WO2019088517A1 - 2,3-substituted naphthylamine derivative organic light emitting compound and organic electroluminescent element - Google Patents

2,3-substituted naphthylamine derivative organic light emitting compound and organic electroluminescent element Download PDF

Info

Publication number
WO2019088517A1
WO2019088517A1 PCT/KR2018/012249 KR2018012249W WO2019088517A1 WO 2019088517 A1 WO2019088517 A1 WO 2019088517A1 KR 2018012249 W KR2018012249 W KR 2018012249W WO 2019088517 A1 WO2019088517 A1 WO 2019088517A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituted
compound
mmol
layer
Prior art date
Application number
PCT/KR2018/012249
Other languages
French (fr)
Korean (ko)
Inventor
김경우
민병우
안도환
임현철
이대균
안중복
배호기
Original Assignee
(주)씨엠디엘
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 (주)씨엠디엘 filed Critical (주)씨엠디엘
Priority to CN202311373601.2A priority Critical patent/CN117417261A/en
Priority to CN201880071653.5A priority patent/CN111315717A/en
Publication of WO2019088517A1 publication Critical patent/WO2019088517A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • 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
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H10K50/181—Electron blocking 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
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • 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
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Definitions

  • An electroluminescence device is a self-emissive type display device having a high response speed and a wide viewing angle.
  • Eastman Kodak Company first developed an organic EL device using a low molecular aromatic diamine and an aluminum complex as a light emitting layer material [Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor for determining the luminous efficiency in an organic electroluminescent device is a luminescent material.
  • the phosphorescent material of the luminescent material can theoretically improve the luminous efficiency up to 4 times as compared with the fluorescent material.
  • iridium (III) complexes and carbazole-based materials have been widely known as phosphorescent materials, and new phosphorescent materials are being studied in recent years.
  • organic electroluminescent phenomenon is that when a voltage is applied between two electrodes when an organic thin film layer exists between a cathode and an anode, electrons and holes are injected into the organic thin film layer from the cathode and the anode, respectively. Electrons and holes injected into the organic thin film layer are recombined to form an exciton, and the exciton falls back to the ground state to emit light.
  • An organic electroluminescent device using this principle can be generally constituted of an organic thin film layer including a cathode, an anode and an organic thin film layer disposed therebetween, for example, a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer.
  • a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material Can be distinguished.
  • an organic material having a p-type property that is, an organic material which is easily oxidized and electrochemically stable at the time of oxidation
  • an electron injecting material and an electron transporting material an organic material having an n-type property, that is, an organic material which is easily reduced and electrochemically stable at the time of reduction is mainly used.
  • the light emitting layer material a material having both a p-type property and an n-type property, that is, a material having both a stable state in oxidation and in a reduced state is preferable, and a material having a high luminous efficiency for converting an exciton into light desirable. Accordingly, there is a need in the art to develop new organic materials having the above-described requirements.
  • One embodiment of the present invention provides 2,3-substituted naphthylamine derivative compounds having appropriate energy levels, electrochemical stability, and thermal stability.
  • Another embodiment of the present invention provides an organic electroluminescent device comprising the 2,3-substituted naphthylamine derivative compound.
  • L 1 is a single bond, a phenylene group or a biphenylene group
  • L 2 is a single bond, a phenylene group or a biphenylene group
  • Ar 1 Is a substituted or unsubstituted C3-C60 heteroaryl group, a C1-C30 alkyl group or a C6-C30 aryl group, and when the Ar1 is substituted, the substituent may be a C1-C30 alkyl group, a C6- C5 to C30 heteroaryl group, substituted or unsubstituted silyl group, and combinations thereof, and the secondary substituent when the silyl group is substituted is C6 to C30 aryl group, When Ar 1 is an alkyl group having 1 to 30 carbon atoms, L 1 is not a single bond,
  • Ar 2 Is a substituted or unsubstituted aryl groups, unsubstituted C6 ⁇ C30 heteroaryl or a substituted or unsubstituted C3-C60 group, and the substituent in the case where the Ar 2 is substituted with a heavy hydrogen, a cyano group, a nitrile group, a halogen group, C1- C60 alkyl group, C6-C60 aryl group, C3-C60 heteroaryl group, and combinations thereof,
  • R 1 and R 2 are each independently hydrogen, deuterium, cyano, nitrile, halogen, C 1 -C 12 alkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 3 -C 60 And R < 1 > and R < 2 > Is a C1-C30 alkyl group or a C6-C30 aryl group, a C5-C30 heteroaryl group, or a combination thereof,
  • X is absent, oxygen, sulfur, or C (R 3 R 4 ), R 3 and R 4 Are the same or different and each is independently hydrogen, an alkyl group of C1-C20, aryl group of C5-C30 to each other, wherein R 3 and R 4 May each be linked to a bondable carbon in the reduction of the X-containing polycyclic ring to form a saturated or unsaturated condensed ring.
  • the 2,3-substituted naphthylamine derivative compound can satisfactorily satisfy the conditions required for a material usable in an organic electroluminescent device, for example, suitable energy level, electrochemical stability and thermal stability, And can play various roles required in organic electroluminescent devices.
  • 1 to 3 are graphs showing lifetime characteristics evaluation results of the organic electroluminescent devices manufactured in Examples 1 to 17 and Comparative Examples 1 to 5.
  • substituted means an alkyl group, an amino group, a nitrile group, a C3-C7 cycloalkyl group, a C2-C12 alkenyl group, a C3-C7 cycloalkenyl group, a C2 Substituted with a substituent selected from the group consisting of a C5-C50 alkynyl group, a C5-C50 cycloalkynyl group, a cyano group, a C1-C12 alkoxy group, a C6-C60 aryl group, and a C7-C60 arylalkyl group, .
  • combination thereof means that two or more substituents are bonded to each other via a linking group or two or more substituents are condensed and bonded.
  • Hetero as used herein, unless otherwise defined, means containing a heteroatom in one compound or substituent, wherein the heteroatom is selected from the group consisting of N, O, S, P, Lt; / RTI > For example, it may mean one to three heteroatoms in the one compound or substituent, and the remainder is carbon.
  • Quot means a moiety that is linked to the same or different atom or formula.
  • L 1 is a single bond, a phenylene group or a biphenylene group
  • L 2 is a single bond, a phenylene group or a biphenylene group
  • Ar 1 Is a substituted or unsubstituted C3-C60 heteroaryl group, a C1-C30 alkyl group or a C6-C30 aryl group, and when the Ar1 is substituted, the substituent may be a C1-C30 alkyl group, a C6- C5 to C30 heteroaryl group, substituted or unsubstituted silyl group, and combinations thereof, and the secondary substituent when the silyl group is substituted is C6 to C30 aryl group, When Ar 1 is an alkyl group having 1 to 30 carbon atoms, L 1 is not a single bond,
  • Ar 2 Is a substituted or unsubstituted aryl groups, unsubstituted C6 ⁇ C30 heteroaryl or a substituted or unsubstituted C3-C60 group, and the substituent in the case where the Ar 2 is substituted with a heavy hydrogen, a cyano group, a nitrile group, a halogen group, C1- C60 alkyl group, C6-C60 aryl group, C3-C60 heteroaryl group, and combinations thereof,
  • R 1 and R 2 are each independently hydrogen, deuterium, cyano, nitrile, halogen, C 1 -C 12 alkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 3 -C 60 And R < 1 > and R < 2 > Is a C1-C30 alkyl group or a C6-C30 aryl group, a C5-C30 heteroaryl group, or a combination thereof,
  • X is absent, oxygen, sulfur, or C (R 3 R 4 ), R 3 and R 4 Are the same or different and each is independently hydrogen, an alkyl group of C1-C20, aryl group of C5-C30 to each other, wherein R 3 and R 4 May each be linked to a bondable carbon in the reduction of the X-containing polycyclic ring to form a saturated or unsaturated condensed ring.
  • the saturated or unsaturated condensed ring may be a condensed form of a polycyclic ring containing X and a C3-C7 ring.
  • the condensed form means a form in which two rings, that is, the polycyclic ring containing X and the ring of C3-C7 share at least two reductions.
  • the above-mentioned formula (a) may be a compound selected from any one of the compounds represented by the chemical formula a-1, a-2, a-3 and a-4.
  • R 1 , R 2 , R 3 , R 4 , L 1 , L 2 , X, Ar 1 and Ar 2 are as defined in formula a above
  • Ar 1 Is a group selected from the group consisting of a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthrene group, a fluorene group, a spirobifluorene group, a benzothiophene group, a benzofuran group, a dibenzofurane group, A phenanthrene group, a phenyldibenzothiophene group, a phenylphene-threne group, a tetraphenylsilyl group, or a biphenyltriphenylsilyl group.
  • L 1 and L 2 each independently represent any one of groups represented by the following structural formulas.
  • the 2,3-substituted naphthylamine derivative compound represented by Formula (a) may be any one of the following 1 to 156 compounds.
  • the 2,3-substituted naphthylamine derivative organic compound is used as a material for an organic electroluminescence device, it is preferable that the 2,3-substituted naphthylamine derivative organic compound is a compound represented by the following formula Can be satisfactorily satisfied, and can play various roles required in the organic electroluminescent device depending on the substituent.
  • At least one organic thin film layer is sandwiched between a cathode and an anode, wherein the organic thin film layer has a multi-layer structure including at least one light emitting layer, And at least one layer in the organic thin film layer comprises the organic compound of the 2,3-substituted naphthylamine derivative alone or a mixture of two or more thereof.
  • the 2,3-substituted naphthylamine derivative organic compound contained in the organic thin film layer of the organic electroluminescent device is a compound represented by the above formula (a), and a detailed description thereof is as described above.
  • the organic thin film layer may include a hole transporting region interposed between the cathode and the light emitting layer and including at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, and an electron blocking layer .
  • the hole transporting region may include the 2,3-substituted naphthylamine derivative organic compound.
  • at least one of the functional layer, the buffer layer, and the electron blocking layer may include the 2,3-substituted naphthylamine derivative organic compound.
  • the 2,3-substituted naphthylamine derivative organic compound may be used as an electron blocking layer, a hole transporting layer, or a hole injecting layer material in an organic electroluminescent device. That is, the organic thin film layer containing the 2,3-substituted naphthylamine derivative organic compound may be a light emitting layer, an electron blocking layer, a hole transporting layer, or a hole injecting layer.
  • the organic thin film layer may include at least one of a luminescent layer, a hole injecting layer, a hole transporting layer, a functional layer, a buffer layer, an electron blocking layer, And a combination thereof.
  • the light emitting layer, the hole injecting layer, the hole transporting layer, the functional layer, the buffer layer, the electron blocking layer, the luminescent layer hole blocking layer electron transporting layer, the electron injecting layer, etc. forming the organic thin film layer can be formed using known materials, respectively , Or a 2,3-substituted naphthylamine derivative organic compound represented by the formula (a).
  • the intermediate compound [21-1] was prepared in 42% yield using 2-bromo-7-methoxynaphthalene in the same manner as in [Synthesis Example 4].
  • the intermediate compound [100-1] was prepared in a yield of 56% using the compound [5-1] and 1-bromo-3-methylbenzene in the same manner as in [Synthesis Example 11].
  • the anode was prepared by cutting Corning's 15 ⁇ / cm 2 (1000 ⁇ ) ITO glass substrate to a size of 25 mm ⁇ 25 mm ⁇ 0.7 mm, ultrasonically cleaning it in acetone isopropyl alcohol and pure water for 15 minutes each, UV ozone cleaning was used.
  • 2-TNATA was vacuum deposited on the substrate to form a 60 nm thick hole injection layer.
  • ⁇ -NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm.
  • a compound represented by Formula f and a compound represented by Formula g (doping ratio: 4 wt%) were vacuum-deposited on the hole transport layer to form a light emitting layer having a thickness of 30 nm.
  • Comparative Sample 1 Liq 1 nm (electron injecting layer) and Al 100 nm (cathode) were sequentially vacuum-deposited on the electron transporting layer to produce an organic light emitting device as shown in Table 3. This is referred to as Comparative Sample 1.
  • An organic light emitting device having the following structure was produced by using the above Comparative Compounds b, c, d and e in place of the hole transport layer compound ⁇ -NPD in Comparative Example 1: ITO / 2-TNATA 60 (30 nm) / compound b, c, d, or e (30 nm) / compound f + compound g (30 nm) / Alq3 (25 nm) / Liq (1 nm) / Al (100 nm).
  • Evaluation Example 1 Evaluation of luminescence characteristics and life span of Comparative Examples 1 to 5 and Examples 1 to 17
  • the time (LT97) at which the luminance (L) reached 97% on the basis of the initial luminance (L 0 ) of 1000 nits was measured using a M6000S lifetime measuring device of Mac Science Inc., and the results are shown in Table 3 and Figs. Respectively.
  • Examples 1 to 17 exhibited low-voltage driving and improved luminescence characteristics as compared with Comparative Examples 1 to 5.
  • FIGS. 1, 2 and 3 are graphs showing lifetime characteristics of the organic electroluminescent devices manufactured in Examples 1 to 17 and Comparative Examples 1 to 5, respectively, showing the results of the measurement.
  • Examples 1 to 17 exhibited improved life characteristics compared to Comparative Examples 1 to 5.
  • the above compounds of 2,3-substituted naphthylamine derivatives exhibit excellent performance and lifetime.

Abstract

Provided is a novel 2,3-substitued naphthylamine derivative organic compound.

Description

2,3-치환된 나프틸아민 유도체 유기발광 화합물 및 유기 전계 발광 소자2,3-Substituted naphthylamine derivatives Organic light-emitting compounds and organic electroluminescent devices
2,3-치환된 나프틸아민 유도체 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것이다.2,3-substituted naphthylamine derivative compounds and organic electroluminescent devices comprising the same.
전계 발광 소자(electroluminescence device: EL device)는 자체 발광형 표시 소자로서 응답 속도가 빠르고, 시야각이 넓다는 장점을 가지고 있다. 1987년 이스트만 코닥(Eastman Kodak)사는 발광층 재료로서 저분자 방향족 디아민과 알루미늄 착물을 이용한 유기EL 소자를 처음으로 개발하였다[Appl. Phys. Lett. 51, 913, 1987].An electroluminescence device (EL device) is a self-emissive type display device having a high response speed and a wide viewing angle. In 1987, Eastman Kodak Company first developed an organic EL device using a low molecular aromatic diamine and an aluminum complex as a light emitting layer material [Appl. Phys. Lett. 51, 913, 1987].
유기 전계 발광 소자에서 발광 효율을 결정하는 가장 중요한 요인은 발광 재료인데, 발광 재료 중 인광 재료는 이론적으로 형광 재료 대비 4배까지 발광 효율을 개선시킬 수 있다. 현재까지 이리듐(III)착물 계열과 카바졸 계열의 재료들이 인광 발광 재료로 널리 알려져 있으며, 최근 새로운 인광 재료들이 연구되고 있다.The most important factor for determining the luminous efficiency in an organic electroluminescent device is a luminescent material. The phosphorescent material of the luminescent material can theoretically improve the luminous efficiency up to 4 times as compared with the fluorescent material. Until now, iridium (III) complexes and carbazole-based materials have been widely known as phosphorescent materials, and new phosphorescent materials are being studied in recent years.
유기 전계 발광 현상의 원리는, 음극과 양극 사이에 유기 박막층이 있을 때 두 전극 사이에 전압을 걸어주면 음극과 양극으로부터 각각 전자와 정공이 유기 박막층으로 주입된다. 유기 박막층으로 주입된 전자와 정공은 재결합하여 엑시톤 (exciton)을 형성하고, 이 엑시톤이 다시 바닥 상태로 떨어지면서 빛이 나게 된다. 이러한 원리를 이용하는 유기 전계 발광 소자는 일반적으로 음극과 양극 및 그 사이에 위치한 유기 박막층, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층을 포함하는 유기 박막층으로 구성될 수 있다.The principle of organic electroluminescent phenomenon is that when a voltage is applied between two electrodes when an organic thin film layer exists between a cathode and an anode, electrons and holes are injected into the organic thin film layer from the cathode and the anode, respectively. Electrons and holes injected into the organic thin film layer are recombined to form an exciton, and the exciton falls back to the ground state to emit light. An organic electroluminescent device using this principle can be generally constituted of an organic thin film layer including a cathode, an anode and an organic thin film layer disposed therebetween, for example, a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer.
유기 전계 발광 소자에서 사용되는 재료로는 순수 유기물 또는 유기물과 금속이 착물을 이루는 착화합물이 대부분을 차지하고 있으며, 용도에 따라 정공주입 재료, 정공수송 재료, 발광 재료, 전자수송 재료, 전자주입 재료 등으로 구분될 수 있다. 여기서, 정공주입 재료나 정공수송 재료로는 p-타입의 성질을 가지는 유기 재료, 즉 쉽게 산화가 되고 산화시에 전기화학적으로 안정한 상태를 가지는 유기물이 주로 사용되고 있다. 한편, 전자주입 재료나 전자수송 재료로는 n-타입 성질을 가지는 유기 재료, 즉 쉽게 환원이 되고 환원시에 전기화학적으로 안정한 상태를 가지는 유기물이 주로 사용되고 있다. 발광층 재료로는 p-타입 성질과 n-타입 성질을 동시에 가진 재료, 즉 산화와 환원 상태에서 모두 안정한 형태를 갖는 재료가 바람직하며, 엑시톤이 형성되었을 때 이를 빛으로 전환하는 발광 효율이 높은 재료가 바람직하다. 따라서, 당 기술 분야에서는 상기와 같은 요건을 갖춘 새로운 유기 재료의 개발이 요구되고 있다.Most of materials used in organic electroluminescent devices are pure organic materials or complexes in which an organic material and a metal form a complex with each other. Depending on the application, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, Can be distinguished. As the hole injecting material and the hole transporting material, an organic material having a p-type property, that is, an organic material which is easily oxidized and electrochemically stable at the time of oxidation, is mainly used. On the other hand, as an electron injecting material and an electron transporting material, an organic material having an n-type property, that is, an organic material which is easily reduced and electrochemically stable at the time of reduction is mainly used. As the light emitting layer material, a material having both a p-type property and an n-type property, that is, a material having both a stable state in oxidation and in a reduced state is preferable, and a material having a high luminous efficiency for converting an exciton into light desirable. Accordingly, there is a need in the art to develop new organic materials having the above-described requirements.
본 발명의 일 구현예는 적절한 에너지 준위, 전기화학적 안정성 및 열적 안정성을 가지는 2,3-치환된 나프틸아민 유도체 화합물을 제공한다.One embodiment of the present invention provides 2,3-substituted naphthylamine derivative compounds having appropriate energy levels, electrochemical stability, and thermal stability.
본 발명의 또 다른 구현예는 상기 2,3-치환된 나프틸아민 유도체 화합물을 포함하는 유기 전계 발광 소자를 제공한다.Another embodiment of the present invention provides an organic electroluminescent device comprising the 2,3-substituted naphthylamine derivative compound.
본 발명의 일 구현예에서, 하기 화학식 a로 표시되는 2,3-치환된 나프틸아민 유도체 유기화합물을 제공한다.In one embodiment of the present invention, there is provided a 2,3-substituted naphthylamine derivative organic compound represented by the following formula (a).
<화학식 a><Formula a>
Figure PCTKR2018012249-appb-img-000001
Figure PCTKR2018012249-appb-img-000001
상기 식에서, In this formula,
L 1은 단일결합, 페닐렌기 이거나 비페닐렌기이고,L 1 is a single bond, a phenylene group or a biphenylene group,
L 2는 단일결합, 페닐렌기 이거나 비페닐렌기이고, L 2 is a single bond, a phenylene group or a biphenylene group,
Ar 1 은 치환 또는 비치환된 C3-C60의 헤테로아릴기, C1~C30의 알킬기 또는 C6~C30의 아릴기이고, 상기 Ar1이 치환된 경우의 치환기는 C1~C30의 알킬기, C6~C30의 아릴기, C5~C30의 헤테로아릴기, 치환 또는 비치환된 실릴기 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나이고, 상기 실릴기가 치환된 경우의 2차 치환기는 C6~C30의 아릴기이고, 단, 상기 Ar 1 은 C1~C30의 알킬기인 경우, L 1은 단일결합이 아니고,Ar 1 Is a substituted or unsubstituted C3-C60 heteroaryl group, a C1-C30 alkyl group or a C6-C30 aryl group, and when the Ar1 is substituted, the substituent may be a C1-C30 alkyl group, a C6- C5 to C30 heteroaryl group, substituted or unsubstituted silyl group, and combinations thereof, and the secondary substituent when the silyl group is substituted is C6 to C30 aryl group, When Ar 1 is an alkyl group having 1 to 30 carbon atoms, L 1 is not a single bond,
Ar 2 는 치환 또는 비치환된 C6~C30의 아릴기 또는 치환 또는 비치환된 C3-C60의 헤테로아릴기이고, 상기 Ar 2가 치환된 경우의 치환기는 중수소, 시아노기, 니트릴기, 할로겐기, C1-C12의 알킬기, C6-C60의 아릴기, C3-C60의 헤테로아릴기 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나이고,Ar 2 Is a substituted or unsubstituted aryl groups, unsubstituted C6 ~ C30 heteroaryl or a substituted or unsubstituted C3-C60 group, and the substituent in the case where the Ar 2 is substituted with a heavy hydrogen, a cyano group, a nitrile group, a halogen group, C1- C60 alkyl group, C6-C60 aryl group, C3-C60 heteroaryl group, and combinations thereof,
R 1 및 R 2 는, 각각 독립적으로, 수소, 중수소, 시아노기, 니트릴기, 할로겐기, C1-C12의 알킬기, 치환 또는 비치환된 C6-C60의 아릴기, 치환 또는 비치환된 C3-C60의 헤테로아릴기이고, 상기 R 1 및 R 2 가 치환된 경우의 치환기는 C1~C30의 알킬기 또는 C6~C30의 아릴기, C5~C30의 헤테로 아릴기 및 이들의 조합으로 이루어진 군으로부터 선택된 하나이고, R 1 and R 2 are each independently hydrogen, deuterium, cyano, nitrile, halogen, C 1 -C 12 alkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 3 -C 60 And R &lt; 1 &gt; and R &lt; 2 &gt; Is a C1-C30 alkyl group or a C6-C30 aryl group, a C5-C30 heteroaryl group, or a combination thereof,
X 는 부존재, 산소, 황, 또는 C(R 3R 4) 이고, R 3 및 R 4 는 서로 동일하거나 또는 상이하며 각각 독립적으로 수소, C1-C20의 알킬기, C5-C30의 아릴기 이고, 상기 R 3 및 R 4 는 각각 상기 X가 함유된 다환 고리의 환원 중 결합가능한 탄소와 연결되어 포화 또는 불포화 축합고리를 형성할 수 있다.X is absent, oxygen, sulfur, or C (R 3 R 4 ), R 3 and R 4 Are the same or different and each is independently hydrogen, an alkyl group of C1-C20, aryl group of C5-C30 to each other, wherein R 3 and R 4 May each be linked to a bondable carbon in the reduction of the X-containing polycyclic ring to form a saturated or unsaturated condensed ring.
상기 2,3-치환된 나프틸아민 유도체 화합물은 유기 전계 발광 소자에서 사용 가능한 물질에 요구되는 조건, 예컨대 적절한 에너지 준위, 전기화학적 안정성 및 열적 안정성 등을 모두 우수하게 만족시킬 수 있으며, 치환기에 따라 유기 전계 발광 소자에서 요구되는 다양한 역할을 할 수 있다.The 2,3-substituted naphthylamine derivative compound can satisfactorily satisfy the conditions required for a material usable in an organic electroluminescent device, for example, suitable energy level, electrochemical stability and thermal stability, And can play various roles required in organic electroluminescent devices.
도 1 내지 도 3은 실시예 1~17 및 비교예 1~5에서 제조된 유기 전계 발광 소자에 대하여 측정 결과를 나타낸 수명 특성 평가 그래프이다.1 to 3 are graphs showing lifetime characteristics evaluation results of the organic electroluminescent devices manufactured in Examples 1 to 17 and Comparative Examples 1 to 5.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구항의 범주에 의해 정의될 뿐이다. Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
본 명세서에서 "치환"된 경우는 별도의 정의가 없는 한, C1-C12의 알킬기, 아미노기, 니트릴기, C3-C7의 시클로알킬기, C2-C12의 알케닐기, C3-C7의 시클로알케닐기, C2-C50의 알키닐기, C5-C50의 시클로알키닐기, 시아노기, C1-C12의 알콕시기, C6-C60의 아릴기, 및 C7-C60의 아릴알킬기 및 이들의 조합으로 이루어진 군에서 선택된 치환기로 치환된 경우를 포함한다.Unless defined otherwise, the term "substituted" as used herein means an alkyl group, an amino group, a nitrile group, a C3-C7 cycloalkyl group, a C2-C12 alkenyl group, a C3-C7 cycloalkenyl group, a C2 Substituted with a substituent selected from the group consisting of a C5-C50 alkynyl group, a C5-C50 cycloalkynyl group, a cyano group, a C1-C12 alkoxy group, a C6-C60 aryl group, and a C7-C60 arylalkyl group, .
본 명세서에서 "이들의 조합"이란 별도의 정의가 없는 한, 둘 이상의 치환기가 연결기로 결합되어 있거나, 둘 이상의 치환기가 축합하여 결합되어 있는 것을 의미한다. In the present specification, the term " combination thereof " means that two or more substituents are bonded to each other via a linking group or two or more substituents are condensed and bonded.
본 명세서에서 "헤테로"란 별도의 정의가 없는 한, 하나의 화합물 또는 치환기 내에 헤테로 원자를 포함함을 의미하고, 상기 헤테로 원자는 N, O, S, P 및 이들의 조합으로 이루어진 군에서 선택된 하나일 수 있다. 예를 들어, 상기 하나의 화합물 또는 치환기 내에 헤테로 원자를 1 내지 3 포함하고, 나머지는 탄소인 경우를 의미할 수 있다.&Quot; Hetero " as used herein, unless otherwise defined, means containing a heteroatom in one compound or substituent, wherein the heteroatom is selected from the group consisting of N, O, S, P, Lt; / RTI &gt; For example, it may mean one to three heteroatoms in the one compound or substituent, and the remainder is carbon.
또한, 본 명세서의 구조식 중 "
Figure PCTKR2018012249-appb-img-000002
"는 동일하거나 상이한 원자 또는 화학식과 연결되는 부분을 의미한다.In the structural formula of the present specification,
Figure PCTKR2018012249-appb-img-000002
Quot; means a moiety that is linked to the same or different atom or formula.
본 발명의 일 구현예에서, 신규한 하기 화학식 a로 표시되는 2,3-치환 나프틸아민 유도체 유기화합물을 제공한다.In one embodiment of the present invention, there is provided a novel 2,3-substituted naphthylamine derivative organic compound represented by the following formula (a).
<화학식 a><Formula a>
Figure PCTKR2018012249-appb-img-000003
Figure PCTKR2018012249-appb-img-000003
상기 식에서, In this formula,
L 1은 단일결합, 페닐렌기 또는 비페닐렌기이고,L 1 is a single bond, a phenylene group or a biphenylene group,
L 2는 단일결합, 페닐렌기 또는 비페닐렌기이고, L 2 is a single bond, a phenylene group or a biphenylene group,
Ar 1 은 치환 또는 비치환된 C3-C60의 헤테로아릴기, C1~C30의 알킬기 또는 C6~C30의 아릴기이고, 상기 Ar1이 치환된 경우의 치환기는 C1~C30의 알킬기, C6~C30의 아릴기, C5~C30의 헤테로아릴기, 치환 또는 비치환된 실릴기 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나이고, 상기 실릴기가 치환된 경우의 2차 치환기는 C6~C30의 아릴기이고, 단, 상기 Ar 1 은 C1~C30의 알킬기인 경우, L 1은 단일결합이 아니고,Ar 1 Is a substituted or unsubstituted C3-C60 heteroaryl group, a C1-C30 alkyl group or a C6-C30 aryl group, and when the Ar1 is substituted, the substituent may be a C1-C30 alkyl group, a C6- C5 to C30 heteroaryl group, substituted or unsubstituted silyl group, and combinations thereof, and the secondary substituent when the silyl group is substituted is C6 to C30 aryl group, When Ar 1 is an alkyl group having 1 to 30 carbon atoms, L 1 is not a single bond,
Ar 2 는 치환 또는 비치환된 C6~C30의 아릴기 또는 치환 또는 비치환된 C3-C60의 헤테로아릴기이고, 상기 Ar 2가 치환된 경우의 치환기는 중수소, 시아노기, 니트릴기, 할로겐기, C1-C12의 알킬기, C6-C60의 아릴기, C3-C60의 헤테로아릴기 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나이고,Ar 2 Is a substituted or unsubstituted aryl groups, unsubstituted C6 ~ C30 heteroaryl or a substituted or unsubstituted C3-C60 group, and the substituent in the case where the Ar 2 is substituted with a heavy hydrogen, a cyano group, a nitrile group, a halogen group, C1- C60 alkyl group, C6-C60 aryl group, C3-C60 heteroaryl group, and combinations thereof,
R 1 및 R 2 는, 각각 독립적으로, 수소, 중수소, 시아노기, 니트릴기, 할로겐기, C1-C12의 알킬기, 치환 또는 비치환된 C6-C60의 아릴기, 치환 또는 비치환된 C3-C60의 헤테로아릴기이고, 상기 R 1 및 R 2 가 치환된 경우의 치환기는 C1~C30의 알킬기 또는 C6~C30의 아릴기, C5~C30의 헤테로 아릴기 및 이들의 조합으로 이루어진 군으로부터 선택된 하나이고, R 1 and R 2 are each independently hydrogen, deuterium, cyano, nitrile, halogen, C 1 -C 12 alkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 3 -C 60 And R &lt; 1 &gt; and R &lt; 2 &gt; Is a C1-C30 alkyl group or a C6-C30 aryl group, a C5-C30 heteroaryl group, or a combination thereof,
X 는 부존재, 산소, 황, 또는 C(R 3R 4) 이고, R 3 및 R 4 는 서로 동일하거나 또는 상이하며 각각 독립적으로 수소, C1-C20의 알킬기, C5-C30의 아릴기 이고, 상기 R 3 및 R 4 는 각각 상기 X가 함유된 다환 고리의 환원 중 결합가능한 탄소와 연결되어 포화 또는 불포화 축합고리를 형성할 수 있다. X is absent, oxygen, sulfur, or C (R 3 R 4 ), R 3 and R 4 Are the same or different and each is independently hydrogen, an alkyl group of C1-C20, aryl group of C5-C30 to each other, wherein R 3 and R 4 May each be linked to a bondable carbon in the reduction of the X-containing polycyclic ring to form a saturated or unsaturated condensed ring.
예를 들어, 상기 포화 또는 불포화 축합고리는 상기 X가 함유된 다환 고리와 C3-C7의 고리가 축합된 형태일 수 있다. 축합된 형태는 2개의 고리, 즉, 상기 X가 함유된 다환 고리와 상기 C3-C7의 고리가 적어도 2개의 환원을 공유하는 형태를 의미한다.For example, the saturated or unsaturated condensed ring may be a condensed form of a polycyclic ring containing X and a C3-C7 ring. The condensed form means a form in which two rings, that is, the polycyclic ring containing X and the ring of C3-C7 share at least two reductions.
상기 화학식 a는 화기 화학식 a-1, a-2, a-3 및 a-4로 표시되는 화합물 중 어느 하나로 선택되는 화합물일 수 있다.The above-mentioned formula (a) may be a compound selected from any one of the compounds represented by the chemical formula a-1, a-2, a-3 and a-4.
<화학식 a-1>&Lt; Formula (a-1)
Figure PCTKR2018012249-appb-img-000004
Figure PCTKR2018012249-appb-img-000004
<화학식 a-2><Formula a-2>
Figure PCTKR2018012249-appb-img-000005
Figure PCTKR2018012249-appb-img-000005
<화학식 a-3> <Formula a-3>
Figure PCTKR2018012249-appb-img-000006
Figure PCTKR2018012249-appb-img-000006
<화학식 a-4> <Chemical Formula a-4>
Figure PCTKR2018012249-appb-img-000007
Figure PCTKR2018012249-appb-img-000007
상기 식에서, R 1, R 2, R 3, R 4, L 1, L 2, X, Ar 1 및 Ar 2 는 상기 화학식 a에서 정의된 바와 같다 Wherein R 1 , R 2 , R 3 , R 4 , L 1 , L 2 , X, Ar 1 and Ar 2 are as defined in formula a above
구체적으로, Ar 1 은, 페닐기, 톨릴기, 나프틸기, 비페닐기, 터페닐기, 페안트렌기, 플루오렌기, 스파이로플루오렌기, 벤조티오펜기, 벤조퓨란기, 디벤조퓨란기, 디벤조티오펜기, 피리딜기, 페닐나프틸기, 페닐플루오렌기, 페닐디벤조퓨란기, 페닐디벤조티오펜기, 페닐펜안트렌기, 테트라페닐실릴기, 또는 비페닐트리페닐실릴기일 수 있다.Specifically, Ar 1 Is a group selected from the group consisting of a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthrene group, a fluorene group, a spirobifluorene group, a benzothiophene group, a benzofuran group, a dibenzofurane group, A phenanthrene group, a phenyldibenzothiophene group, a phenylphene-threne group, a tetraphenylsilyl group, or a biphenyltriphenylsilyl group.
구체적으로, 상기 L 1 및 L 2는, 각각 독립적으로, 하기 구조식으로 표시되는 기 중 어느 하나일 수 있다.Specifically, L 1 and L 2 each independently represent any one of groups represented by the following structural formulas.
Figure PCTKR2018012249-appb-img-000008
Figure PCTKR2018012249-appb-img-000008
Figure PCTKR2018012249-appb-img-000009
Figure PCTKR2018012249-appb-img-000009
예를 들어, 상기 화학식 a로 표시되는 2,3-치환 나프틸아민 유도체 화합물은 하기 1 내지 156 중의 어느 하나의 화합물일 수 있다.For example, the 2,3-substituted naphthylamine derivative compound represented by Formula (a) may be any one of the following 1 to 156 compounds.
Figure PCTKR2018012249-appb-img-000010
Figure PCTKR2018012249-appb-img-000010
Figure PCTKR2018012249-appb-img-000011
Figure PCTKR2018012249-appb-img-000011
Figure PCTKR2018012249-appb-img-000012
Figure PCTKR2018012249-appb-img-000012
Figure PCTKR2018012249-appb-img-000013
Figure PCTKR2018012249-appb-img-000013
Figure PCTKR2018012249-appb-img-000014
Figure PCTKR2018012249-appb-img-000014
Figure PCTKR2018012249-appb-img-000015
Figure PCTKR2018012249-appb-img-000015
상기 2,3-치환 나프틸아민 유도체 유기화합물은 유기 전계 발광 소자용 재료로 사용되는 경우, 유기 전계 발광 소자에서 사용 가능한 물질에 요구되는 조건, 예컨대 적절한 에너지 준위, 전기화학적 안정성 및 열적 안정성 등을 모두 우수하게 만족시킬 수 있으며, 치환기에 따라 유기 전계 발광 소자에서 요구되는 다양한 역할을 할 수 있다.When the 2,3-substituted naphthylamine derivative organic compound is used as a material for an organic electroluminescence device, it is preferable that the 2,3-substituted naphthylamine derivative organic compound is a compound represented by the following formula Can be satisfactorily satisfied, and can play various roles required in the organic electroluminescent device depending on the substituent.
본 발명의 또 다른 구현예에서, 음극과 양극 사이에 적어도 하나의 유기 박막층이 협지되어 있는 유기 전계 발광 소자에 있어서, 상기 유기 박막층은 적어도 하나의 발광층을 포함하는 다층 구조이고, 상기 발광층 이외의 상기 유기 박막층 내의 적어도 하나의 층이 상기 2,3-치환 나프틸아민 유도체 유기화합물을 단독 또는 2종 이상의 혼합물을 포함하는 유기 전계 발광 소자를 제공한다.In another embodiment of the present invention, at least one organic thin film layer is sandwiched between a cathode and an anode, wherein the organic thin film layer has a multi-layer structure including at least one light emitting layer, And at least one layer in the organic thin film layer comprises the organic compound of the 2,3-substituted naphthylamine derivative alone or a mixture of two or more thereof.
상기 유기 전계 발광 소자의 유기 박막층에 포함되는 상기 2,3-치환 나프틸아민 유도체 유기화합물은 상기 화학식 a로 표시되는 화합물이고, 그에 대한 상세한 설명은 전술한 바와 같다.The 2,3-substituted naphthylamine derivative organic compound contained in the organic thin film layer of the organic electroluminescent device is a compound represented by the above formula (a), and a detailed description thereof is as described above.
상기 유기 박막층은 음극과 발광층 사이에 개재되며, 정공주입층, 정공수송층, 정공주입 기능 및 정공수송 기능을 동시에 갖는 기능층, 버퍼층 및 전자차단층 중 적어도 하나를 포함한 정공 수송 영역을 포함할 수 있다.The organic thin film layer may include a hole transporting region interposed between the cathode and the light emitting layer and including at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, and an electron blocking layer .
상기 정공 수송 영역은 상기 2,3-치환 나프틸아민 유도체 유기화합물을 포함할 수 있다. 구체적으로, 상기 기능층, 상기 버퍼층 및 상기 전자차단층 중 적어도 하나가 상기 2,3-치환 나프틸아민 유도체 유기화합물을 포함할 수 있다.The hole transporting region may include the 2,3-substituted naphthylamine derivative organic compound. Specifically, at least one of the functional layer, the buffer layer, and the electron blocking layer may include the 2,3-substituted naphthylamine derivative organic compound.
일 구현예에서, 상기 2,3-치환 나프틸아민 유도체 유기화합물은 유기전기발광소자용 재료 중 전자차단층, 정공수송층 또는 정공주입층 물질로 사용될 수 있다. 즉, 상기 2,3-치환 나프틸아민 유도체 유기화합물을 포함하는 유기 박막층은 발광층, 전자차단층, 정공수송층 또는 정공주입층일 수 있다.In one embodiment, the 2,3-substituted naphthylamine derivative organic compound may be used as an electron blocking layer, a hole transporting layer, or a hole injecting layer material in an organic electroluminescent device. That is, the organic thin film layer containing the 2,3-substituted naphthylamine derivative organic compound may be a light emitting layer, an electron blocking layer, a hole transporting layer, or a hole injecting layer.
상기 유기 박막층은 상기 2,3-치환 나프틸아민 유도체 유기화합물을 포함하는 층 이외에도, 발광층, 정공주입층, 정공수송층, 기능층, 버퍼층, 전자차단층, 발광층 정공차단층 전자수송층, 전자주입층 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 더 포함할 수 있다.In addition to the layer containing the organic compound of the 2,3-substituted naphthylamine derivative, the organic thin film layer may include at least one of a luminescent layer, a hole injecting layer, a hole transporting layer, a functional layer, a buffer layer, an electron blocking layer, And a combination thereof.
상기 유기 박막층을 형성하는, 발광층, 정공주입층, 정공수송층, 기능층, 버퍼층, 전자차단층, 발광층 정공차단층 전자수송층, 전자주입층 등은, 각각, 공지된 물질을 사용하여 형성될 수 있고, 또는, 이들의 적어도 하나 이상이 상기 화학식 a로 표시되는 2,3-치환 나프틸아민 유도체 유기화합물을 1종 이상 포함할 수 있다.The light emitting layer, the hole injecting layer, the hole transporting layer, the functional layer, the buffer layer, the electron blocking layer, the luminescent layer hole blocking layer electron transporting layer, the electron injecting layer, etc. forming the organic thin film layer can be formed using known materials, respectively , Or a 2,3-substituted naphthylamine derivative organic compound represented by the formula (a).
상기 유기 박막층에 포함된 상기 화학식 a로 표시되는 2,3-치환 나프틸아민 유도체 유기화합물에 관한 상세한 설명은 전술한 바와 같다.The detailed description of the 2,3-substituted naphthylamine derivative organic compound represented by the formula (a) contained in the organic thin film layer is as described above.
이하 본 발명의 실시예 및 비교예를 기재한다. 하기한 실시예는 본 발명의 일 실시예일뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, examples and comparative examples of the present invention will be described. The following embodiments are only examples of the present invention and the present invention is not limited to the following embodiments.
(실시예)(Example)
이하에서, 합성예 및 비교예를 구체적으로 예시하지만, 본 발명이 하기의 반응예 및 실시예로 한정되는 것은 아니다. 이하의 합성예에서 중간체 화합물은 최종 생성물의 번호에 일련번호를 추가하는 방식으로 표기한다. 예를 들어, 화합물 1은 화합물 [1] 로 상기 화합물의 중간체 화합물은 [1-1] 등으로 표기한다. 본 명세서에서 화합물의 번호는 상기 표 1에 기재된 화학식의 번호로서 표기한다. 예를 들어, 표 1에서 1로 표시된 화합물은 화합물 1로 표기한다.Hereinafter, Synthesis Examples and Comparative Examples will be specifically exemplified, but the present invention is not limited to the following Reaction Examples and Examples. In the following synthesis examples, the intermediate compounds are indicated by adding the serial number to the final product number. For example, Compound 1 is represented by the compound [1], and the intermediate compound of the above compound is represented by [1-1] or the like. In the present specification, the numbers of the compounds are represented by the numbers of the formulas shown in Table 1 above. For example, compounds designated 1 in Table 1 are designated Compound 1.
[합성예 1] 화합물 [5]의 제조[Synthesis Example 1] Preparation of compound [5]
[반응식 1][Reaction Scheme 1]
Figure PCTKR2018012249-appb-img-000016
Figure PCTKR2018012249-appb-img-000016
중간체 화합물 [5-2]의 제조Preparation of intermediate compound [5-2]
1L 반응플라스크에 화합물 [5-1] 30g(148.51mmol), 브로모벤젠 34.9g(222.76mmol), 테트라키스(트리페닐포스핀)팔라듐 1.7g(1.49mmol), 포타슘카보네이트 30.8g(222.76mmol), 톨루엔 300ml, 증류수 150ml를 가하고 18시간 환류 교반한다. 반응 종료 후 에틸아세테이트, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고, 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 실리카겔 크로마토그라프로 분리정제하여, 흰색 고체의 중간체 화합물 [5-2] 31.7g (91%)을 제조하였다.To a 1 L reaction flask were added 30 g (148.51 mmol) of the compound [5-1], 34.9 g (222.76 mmol) of bromobenzene, 1.7 g (1.49 mmol) of tetrakis (triphenylphosphine) palladium, , 300 ml of toluene and 150 ml of distilled water were added, and the mixture was stirred under reflux for 18 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using dichloromethane and hexane to obtain an intermediate compound [5-2 (91%). & Lt ; / RTI &gt;
중간체 화합물 [5-3]의 제조Preparation of intermediate compound [5-3]
1L 반응플라스크에 화합물 [5-2] 30g(128.05mmol), 디클로로메탄 300ml를 가하고, 0℃에서 보론 트리브로마이드 14.81ml(235.09mmol)를 천천히 적가하여 2시간 교반 후 소듐비카보네이트 수용액에 반응물을 천천히 적가 한다. 디클로로메탄, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 재결정하여 흰색 고체의 중간체 화합물 [5-3] 25.9g (92%)을 제조하였다.30 g (128.05 mmol) of the compound [5-2] and 300 ml of dichloromethane were added to a 1 L reaction flask, 14.81 ml (235.09 mmol) of boron tribromide was slowly added dropwise at 0 ° C and the mixture was stirred for 2 hours. Drop it. The reaction mixture was extracted with dichloromethane and distilled water, treated with anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The residue was recrystallized from dichloromethane and hexane to obtain 25.9 g (92%) of an intermediate compound [5-3] .
중간체 화합물 [5-4]의 제조Preparation of intermediate compound [5-4]
1L 반응플라스크에 화합물 [5-3] 25g(113.49mmol), 디클로로메탄 250ml, 피리딘 13.7ml(170.24mmol)를 가하고, 0℃에서 트리플루오로메탄설포네이트 22.9ml(136.19mmol)를 천천히 가한다. 상온에서 2시간 교반 후, 증류수 100ml를 천천히 가하고, 디클로로메탄, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 재결정화하여 흰색 고체의 중간체 화합물 [5-4] 33.9g (85%)을 제조하였다.25 g (113.49 mmol) of the compound [5-3], 250 ml of dichloromethane and 13.7 ml (170.24 mmol) of pyridine were added to a 1 L reaction flask and 22.9 ml (136.19 mmol) of trifluoromethane sulfonate was added slowly at 0 ° C. After stirring at room temperature for 2 hours, 100 ml of distilled water was added slowly, extracted with dichloromethane, distilled water, treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and recrystallized using dichloromethane and hexane to obtain an intermediate compound [5-4] (33.9 g, 85%).
중간체 화합물 [5-5]의 제조Preparation of intermediate compound [5-5]
1L 반응플라스크에 화합물 [5-4] 33g(93.66mmol), 9,9-디메틸플루오렌-2-아민 18.38g(93.66mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.86g(0.94mmol), 트리(테르트-부틸)포스핀 0.43ml(1.87mmol), 소듐테르트-부톡시드 13.5g(140.49mmol), 톨루엔 330ml를 가하고 18시간 환류 교반한다. 반응 종료 후 에틸아세테이트, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고, 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 실리카겔 크로마토그라프로 분리정제하여, 노랑색 고체의 중간체 화합물 [5-5] 23.9g (62%)을 제조하였다.(93.66 mmol) of compound [5-4], 18.38 g (93.66 mmol) of 9,9-dimethylfluorene-2-amine and 0.86 g (0.94 mmol) of tris (dibenzylideneacetone) dipalladium in a 1 L reaction flask, 0.43 ml (1.87 mmol) of tri (tert-butyl) phosphine, 13.5 g (140.49 mmol) of sodium tert-butoxide and 330 ml of toluene were added and the mixture was stirred under reflux for 18 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using dichloromethane and hexane to obtain an intermediate compound [5-5 ] was prepared in a 23.9g (62%).
화합물 [5]의 제조Preparation of compound [5]
500mL 반응플라스크에 화합물 [5-5] 23g(55.89mmol), 4-브로모비페닐 13.03g(55.89mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.51g(0.56mmol), 트리(테르트-부틸)포스핀 0.26ml(1.12mmol), 소듐테르트-부톡시드 8.06g(83.84mmol), 톨루엔 230ml를 가하고 12시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 메탄올, 톨루엔을 이용하여 재결정화하여 옅은 노랑색 고체의 목적화합물 [5] 19.8g (63%)을 제조하였다.(55.89 mmol) of compound [5-5], 13.03 g (55.89 mmol) of 4-bromobiphenyl, 0.51 g (0.56 mmol) of tris (dibenzylidineacetone) dipalladium, Butyl) phosphine, 8.06 g (83.84 mmol) of sodium tert-butoxide and 230 ml of toluene were added, and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone, methanol, and toluene to obtain 19.8 g (63%) of the desired compound [5] as a pale yellow solid.
[합성예 2] 화합물 [10]의 제조[Synthesis Example 2] Preparation of compound [10]
[반응식 2][Reaction Scheme 2]
Figure PCTKR2018012249-appb-img-000017
Figure PCTKR2018012249-appb-img-000017
중간체 화합물 [10-1]의 제조Preparation of intermediate compound [10-1]
500mL 반응플라스크에 화합물 [5-4] 20g(56.76mmol), 나프탈렌-1-아민 8.9g(62.47mmol), 트리스(디벤질이딘아세톤)디팔라듐 1.04g(1.14mmol), 트리(테르트-부틸)포스핀 0.53ml(2.28mmol), 소듐테르트-부톡시드 8.18g(85.14mmol), 톨루엔 200ml를 가하고 24시간 환류 교반한다. 반응 종료 후 에틸아세테이트, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고, 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 실리카겔 크로마토그라프로 분리정제하여, 옅은 노랑색 고체의 중간체 화합물 [10-1] 13.1g (65%)을 제조하였다.To a 500 mL reaction flask were added 20 g (56.76 mmol) of the compound [5-4], 8.9 g (62.47 mmol) of naphthalene-1-amine, 1.04 g (1.14 mmol) of tris (dibenzylidineacetone) Butyl) phosphine, 8.18 g (85.14 mmol) of sodium tert-butoxide and 200 ml of toluene were added, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using dichloromethane and hexane to obtain a pale yellow solid intermediate compound [ 1] (13.1 g, 65%).
화합물 [10]의 제조Preparation of compound [10]
500mL 반응플라스크에 화합물 [10-1] 13g(36.68mmol), 2-브로모-9,9-디페닐-플루오렌 17.49g(44.02mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.67g(0.73mmol), 트리(테르트-부틸)포스핀 0.34ml(1.46mmol), 소듐테르트-부톡시드 7.93g(mmol), 톨루엔 130ml를 가하고 16시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 메탄올, 톨루엔을 이용하여 재결정화하여 옅은 노랑색 고체의 목적화합물 [10] 15.7g (63%)을 제조하였다.To a 500 mL reaction flask was added 13 g (36.68 mmol) of the compound [10-1], 17.49 g (44.02 mmol) of 2-bromo-9,9-diphenyl-fluorene, 0.67 g 0.34 mmol (1.46 mmol) of tri (tert-butyl) phosphine, 7.93 g (mmol) of sodium tert-butoxide and 130 ml of toluene were added and the mixture was stirred under reflux for 16 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone, methanol, and toluene to obtain 15.7 g (63%) of the desired compound [10] as a pale yellow solid.
[합성예 3] 화합물 [15]의 제조[Synthesis Example 3] Preparation of compound [15]
[반응식 3][Reaction Scheme 3]
Figure PCTKR2018012249-appb-img-000018
Figure PCTKR2018012249-appb-img-000018
중간체 화합물 [15-1]의 제조Preparation of intermediate compound [15-1]
500mL 반응플라스크에 화합물 [5-4] 20g(56.76mmol), 아닐린 5.82g(62.47mmol), 트리스(디벤질이딘아세톤)디팔라듐 1.04g(1.14mmol), 트리(테르트-부틸)포스핀 0.53ml(2.28mmol), 소듐테르트-부톡시드 8.18g(85.14mmol), 톨루엔 200ml를 가하고 20시간 환류 교반한다. 반응 종료 후 에틸아세테이트, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고, 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 실리카겔 크로마토그라프로 분리정제하여, 노랑색 고체의 중간체 화합물 [10-1] 9.89g (59%)을 제조하였다.To a 500 mL reaction flask were added 20 g (56.76 mmol) of the compound [5-4], 5.82 g (62.47 mmol) of aniline, 1.04 g (1.14 mmol) of tris (dibenzylideneacetone) dipalladium, , 8.18 g (85.14 mmol) of sodium tert-butoxide and 200 ml of toluene were added, and the mixture was stirred under reflux for 20 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using dichloromethane and hexane to obtain an intermediate compound [10-1 ] (9.89 g, 59%).
화합물 [15]의 제조Preparation of compound [15]
250mL 반응플라스크에 화합물 [15-1] 9g(30.47mmol), 2-브로모-9,9-디메틸-7-페닐-플루오렌 12.77g(36.56mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.56g(0.61mmol), 트리(테르트-부틸)포스핀 0.28ml(1.22mmol), 소듐테르트-부톡시드 4.39g(45.71mmol), 톨루엔 90ml를 가하고 12시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 톨루엔을 이용하여 재결정화하여 옅은 노랑색 고체의 목적화합물 [15] 12.5g (73%)을 제조하였다.To a 250 mL reaction flask were added 9 g (30.47 mmol) of the compound [15-1], 12.77 g (36.56 mmol) of 2-bromo-9,9-dimethyl- 0.28 ml (1.22 mmol) of tri (tert-butyl) phosphine, 4.39 g (45.71 mmol) of sodium tert-butoxide and 90 ml of toluene were added and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to obtain 12.5 g (73%) of the desired compound [15] as a pale yellow solid.
[합성예 4] 화합물 [19]의 제조[Synthesis Example 4] Preparation of compound [19]
[반응식 4][Reaction Scheme 4]
Figure PCTKR2018012249-appb-img-000019
Figure PCTKR2018012249-appb-img-000019
중간체 화합물 [19-1]의 제조Preparation of intermediate compound [19-1]
500mL 반응플라스크에 2-브로모-6-메톡시나프탈렌 20g(84.35mmol), 페닐보론산 10.29g(88.56mmol), 테트라키스(트리페닐포스핀)팔라듐 1.95g(1.69mmol), 포타슘카보네이트 17.49g(126.53mmol), 톨루엔 200ml, 증류수 60ml를 가하고 14시간 환류 교반한다. 반응 종료 후 에틸아세테이트, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고, 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 실리카겔 크로마토그라프로 분리정제하여, 흰색 고체의 중간체 화합물 [19-1] 18.4g (93%)을 제조하였다.To a 500 mL reaction flask were added 20 g (84.35 mmol) of 2-bromo-6-methoxynaphthalene, 10.29 g (88.56 mmol) of phenylboronic acid, 1.95 g (1.69 mmol) of tetrakis (triphenylphosphine) palladium, (126.53 mmol), 200 ml of toluene and 60 ml of distilled water were added, and the mixture was stirred under reflux for 14 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and then separated and purified by silica gel chromatography using dichloromethane and hexane to obtain the intermediate compound [19-1 ] was prepared in a 18.4g (93%).
중간체 화합물 [19-2]의 제조Preparation of intermediate compound [19-2]
500mL 반응플라스크에 화합물 [19-1] 18g(76.83mmol) 을 무수테트라히드로퓨란 180mL로 녹인 후 -78℃에서 교반한다. n-부틸리튬(2.5M in hexane) 36.88mL(92.19mmol)를 동온도에서 적가시키고 30분 후에 트리메틸 보레이트 10.28ml(92.19mmol)을 적가한다. 반응온도를 상온까지 올리고 에틸아세테이트와 포화암모늄 수용액으로 추출한 후 무수황산 마그네슘으로 건조하여 여과하고, 여과액을 감압 농축한 뒤 디클로로메탄, 헥산을 이용하여 재결정화하여 흰색 고체의 중간체 화합물 [19-2] 15.4g(72%)을 제조하였다.18 g (76.83 mmol) of the compound [19-1] was dissolved in 180 mL of anhydrous tetrahydrofuran in a 500 mL reaction flask and stirred at -78 ° C. 36.88 mL (92.19 mmol) of n-butyllithium (2.5 M in hexane) is added dropwise at the same temperature, and 30 minutes later, 10.28 ml (92.19 mmol) of trimethylborate is added dropwise. The reaction temperature was raised to room temperature, extracted with ethyl acetate and saturated aqueous ammonium chloride, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized from dichloromethane and hexane to give the intermediate compound [19-2 ] was prepared in a 15.4g (72%).
중간체 화합물 [19-3]의 제조Preparation of intermediate compound [19-3]
500mL 반응플라스크에 [19-2] 15g(53.94mmol), 브로모벤젠 10.16g(64.73mmol), 테트라키스(트리페닐포스핀)팔라듐 1.25g(1.08mmol), 포타슘카보네이트 11.18g(80.91mmol), 톨루엔 150ml, 증류수 45ml를 가하고 18시간 환류 교반한다. 반응 종료 후 에틸아세테이트, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고, 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 실리카겔 크로마토그라프로 분리정제하여, 흰색 고체의 중간체 화합물 [19-3] 14.7g (88%)을 제조하였다.15 g (53.94 mmol) of [19-2], 10.16 g (64.73 mmol) of bromobenzene, 1.25 g (1.08 mmol) of tetrakis (triphenylphosphine) palladium, 11.18 g (80.91 mmol) of potassium carbonate, 150 ml of toluene and 45 ml of distilled water are added, and the mixture is stirred under reflux for 18 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and then separated and purified by silica gel chromatography using dichloromethane and hexane to obtain an intermediate compound [19-3 ] was prepared in a 14.7g (88%).
중간체 화합물 [19-4]의 제조Preparation of intermediate compound [19-4]
500mL 반응플라스크에 화합물 [19-3] 14g(45.11mmol), 디클로로메탄 140ml를 가하고, 0℃에서 보론 트리브로마이드 5.22ml(54.13mmol)를 천천히 적가하여 2시간 교반 후 소듐비카보네이트 수용액에 반응물을 천천히 적가 한다. 디클로로메탄, 증류수로 추출, 무수황산 마그네슘 처리 여과하고 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 재결정하여 흰색 고체의 중간체 화합물 [19-4] 13.4g (91%)을 제조하였다.14 g (45.11 mmol) of the compound [19-3] and 140 ml of dichloromethane were added to a 500 ml reaction flask, and 5.22 ml (54.13 mmol) of boron tribromide was slowly added dropwise at 0 ° C. The mixture was stirred for 2 hours, Drop it. The reaction mixture was extracted with dichloromethane and distilled water, and the mixture was treated with anhydrous magnesium sulfate. The filtrate was concentrated under reduced pressure, and recrystallized from dichloromethane and hexane to obtain 13.4 g (91%) of intermediate compound [19-4] as a white solid.
중간체 화합물 [19-5]의 제조Preparation of intermediate compound [19-5]
500mL 반응플라스크에 화합물 [19-4] 13g(43.87mmol), 디클로로메탄 130ml, 피리딘 5.31ml(65.81mmol)를 가하고, 0℃에서 트리플루오로메탄설포네이트 8.63ml (52.64mmol)를 천천히 가한다. 상온에서 2시간 교반 후, 증류수 50ml를 천천히 가하고, 디클로로메탄, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 재결정화하여 흰색 고체의 중간체 화합물 [19-5] 15.2g (81%)을 제조하였다.13 g (43.87 mmol) of the compound [19-4], 130 ml of dichloromethane and 5.31 ml (65.81 mmol) of pyridine are added to a 500 ml reaction flask and 8.63 ml (52.64 mmol) of trifluoromethane sulfonate is added slowly at 0 ° C. After stirring at room temperature for 2 hours, 50 ml of distilled water was added slowly, extracted with dichloromethane and distilled water, treated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure and recrystallized from dichloromethane and hexane to obtain an intermediate compound 15.2 g (81%) of [19-5] was prepared.
화합물 [19]의 제조 Preparation of compound [19]
500mL 반응플라스크에 화합물 [19-5] 15g(35.01mmol), N-(4-비페닐)-9,9-디메틸-플루오렌-2-아민 13.92g(38.51mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.64g(0.7mmol), 트리(테르트-부틸)포스핀 0.33ml(1.4mmol), 소듐테르트-부톡시드 5.05g(52.52mmol), 톨루엔 150ml를 가하고 16시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 메탄올, 톨루엔을 이용하여 재결정화 하여 옅은 노랑색 고체의 목적화합물 [19] 14.5g (65%)을 제조하였다.To a 500 mL reaction flask were added 15 g (35.01 mmol) of the compound [19-5], 13.92 g (38.51 mmol) of N- (4-biphenyl) -9,9- Acetone) dipalladium, 0.33 ml (1.4 mmol) of tri (tert-butyl) phosphine, 5.05 g (52.52 mmol) of sodium tert-butoxide and 150 ml of toluene were added and the mixture was stirred under reflux for 16 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to obtain 14.5 g (65%) of the desired compound [19] as a pale yellow solid.
[합성예 5] 화합물 [21]의 제조[Synthesis Example 5] Preparation of compound [21]
[반응식 5][Reaction Scheme 5]
Figure PCTKR2018012249-appb-img-000020
Figure PCTKR2018012249-appb-img-000020
중간체 화합물 [21-1]의 제조 Preparation of intermediate compound [21-1]
[합성예 4]과 동일한 방법으로 2-브로모-7-메톡시나프탈렌을 사용하여 중간체 화합물 [21-1] 으로 42% 의 수율로 제조하였다.The intermediate compound [21-1] was prepared in 42% yield using 2-bromo-7-methoxynaphthalene in the same manner as in [Synthesis Example 4].
화합물 [21]의 제조 Preparation of compound [21]
250mL 반응플라스크에 화합물 [21-1] 12g(28.01mmol), N-(4-비페닐)-9,9-디메틸-플루오렌-2-아민 12.15g(33.61mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.51g(0.56mmol), 트리(테르트-부틸)포스핀 0.26ml(1.12mmol), 소듐테르트-부톡시드 4.04g(42.02mmol), 톨루엔 120ml를 가하고 20시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 톨루엔을 이용하여 재결정화 하여 옅은 노랑색 고체의 목적화합물 [21] 11.1g (62%)을 제조하였다.12.15 g (33.61 mmol) of N- (4-biphenyl) -9,9-dimethyl-fluorene-2-amine, 12 g Acetone) dipalladium, 0.26 ml (1.12 mmol) of tri (tert-butyl) phosphine, 4.04 g (42.02 mmol) of sodium tert-butoxide and 120 ml of toluene were added and the mixture was stirred under reflux for 20 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to obtain 11.1 g (62%) of the desired compound [21] as a pale yellow solid.
[합성예 6] 화합물 [26]의 제조[Synthesis Example 6] Preparation of compound [26]
[반응식 6][Reaction Scheme 6]
Figure PCTKR2018012249-appb-img-000021
Figure PCTKR2018012249-appb-img-000021
중간체 화합물 [26-1]의 제조 Preparation of intermediate compound [26-1]
[합성예 1]과 동일한 방법으로 화합물 [5-1]과 1-브로모나프탈렌을 을 사용하여 중간체 화합물 [26-1] 65% 의 수율로 제조하였다.The compound [5-1] and 1-bromonaphthalene were used in the same manner as in [Synthesis Example 1] to give an intermediate compound [26-1] at a yield of 65%.
화합물 [26]의 제조 Preparation of compound [26]
500mL 반응플라스크에 화합물 [26-1] 15g(37.28mmol), N-(4-비페닐)-9,9-디메틸-플루오렌-2-아민 16.17g(44.74mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.69g(0.75mmol), 트리(테르트-부틸)포스핀 0.35ml(1.49mmol), 소듐테르트-부톡시드 5.37g(55.92mmol), 톨루엔 150ml를 가하고 20시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 메탄올, 톨루엔을 이용하여 재결정화하여 미색고체의 목적화합물 [26] 13.9g (61%)을 제조하였다.To a 500 mL reaction flask was added 15 g (37.28 mmol) of the compound [26-1], 16.17 g (44.74 mmol) of N- (4-biphenyl) -9,9- (Tert-butyl) phosphine, 5.37 g (55.92 mmol) of sodium tert-butoxide, and 150 ml of toluene were added, and the mixture was stirred under reflux for 20 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to obtain 13.9 g (61%) of the desired compound as an off-white solid [26] .
[합성예 7] 화합물 [47]의 제조[Synthesis Example 7] Preparation of compound [47]
[반응식 7][Reaction Scheme 7]
Figure PCTKR2018012249-appb-img-000022
Figure PCTKR2018012249-appb-img-000022
화합물 [47]의 제조 Preparation of compound [47]
250mL 반응플라스크에 화합물 [5-5] 10g(24.29mmol), 4-(4-브로모페닐)디벤조[b,d]퓨란 9.42g(29.15mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.44g(0.48mmol), 트리(테르트-부틸)포스핀 0.22ml(0.97mmol), 소듐테르트-부톡시드 3.5g(36.43mmol), 톨루엔 100ml를 가하고 12시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 톨루엔을 이용하여 재결정화 하여 미색고체의 목적화합물 [47] 10.6g (67%)을 제조하였다.To a 250 mL reaction flask were added 10 g (24.29 mmol) of the compound [5-5], 9.42 g (29.15 mmol) of 4- (4-bromophenyl) dibenzo [b, d] furan and tris (dibenzylidineacetone) dipalladium (Tert-butyl) phosphine (0.22 ml, 0.97 mmol), sodium tert-butoxide (3.5 g, 36.43 mmol) and toluene (100 ml) were added and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized using acetone and toluene to obtain 10.6 g (67%) of the desired compound as an off-white solid [47] .
[합성예 8] 화합물 [49]의 제조[Synthetic Example 8] Preparation of compound [49]
[반응식 8][Reaction Scheme 8]
Figure PCTKR2018012249-appb-img-000023
Figure PCTKR2018012249-appb-img-000023
중간체 화합물 [49-1]의 제조Preparation of intermediate compound [49-1]
500mL 반응플라스크에 4,4'-디브로모비페닐 20g(64.11mmol) 을 무수테트라히드로퓨란 200mL로 녹인 후 -78℃에서 교반한다. n-부틸리튬(2.5M in hexane) 25.64mL(64.11mmol)를 동온도에서 적가시키고 30분 후에 클로로트리페닐실란 22.68g(76.93mmol)을 적가한다. 반응온도를 상온까지 올리고 에틸아세테이트와 정제수로 추출한 후 무수황산 마그네슘으로 건조하여 여과하고, 여과액을 감압 농축한 뒤 디클로로메탄, 헥산을 이용하여 재결정화하여 흰색 고체의 중간체 화합물 [49-1] 17.6g (56%)을 제조하였다.20 g (64.11 mmol) of 4,4'-dibromobiphenyl was dissolved in 200 mL of anhydrous tetrahydrofuran, and the mixture was stirred at -78 ° C. 25.64 mL (64.11 mmol) of n-butyllithium (2.5 M in hexane) was added dropwise at the same temperature and after 30 minutes, 22.68 g (76.93 mmol) of chlorotriphenylsilane was added dropwise. The reaction mixture was heated to room temperature, extracted with ethyl acetate and purified water, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized from dichloromethane and hexane to obtain the intermediate compound [49-1] 17.6 g (56%).
* 화합물 [49]의 제조 * Preparation of compound [49]
500mL 반응플라스크에 화합물 [49-1] 17g(34.59mmol), 화합물 [5-5] 14.95g(36.32mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.63g(.0.69mmol), 트리(테르트-부틸)포스핀 0.32ml(1.38mmol), 소듐테르트-부톡시드 4.98g(51.89mmol), 톨루엔 170ml를 가하고 18시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 메탄올, 톨루엔을 이용하여 재결정화하여 옅은 노랑색 고체의 목적화합물 [49] 19.9g (70%)을 제조하였다.(34.59 mmol) of the compound [49-1], 14.95 g (36.32 mmol) of the compound [5-5], 0.63 g (0.069 mmol) of tris (dibenzylidineacetone) dipalladium, (1.38 mmol) of sodium tert-butoxide, 4.98 g (51.89 mmol) of sodium tert-butoxide and 170 ml of toluene were added and the mixture was stirred under reflux for 18 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to obtain 19.9 g (70%) of the target compound [49] as a pale yellow solid.
[합성예 9] 화합물 [51]의 제조[Synthesis Example 9] Preparation of compound [51]
[반응식 9][Reaction Scheme 9]
Figure PCTKR2018012249-appb-img-000024
Figure PCTKR2018012249-appb-img-000024
화합물 [51]의 제조Preparation of compound [51]
250mL 반응플라스크에 화합물 [5-5] 10g(24.29mmol), 1-(4-브로모페닐)나프탈렌 8.25g(29.15mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.44g(0.48mmol), 트리(테르트-부틸)포스핀 0.23ml(0.97mmol), 소듐테르트-부톡시드 3.5g(36.43mmol), 톨루엔 100ml를 가하고 16시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 톨루엔을 이용하여 재결정화하여 미색고체의 목적화합물 [51] 10.1g (68%)을 제조하였다.(24.29mmol) of compound [5-5], 8.25g (29.15mmol) of 1- (4-bromophenyl) naphthalene, 0.44g (0.48mmol) of tris (dibenzylideneacetone) dipalladium, 0.23 ml (0.97 mmol) of tri (tert-butyl) phosphine, 3.5 g (36.43 mmol) of sodium tert-butoxide and 100 ml of toluene were added and the mixture was stirred under reflux for 16 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to obtain 10.1 g (68%) of the desired compound [51] as an off-white solid.
[합성예 10] 화합물 [77]의 제조[Synthesis Example 10] Synthesis of Compound [77]
[반응식 10][Reaction Scheme 10]
Figure PCTKR2018012249-appb-img-000025
Figure PCTKR2018012249-appb-img-000025
중간체 화합물 [77-1]의 제조Preparation of intermediate compound [77-1]
500mL 반응플라스크에 화합물 [5-4] 20g(56.76mmol), 비페닐-4-아민 11.53g(68.11mmol), 트리스(디벤질이딘아세톤)디팔라듐 1.04g(1.14mmol), 트리(테르트-부틸)포스핀 0.53ml(2.27mmol), 소듐테르트-부톡시드 8.18g(85.14mmol), 톨루엔 200ml를 가하고 20시간 환류 교반한다. 반응 종료 후 여과하고, 여과액을 감압 농축한 뒤 디클로로메탄, 헥산을 이용하여 실리카겔 크로마토그라프로 분리정제하여, 미색고체의 중간체 화합물 [77-1] 15.4g (73%)을 제조하였다.To a 500 mL reaction flask was added 20 g (56.76 mmol) of the compound [5-4], 11.53 g (68.11 mmol) of biphenyl-4-amine, 1.04 g (1.14 mmol) of tris (dibenzylidineacetone) dipalladium, -Butyl) phosphine, 8.18 g (85.14 mmol) of sodium tert-butoxide and 200 ml of toluene were added, and the mixture was stirred under reflux for 20 hours. After completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The filtrate was separated and purified by silica gel chromatography using dichloromethane and hexane to obtain 15.4 g (73%) of an intermediate compound [77-1] as a off-white solid.
화합물 [77]의 제조Preparation of compound [77]
500mL 반응플라스크에 화합물 [77-1] 15g(40.38mmol), 3-브로모디벤조[b,d]퓨란 11.97g(48.46mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.74g(0.81mmol), 트리(테르트-부틸)포스핀 0.38ml(1.62mmol), 소듐테르트-부톡시드 5.82g(60.57mmol), 톨루엔 150ml를 가하고 24시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 메탄올, 톨루엔을 이용하여 재결정화하여 미색고체의 목적화합물 [77] 13.5g (62%)을 제조하였다.15 g (40.38 mmol) of the compound [77-1], 11.97 g (48.46 mmol) of 3-bromodibenzo [b, d] furan and 0.74 g (0.81 mmol) of tris (dibenzylidineacetone) dipalladium were placed in a 500- , 0.38 ml (1.62 mmol) of tri (tert-butyl) phosphine, 5.82 g (60.57 mmol) of sodium tert-butoxide and 150 ml of toluene were added and the mixture was stirred under reflux for 24 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to obtain 13.5 g (62%) of the target compound [77] as a off-white solid.
[합성예 11] 화합물 [78]의 제조[Synthesis Example 11] Preparation of compound [78]
[반응식 11][Reaction Scheme 11]
Figure PCTKR2018012249-appb-img-000026
Figure PCTKR2018012249-appb-img-000026
화합물 [78]의 제조Preparation of compound [78]
250mL 반응플라스크에 화합물 [77-1] 10g(26.92mmol), 3-브로모디벤조[b,d]싸이오펜 8.51g(32.31mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.49g(0.54mmol), 트리(테르트-부틸)포스핀 0.25ml(1.07mmol), 소듐테르트-부톡시드 3.88g(40.38mmol), 톨루엔 100ml를 가하고 14시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 톨루엔을 이용하여 재결정화하여 미색고체의 목적화합물 [78] 9.9g (69%)을 제조하였다.To a 250 mL reaction flask were added 10 g (26.92 mmol) of the compound [77-1], 8.51 g (32.31 mmol) of 3-bromodibenzo [b, d] thiophene, 0.49 g 0.25 ml (1.07 mmol) of tri (tert-butyl) phosphine, 3.88 g (40.38 mmol) of sodium tert-butoxide and 100 ml of toluene were added and the mixture was stirred under reflux for 14 hours. After the reaction was filtered off, recrystallized with acetone, toluene to prepare the target compound [78] 9.9g (69%) of off-white solid.
[합성예 12] 화합물 [82]의 제조[Synthesis Example 12] Preparation of compound [82]
[반응식 12][Reaction Scheme 12]
Figure PCTKR2018012249-appb-img-000027
Figure PCTKR2018012249-appb-img-000027
중간체 화합물 [82-1]의 제조Preparation of intermediate compound [82-1]
500mL 반응플라스크에 화합물 [5-4] 20g(56.76mmol), 4-브로모페닐보론산 12.54g(62.43mmol), 테트라키스(트리페닐포스핀)팔라듐 1.32g(1.14mmol), 포타슘카보네이트 11.77g(85.14mmol), 톨루엔 200ml, 증류수 80ml를 가하고 10시간 환류 교반한다. 반응 종료 후 에틸아세테이트, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고, 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 실리카겔 크로마토그라프로 분리정제하여, 흰색 고체의 중간체 화합물 [82-1] 17.5g (86%)을 제조하였다.20 g (56.76 mmol) of the compound [5-4], 12.54 g (62.43 mmol) of 4- bromophenylboronic acid, 1.32 g (1.14 mmol) of tetrakis (triphenylphosphine) palladium, 11.77 g (85.14 mmol), toluene (200 ml) and distilled water (80 ml), and the mixture was refluxed with stirring for 10 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and then separated and purified by silica gel chromatography using dichloromethane and hexane to obtain the intermediate compound [82-1 ] was prepared in a 17.5g (86%).
중간체 화합물 [82-2]의 제조Preparation of intermediate compound [82-2]
500mL 반응플라스크에 화합물 [82-1] 17g(47.32mmol), 9,9-디메틸플루오렌-2-아민 11.88g(56.78mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.87g(0.95mmol), 트리(테르트-부틸)포스핀 0.43ml(1.89mmol), 소듐테르트-부톡시드 6.82g(70.98mmol), 톨루엔 170ml를 가하고 20시간 환류 교반한다. 에틸아세테이트, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고, 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 실리카겔 크로마토그라프로 분리정제하여, 미색고체의 중간체 화합물 [82-2] 14.7g (59%)을 제조하였다.17.5 g (47.32 mmol) of the compound [82-1], 11.88 g (56.78 mmol) of 9,9-dimethylfluorene-2-amine and 0.87 g (0.95 mmol) of tris (dibenzylidineacetone) dipalladium were placed in a 500- 0.43 ml (1.89 mmol) of tri (tert-butyl) phosphine, 6.82 g (70.98 mmol) of sodium tert-butoxide and 170 ml of toluene were added and the mixture was stirred under reflux for 20 hours. The reaction mixture was extracted with ethyl acetate and distilled water and subjected to anhydrous magnesium sulfate treatment. The filtrate was concentrated under reduced pressure and then purified by silica gel chromatography using dichloromethane and hexane to obtain 14.7 g of an intermediate compound [82-2] (59%).
화합물 [82]의 제조Preparation of compound [82]
250mL 반응플라스크에 화합물 [82-2] 14g(28.71mmol), 1-브로모나프탈렌 7.13g(34.45mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.52g(0.57mmol), 트리(테르트-부틸)포스핀 0.27ml(1.15mmol), 소듐테르트-부톡시드 4.14g(43.07mmol), 톨루엔 140ml를 가하고 20시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 톨루엔을 이용하여 재결정화하여 미색고체의 목적화합물 [82] 12.7g (72%)을 제조하였다.(28.71 mmol) of compound [82-2], 7.13 g (34.45 mmol) of 1-bromonaphthalene, 0.52 g (0.57 mmol) of tris (dibenzylidineacetone) dipalladium, Butyl) phosphine, 4.14 g (43.07 mmol) of sodium tert-butoxide and 140 ml of toluene were added, and the mixture was stirred under reflux for 20 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to obtain 12.7 g (72%) of the target compound [82] as a off-white solid.
[합성예 13] 화합물 [84]의 제조[Synthesis Example 13] Synthesis of Compound [84]
[반응식 13][Reaction Scheme 13]
Figure PCTKR2018012249-appb-img-000028
Figure PCTKR2018012249-appb-img-000028
화합물 [84]의 제조Preparation of compound [84]
500mL 반응플라스크에 화합물 [82-1] 20g(55.67mmol), N-(4-비페닐)-9,9-디메틸-플루오렌-2-아민 24.15g(66.81mmol), 트리스(디벤질이딘아세톤)디팔라듐 1.02g(1.11mmol), 트리(테르트-부틸)포스핀 0.52ml(2.23mmol), 소듐테르트-부톡시드 8.03g(83.51mmol), 톨루엔 200ml를 가하고 16시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 메탄올, 톨루엔을 이용하여 재결정화하여 미색고체의 목적화합물 [82] 22.4g (63%)을 제조하였다.To a 500 mL reaction flask was added 20 g (55.67 mmol) of the compound [82-1], 24.15 g (66.81 mmol) of N- (4-biphenyl) -9,9- Acetone) dipalladium, 0.52 ml (2.23 mmol) of tri (tert-butyl) phosphine, 8.03 g (83.51 mmol) of sodium tert-butoxide and 200 ml of toluene were added and the mixture was stirred under reflux for 16 hours. After the reaction was filtered off, recrystallized with acetone, methanol and toluene to prepare the target compound [82] 22.4g (63%) of off-white solid.
[합성예 14] 화합물 [100]의 제조[Synthesis Example 14] Synthesis of Compound [100]
[반응식 14][Reaction Scheme 14]
Figure PCTKR2018012249-appb-img-000029
Figure PCTKR2018012249-appb-img-000029
중간체 화합물 [100-1]의 제조Preparation of intermediate compound [100-1]
[합성예 11]과 동일한 방법으로 화합물 [5-1]과 1-브로모-3-메틸벤젠을 이용하여 중간체 화합물 [100-1] 56% 의 수율로 제조하였다.The intermediate compound [100-1] was prepared in a yield of 56% using the compound [5-1] and 1-bromo-3-methylbenzene in the same manner as in [Synthesis Example 11].
화합물 [100]의 제조Preparation of compound [100]
500mL 반응플라스크에 화합물 [100-1] 15g(40.18mmol), N-(4-비페닐)-9,9-디메틸-플루오렌-2-아민 17.43g(48.22mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.74g(0.81mmol), 트리(테르트-부틸)포스핀 0.37ml(1.61mmol), 소듐테르트-부톡시드 5.79g(60.27mmol), 톨루엔 150ml를 가하고 18시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 톨루엔을 이용하여 재결정화하여 옅은 노랑색 고체의 목적화합물 [100] 15.2g (58%)을 제조하였다.To a 500 mL reaction flask were added 15 g (40.18 mmol) of the compound [100-1], 17.43 g (48.22 mmol) of N- (4-biphenyl) -9,9- Acetone) dipalladium, 0.37 ml (1.61 mmol) of tri (tert-butyl) phosphine, 5.79 g (60.27 mmol) of sodium tert-butoxide and 150 ml of toluene were added and the mixture was stirred under reflux for 18 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to obtain 15.2 g (58%) of the desired compound [100] as a pale yellow solid.
[합성예 15] 화합물 [102]의 제조[Synthesis Example 15] Synthesis of Compound [102]
[반응식 15][Reaction Scheme 15]
Figure PCTKR2018012249-appb-img-000030
Figure PCTKR2018012249-appb-img-000030
중간체 화합물 [102-1]의 제조Preparation of intermediate compound [102-1]
500mL 반응플라스크에 화합물 [19-5] 20g(46.68mmol), 4-브로모페닐보론산 10.31g(51.35mmol), 테트라키스(트리페닐포스핀)팔라듐 1.07g(0.93mmol), 포타슘카보네이트 9.68g(70.02mmol), 톨루엔 200ml, 증류수 80ml를 가하고 8시간 환류 교반한다. 반응 종료 후 에틸아세테이트, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고, 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 실리카겔 크로마토그라프로 분리정제하여, 흰색 고체의 중간체 화합물 [102-1] 18.7g (92%)을 제조하였다.To a 500 mL reaction flask were added 20 g (46.68 mmol) of the compound [19-5], 10.31 g (51.35 mmol) of 4- bromophenylboronic acid, 1.07 g (0.93 mmol) of tetrakis (triphenylphosphine) palladium, (70.02 mmol), toluene (200 ml) and distilled water (80 ml) were added, and the mixture was refluxed and stirred for 8 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and then separated and purified by silica gel chromatography using dichloromethane and hexane to obtain white solid intermediate compound [ ] was prepared in a 18.7g (92%).
화합물 [102]의 제조Preparation of compound [102]
500mL 반응플라스크에 화합물 [102-1] 18g(41.35mmol), 9,9-디메틸-N-페닐플루오렌-2-아민 14.16g(49.62mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.76g(0.83mmol), 트리(테르트-부틸)포스핀 0.38ml(1.65mmol), 소듐테르트-부톡시드 5.96g(62.03mmol), 톨루엔 180ml를 가하고 24시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 톨루엔을 이용하여 재결정화하여 노랑색 고체의 목적화합물 [102] 17.2g (65%)을 제조하였다.In a 500 mL reaction flask, 18 g (41.35 mmol) of the compound [102-1], 14.16 g (49.62 mmol) of 9,9-dimethyl-N-phenylfluorene- 0.38 ml (1.65 mmol) of tri (tert-butyl) phosphine, 5.96 g (62.03 mmol) of sodium tert-butoxide and 180 ml of toluene were added and the mixture was stirred under reflux for 24 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to obtain 17.2 g (65%) of the target compound [102] as a yellow solid.
[합성예 16] 화합물 [134]의 제조[Synthesis Example 16] Preparation of compound [134]
[반응식 16][Reaction Scheme 16]
Figure PCTKR2018012249-appb-img-000031
Figure PCTKR2018012249-appb-img-000031
중간체 화합물 [134-1]의 제조Preparation of intermediate compound [134-1]
500mL 반응플라스크에 화합물 [82-1] 20g(55.67mmol), 비페닐-4-아민 10.36g(61.24mmol), 트리스(디벤질이딘아세톤)디팔라듐 1.02g(1.11mmol), 트리(테르트-부틸)포스핀 0.52ml(2.23mmol), 소듐테르트-부톡시드 8.03g(83.51mmol), 톨루엔 200ml를 가하고 20시간 환류 교반한다. 반응 종료 후 에틸아세테이트, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고, 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 실리카겔 크로마토그라프로 분리정제하여, 미색고체의 중간체 화합물 [134-1] 18.19g (73%)을 제조하였다.To a 500 mL reaction flask were added 20 g (55.67 mmol) of the compound [82-1], 10.36 g (61.24 mmol) of biphenyl-4-amine, 1.02 g (1.11 mmol) of tris (dibenzylidineacetone) dipalladium, (Butylphosphine) phosphine, 8.03 g (83.51 mmol) of sodium tert-butoxide and 200 ml of toluene were added and the mixture was stirred under reflux for 20 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and then separated and purified by silica gel chromatography using dichloromethane and hexane to obtain the intermediate compound [134-1 (73%). & Lt ; / RTI &gt;
화합물 [134]의 제조Preparation of compound [134]
500mL 반응플라스크에 화합물 [134-1] 18g(40.22mmol), 1-(4-브로모페닐)나프탈렌 12.53g(44.24mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.74g(0.81mmol), 트리(테르트-부틸)포스핀 0.37ml(1.61mmol), 소듐테르트-부톡시드 5.79g(60.33mmol), 톨루엔 180ml를 가하고 18시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 메탄올, 톨루엔을 이용하여 재결정화하여 노랑색 고체의 목적화합물 [134] 15.2g (58%)을 제조하였다.(40.22 mmol) of the compound [134-1], 12.53 g (44.24 mmol) of 1- (4-bromophenyl) naphthalene, 0.74 g (0.81 mmol) of tris (dibenzylidineacetone) dipalladium, 0.37 ml (1.61 mmol) of tri (tert-butyl) phosphine, 5.79 g (60.33 mmol) of sodium tert-butoxide and 180 ml of toluene were added and the mixture was stirred under reflux for 18 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone, methanol and toluene to obtain 15.2 g (58%) of the target compound [134] as a yellow solid.
[합성예 17] 화합물 [150]의 제조[Synthesis Example 17] Synthesis of Compound [150]
[반응식 17][Reaction Scheme 17]
Figure PCTKR2018012249-appb-img-000032
Figure PCTKR2018012249-appb-img-000032
중간체 화합물 [150-1]의 제조Preparation of intermediate compound [150-1]
500mL 반응플라스크에 화합물 [5-4] 20g(56.76mmol), 4'-브로모비페닐-4-보론산 18.86g(68.11mmol), 테트라키스(트리페닐포스핀)팔라듐 1.31g(1.14mmol), 포타슘카보네이트 11.77g(85.14mmol), 톨루엔 200ml, 증류수 80ml를 가하고 12시간 환류 교반한다. 반응 종료 후 에틸아세테이트, 증류수로 추출, 무수황산 마그네슘 처리하여 여과하고, 여과액은 감압 농축한 뒤, 디클로로메탄, 헥산을 이용하여 실리카겔 크로마토그라프로 분리정제하여, 흰색 고체의 중간체 화합물 [150-1] 21.7g (88%)을 제조하였다.20 g (56.76 mmol) of the compound [5-4], 18.86 g (68.11 mmol) of 4'-bromobiphenyl-4-boronic acid, 1.31 g (1.14 mmol) of tetrakis (triphenylphosphine) palladium, 11.77 g (85.14 mmol) of potassium carbonate, 200 ml of toluene and 80 ml of distilled water were added, and the mixture was refluxed and stirred for 12 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water, treated with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and then separated and purified by silica gel chromatography using dichloromethane and hexane to obtain an intermediate compound [150-1 ] was prepared in a 21.7g (88%).
화합물 [150]의 제조Preparation of Compound [150]
500mL 반응플라스크에 화합물 [150-1] 20g(45.94mmol), 9,9-디메틸-N-(1-나프탈렌)-플루오렌-2-아민 18.49g(55.13mmol), 트리스(디벤질이딘아세톤)디팔라듐 0.84g(0.92mmol), 트리(테르트-부틸)포스핀 0.43ml(1.84mmol), 소듐테르트-부톡시드 6.62g(68.91mmol), 톨루엔 200ml를 가하고 20시간 환류 교반한다. 반응 종료 후 여과하고, 아세톤, 톨루엔을 이용하여 재결정화 하여 미색고체의 목적화합물 [150] 21.2g (67%)을 제조하였다.To a 500 mL reaction flask were added 20 g (45.94 mmol) of the compound [150-1], 18.49 g (55.13 mmol) of 9,9-dimethyl-N- (1-naphthalene) ), 0.43 ml (1.84 mmol) of tri (tert-butyl) phosphine, 6.62 g (68.91 mmol) of sodium tert-butoxide and 200 ml of toluene were added and the mixture was refluxed with stirring for 20 hours. After completion of the reaction, the reaction mixture was filtered and recrystallized from acetone and toluene to obtain 21.2 g (67%) of the desired compound [150] as a off-white solid.
상기 합성예 1 내지 17의 제조 방법에 따라 화합물 1 내지 화합물 156을 제조하였고 그 결과를 하기의 표 2에 나타내었다.Compounds 1 to 156 were prepared according to the production methods of Synthesis Examples 1 to 17, and the results are shown in Table 2 below.
[표 2][Table 2]
*
Figure PCTKR2018012249-appb-img-000033
*
Figure PCTKR2018012249-appb-img-000033
Figure PCTKR2018012249-appb-img-000034
Figure PCTKR2018012249-appb-img-000034
Figure PCTKR2018012249-appb-img-000035
Figure PCTKR2018012249-appb-img-000035
Figure PCTKR2018012249-appb-img-000036
Figure PCTKR2018012249-appb-img-000036
Figure PCTKR2018012249-appb-img-000037
Figure PCTKR2018012249-appb-img-000037
Figure PCTKR2018012249-appb-img-000038
Figure PCTKR2018012249-appb-img-000038
비교예 화합물Comparative Example Compound
<화학식 b><Formula b>
Figure PCTKR2018012249-appb-img-000039
Figure PCTKR2018012249-appb-img-000039
<화학식 c><Formula c>
Figure PCTKR2018012249-appb-img-000040
Figure PCTKR2018012249-appb-img-000040
<화학식 d><Formula d>
Figure PCTKR2018012249-appb-img-000041
Figure PCTKR2018012249-appb-img-000041
<화학식 e><Formula e>
Figure PCTKR2018012249-appb-img-000042
Figure PCTKR2018012249-appb-img-000042
비교예 1Comparative Example 1
하기 화학식 f로 표시되는 화합물 f를 형광 청색 호스트로 사용하고, 하기 화학식 g로 표시되는 화합물 g를 형광 청색 도판트로 사용하고, 2-TNATA(4,4’,4”-tris(N-naphthalen-2-yl)-N-phenylamino)-triphenylamine)을 정공주입층 물질로 사용하고, α-NPD(N,N’-di(naphthalene-1-yl)-N,N’-diphenylbenzidine)을 정공수송층 물질로 사용하여 다음과 같은 구조를 갖는 유기발광소자를 제작하였다: ITO/2-TNATA(60 nm)/α-NPD(30 nm)/ 화합물f + 화합물 g(30 nm)/Alq 3(25 nm)/Liq(1 nm)/ Al(100 nm).(4,4 ', 4 &quot; -tris (N-naphthalen-2-yl) phthalocyanine), using compound f represented by the following formula f as a fluorescent blue host and using compound g represented by the following formula g as a fluorescent blue dopant: 2-yl) -N-phenylamino) -triphenylamine was used as a hole injection layer material and α-NPD (N, N'-di (naphthalene- (30 nm) / compound f + compound g (30 nm) / Alq 3 (25 nm) was used as an organic light emitting device having the following structure: ITO / 2-TNATA / Liq (1 nM) / Al (100 nM).
애노드는 코닝(Corning)사의 15Ω/cm 2 (1000Å) ITO 유리 기판을 25 mm x 25 mm x 0.7 mm크기로 잘라서 아세톤 이소프로필 알콜과 순수한 물 속에서 각 15분 동안 초음파 세정한 후, 30분 동안 UV 오존 세정하여 사용하였다. 상기 기판 상부에 2-TNATA를 진공 증착하여 60 nm 두께의 정공주입층을 형성하였다. 상기 정공주입층 상부에, α-NPD를 진공 증착하여 30 nm 두께의 정공수송층을 형성하였다. 상기 정공수송층 상부에 화학식 f로 표시되는 화합물 및 화학식 g로 표시되는 화합물(도핑율: 4wt%)를 진공 증착하여 30 nm두께의 발광층을 형성하였다. 이후, 상기 발광층 상부에 Alq 3 화합물을 25 nm의 두께로 진공증착하여 전자수송층을 형성하였다. 상기 전자수송층 상부에 Liq 1 nm(전자주입층)과 Al 100 nm(캐소드)를 순차적으로 진공증착하여, 표 3에 표시된 바와 같은 유기발광소자를 제조하였다. 이를 비교샘플 1이라고 한다.The anode was prepared by cutting Corning's 15 Ω / cm 2 (1000 Å) ITO glass substrate to a size of 25 mm × 25 mm × 0.7 mm, ultrasonically cleaning it in acetone isopropyl alcohol and pure water for 15 minutes each, UV ozone cleaning was used. 2-TNATA was vacuum deposited on the substrate to form a 60 nm thick hole injection layer. On top of the hole injection layer, α-NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. A compound represented by Formula f and a compound represented by Formula g (doping ratio: 4 wt%) were vacuum-deposited on the hole transport layer to form a light emitting layer having a thickness of 30 nm. Then, an Alq 3 compound was vacuum deposited on the light emitting layer to a thickness of 25 nm to form an electron transporting layer. Liq 1 nm (electron injecting layer) and Al 100 nm (cathode) were sequentially vacuum-deposited on the electron transporting layer to produce an organic light emitting device as shown in Table 3. This is referred to as Comparative Sample 1.
<화학식 f><Formula f>
Figure PCTKR2018012249-appb-img-000043
Figure PCTKR2018012249-appb-img-000043
<화학식 g><Formula g>
Figure PCTKR2018012249-appb-img-000044
Figure PCTKR2018012249-appb-img-000044
<Alq3>&Lt; Alq3 &
Figure PCTKR2018012249-appb-img-000045
Figure PCTKR2018012249-appb-img-000045
비교예 2 ~ 5Comparative Examples 2 to 5
상기 비교예 1 중, 정공수송층 화합물 α-NPD 대신에 상기 비교예 화합물 b, c, d 및 e 를 각각 사용하여, 다음과 같은 구조를 갖는 유기발광소자를 제작하였다: ITO/2-TNATA(60 nm)/화합물 b, c, d, 또는 e (30 nm)/ 화합물 f + 화합물 g(30 nm)/Alq3 (25 nm)/Liq(1 nm)/ Al(100 nm).An organic light emitting device having the following structure was produced by using the above Comparative Compounds b, c, d and e in place of the hole transport layer compound α-NPD in Comparative Example 1: ITO / 2-TNATA 60 (30 nm) / compound b, c, d, or e (30 nm) / compound f + compound g (30 nm) / Alq3 (25 nm) / Liq (1 nm) / Al (100 nm).
이를 비교예 2 내지 5 라고 한다.These are referred to as Comparative Examples 2 to 5.
실시예 1 ~ 17Examples 1 to 17
정공 수송층으로 사용되는 α-NPD 대신 상기 표1에 개시된 화합물 5, 10, 15, 19, 21, 26, 47, 49, 51, 77, 78, 82, 84, 100, 102, 134, 150 들을 승화 정제 과정을 거쳐 정공 수송층으로 각각 이용한 것을 제외하고는 상기 비교예 1과 동일한 방법으로 유기발광소자를 제조하여 표 3에 나타내었다. 이를 각각 실시예 1 내지 17 이라고 한다.10, 15, 19, 21, 26, 47, 49, 51, 77, 78, 82, 84, 100, 102, 134, 150 shown in Table 1 were sublimed in place of? -NPD used as a hole transport layer. The organic light emitting device was fabricated in the same manner as in Comparative Example 1, except that the hole transport layer was used as a hole transport layer. These are referred to as Examples 1 to 17, respectively.
평가예 1: 비교예 1 ~ 5 및 실시예 1 ~ 17의 발광 특성 및 수명 평가Evaluation Example 1: Evaluation of luminescence characteristics and life span of Comparative Examples 1 to 5 and Examples 1 to 17
비교예 1 ~ 5 및 실시예 1 ~ 17 에 대하여, Keithley sourcemeter “2400”, KONIKA MINOLTA “CS-2000”을 이용하여 발광피크, 발광효율을 평가 하였고, The emission peak and the luminous efficiency were evaluated using Keithley source meter "2400" and KONIKA MINOLTA "CS-2000" for Comparative Examples 1 to 5 and Examples 1 to 17,
맥사이언스사의 M6000S 수명측정장치를 이용하여 초기휘도 (L 0) 1000 nit를 기준으로 휘도 (L)가 97%에 도달하는 시간(LT97)을 각각 측정하여, 그 결과를 하기 표 3 및 도면 1 내지 3에 나타내었다.The time (LT97) at which the luminance (L) reached 97% on the basis of the initial luminance (L 0 ) of 1000 nits was measured using a M6000S lifetime measuring device of Mac Science Inc., and the results are shown in Table 3 and Figs. Respectively.
[표 3][Table 3]
Figure PCTKR2018012249-appb-img-000046
Figure PCTKR2018012249-appb-img-000046
상기 표 3 에 보여지는 바와 같이 실시예 1~17 은 비교예 1~5 에 비하여 저전압 구동 및 향상된 발광 특성을 나타내었다. As shown in Table 3, Examples 1 to 17 exhibited low-voltage driving and improved luminescence characteristics as compared with Comparative Examples 1 to 5.
도 1, 2 및 3은 실시예 1~17 및 비교예 1 내지 5에서 제조된 유기 전계 발광 소자에 대하여 상기 측정 결과를 나타낸 수명 특성 평가 그래프이다.FIGS. 1, 2 and 3 are graphs showing lifetime characteristics of the organic electroluminescent devices manufactured in Examples 1 to 17 and Comparative Examples 1 to 5, respectively, showing the results of the measurement.
상기 표 3에 보여지는 바와 같이 실시예 1 내지 17 은 비교예 1~5 에 비하여 향상된 수명 특성을 나타내었다. 특히 2,3-치환된 나프틸 아민 유도체의 상기 화합물들이 우수한 성능과 수명을 나타내었다.As shown in Table 3, Examples 1 to 17 exhibited improved life characteristics compared to Comparative Examples 1 to 5. In particular, the above compounds of 2,3-substituted naphthylamine derivatives exhibit excellent performance and lifetime.
이상에서 본 발명의 바람직한 실시예들에 대하여 상세하게 설명하였지만 본 발명의 권리 범위는 이에 한정되는 것은 아니고 다음의 청구 범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리 범위에 속하는 것이다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims (8)

  1. 하기 화학식 a로 표시되는 2,3-치환된 나프틸아민 유도체 유기화합물:Substituted 2,3-substituted naphthylamine derivatives represented by formula (a) Organic compounds:
    <화학식 a><Formula a>
    Figure PCTKR2018012249-appb-img-000047
    Figure PCTKR2018012249-appb-img-000047
    상기 식에서, In this formula,
    L 1은 단일결합, 페닐렌기 또는 비페닐렌기이고,L 1 is a single bond, a phenylene group or a biphenylene group,
    L 2는 단일결합, 페닐렌기 또는 비페닐렌기이고, L 2 is a single bond, a phenylene group or a biphenylene group,
    Ar 1 은 치환 또는 비치환된 C3-C60의 헤테로아릴기, C1~C30의 알킬기 또는 C6~C30의 아릴기이고, 상기 Ar1이 치환된 경우의 치환기는 C1~C30의 알킬기, C6~C30의 아릴기, C5~C30의 헤테로아릴기, 치환 또는 비치환된 실릴기 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나이고, 상기 실릴기가 치환된 경우의 2차 치환기는 C6~C30의 아릴기이고, 단, 상기 Ar 1 은 C1~C30의 알킬기인 경우, L 1은 단일결합이 아니고,Ar 1 Is a substituted or unsubstituted C3-C60 heteroaryl group, a C1-C30 alkyl group or a C6-C30 aryl group, and when the Ar1 is substituted, the substituent may be a C1-C30 alkyl group, a C6- C5 to C30 heteroaryl group, substituted or unsubstituted silyl group, and combinations thereof, and the secondary substituent when the silyl group is substituted is C6 to C30 aryl group, When Ar 1 is an alkyl group having 1 to 30 carbon atoms, L 1 is not a single bond,
    Ar 2 는 치환 또는 비치환된 C6~C30의 아릴기 또는 치환 또는 비치환된 C3-C60의 헤테로아릴기이고, 상기 Ar 2가 치환된 경우의 치환기는 중수소, 시아노기, 니트릴기, 할로겐기, C1-C12의 알킬기, C6-C60의 아릴기, C3-C60의 헤테로아릴기 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나이고,Ar 2 Is a substituted or unsubstituted aryl groups, unsubstituted C6 ~ C30 heteroaryl or a substituted or unsubstituted C3-C60 group, and the substituent in the case where the Ar 2 is substituted with a heavy hydrogen, a cyano group, a nitrile group, a halogen group, C1- C60 alkyl group, C6-C60 aryl group, C3-C60 heteroaryl group, and combinations thereof,
    R 1 및 R 2 는, 각각 독립적으로, 수소, 중수소, 시아노기, 니트릴기, 할로겐기, C1-C12의 알킬기, 치환 또는 비치환된 C6-C60의 아릴기, 치환 또는 비치환된 C3-C60의 헤테로아릴기이고, 상기 R 1 및 R 2 가 치환된 경우의 치환기는 C1~C30의 알킬기 또는 C6~C30의 아릴기, C5~C30의 헤테로 아릴기 및 이들의 조합으로 이루어진 군으로부터 선택된 하나이고, R 1 and R 2 are each independently hydrogen, deuterium, cyano, nitrile, halogen, C 1 -C 12 alkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 3 -C 60 And R &lt; 1 &gt; and R &lt; 2 &gt; Is a C1-C30 alkyl group or a C6-C30 aryl group, a C5-C30 heteroaryl group, or a combination thereof,
    X 는 부존재, 산소, 황, 또는 C(R 3R 4) 이고, R 3 및 R 4 는 서로 동일하거나 또는 상이하며 각각 독립적으로 수소, C1-C20의 알킬기, C5-C30의 아릴기 이고, 상기 R 3 및 R 4 는 각각 상기 X가 함유된 다환 고리의 환원 중 결합가능한 탄소와 연결되어 포화 또는 불포화 축합고리를 형성할 수 있다.X is absent, oxygen, sulfur, or C (R 3 R 4 ), R 3 and R 4 Are the same or different and each is independently hydrogen, an alkyl group of C1-C20, aryl group of C5-C30 to each other, wherein R 3 and R 4 May each be linked to a bondable carbon in the reduction of the X-containing polycyclic ring to form a saturated or unsaturated condensed ring.
  2. 제1항에 있어서,The method according to claim 1,
    상기 화학식 a는 화기 화학식 a-1, a-2, a-3 및 a-4 로 표시되는 화합물 중 어느 하나로 선택되는 The above-mentioned formula (a) is selected from any one of the compounds represented by the flame a-formulas a-1, a-2, a-3 and a-4
    2,3-치환 나프틸아민 유도체 화합물:2,3-substituted naphthylamine derivative compound:
    <화학식 a-1>&Lt; Formula (a-1)
    Figure PCTKR2018012249-appb-img-000048
    Figure PCTKR2018012249-appb-img-000048
    <화학식 a-2><Formula a-2>
    Figure PCTKR2018012249-appb-img-000049
    Figure PCTKR2018012249-appb-img-000049
    <화학식 a-3> <Formula a-3>
    Figure PCTKR2018012249-appb-img-000050
    Figure PCTKR2018012249-appb-img-000050
    <화학식 a-4> <Chemical Formula a-4>
    Figure PCTKR2018012249-appb-img-000051
    Figure PCTKR2018012249-appb-img-000051
    상기 식에서, R 1, R 2, R 3, R 4, L 1, L 2, X, Ar 1 및 Ar 2 는 상기 화학식 a 에서 정의된 바와 같다.Wherein R 1 , R 2 , R 3 , R 4 , L 1 , L 2 , X, Ar 1 and Ar 2 are as defined in Formula a above.
  3. 제1항에 있어서,The method according to claim 1,
    Ar 1 은, 페닐기, 톨릴기, 나프틸기, 비페닐기, 터페닐기, 페안트렌기, 플루오렌기, 스파이로플루오렌기, 벤조티오펜기, 벤조퓨란기, 디벤조퓨란기, 디벤조티오펜기, 피리딜기, 페닐나프틸기, 페닐플루오렌기, 페닐디벤조퓨란기, 페닐디벤조티오펜기, 페닐펜안트렌기, 테트라페닐실릴기, 또는 비페닐트리페닐실릴기인 Ar 1 Is a group selected from the group consisting of a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthrene group, a fluorene group, a spirobifluorene group, a benzothiophene group, a benzofurane group, a dibenzofurane group, A phenylphenyl group, a phenylphenyl group, a phenylphenyl group, a phenylphenyl group, a phenylphenyl group, a pyridyl group, a phenylnaphthyl group, a phenylfluorene group, a phenyldibenzofurane group, a phenyldibenzothiophene group,
    2,3-치환 나프틸아민 유도체 유기화합물.2,3-Substituted Naphthylamine Derivative Organic Compound.
  4. 제1항에 있어서,The method according to claim 1,
    상기 L 1 및 L 2는, 각각 독립적으로, 하기 구조식으로 표시되는 기 중 어느 하나인Wherein L 1 and L 2 are each independently any one of groups represented by the following structural formulas
    2,3-치환 나프틸아민 유도체 유기화합물.2,3-Substituted Naphthylamine Derivative Organic Compound.
    Figure PCTKR2018012249-appb-img-000052
    Figure PCTKR2018012249-appb-img-000052
    Figure PCTKR2018012249-appb-img-000053
    Figure PCTKR2018012249-appb-img-000053
  5. 제1항에 있어서,The method according to claim 1,
    상기 화학식 a 는 하기 1 내지 156 중의 어느 하나인(A) is any one of the following 1 to 156
    2,3-치환 나프틸아민 유도체 유기화합물.2,3-Substituted Naphthylamine Derivative Organic Compound.
    Figure PCTKR2018012249-appb-img-000054
    Figure PCTKR2018012249-appb-img-000054
    Figure PCTKR2018012249-appb-img-000055
    Figure PCTKR2018012249-appb-img-000055
    Figure PCTKR2018012249-appb-img-000056
    Figure PCTKR2018012249-appb-img-000056
    Figure PCTKR2018012249-appb-img-000057
    Figure PCTKR2018012249-appb-img-000057
    Figure PCTKR2018012249-appb-img-000058
    Figure PCTKR2018012249-appb-img-000058
    Figure PCTKR2018012249-appb-img-000059
    Figure PCTKR2018012249-appb-img-000059
  6. 제1항에 있어서,The method according to claim 1,
    상기 2,3-치환 나프틸아민 유도체 유기화합물은 유기전기발광소자용 재료 중 전자차단층 정공수송층 또는 정공주입층 물질로 사용되는The 2,3-substituted naphthylamine derivative organic compound is used as a hole transport layer or a hole injection layer material in an electron blocking layer
    2,3-치환된 나프틸아민 유도체 유기화합물.2,3-Substituted naphthylamine derivatives organic compounds.
  7. 음극과 양극 사이에 적어도 하나의 유기 박막층이 협지되어 있는 유기 전계 발광 소자에 있어서, 상기 유기 박막층은 적어도 하나의 발광층을 포함하는 다층 구조이고, 상기 발광층 이외의 상기 유기 박막층 내의 적어도 하나의 층이 제1항 내지 제6항 중 어느 한 항에 따른 상기 2,3-치환 나프틸아민 유도체 유기화합물을 단독 또는 2종 이상의 혼합물을 포함하는 유기 전계 발광 소자.At least one organic thin film layer sandwiched between a cathode and an anode, wherein the organic thin film layer is a multi-layer structure including at least one light emitting layer, and at least one layer in the organic thin film layer other than the light emitting layer The organic electroluminescent device according to any one of claims 1 to 6, wherein the 2,3-substituted naphthylamine derivative organic compound is used singly or in combination of two or more.
  8. 제7항에 있어서, 8. The method of claim 7,
    상기 유기 박막층은 음극과 발광층 사이에 개재되며, 정공주입층, 정공수송층, 정공주입 기능 및 정공수송 기능을 동시에 갖는 기능층, 버퍼층 및 전자차단층 중 적어도 하나를 포함한 정공 수송 영역을 포함하는Wherein the organic thin film layer includes a hole transporting region interposed between the cathode and the light emitting layer and including at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer,
    유기 전계 발광 소자.Organic electroluminescent device.
PCT/KR2018/012249 2017-11-03 2018-10-17 2,3-substituted naphthylamine derivative organic light emitting compound and organic electroluminescent element WO2019088517A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202311373601.2A CN117417261A (en) 2017-11-03 2018-10-17 2, 3-substituted naphthylamine derivative organic light-emitting compound and organic electroluminescent device
CN201880071653.5A CN111315717A (en) 2017-11-03 2018-10-17 2, 3-substituted naphthylamine derivative organic luminescent compound and organic electroluminescent device

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2017-0146028 2017-11-03
KR1020170146028A KR102081739B1 (en) 2017-11-03 2017-11-03 2,3 substituted naphthylamine derivative organic compounds and organic electroluminescent device including the same

Publications (1)

Publication Number Publication Date
WO2019088517A1 true WO2019088517A1 (en) 2019-05-09

Family

ID=66332127

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/012249 WO2019088517A1 (en) 2017-11-03 2018-10-17 2,3-substituted naphthylamine derivative organic light emitting compound and organic electroluminescent element

Country Status (3)

Country Link
KR (1) KR102081739B1 (en)
CN (2) CN111315717A (en)
WO (1) WO2019088517A1 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020189316A1 (en) * 2019-03-15 2020-09-24 出光興産株式会社 Compound, material for organic electroluminescent elements, organic electroluminescent element and electronic device
CN111995530A (en) * 2019-05-27 2020-11-27 东进世美肯株式会社 Organic compound for capping layer and organic light emitting device including the same
CN112745231A (en) * 2019-10-29 2021-05-04 东进世美肯株式会社 Novel compound and organic light-emitting element comprising same
WO2021103058A1 (en) * 2019-11-25 2021-06-03 武汉华星光电半导体显示技术有限公司 Hole transport material, preparation method thereof, and electroluminescent device
CN112979478A (en) * 2019-12-18 2021-06-18 北京鼎材科技有限公司 Compound, application thereof and organic electroluminescent device comprising compound
CN113024387A (en) * 2019-09-10 2021-06-25 北京鼎材科技有限公司 Organic compound and organic electroluminescent device containing the same
CN113045481A (en) * 2019-12-27 2021-06-29 合肥鼎材科技有限公司 Compound, application thereof and organic electroluminescent device comprising compound
WO2021134820A1 (en) * 2019-12-31 2021-07-08 南京高光半导体材料有限公司 New organic electroluminescent compound and organic electroluminescent device
WO2021193654A1 (en) * 2020-03-25 2021-09-30 出光興産株式会社 Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device
US11805697B2 (en) 2018-01-26 2023-10-31 Samsung Display Co., Ltd. Organic electroluminescence device and monoamine compound for organic electroluminescence device
US11849632B2 (en) 2019-03-20 2023-12-19 Samsung Display Co., Ltd. Amine-based compound and organic light-emitting device including the same
US11871656B2 (en) * 2018-01-26 2024-01-09 Samsung Display Co., Ltd. Organic electroluminescence device and monoamine compound for organic electroluminescence device
CN113024387B (en) * 2019-09-10 2024-04-30 北京鼎材科技有限公司 Organic compound and organic electroluminescent device containing the same

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200139398A (en) * 2019-06-04 2020-12-14 주식회사 동진쎄미켐 Compound for capping layer and organic electroluminescent divice including the same
KR102267451B1 (en) * 2019-09-17 2021-06-23 엘티소재주식회사 Heterocyclic compound and organic light emitting device comprising same
KR20210068642A (en) 2019-11-29 2021-06-10 삼성디스플레이 주식회사 Amine compound and light emitting device comprising the same
KR20230061616A (en) * 2021-10-28 2023-05-09 엘티소재주식회사 Amine compound and organic light emitting device comprising same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100901887B1 (en) * 2008-03-14 2009-06-09 (주)그라쎌 Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR20150006374A (en) * 2013-07-08 2015-01-16 주식회사 엘지화학 Hetero-cyclic compound and organic light emitting device comprising the same
KR20160113783A (en) * 2015-03-23 2016-10-04 덕산네오룩스 주식회사 Compound for organic electric element, organic electric element comprising the same and electronic device thereof
KR20170031614A (en) * 2015-09-10 2017-03-21 주식회사 동진쎄미켐 Novel compound and organic electroluminescent device comprising same
US20170288148A1 (en) * 2016-04-01 2017-10-05 Duk San Neolux Co., Ltd. Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100901887B1 (en) * 2008-03-14 2009-06-09 (주)그라쎌 Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR20150006374A (en) * 2013-07-08 2015-01-16 주식회사 엘지화학 Hetero-cyclic compound and organic light emitting device comprising the same
KR20160113783A (en) * 2015-03-23 2016-10-04 덕산네오룩스 주식회사 Compound for organic electric element, organic electric element comprising the same and electronic device thereof
KR20170031614A (en) * 2015-09-10 2017-03-21 주식회사 동진쎄미켐 Novel compound and organic electroluminescent device comprising same
US20170288148A1 (en) * 2016-04-01 2017-10-05 Duk San Neolux Co., Ltd. Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11871656B2 (en) * 2018-01-26 2024-01-09 Samsung Display Co., Ltd. Organic electroluminescence device and monoamine compound for organic electroluminescence device
US11805697B2 (en) 2018-01-26 2023-10-31 Samsung Display Co., Ltd. Organic electroluminescence device and monoamine compound for organic electroluminescence device
US11618740B2 (en) 2019-03-15 2023-04-04 Idemitsu Kosan Co., Ltd. Compound, material for organic electroluminescence devices, organic electroluminescence device, and electronic device
WO2020189316A1 (en) * 2019-03-15 2020-09-24 出光興産株式会社 Compound, material for organic electroluminescent elements, organic electroluminescent element and electronic device
US11849632B2 (en) 2019-03-20 2023-12-19 Samsung Display Co., Ltd. Amine-based compound and organic light-emitting device including the same
CN111995530A (en) * 2019-05-27 2020-11-27 东进世美肯株式会社 Organic compound for capping layer and organic light emitting device including the same
CN113024387B (en) * 2019-09-10 2024-04-30 北京鼎材科技有限公司 Organic compound and organic electroluminescent device containing the same
CN113024387A (en) * 2019-09-10 2021-06-25 北京鼎材科技有限公司 Organic compound and organic electroluminescent device containing the same
CN113045436A (en) * 2019-09-10 2021-06-29 北京鼎材科技有限公司 Organic compound and organic electroluminescent device containing the same
CN112745231A (en) * 2019-10-29 2021-05-04 东进世美肯株式会社 Novel compound and organic light-emitting element comprising same
US11678570B2 (en) 2019-11-25 2023-06-13 Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. Hole transport material, preparation method thereof, and electroluminescent device
WO2021103058A1 (en) * 2019-11-25 2021-06-03 武汉华星光电半导体显示技术有限公司 Hole transport material, preparation method thereof, and electroluminescent device
WO2021121230A1 (en) * 2019-12-18 2021-06-24 北京鼎材科技有限公司 Compound, application thereof, and organic electroluminescent device containing same
CN112979478A (en) * 2019-12-18 2021-06-18 北京鼎材科技有限公司 Compound, application thereof and organic electroluminescent device comprising compound
CN112979478B (en) * 2019-12-18 2024-03-15 北京鼎材科技有限公司 Compound and application thereof, and organic electroluminescent device comprising compound
CN113045481A (en) * 2019-12-27 2021-06-29 合肥鼎材科技有限公司 Compound, application thereof and organic electroluminescent device comprising compound
WO2021134820A1 (en) * 2019-12-31 2021-07-08 南京高光半导体材料有限公司 New organic electroluminescent compound and organic electroluminescent device
WO2021193654A1 (en) * 2020-03-25 2021-09-30 出光興産株式会社 Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device

Also Published As

Publication number Publication date
KR102081739B1 (en) 2020-02-26
KR20190050525A (en) 2019-05-13
CN111315717A (en) 2020-06-19
CN117417261A (en) 2024-01-19

Similar Documents

Publication Publication Date Title
WO2019088517A1 (en) 2,3-substituted naphthylamine derivative organic light emitting compound and organic electroluminescent element
WO2020171381A2 (en) Organic electroluminescent composition, and organic electroluminescent element comprising same
WO2014104585A1 (en) Compound for organic electronic element, organic electronic element using same, and electronic device thereof
WO2016140497A2 (en) Compound for organic electric device, organic electric device using same, and electronic device thereof
WO2015178585A1 (en) Compound for electro-organic device, electro-organic device using same, and electronic device therefor
WO2011081423A2 (en) Triphenylene compound and organic electroluminescence device including the same
WO2015053572A1 (en) Organic light emitting compound and organic light emitting device comprising same
WO2010044607A1 (en) Benzimidazole compounds and organic photoelectric device with the same
WO2018016786A1 (en) Compound for organic electronic device, organic electronic device using same, and electronic apparatus thereof
WO2017065415A1 (en) Organic light emitting diode having improved luminance reduction rate in low grayscale area
WO2014021569A1 (en) Compound for organic electroluminescent device and organic electroluminescent device including the same
WO2018070824A1 (en) Compound for organic electric element, organic electric element using same, and electronic device thereof
WO2021085969A1 (en) Compound for organic optoelectronic element, composition for organic optoelectronic element, organic optoelectronic element, and display device
WO2020149710A1 (en) Compound for organic electronic element, organic electronic element using same, and electronic device thereof
WO2017104994A1 (en) Composition for organic electronic element, organic electronic element using same, and electronic device thereof
WO2017217654A1 (en) Compound for organic electronic device, organic electronic device using same, and electronic apparatus thereof
WO2020085797A1 (en) Compound for organic electric element, organic electric element using same, and electronic device thereof
WO2022225198A1 (en) Compound for organic electric element, organic electric element using same, and electronic device comprising same
WO2020159099A1 (en) Organic electroluminescent composition and organic electroluminescent element comprising same
WO2019147077A1 (en) Compound and organic light-emitting device comprising same
WO2019022435A1 (en) Compound for organic electronic device, organic electronic device using same, and electronic apparatus thereof
WO2021153931A1 (en) Compound for organic electric element, organic electric element using same, and electronic device thereof
WO2020045831A1 (en) Compound for organic electric element, organic electric element using same, and electronic device comprising same
WO2014098447A1 (en) Organic compound and organic electroluminescent element comprising same
WO2011081449A2 (en) Triphenylene-based compound and organic electro-luminescence device including 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: 18874737

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18874737

Country of ref document: EP

Kind code of ref document: A1