrate is cleaned for 5 minutes by UV and vacuum evaporator The organic substrate coated with was transferred.
이렇게 준비된 ITO 투명 유리 기판(전극) 위에, m-MTDATA (60 nm)/TCTA (80 nm)/ 90%의 화합물 5 + 10%의 (piq)2Ir(acac) (300 nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 적색 유기 전계 발광 소자를 제조하였다.On the thus prepared ITO transparent glass substrate (electrode), m-MTDATA (60 nm) / TCTA (80 nm) / 90% of compound 5 + 10% of (piq) 2 Ir (acac) (300 nm) / BCP (10 A red organic electroluminescent device was manufactured by laminating in order of nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm).
[실시예 13 내지 22] 적색 유기 전계 발광 소자의 제조Examples 13 to 22 Fabrication of Red Organic Electroluminescent Device
적색 발광 호스트 물질로서 화합물 5 대신 합성예 13~22에서 합성된 각각의 화합물을 사용하는 것을 제외하고는, 상기 실시예 12와 동일하게 수행하여 적색 유기 전계 발광 소자를 제조하였다.A red organic electroluminescent device was manufactured in the same manner as in Example 12, except that each compound synthesized in Synthesis Examples 13 to 22 was used instead of the compound 5 as a red light emitting host material.
[비교예 2]Comparative Example 2
적색 발광 호스트 물질로서 화합물 5 대신 CBP를 사용한 것을 제외하고는, 상기 실시예 12와 동일하게 수행하여 적색 유기 전계 발광 소자를 제조하였다.A red organic electroluminescent device was manufactured in the same manner as in Example 12, except that CBP was used instead of compound 5 as a red light emitting host material.
한편 상기 실시예 12 내지 22 및 비교예 2에서 사용된 m-MTDATA, NPB, (piq)2Ir(acac) 및 CBP의 구조는 하기와 같다.Meanwhile, the structures of m-MTDATA, NPB, (piq) 2 Ir (acac) and CBP used in Examples 12 to 22 and Comparative Example 2 are as follows.
Figure PCTKR2017005670-appb-I000061
Figure PCTKR2017005670-appb-I000061
[평가예 2][Evaluation Example 2]
실시예 12 내지 22 및 비교예 2에서 각각 제조된 적색 유기 전계 발광 소자에 대하여, 전류밀도 10 mA/㎠에서의 구동전압 및 전류효율을 측정하였고, 그 결과를 하기 표 2에 나타내었다.For the red organic electroluminescent devices manufactured in Examples 12 to 22 and Comparative Example 2, the driving voltage and the current efficiency at the current density of 10 mA / cm 2 were measured, and the results are shown in Table 2 below.
샘플Sample 호스트Host 구동 전압(V)Drive voltage (V) 전류효율(cd/A)Current efficiency (cd / A)
실시예 12Example 12 화합물 5Compound 5 4.944.94 12.712.7
실시예 13Example 13 화합물 10Compound 10 4.854.85 12.612.6
실시예 14Example 14 화합물 175Compound 175 4.734.73 12.912.9
실시예 15Example 15 화합물 195Compound 195 4.964.96 13.813.8
실시예 16Example 16 화합물 55Compound 55 4.924.92 12.612.6
실시예 17Example 17 화합물 60Compound 60 4.844.84 13.613.6
실시예 18Example 18 화합물 235Compound 235 4.284.28 14.814.8
실시예 19Example 19 화합물 255Compound 255 4.144.14 15.815.8
실시예 20Example 20 화합물 110Compound 110 4.324.32 14.714.7
실시예 21Example 21 화합물 300Compound 300 4.254.25 14.614.6
실시예 22Example 22 화합물 320Compound 320 4.284.28 15.815.8
비교예 2Comparative Example 2 CBPCBP 5.255.25 8.28.2
상기 표 2에 나타낸 바와 같이, 본 발명에 따른 화합물을 발광층에 사용한 실시예 12 내지 22의 적색 유기 전계 발광 소자는, 종래 CBP를 발광층에 사용한 비교예 2의 적색 유기 전계 발광 소자에 비해 전류효율 및 구동전압이 우수하다는 것을 알 수 있다.As shown in Table 2, the red organic electroluminescent devices of Examples 12 to 22 using the compound according to the present invention in the light emitting layer, compared to the red organic electroluminescent device of Comparative Example 2 using the conventional CBP in the light emitting layer, It can be seen that the driving voltage is excellent.
본 발명의 화학식 1로 표시되는 화합물은 열적 안정성 및 발광 특성이 우수하기 때문에 유기 전계 발광 소자의 유기물 층의 재료로 사용될 수 있다. 특히, 본 발명의 화학식 1로 표시되는 화합물을 인광 호스트 재료로 사용할 경우, 종래의 호스트 재료에 비해 열적 안정성, 우수한 발광 성능, 낮은 구동전압, 높은 효율 및 장수명을 갖는 유기 전계 발광 소자를 제조할 수 있고, 나아가 성능 및 수명이 향상된 풀 칼라 디스플레이 패널도 제조할 수 있다.The compound represented by Chemical Formula 1 of the present invention may be used as a material of the organic material layer of the organic electroluminescent device because of its excellent thermal stability and luminescence properties. In particular, when the compound represented by Chemical Formula 1 of the present invention is used as a phosphorescent host material, an organic electroluminescent device having thermal stability, excellent light emission performance, low driving voltage, high efficiency, and long life compared to a conventional host material can be manufactured. In addition, it is possible to manufacture a full color display panel with improved performance and lifespan.

Claims (8)

  1. 하기 화학식 1로 표시되는 화합물:Compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2017005670-appb-I000062
    Figure PCTKR2017005670-appb-I000062
    상기 화학식 1에서,In Chemical Formula 1,
    A 고리는 단일환 또는 다환의 방향족 고리이고;A ring is a monocyclic or polycyclic aromatic ring;
    X는 -O-, -S-, 또는 -C(R5R6)- 이며;X is -O-, -S-, or -C (R 5 R 6 )-;
    L1 및 L2는 단일결합이거나, 또는 C6~C18의 아릴렌기 및 핵원자수 5 내지 18의 헤테로아릴렌기로 이루어진 군에서 선택되고;L 1 and L 2 are a single bond or are selected from the group consisting of a C 6 -C 18 arylene group and a heteroarylene group having 5 to 18 nuclear atoms;
    Ar1은 하기 화학식 2 내지 화학식 4 중 어느 하나로 표시되고;Ar 1 is represented by any one of the following Formulas 2 to 4;
    [화학식 2][Formula 2]
    Figure PCTKR2017005670-appb-I000063
    Figure PCTKR2017005670-appb-I000063
    [화학식 3][Formula 3]
    Figure PCTKR2017005670-appb-I000064
    Figure PCTKR2017005670-appb-I000064
    [화학식 4][Formula 4]
    Figure PCTKR2017005670-appb-I000065
    Figure PCTKR2017005670-appb-I000065
    상기 화학식 2 내지 4에서,In Chemical Formulas 2 to 4,
    *은 결합이 이루어지는 부분을 의미하고;* Means the part where the bond is made;
    Y1 내지 Y17은 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R7)에서 선택되고, 이때 R7이 복수인 경우, 복수의 R7은 서로 같거나 또는 상이하며;Y 1 to Y 17 are the same as or different from each other, and are each independently selected from N or C (R 7 ), wherein when R 7 is plural, a plurality of R 7 are the same or different from each other;
    상기 화학식 3에서 L1에 결합되는 Y6 내지 Y9 중 어느 하나는 C(R7)이고;In Formula 3, any one of Y 6 to Y 9 bonded to L 1 is C (R 7 );
    Z1은 N 또는 C(R7)이며,Z 1 is N or C (R 7 ),
    R1 내지 R4 및 R7은 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,R 1 to R 4 and R 7 are each independently hydrogen, deuterium, halogen, cyano group, C 1 to C 40 alkyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C Aryl group of 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C 1 to C 40 , aryloxy group of C 6 to C 60 , alkylsilyl group of C 3 to C 40 , C 6 ~ C 60 aryl silyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C of the group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ aryl phosphine oxide of the C 60 group And it is selected from the group consisting of C 6 ~ C 60 arylamine group,
    R5 및 R6는 수소, 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 서로 결합하여 축합 고리를 형성하며,R 5 and R 6 are hydrogen, deuterium, halogen, cyano group, C 1 -C 40 alkyl group, C 3 -C 40 cycloalkyl group, nuclear atom 3-40 heterocycloalkyl group, C 6 -C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, C 1 ~ C 40 alkyloxy group of, C 6 ~ C 60 aryloxy group, C group 3 ~ C 40 alkylsilyl, C 6 ~ aryl of C 60 silyl group, C 1 ~ C 40 group of an alkyl boron, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ aryl phosphine oxide of a C 60 group, and a C 6 ~ C 60 Is selected from the group consisting of arylamine groups, or combine with each other to form a condensed ring,
    R1 내지 R7의 알킬기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴아민기는 각각 독립적으로, 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~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,An alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, an arylphosphine group of R 1 to R 7 , The arylphosphine oxide group and the arylamine group are each independently deuterium, halogen, cyano group, C 1 ~ C 40 alkyl group, C 3 ~ C 40 cycloalkyl group, 3 to 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C 1 ~ C 40 alkyloxy group of, C 6 ~ aryloxy C 60, C 3 ~ C 40 alkyl silyl group, C 6 ~ C 60 aryl silyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ aryl phosphine oxide of a C 60 group, and Is substituted or unsubstituted with one or more substituents selected from the group consisting of C 6 ~ C 60 arylamine group,
    a 내지 d는 각각 1 내지 4의 정수이다.a to d are each an integer of 1 to 4;
  2. 제1항에 있어서,The method of claim 1,
    상기 화학식 1의 화합물은 하기 화학식 5로 표시되는 화합물:The compound of Formula 1 is a compound represented by the following formula (5):
    [화학식 5][Formula 5]
    Figure PCTKR2017005670-appb-I000066
    Figure PCTKR2017005670-appb-I000066
    상기 화학식 5에서,In Chemical Formula 5,
    L1은 단일결합 또는 하기 구조에서 선택되는 아릴렌이고;L 1 is a single bond or arylene selected from the following structures;
    Figure PCTKR2017005670-appb-I000067
    Figure PCTKR2017005670-appb-I000067
    n은 0 내지 2의 정수이며;n is an integer from 0 to 2;
    A, X, Ar1, R1 내지 R4, 및 a 내지 d는 각각 제1항에서 정의된 바와 같다.A, X, Ar 1 , R 1 to R 4 , and a to d are each as defined in claim 1.
  3. 제1항에 있어서,The method of claim 1,
    상기 L1은 단일결합이고,L 1 is a single bond,
    상기 Ar1은 화학식 2 또는 3으로 표시되고, 여기서 Y1 내지 Y5, 및 Y6 내지 Y9 중에서 2 이상은 N이고,Ar 1 is represented by Formula 2 or 3, wherein two or more of Y 1 to Y 5 , and Y 6 to Y 9 are N,
    상기 L2는 C6~C18의 아릴렌기인 화합물.L 2 is a C 6 ~ C 18 arylene group.
  4. 제1항에 있어서,The method of claim 1,
    상기 화학식 2 및 3으로 표시되는 치환체는 하기 화학식 S1 내지 S5로 표시되는 치환체로 이루어진 군에서 선택되는 화합물:Substituents represented by Formulas 2 and 3 is a compound selected from the group consisting of substituents represented by the following formulas S1 to S5:
    Figure PCTKR2017005670-appb-I000068
    Figure PCTKR2017005670-appb-I000068
  5. 제1항에 있어서,The method of claim 1,
    상기 R1 내지 R4는 모두 수소인 화합물.R 1 to R 4 are all hydrogen.
  6. 제1항에 있어서,The method of claim 1,
    상기 R5 및 R6는 각각 독립적으로, 수소, C1~C40의 알킬기 및 C6~60의 아릴기로 이루어진 군에서 선택되는 화합물.R 5 and R 6 are each independently selected from the group consisting of hydrogen, C 1 ~ C 40 alkyl group and C 6 ~ 60 aryl group.
  7. 양극, 음극 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중에서 적어도 하나는 제1항 내지 제6항 중 어느 한 항에 기재된 화합물을 포함하는 유기 전계 발광 소자.An organic material comprising an anode, a cathode and at least one organic material layer interposed between the anode and the cathode, wherein at least one of the at least one organic material layer comprises the compound according to any one of claims 1 to 6. EL device.
  8. 제7항에 있어서,The method of claim 7, wherein
    상기 화합물을 포함하는 유기물층은 발광층, 전자 수송층 및 전자수송 보조층으로 구성된 군에서 선택되는 유기 전계 발광 소자.The organic material layer containing the compound is an organic EL device selected from the group consisting of a light emitting layer, an electron transport layer and an electron transport auxiliary layer.
PCT/KR2017/005670 2016-06-14 2017-05-31 Organic luminescent compound and organic electroluminescent element including same WO2017217676A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2016-0073745 2016-06-14
KR1020160073745A KR102620860B1 (en) 2016-06-14 2016-06-14 Organic light-emitting compound and organic electroluminescent device using the same

Publications (1)

Publication Number Publication Date
WO2017217676A1 true WO2017217676A1 (en) 2017-12-21

Family

ID=60663158

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/005670 WO2017217676A1 (en) 2016-06-14 2017-05-31 Organic luminescent compound and organic electroluminescent element including same

Country Status (2)

Country Link
KR (2) KR102620860B1 (en)
WO (1) WO2017217676A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102530155B1 (en) * 2017-10-23 2023-05-10 솔루스첨단소재 주식회사 Organic compounds and organic electro luminescence device comprising the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130130236A (en) * 2011-05-03 2013-12-02 롬엔드하스전자재료코리아유한회사 Novel organic electroluminescent compounds and an organic electroluminescent device using the same
KR20130139535A (en) * 2012-06-13 2013-12-23 롬엔드하스전자재료코리아유한회사 Novel organic electroluminescence compounds and organic electroluminescence device containing the same
KR20140082351A (en) * 2012-12-24 2014-07-02 롬엔드하스전자재료코리아유한회사 Organic Electroluminescent Compounds and Organic Electroluminescent Device Comprising the Same
KR20150110101A (en) * 2014-03-24 2015-10-02 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same
KR20160044690A (en) * 2014-10-15 2016-04-26 삼성디스플레이 주식회사 Organic light emitting diode and organic light emitting display device including the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130130236A (en) * 2011-05-03 2013-12-02 롬엔드하스전자재료코리아유한회사 Novel organic electroluminescent compounds and an organic electroluminescent device using the same
KR20130139535A (en) * 2012-06-13 2013-12-23 롬엔드하스전자재료코리아유한회사 Novel organic electroluminescence compounds and organic electroluminescence device containing the same
KR20140082351A (en) * 2012-12-24 2014-07-02 롬엔드하스전자재료코리아유한회사 Organic Electroluminescent Compounds and Organic Electroluminescent Device Comprising the Same
KR20150110101A (en) * 2014-03-24 2015-10-02 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same
KR20160044690A (en) * 2014-10-15 2016-04-26 삼성디스플레이 주식회사 Organic light emitting diode and organic light emitting display device including the same

Also Published As

Publication number Publication date
KR20170140951A (en) 2017-12-22
KR20230047988A (en) 2023-04-10
KR102620860B1 (en) 2024-01-03

Similar Documents

Publication Publication Date Title
WO2017095100A1 (en) Organic compound and organic electroluminescent element comprising same
WO2016105161A2 (en) Organic compound and organic electroluminescent element comprising same
WO2019017616A1 (en) Organic light emitting compound and organic electroluminescent device using same
WO2018230782A1 (en) Organic compound and organic electroluminescent device comprising same
WO2015060684A2 (en) Organic compound and organic electroluminescent device comprising same
WO2014098447A1 (en) Organic compound and organic electroluminescent element comprising same
WO2017099431A1 (en) Organic compound and organic electroluminescent device containing same
WO2017111544A1 (en) Organic compound and organic electroluminescent device comprising same
WO2013100497A1 (en) Organic light-emitting compound and organic electroluminescent device using same
WO2013168927A2 (en) Novel compound and organic electroluminescent device comprising same
WO2017209488A1 (en) Organic compound and organic electroluminescent device comprising same
WO2017111543A1 (en) Organic compound and organic electroluminescent device comprising same
WO2015133804A1 (en) Organic compound and organic electroluminescent device comprising same
WO2015111943A1 (en) Organic compound, and organic electroluminescent device containing same
WO2016105123A2 (en) Organic compound and organic electroluminescent device comprising same
WO2013191355A1 (en) Novel compound and organic electroluminescent element comprising same
WO2017111389A1 (en) Organic compound and organic electroluminescent diode including same
WO2015060635A1 (en) Organic compound and organic electroluminescent element comprising same
WO2018043913A1 (en) Organic compound and organic electroluminescent device comprising same
WO2020218680A1 (en) Organic compound and organic electroluminescent diode using same
WO2019103397A1 (en) Organic compound and organic electroluminescent device comprising same
WO2016104954A2 (en) Organic compound and organic electroluminescent device comprising same
WO2018186551A1 (en) Organic compound and organic electroluminescent element comprising same
WO2015099477A2 (en) Organic compound and organic light-emitting diode device using same
WO2015046982A2 (en) Organic compound and organic electroluminescent element comprising same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17813501

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 17/04/2019)

122 Ep: pct application non-entry in european phase

Ref document number: 17813501

Country of ref document: EP

Kind code of ref document: A1