Organic electroluminescent device and amine compound for organic electroluminescent device

Abstract

To provide an amine compound that is capable of improving emission efficiency and / or device life of an organic electroluminescence device.SOLUTION: The present invention provides an amine compound represented by the following formula 1. (Arand Arindependently represent a substitutable aryl group or the like; L is a single bond, a substitutable arylene group or the like; HT is an indolizine ring with condensed one to three benzene rings, where the benzene rings and indolizine ring may be substituted.)SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an amine compound and an organic electroluminescent device including the same, and more particularly to an amine compound used in a hole transport region and an organic electroluminescent device including the same. [Background technology]

[0002] Recently, organic electroluminescence devices have been actively developed as image display devices. Unlike liquid crystal display devices, organic electroluminescence displays are so-called self-luminous display devices that realize display by causing holes and electrons injected from a first electrode and a second electrode to recombine in a light-emitting layer, thereby causing a light-emitting material containing an organic compound in the light-emitting layer to emit light.

[0003] In order to apply organic electroluminescent elements to display devices, there is a demand for lower driving voltages, higher luminous efficiency, and longer life for the organic electroluminescent elements, and there is a continuing demand for the development of materials for organic electroluminescent elements that can stably achieve these goals.

[0004] Furthermore, in order to realize a highly efficient organic electroluminescent device, development is being carried out on materials for the hole transport layer to suppress the diffusion of exciton energy in the light emitting layer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2010-0113204 [Patent Document 2] Korean Patent Publication No. 10-2016-0028979 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide an amine compound, which is a material for an organic electroluminescent device, capable of improving the luminous efficiency and device life.

[0007] Another object of the present invention is to provide an organic electroluminescent device which includes an amine compound containing pyridoindole and has improved thermal charge resistance. [Means for solving the problem]

[0008] One embodiment provides an organic electroluminescent device including a first electrode, a second electrode disposed on the first electrode, and a plurality of organic layers disposed between the first electrode and the second electrode, at least one of the organic layers including an amine compound represented by Chemical Formula 1 below:

[0009] [ka]

[0010] In the above formula 1, Ar 1 and Ar 2 are each independently a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms; L is a single bond, a substituted or unsubstituted arylene group having from 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having from 2 to 30 ring carbon atoms; and HT is represented by chemical formula 2 below.

[0011] [ka]

[0012] In the above formula 2, R 1 ~R 9are each independently a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms; R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 At least one pair of R 2 and R 3 , R 3 and R 4 and the R 4 and R 5 When at least one pair of the above forms a hexagonal hydrocarbon ring, R 8 is a hydrogen atom.

[0013] The organic layer may include a light-emitting layer and a hole-transporting region disposed between the first electrode and the light-emitting layer, and the hole-transporting region may include the amine compound represented by Chemical Formula 1.

[0014] The light-emitting layer can emit blue or green light.

[0015] The organic layer may include an emissive layer, a hole injection layer disposed between the first electrode and the emissive layer, and a hole transport layer disposed between the hole injection layer and the emissive layer, and the hole transport layer may include an amine compound represented by Chemical Formula 1.

[0016] R 2 and R 3 , R 3 and R 4 and the R 4 and R 5One or two pairs selected from the following may form the hexagonal hydrocarbon ring.

[0017] R 6 and R 7 , R 7 and R 8 and the R 8 and R 9 One or two pairs selected from the following may form the hexagonal hydrocarbon ring.

[0018] The hexagonal hydrocarbon ring may be represented by the following Chemical Formula 3:

[0019] [ka]

[0020] In the above formula 3, R 10 ~R 13 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, and * is a moiety that bonds to chemical formula 2 above.

[0021] R that does not form a hexagonal hydrocarbon ring 2 ~R 9 Any one of the above or the R 10 ~R 13 Any one of these may be bonded to L in Chemical Formula 1.

[0022] The formula 2 may be represented by any one of the following formulas 2-1a to 2-1d.

[0023] [ka]

[0024] [ka]

[0025] [ka]

[0026] [ka]

[0027] In the above Chemical Formula 2-1d, R 20 ~R 23 , and R 30 ~R 33 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, and in Chemical Formula 2-1a to Chemical Formula 2-1d, R 1 ~R 9 is the same as defined in Chemical Formula 2, R 10 ~R 13 is the same as defined in Chemical Formula 3 above.

[0028] The formula 2 may be represented by any one of the following formulas 2-2a to 2-2d.

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] [ka]

[0033] In the above Chemical Formula 2-2d, R 20 ~R 23 , and R 30 ~R 33 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, and in Chemical Formula 2-2a to Chemical Formula 2-2d, R 1 ~R 9 is the same as defined in Chemical Formula 2, R 10 ~R 13 is the same as defined in Chemical Formula 3 above.

[0034] R 1 may be an unsubstituted phenyl group, an unsubstituted naphthyl group, an unsubstituted biphenylyl group, an unsubstituted dibenzofuranyl group, or an unsubstituted dibenzothiophenyl group.

[0035] L may be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylylene group, a substituted or unsubstituted terphenylylene group, a substituted or unsubstituted phenanthrenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted dibenzofuranylene group.

[0036] Another embodiment provides an amine compound represented by the following formula 1:

[0037] [ka]

[0038] In the above formula 1, Ar1 and Ar 2 are each independently a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms; L is a single bond, a substituted or unsubstituted arylene group having from 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having from 2 to 30 ring carbon atoms; and HT is represented by chemical formula 2 below.

[0039] [ka]

[0040] In the above formula 2, R 1 ~R 9 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms; R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 At least one pair of R 2 and R 3 , R 3 and R 4 and the R 4 and R 5 When at least one pair of the above forms a hexagonal hydrocarbon ring, R 8 is a hydrogen atom.

[0041] R 2 and R 3 , R 3 and R4 and the R 4 and R 5 One or two pairs selected from the following may form the hexagonal hydrocarbon ring.

[0042] R 6 and R 7 , R 7 and R 8 and the R 8 and R 9 one pair or two pairs selected from the above are amine compounds forming the hexagonal hydrocarbon ring.

[0043] The hexagonal hydrocarbon ring may be represented by the following Chemical Formula 3:

[0044] [ka]

[0045] In the above formula 3, R 10 ~R 13 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, and * is a moiety that bonds to chemical formula 2 above.

[0046] R that does not form a hexagonal hydrocarbon ring 2 ~R 9 Any one of the above or the R 10 ~R 13 Any one of these may be bonded to L in Chemical Formula 1.

[0047] The formula 2 may be represented by any one of the following formulas 2-1a to 2-1d.

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] In the above Chemical Formula 2-1d, R 20 ~R 23 , and R 30 ~R 33 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, and in Chemical Formula 2-1a to Chemical Formula 2-1d, R 1 ~R 9 is the same as defined in Chemical Formula 2, R 10 ~R 13 is the same as defined in Chemical Formula 3 above.

[0053] The formula 2-2 may be represented by any one of the following formulas 2-2a to 2-2d.

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] In the above Chemical Formula 2-2d, R 20 ~R 23 , and R 30 ~R 33 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, and in Chemical Formula 2-2a to Chemical Formula 2-2d, R 1 ~R 9 is the same as defined in Chemical Formula 2, R 10 ~R 13 is the same as defined in Chemical Formula 3 above.

[0059] R 1 may be an unsubstituted phenyl group, an unsubstituted naphthyl group, an unsubstituted biphenylyl group, an unsubstituted dibenzofuranyl group, or an unsubstituted dibenzothiophenyl group.

[0060] L may be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylylene group, a substituted or unsubstituted terphenylylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted dibenzofullerylene group.

[0061] Ar 1 and Ar 2may each independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted pyridinyl group.

[0062] Ar 1 and Ar 2 may each independently be an aryl group having 6 to 40 ring carbon atoms and substituted or unsubstituted with at least one substituent selected from a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a triarylsilyl group having 18 to 50 carbon atoms, and an adamantyl group, or a heteroaryl group having 2 to 40 ring carbon atoms and substituted or unsubstituted with at least one substituent selected from a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a triarylsilyl group having 18 to 50 carbon atoms, and an adamantyl group. Effect of the Invention

[0063] The amine compound of one embodiment can improve the luminous efficiency and device life of an organic electroluminescent device.

[0064] The organic electroluminescent device of the embodiment can achieve high efficiency by including the amine compound of the embodiment in the hole transport region. [Brief description of the drawings]

[0065] [Figure 1] 1 is a cross-sectional view illustrating an organic electroluminescent device according to an embodiment of the present invention. [Diagram 2]1 is a cross-sectional view illustrating an organic electroluminescent device according to an embodiment of the present invention. [Diagram 3] 1 is a cross-sectional view illustrating an organic electroluminescent device according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0066] Since the present invention can be modified in various ways and can have various forms, specific embodiments are illustrated in the drawings and described in detail in the text, but it should be understood that the present invention is not limited to the specific disclosed forms, and includes all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0067] In describing each drawing, similar reference numerals are used for similar components. In the accompanying drawings, the dimensions of structures are exaggerated to clarify the present invention. Terms such as first and second are used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another component. For example, the first component may be named the second component, and similarly, the second component may be named the first component, without departing from the scope of the present invention. A singular expression includes a plural expression unless the context clearly indicates otherwise.

[0068] In this application, the terms "comprise" or "have" and the like are used to specify the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, and are not to be understood as precluding the presence or possibility of addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof. In addition, when a part such as a layer, film, region, or plate is said to be "on" another part, it includes not only the case where it is "directly on" the other part, but also the case where there is another part between them.

[0069] In this specification, "-*" refers to the position of linkage.

[0070] In this specification, "substituted or unsubstituted" can mean substituted or unsubstituted with one or more substituents selected from the group consisting of a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a silyl group, a boron group, a phosphine oxide group, a phosphine sulfide group, an alkyl group, an alkenyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a hydrocarbon ring group, an aryl group, and a heterocyclic group. In addition, each of the exemplified substituents may be substituted or unsubstituted. For example, a biphenylyl group can be interpreted as an aryl group, or as a phenyl group substituted with a phenyl group.

[0071] In this specification, examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0072] In this specification, the alkyl group may be linear, branched or cyclic. The number of carbon atoms in the alkyl group is 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, i-butyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, i-pentyl, neopentyl, t-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl ...3,3-dimethylbutyl, n-pentyl, i-pentyl, neopentyl, Hexyl group, 2-butylhexyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-t-butylcyclohexyl group, n-heptyl group, 1-methylheptyl group, 2,2-dimethylheptyl group, 2-ethylheptyl group, 2-butylheptyl group, n-octyl group, t-octyl group, 2-ethyloctyl group, 2-butyloctyl group, 2-hexyloctyl group, 3,7-dimethyloctyl group, cyclooctyl group, n-nonyl group, n-decyl group, adamantyl group n-ethyl group, 2-ethyldecyl group, 2-butyldecyl group, 2-hexyldecyl group, 2-octyldecyl group, n-undecyl group, n-dodecyl group, 2-ethyldodecyl group, 2-butyldodecyl group, 2-hexyldodecyl group, 2-octyldodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, 2-ethylhexadecyl group, 2-butylhexadecyl group, 2-hexylhexadecyl group, 2-octylhexadecyl group, Examples of the alkyl group include, but are not limited to, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, 2-ethylicosyl, 2-butylicosyl, 2-hexylicosyl, 2-octylicosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, and n-triacontyl groups.

[0073] In the present specification, the hydrocarbon ring group may mean any functional group or substituent derived from an aliphatic hydrocarbon ring, or any functional group or substituent derived from an aromatic hydrocarbon ring. The hydrocarbon ring group may be a ring having no heteroatom and 5 to 20 ring carbon atoms. The hydrocarbon ring group may be a monocyclic ring, and for example, in the present specification, a hexagonal (six-membered) hydrocarbon ring may be a benzene ring.

[0074] In this specification, an aryl group means any functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. The number of ring carbon atoms of the aryl group may be 6 to 30, 6 to 20, or 6 to 15. Examples of aryl groups include, but are not limited to, a phenyl group, a naphthyl group, a fluorenyl group, an anthracenyl group, a phenanthryl group, a biphenylyl group, a terphenylyl group, a quaterphenylyl group, a quinquephenylyl group, a sexiphenylyl group, a triphenylenyl group, a pyrenylyl group, a benzofluoranthenyl group, and a chrysenyl group.

[0075] In this specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. Examples of fluorenyl groups that may be substituted are as follows. However, they are not limited to these.

[0076] [ka]

[0077] In this specification, the heteroaryl group may be a heteroaryl group containing one or more of the hetero elements O, N, P, Si, and S. The number of ring carbon atoms of the heteroaryl group is 2 to 30, or 2 to 20. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The polycyclic heteroaryl group may have, for example, a two-ring or three-ring structure. Examples of the heteroaryl group include a thiophenyl group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a triazolyl group, a pyridinyl group, a bipyridinyl group, a pyrimidinyl group, a triazinyl group, a triazolyl group, an acridyl group, a pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phenoxazinyl group, a butazinyl group, a pyridopyrimidinyl group, a pyridopyrazinyl group, a pyrazinopyrazinyl group, an isoquinolinyl group, an indolyl group, a carbazolyl group, Examples of such alkyl groups include, but are not limited to, an N-aryl group, an N-arylcarbazolyl group, an N-heteroarylcarbazolyl group, an N-alkylcarbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a benzothiophenyl group, a dibenzothiophenyl group, a thienothiophenyl group, a benzofuranyl group, a phenanthrolinyl group, a thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a phenothiazinyl group, a dibenzosilolyl group, and a dibenzofuranyl group.

[0078] In this specification, the silyl group includes an alkylsilyl group and an arylsilyl group. Examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.

[0079] In this specification, the oxy group may include an alkoxy group and an aryloxy group. The alkoxy group may be linear, branched, or cyclic. The number of carbon atoms in the alkoxy group is not particularly limited, but may be, for example, 1 to 20 or 1 to 10. Examples of the oxy group include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, octyloxy, nonyloxy, decyloxy, and benzyloxy.

[0080] In this specification, the number of carbon atoms of the amino group is not particularly limited, but may be 1 or more and 30 or less. The amino group may include an alkylamino group and an arylamino group. Examples of the amino group include, but are not limited to, a methylamino group, a dimethylamino group, a phenylamino group, a diphenylamino group, a naphthylamino group, a 9-methyl-anthracenylamino group, and a triphenylamino group.

[0081] Hereinafter, an organic electroluminescent device according to an embodiment of the present invention and an amine compound included therein will be described with reference to the drawings.

[0082] 1 to 3 are cross-sectional views each showing a schematic configuration of an organic electroluminescent device according to an embodiment of the present invention. Referring to Fig. 1 to Fig. 3, an organic electroluminescent device 10 according to an embodiment of the present invention may include a first electrode EL1, a hole transport region HTR, an emission layer EML, an electron transport region ETR, and a second electrode EL2, which are stacked in order.

[0083] The first electrode EL1 and the second electrode EL2 are disposed opposite to each other, and a plurality of organic layers may be disposed between the first electrode EL1 and the second electrode EL2. The plurality of organic layers may include a hole transport region HTR, an emitting layer EML, and an electron transport region ETR.

[0084] The organic electroluminescent device 10 of the embodiment may contain the amine compound of the embodiment described below in at least one of the organic layers disposed between the first electrode EL1 and the second electrode EL2. Specifically, the amine compound of the embodiment may be contained in the hole transport region HTR.

[0085] Fig. 2 is a cross-sectional view of an organic electroluminescent device 10 according to an embodiment in which the hole transport region HTR includes a hole injection layer HIL and a hole transport layer HTL, and the electron transport region ETR includes an electron injection layer EIL and an electron transport layer ETL, as compared with Fig. 1. Fig. 3 is a cross-sectional view of an organic electroluminescent device 10 according to an embodiment in which the hole transport region HTR includes a hole injection layer HIL, a hole transport layer HTL, and an electron blocking layer EBL, and the electron transport region ETR includes an electron injection layer EIL, an electron transport layer ETL, and a hole blocking layer HBL, as compared with Fig. 1. Meanwhile, in the organic electroluminescent device 10 according to an embodiment, the hole transport layer HTL may include an amine compound according to an embodiment described later.

[0086] Meanwhile, although not shown in the drawings, in the organic electroluminescent device 10 of one embodiment, the hole transport layer HTL may include a plurality of sub-hole transport layers (not shown), and among the sub-hole transport layers (not shown), the sub-hole transport layer adjacent to the emission layer EML may include an amine compound of one embodiment described later.

[0087] The first electrode EL1 has conductivity. The first electrode EL1 may be formed of a metal alloy or a conductive compound. The first electrode EL1 may be an anode. The first electrode EL1 may also be a pixel electrode. The first electrode EL1 may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode. When the first electrode EL1 is a transmissive electrode, the first electrode EL1 may include a transparent metal oxide, for example, ITO (indium tin oxide), IZO (indium zinc oxide), ZnO (zinc oxide), ITZO (indium tin zinc oxide), etc. When the first electrode EL1 is a semi-transmissive electrode or a reflective electrode, the first electrode EL1 may include Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, or a compound or mixture thereof (for example, a mixture of Ag and Mg). Alternatively, the first electrode EL1 may have a multi-layer structure including a reflective film or semi-transparent film formed of these materials and a transparent conductive film formed of ITO, IZO, ZnO, ITZO, etc. For example, the first electrode EL1 may have a three-layer structure of ITO / Ag / ITO, but is not limited thereto. The thickness of the first electrode EL1 may be about 100 nm to about 1000 nm, for example, about 100 nm to about 300 nm.

[0088] The hole transport region HTR is provided on the first electrode EL1. The hole transport region HTR may include at least one of a hole injection layer HIL, a hole transport layer HTL, a hole buffer layer (not shown), and an electron blocking layer EBL.

[0089] The hole transport region HTR can have a single layer of a single material, a single layer of a plurality of different materials, or a multilayer structure having a plurality of layers of a plurality of different materials.

[0090] For example, the hole transport region HTR may have a single layer structure of a hole injection layer HIL or a hole transport layer HTL, or a single layer structure of a hole injection material and a hole transport material. The hole transport region HTR may have a single layer structure of a plurality of different materials, or a structure of a hole injection layer HIL / hole transport layer HTL, a hole injection layer HIL / hole transport layer HTL / hole buffer layer (not shown), a hole injection layer HIL / hole buffer layer (not shown), a hole transport layer HTL / hole buffer layer, or a hole injection layer HIL / hole transport layer HTL / electron blocking layer EBL, which are stacked in this order from the first electrode EL1, but the embodiment is not limited thereto.

[0091] The hole transport region HTR may be formed using various methods such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) method, inkjet printing, laser printing, laser induced thermal imaging (LITI), etc.

[0092] In an embodiment of the organic electroluminescent device 10, at least one of the organic layers between the first electrode EL1 and the second electrode EL2 may contain an amine compound represented by the following Chemical Formula 1. In an embodiment of the organic electroluminescent device 10, the hole transport region HTR may contain an amine compound represented by the following Chemical Formula 1.

[0093] [ka]

[0094] In Chemical Formula 1, Ar 1 and Ar 2are each independently a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, and L is a single bond, a substituted or unsubstituted arylene group having from 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having from 2 to 30 ring carbon atoms.

[0095] In Chemical Formula 1, Ar 1 and Ar 2 may each independently be an aryl group having 6 to 40 ring carbon atoms and substituted or unsubstituted with at least one substituent selected from a halogen atom, a cyano group, an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, an aryloxy group having from 1 to 20 carbon atoms, an aryl group having from 6 to 30 carbon atoms, a triarylsilyl group having from 18 to 50 carbon atoms, and an adamantyl group.

[0096] JPEG0007679171000025.jpg71154

[0097] Ar 1 and Ar 2 may each independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted pyridinyl group.

[0098] Specifically, Ar 1 and Ar 2may each independently be an unsubstituted phenyl group, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a phenyl group, a phenyl group substituted with a deuterium atom, a phenyl group substituted with a halogen atom, a phenyl group substituted with an aryloxy group, a phenyl group substituted with an adamantyl group, an unsubstituted biphenylyl group, a biphenylyl group substituted with a phenyl group, an unsubstituted terphenylyl group, an unsubstituted phenanthrenyl group, an unsubstituted triphenylenyl group, an unsubstituted naphthyl group, a naphthyl group substituted with a phenyl group, an unsubstituted fluorenyl group, a fluorenyl group substituted with a phenyl group, an unsubstituted dibenzofuranyl group, a dibenzofuranyl group substituted with a phenyl group, a substituted or unsubstituted dibenzothiophenyl group, a dibenzothiophenyl group substituted with a phenyl group, or an unsubstituted pyridinyl group. However, the embodiment is not limited thereto.

[0099] In Chemical Formula 1, Ar 1 and Ar 2 may be the same or different from each other.

[0100] In Chemical Formula 1, L may be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylylene group, a substituted or unsubstituted terphenylylene group, a substituted or unsubstituted phenanthrenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted dibenzofuranylene group.

[0101] For example, in Formula 1, L may be a single bond, an unsubstituted phenylene group, an unsubstituted biphenylylene group, an unsubstituted terphenylylene group, a substituted or unsubstituted phenanthrenylene group, an unsubstituted naphthylene group, or an unsubstituted dibenzofuranylene group, but the embodiment is not limited thereto.

[0102] In Chemical Formula 1, HT is represented by the following Chemical Formula 2. That is, the amine compound of one embodiment represented by Chemical Formula 1 may contain a pyridoindole moiety represented by the following Chemical Formula 2.

[0103] [ka]

[0104] In Chemical Formula 2, R 1 ~R 9 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms. 1 ~R 9 may be the same or at least one may be different from each other.

[0105] R 2 ~R 9 Two adjacent substituents among the above may be bonded to each other to form a hexagonal hydrocarbon ring. The hexagonal hydrocarbon ring formed by bonding two substituents to each other may be an aromatic ring and may not contain a heteroatom. In one embodiment, the hexagonal hydrocarbon ring may be a benzene ring.

[0106] In Chemical Formula 2, R 2 ~R 9 Any one of the remaining substituents, excluding those that are bonded together to form a hexagonal hydrocarbon ring, or two substituents that are bonded together to form a hexagonal hydrocarbon ring, can be bonded to L in Chemical Formula 1. 2 ~R 9 The remainder of these groups, excluding the portions which bond to each other to form a hexagonal hydrocarbon ring and the portion which bonds to L in Chemical Formula 1, may be hydrogen atoms.

[0107] In Chemical Formula 2, R 2 and R 3, R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 At least one pair of R can be bonded to each other to form a hexagonal hydrocarbon ring. 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 One or two pairs of these can be linked together to form a hexagonal hydrocarbon ring.

[0108] R 2 ~R 9 Any one of the groups that does not form a hexagonal hydrocarbon ring can be bonded to L in Chemical Formula 1. 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 The hexagonal hydrocarbon ring portion formed by bonding together can be bonded to L in Chemical Formula 1. 2 and R 3 , R 3 and R 4 , and R 4 and R 5 When at least one pair of is bonded to each other to form a hexagonal hydrocarbon ring, R 8 may be a hydrogen atom.

[0109] That is, in one embodiment of the amine compound, R 2 ~R9 Of which R 2 and R 3 , R 3 and R 4 , and R 4 and R 5 When at least one pair of these is bonded to each other to form a hexagonal hydrocarbon ring, R 8 The case where the group is bonded to L in Chemical Formula 1 at the position of

[0110] In Chemical Formula 2, R 1 may be a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms. 1 may be an unsubstituted phenyl group, an unsubstituted naphthyl group, an unsubstituted biphenylyl group, an unsubstituted dibenzofuranyl group, or an unsubstituted dibenzothiophenyl group, but the present embodiment is not limited thereto.

[0111] In Chemical Formula 2, R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 At least one pair of these can be bonded to each other to form a hexagonal hydrocarbon ring represented by the following chemical formula 3.

[0112] [ka]

[0113] In Chemical Formula 3, R 10 ~R 13may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms. On the other hand, in chemical formula 3, * is a moiety that bonds to chemical formula 2.

[0114] That is, in Chemical Formula 2, R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 At least one pair of R in Formula 2 can be bonded to each other to form a benzene ring. 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 At least one pair of these can be linked together to form a benzene ring fused to the pyridoindole moiety.

[0115] With reference to Chemical Formulae 1 to 3, the amine compound of one embodiment may have a fused ring of 4 to 5 rings containing a pyridoindole moiety as a substituent. The amine compound of one embodiment may be a monoamine compound having a fused ring of 4 to 5 rings containing a pyridoindole moiety as a substituent.

[0116] JPEG0007679171000028.jpg61151

[0117] The amine compound of one embodiment can be used as a material for an organic electroluminescence device that further improves the device life by introducing a pyridoindole moiety having excellent heat / charge resistance into an arylamine moiety having a long life characteristic, thereby improving resistance to high temperatures and charges. In addition, the nitrogen atom contained in the pyridoindole moiety further improves the hole transport ability of the entire molecule of the amine compound, thereby increasing the probability of recombination of holes and electrons in the light-emitting layer of the organic electroluminescence device, so that the amine compound of one embodiment can exhibit improved luminous efficiency of the organic electroluminescence device.

[0118] In Chemical Formula 2, R 2 and R 3 , R 3 and R 4 , R 4 and R 5 One or two pairs selected from may form a hexagonal hydrocarbon ring represented by Chemical Formula 3. That is, in Chemical Formula 2, R 2 and R 3 , R 3 and R 4 , R 4 and R 5 form a hexagonal hydrocarbon ring, or R 2 and R 3 , and R 4 and R 5 may each form a hexagonal hydrocarbon ring.

[0119] Chemical Formula 2 can be represented by any one of the following Chemical Formulas 2-1a to 2-1d.

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] Chemical formulas 2-1a to 2-1c are each R 2 and R 3 , R 3 and R 4 , and R 4 and R 5 The chemical formula 2-1d shows that one pair of R 2 and R 3 and R 4 and R 5 This shows that two pairs of these form a hexagonal hydrocarbon ring.

[0125] In Chemical Formula 2-1d, R 20 ~R 23 , and R 30 ~R 33 R may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms. 20 ~R 23 , and R 30 ~R 33 may be the same or at least one may be different from each other.

[0126] In addition, in Chemical Formula 2-1a to Chemical Formula 2-1d, R 1 ~R 9 The same content as that described in Chemical Formula 2 may be applied to R 10 ~R 13 The same content as that described in Chemical Formula 3 may be applied to this.

[0127] In Chemical Formula 2-1a to Chemical Formula 2-1d, R 8may be a hydrogen atom. 8 is not bonded to L in Chemical Formula 1.

[0128] On the other hand, the position of the compound 2-1a that is bonded to L in the compound 1 is R 4 , R 5 , R 6 , R 7 , R 9 , R 10 ~R 13 In Chemical Formula 2-1b, the position at which L in Chemical Formula 1 is bonded may be any one of R 2 , R 5 , R 6 , R 7 , R 9 , R 10 ~R 13 In Chemical Formula 2-1c, the position at which L in Chemical Formula 1 is bonded may be any one of R 2 , R 3 , R 6 , R 7 , R 9 , R 10 ~R 13 In Chemical Formula 2-1d, the position at which L in Chemical Formula 1 is bonded may be any one of R 6 , R 7 , R 9 , R 20 ~R 23 , and R 30 ~R 33 That is, the amine compounds represented by Chemical Formulae 2-1a to 2-1d may be any one of R 1 and R 8 does not bond to L in chemical formula 1.

[0129] Chemical formulae 2-1a to 2-1c show the case where one benzene ring is condensed to pyridoindole, and "HT" in chemical formula 1 forms a fused ring of four rings. Chemical formula 2-1d shows the case where two benzene rings are condensed to pyridoindole, and "HT" in chemical formula 1 forms a fused ring of five rings.

[0130] On the other hand, Chemical Formula 2-1a to Chemical Formula 2-1d show cases where an aromatic hydrocarbon group is condensed to the pyridine portion of the pyridoindole moiety.

[0131] In addition, in Chemical Formula 2, R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 One or two pairs selected from may form a hexagonal hydrocarbon ring represented by Chemical Formula 3. That is, in Chemical Formula 2, R 6 and R 7 , R 7 and R 8 , and R 8 and R 9 form a hexagonal hydrocarbon ring, or R 6 and R 7 , and R 8 and R 9 may each form a hexagonal hydrocarbon ring.

[0132] Chemical Formula 2 can be represented by any one of the following Chemical Formulas 2-2a to 2-2d.

[0133] [ka]

[0134] [ka]

[0135] [ka]

[0136] [ka]

[0137] Chemical formulas 2-2a to 2-2c are R6 and R 7 , R 7 and R 8 , and R 8 and R 9 The formula 2-2d shows that a pair of R forms a hexagonal hydrocarbon ring. 6 and R 7 and R 8 and R 9 This shows that two pairs of these form a hexagonal hydrocarbon ring.

[0138] In the chemical formula 2-2d, R 20 ~R 23 , and R 30 ~R 33 may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms.

[0139] In addition, in Chemical Formula 2-2a to Chemical Formula 2-2d, R 1 ~R 9 The same content as that described in Chemical Formula 2 may be applied to R 10 ~R 13 The same content as that described in Chemical Formula 3 may be applied to this.

[0140] In Chemical Formula 2-2a, the position where L in Chemical Formula 1 is bonded is R 2 ~R 5 , R 8 , R 9 , R 10 ~R 13 In Chemical Formula 2-2b, the position at which L in Chemical Formula 1 is bonded may be any one of R 2 ~R 5 , R 6 , R 9 , R 10 ~R 13 In Chemical Formula 2-2c, the position at which L in Chemical Formula 1 is bonded may be any one of R 2~R 5 , R 6 , R 7 , R 10 ~R 13 In Chemical Formula 2-2d, the position at which L in Chemical Formula 1 is bonded may be any one of R 2 ~R 5 , R 20 ~R 23 , and R 30 ~R 33 It may be any one of the above.

[0141] Chemical formulae 2-2a to 2-2c show the case where one benzene ring is condensed to pyridoindole, and "HT" in chemical formula 1 forms a fused ring of four rings. Chemical formula 2-2d shows the case where two benzene rings are condensed to pyridoindole, and "HT" in chemical formula 1 forms a fused ring of five rings.

[0142] On the other hand, Chemical Formula 2-2a to Chemical Formula 2-2d show the cases where an aromatic hydrocarbon group is condensed to the indole part of the pyridoindole moiety.

[0143] In Chemical Formulae 2-1a to 2-1d and Chemical Formulae 2-2a to 2-2d, R 1 is an unsubstituted phenyl group, and R 2 ~R 13 , R 20 ~R 23 , and R 30 ~R 33 All of the moieties not bonded to Chemical Formula 1 may be hydrogen atoms.

[0144] The amine compound of one embodiment represented by Chemical Formula 1 may be any one of the compounds represented by the following Compound Group 1 and Compound Group 2. That is, the organic electroluminescent device of one embodiment may contain at least one of the compounds represented by the following Compound Group 1 and Compound Group 2 in at least one organic layer.

[0145] Compound group 1 includes amine compounds in which the HT portion of chemical formula 1 is represented by any one of chemical formulas 2-1a to 2-1d. Compound group 2 includes amine compounds in which the HT portion of chemical formula 1 is represented by any one of chemical formulas 2-2a to 2-2d.

[0146] [Compound group 1] [ka] JPEG0007679171000038.jpg37149JPEG0007679171000039.jpg33153JPEG0007679171000040.jpg79153 JPEG0007679171000041.jpg74152 JPEG0007679171000042.jpg65153JPEG0007679171000043.jpg72153 JPEG0007679171000044.jpg74153 JPEG0007679171000045.jpg65152JPEG0007679171000046.jpg67153 JPEG0007679171000047.jpg31153 JPEG0007679171000048.jpg68153 JPEG0007679171000049.jpg65153 JPEG0007679171000050.jpg64153 JPEG0007679171000051.jpg78152 JPEG0007679171000052.jpg76153 JPEG0007679171000053.jpg80153 JPEG0007679171000054.jpg74153 JPEG0007679171000055.jpg66152 JPEG0007679171000056.jpg67153 JPEG0007679171000057.jpg75152 JPEG0007679171000058.jpg72153 JPEG0007679171000059.jpg69153 JPEG0007679171000060.jpg68152 JPEG0007679171000061.jpg66153 JPEG0007679171000062.jpg66153 JPEG0007679171000063.jpg2983 JPEG0007679171000064.jpg76153 JPEG0007679171000065.jpg68153 JPEG0007679171000066.jpg68153 JPEG0007679171000067.jpg65153 JPEG0007679171000068.jpg69153 JPEG0007679171000069.jpg63153 JPEG0007679171000070.jpg75152 JPEG0007679171000071.jpg74153 JPEG0007679171000072.jpg66148 JPEG0007679171000073.jpg68152 JPEG0007679171000074.jpg65153 JPEG0007679171000075.jpg99153 JPEG0007679171000076.jpg76153 JPEG0007679171000077.jpg68153 JPEG0007679171000078.jpg69153 JPEG0007679171000079.jpg67153 JPEG0007679171000080.jpg68153 JPEG0007679171000081.jpg64153 JPEG0007679171000082.jpg36153 JPEG0007679171000083.jpg70158 JPEG0007679171000084.jpg72158 JPEG0007679171000085.jpg68153 JPEG0007679171000086.jpg67153 JPEG0007679171000087.jpg63153 JPEG0007679171000088.jpg69153 JPEG0007679171000089.jpg2884

[0147] [Compound Group 2]

change

[0148] Compounds A1 to A97 in compound group 1 are R 2 and R 3 are bonded to each other to form a hexagonal hydrocarbon ring represented by chemical formula 3. Compounds B1 to B97 in compound group 1 correspond to those in which R 3 and R 4 are bonded to each other to form a hexagonal hydrocarbon ring represented by chemical formula 3. Compounds C1 to C97 in compound group 1 correspond to those in which R 4 and R 5 are bonded to each other to form a hexagonal hydrocarbon ring represented by chemical formula 3. Compounds D1 to D100 in compound group 1 correspond to those in which R 2 and R 3 and R 4 and R 5 are bonded to each other to form a hexagonal hydrocarbon ring represented by chemical formula 3.

[0149] Compounds E1 to E100 in compound group 2 are R 8 and R 9 are bonded to each other to form a hexagonal hydrocarbon ring represented by chemical formula 3. Compounds F1 to F100 in compound group 2 correspond to those in which R 6 and R 7 and R 8 and R 9 are bonded to each other to form a hexagonal hydrocarbon ring represented by chemical formula 3.

[0150] The amine compound according to the embodiment described above contains a fused ring containing a pyridoindole moiety and can be used as a material for an organic electroluminescent device that exhibits good heat / charge resistance and excellent luminous efficiency. In particular, in the pyridoindole moiety represented by Chemical Formula 2, R 8 The position of R in the pyridoindole portion represented by Chemical Formula 2 can be stable without being substituted by an arylamine portion. 1 When the position is not substituted with an arylamine moiety and is used as a material for an organic electroluminescent device, it can improve the efficiency and life characteristics of the organic electroluminescent device.

[0151] [ka]

[0152] 1 to 3, the hole transport region HTR may contain one or more of the amine compounds represented by compound group 1 and compound group 2. Meanwhile, the hole transport region HTR may further contain a known substance in addition to the amine compound of compound group 1 or compound group 2.

[0153] The hole transport region HTR of the organic electroluminescent device 10 according to an embodiment may include the amine compound according to the embodiment described above. When the hole transport region HTR is composed of multiple organic layers, the amine compound according to the embodiment may be included in an organic layer adjacent to the emitting layer EML.

[0154] For example, the amine compound of the embodiment may be included in the hole transport layer HTL of the hole transport region HTR. In addition, when the hole transport layer HTL includes a plurality of organic layers, the amine compound of the embodiment may be included in a layer of the plurality of organic layers adjacent to the light emitting layer EML.

[0155] Specifically, when the hole transport region HTR of the organic electroluminescent device 10 of an embodiment includes a hole injection layer HIL and a hole transport layer HTL, the amine compound of an embodiment may be included in the hole transport layer HTL, and when the hole transport region HTR of the organic electroluminescent device of an embodiment includes a hole injection layer HIL, a hole transport layer HTL, and an electron blocking layer EBL, the amine compound of an embodiment may be included in the electron blocking layer EBL.

[0156] When the hole transport layer HTL of the organic electroluminescent device 10 of an embodiment includes the amine compound of an embodiment, the hole injection layer HIL may include a known hole injection material. For example, the hole injection layer HIL may be formed of a triphenylamine-containing polyether ketone (TPAPEK), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (PPBI), N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-phenyl-4,4'-diamine (DNTPD), a phthalocyanine compound such as copper phthalocyanine, 4,4',4''-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (NPB), N,N'-bis(1-naphthyl)-N,N'-diphenyl-4,4'-diamine (α-NPD), 4,4 ',4''-tris{N,N-diphenylamino}triphenylamine (TDATA), 4,4',4''-tris(N,N-2-naphthylphenylamino)triphenylamine (2-TNATA), polyaniline / dodecylbenzenesulfonic acid (PANI / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (PANI / CSA), polyaniline / poly(4-styrenesulfonate) (PANI / PSS), or HAT-CN (dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile), etc. However, the embodiments are not limited thereto.

[0157] Meanwhile, the hole transport layer HTL of the organic electroluminescent device 10 of the embodiment may further contain a known hole transport material in addition to the amine compound of the embodiment. For example, the hole transport layer HTL may contain a carbazole derivative such as 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N-phenylcarbazole, or polyvinylcarbazole, a fluorine derivative, a triphenylamine derivative such as TPD (N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine) or TCTA (4,4',4''-tris(N-carbazolyl)triphenylamine), NPB (N,N'-di(naphthalene-l-yl)-N,N'-diphenyl-benzidine), TAPC (4,4'-Cyclohexylidene bis[N,N-bis(4-methylphenyl)benzeneamine]), HMTPD (4,4'-Bis[N,N'-(3-tolyl)amino]-3,3'-dimethylbiphenyl), mCP (1,3-Bis(N-carbazolyl)benzene), etc. However, the embodiment is not limited thereto.

[0158] As described above, in the organic electroluminescent device 10 according to an embodiment, the hole transport region HTR may further include at least one of a hole buffer layer and an electron blocking layer EBL in addition to the hole injection layer HIL and the hole transport layer HTL. The hole buffer layer may increase light emission efficiency by compensating for a resonance distance according to the wavelength of light emitted from the emission layer EML. The material contained in the hole buffer layer may be a material that may be contained in the hole transport region HTR.

[0159] On the other hand, when the hole transport region HTR further includes an electron blocking layer EBL disposed between the hole transport layer HTL and the light emitting layer EML, the electron blocking layer EBL can serve to prevent electron injection from the electron transport region ETR to the hole transport region HTR.

[0160] In the organic electroluminescent device 10 according to an embodiment, when the hole transport region HTR includes an electron blocking layer EBL, the electron blocking layer EBL may include the amine compound according to an embodiment. The electron blocking layer EBL may further include a common material known in the art in addition to the amine compound according to an embodiment. The electron blocking layer EBL may contain, for example, a carbazole derivative such as N-phenylcarbazole or polyvinylcarbazole, a fluorine derivative, a triphenylamine derivative such as TPD (N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine) or TCTA (4,4',4''-tris(N-carbazolyl)triphenylamine), NPD (N,N'-di(naphthalene-l-yl)-N,N'-diplienyl-benzidine), TAPC (4,4'-Cyclohexylidene bis[N,N-bis(4-methylphenyl)benzenamine]), HMTPD (4,4'-Bis[N,N'-(3-tolyl)amino]-3,3'-dimethylbiphenyl), or mCP.

[0161] That is, when the hole transport region HTR in the organic electroluminescent device 10 according to an embodiment is a single layer, the hole transport region HTR may contain the amine compound according to the embodiment described above. In this case, the hole transport region HTR may further contain a known hole injection material or a known hole transport material.

[0162] In addition, in the organic electroluminescent device 10 of one embodiment, when the hole transport region HTR includes a plurality of layers, at least one of the layers included in the hole transport region HTR may contain the amine compound of the above-mentioned embodiment. For example, the layer adjacent to the emitting layer EML among the layers included in the hole transport region HTR may contain the amine compound of the above-mentioned embodiment. On the other hand, among the layers, a layer not containing the amine compound of the embodiment may contain a known hole injection material or a known hole transport material. Also, the layer containing the amine compound of the embodiment may further contain a known hole injection material or a known hole transport material.

[0163] The thickness of the hole transport region HTR may be about 10 nm to about 1000 nm, for example, about 10 nm to about 500 nm. The thickness of the hole injection layer HIL may be, for example, about 3 nm to about 100 nm, and the thickness of the hole transport layer HTL may be about 3 nm to about 100 nm. For example, the thickness of the electron blocking layer EBL may be about 1 nm to about 100 nm. When the thicknesses of the hole transport region HTR, the hole injection layer HIL, the hole transport layer HTL, and the electron blocking layer EBL satisfy the above-mentioned ranges, a satisfactory degree of hole transport properties can be obtained without a substantial increase in driving voltage.

[0164] In addition to the above-mentioned materials, the hole transport region HTR may further include a charge generating material to improve conductivity. The charge generating material may be uniformly or non-uniformly distributed in the hole transport region HTR. The charge generating material may be, for example, a p-dopant. The p-dopant may be one of, but is not limited to, a quinone derivative, a metal oxide, and a cyano group-containing compound. For example, non-limiting examples of the p-dopant include, but are not limited to, quinone derivatives such as TCNQ (tetracyanoquinodimethane) and F4-TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), and metal oxides such as tungsten oxide and molybdenum oxide.

[0165] The light-emitting layer EML is provided on the hole-transporting region HTR. The thickness of the light-emitting layer EML may be, for example, about 10 nm to about 30 nm. The light-emitting layer EML may have a single layer structure made of a single material, a single layer structure made of a plurality of different materials, or a multilayer structure having a plurality of layers made of a plurality of different materials.

[0166] The light-emitting layer EML may emit any one of red light, green light, blue light, white light, yellow light, and cyan light. The light-emitting layer EML may include a fluorescent or phosphorescent light-emitting material.

[0167] In the organic electroluminescent device 10 according to an embodiment, the light-emitting layer EML may include an anthracene derivative, a pyrene derivative, a fluoranthene derivative, a chrysene derivative, a dihydrobenzanthracene derivative, or a triphenylene derivative. Specifically, the light-emitting layer EML may include an anthracene derivative or a pyrene derivative.

[0168] The light emitting layer EML may contain an anthracene derivative represented by the following chemical formula 4.

[0169] [ka]

[0170] In Chemical Formula 4, R 51 ~R 60 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkyl group having from 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having from 2 to 30 ring carbon atoms, or may be bonded to an adjacent group to form a ring. 51 ~R 60 may be bonded to adjacent groups to form a saturated or unsaturated hydrocarbon ring.

[0171] In Chemical Formula 4, c and d may each independently be an integer of 0 or more and 5 or less.

[0172] Chemical formula 4 may be represented by any one of the following compounds 4-1 to 4-6.

[0173] [ka] JPEG0007679171000119.jpg33135

[0174] In the organic electroluminescent device 10 according to one embodiment shown in FIGS. 1 to 3, the emission layer EML may include a host and a dopant, and the emission layer EML may include the compound represented by the above-mentioned Chemical Formula 4 as a host material.

[0175] The light-emitting layer EML may further include a common material known in the art as a host material. For example, the light-emitting layer EML may include at least one of DPEPO (Bis[2-(diphenylphosphino)phenyl]ether oxide), CBP (4,4'-Bis(carbazol-9-yl)biphenyl), mCP (1,3-Bis(carbazol-9-yl)benzene), PPF (2,8-Bis(diphenylphosphoryl)dibenzo[b,d]furan), TcTa (4,4',4''-Tris(carbazol-9-yl)-triphenylamine), and TPBi (1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene) as a host material. However, the light-emitting layer EML may include, for example, Alq 3(tris(8-hydroxyquinolino)aluminum), CBP(4,4’-bis(N-carbazolyl)-1,1’-biphenyl), PVK(poly(n-vinylcabazole)), ADN(9,10-di(naphthalene-2-yl)anthracene), TCTA(4,4’,4’’-Tris(carbazol-9-yl)-triphenylamine), TPBi(1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene), TBADN(3-tert-butyl-9,10-di(naphth-2-yl)anthracene), DSA(distyrylarylene), CDBP(4,4’-bis(9-carbazolyl)-2,2’-dimethyl-biphenyl), MADN(2-Methyl-9,10-bis(naphthalen-2-yl)anthracene), DPEPO(bis[2-(diphenylphosphino)phenyl]ether oxide), CP1(Hexaphenyl cyclotriphosphazene), UGH2(1,4-Bis(triphenylsilyl)benzene), DPSiO 3 (Hexaphenylcyclotrisiloxane), DPSiO 4 (Octaphenylcyclotetra siloxane), PPF(2,8-Bis(diphenylphosphoryl)dibenzofuran), etc. can be used as host materials.

[0176] In one embodiment, the light-emitting layer EML may be formed using a known dopant material such as a styryl derivative (e.g., 1,4-bis[2-(3-N-ethylcarbazoryl)vinyl]benzene (BCzVB), 4-(di-p-tolylamino)-4′-[(di-p-tolylamino)styryl]stilbene (DPAVB), N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalen-2-yl)vinyl )phenyl)-N-phenylbenzenamine (N-BDAVBi), perylene and its derivatives (e.g., 2,5,8,11-Tetra-t-butylperylene (TBP)), pyrene and its derivatives (e.g., 2,5,8,11-Tetra-t-butylperylene (TBP) such as 1,1-dipyrene, 1,4-dipyrenylbenzene, and 1,4-Bis(N,N-Diphenylamino)pyrene) may be included.

[0177] When the emitting layer EML emits red light, the emitting layer EML may further include a fluorescent material including, for example, PBD:Eu(DBM) 3 (Phen) (tris(dibenzoylmethanato)phenanthoroline europium) or perylene. When the emitting layer EML emits red light, the dopant contained in the emitting layer EML can be selected from, for example, a metal complex or an organometallic complex such as PIQIr(acac) (bis(1-phenylisoquinoline)acetylacetonate iridium), PQIr(acac) (bis(1-phenylquinoline)acetylacetonate iridium), PQIr (tris(1-phenylquinoline)iridium) and PtOEP (octaethylporphyrin platinum), rubrene and its derivatives, and 4-dicyanomethylene-2-(p-dimethylaminostyryl)-6-methyl-4H-pyran (DCM) and its derivatives.

[0178] When the emitting layer EML emits green light, the emitting layer EML may further include a fluorescent material including, for example, Alq3 (tris(8-hydroxyquinolino)aluminum). When the emitting layer EML emits green light, the dopant included in the emitting layer EML may be selected from, for example, a metal complex compound or an organometallic complex such as Ir(ppy)3 (fac-tris(2-phenylpyridine)iridium), and coumarin and its derivatives.

[0179] When the emitting layer EML emits blue light, the emitting layer EML may further include a fluorescent material including any one selected from the group consisting of spiro-DPVBi, spiro-6P, DSB (distyryl-benzene), DSA (distyryl-arylene), a PFO (polyfluorene)-based polymer, and a PPV (poly(p-phenylene vinylene)-based polymer. When the emitting layer EML emits blue light, a dopant included in the emitting layer EML may be selected from a metal complex compound or an organometallic complex such as (4,6-F2ppy)2Irpic, perylene, and its derivatives.

[0180] Meanwhile, the light-emitting layer EML of the organic electroluminescent device 10 according to an embodiment may emit blue light or green light. The light-emitting layer EML may emit blue light in a wavelength region of 450 nm to 480 nm, or may emit green light in a wavelength region of 490 nm to 560 nm.

[0181] In one embodiment of the organic electroluminescent device 10, an electron transport region ETR is provided on the emitting layer EML. The electron transport region ETR may include, but is not limited to, at least one of a hole blocking layer HBL, an electron transport layer ETL, and an electron injection layer EIL.

[0182] The electron transport region ETR can have a single layer of a single material, a single layer of multiple different materials, or a multi-layer structure having multiple layers of multiple different materials.

[0183] For example, the electron transport region ETR may have a single-layer structure of an electron injection layer EIL or an electron transport layer ETL, or may have a single-layer structure made of an electron injection material and an electron transport material. The electron transport region ETR may have a single-layer structure made of a plurality of different materials, or may have a structure of an electron transport layer ETL / electron injection layer EIL or a hole blocking layer HBL / electron transport layer ETL / electron injection layer EIL stacked in this order from the light emitting layer EML, but is not limited thereto. The thickness of the electron transport region ETR may be, for example, about 10 nm to about 150 nm.

[0184] The electron transport region ETR may be formed by using various methods such as vacuum deposition, spin coating, casting, LB method, inkjet printing, laser printing, and laser thermal transfer.

[0185] In the case where the electron transport region ETR includes the electron transport layer ETL, for example, the electron transport region ETR may be formed of Alq3 (Tris(8-hydroxyquinolinato)aluminum), 1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene, 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine, 2-(4-(N-phenylbenzoimidazolyl-1-ylphenyl)-9,10-dinaphthylanthracene, TPBi (1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene), BCP (2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-Diphenyl-1,10-phenanthroline), or the like. line), TAZ (3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole), NTAZ (4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole), tBu-PBD (2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole), BAlq (Bis(2-methyl-8-quinolinolato-N1,O8)-(1,1'-biphenyl-4-olato)aluminum), Bebq2 (berylliumbis(benzoquinolin-10-olate), ADN (9,10-di(naphthalene-2-yl)anthracene), and mixtures thereof, but embodiments are not limited thereto.

[0186] When the electron transport region ETR includes the electron transport layer ETL, the thickness of the electron transport layer ETL may be about 10 nm to about 100 nm, for example, about 15 nm to about 50 nm. When the thickness of the electron transport layer ETL satisfies the above-mentioned range, a satisfactory level of electron transport properties can be obtained without a substantial increase in driving voltage.

[0187] When the electron transport region ETR includes an electron injection layer EIL, the electron transport region ETR may be, for example, LiF, LiQ (8-hydroxyquinolinnolata-lithium), Li 2 Lanthanide metals such as O, BaO, NaCl, CsF, and Yb, or metal halides such as RbCl, RbI, and KI may be used, but the embodiment is not limited thereto. Also, the electron injection layer EIL may be made of a material in which an electron transport material and an insulating organo metal salt are mixed. The organo metal salt may be a material having an energy band gap of about 4 eV or more. Specifically, for example, the organo metal salt may include metal acetate, metal benzoate, metal acetoacetate, metal acetylacetonate, or metal stearate.

[0188] When the electron transport region ETR includes an electron injection layer EIL, the thickness of the electron injection layer EIL may be about 0.1 nm to about 10 nm, or about 0.3 nm to about 9 nm. When the thickness of the electron injection layer EIL satisfies the above-mentioned range, a satisfactory level of electron injection characteristics can be obtained without a substantial increase in driving voltage.

[0189] The electron transport region ETR may include a hole blocking layer HBL as described above. The hole blocking layer HBL may include, for example, at least one of BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) and Bphen (4,7-diphenyl-1,10-phenanthroline), but is not limited thereto.

[0190] The second electrode EL2 is provided on the electron transport region ETR. The second electrode EL2 has electrical conductivity. The second electrode EL2 may be formed of a metal alloy or a conductive compound. The second electrode EL2 may be a cathode. The second electrode EL2 may be a transmissive electrode, a semi-transmissive electrode or a reflective electrode. When the second electrode EL2 is a transmissive electrode, the second electrode EL2 may be made of a transparent metal oxide, such as ITO, IZO, ZnO, ITZO, etc.

[0191] When the second electrode EL2 is a semi-transmissive electrode or a reflective electrode, the second electrode EL2 may include Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, or a compound or mixture thereof (e.g., a mixture of Ag and Mg). Alternatively, the second electrode EL2 may have a multi-layer structure including a reflective film or semi-transmissive film formed of the exemplified materials and a transparent conductive film formed of ITO, IZO, ZnO, ITZO, or the like.

[0192] Although not shown, the second electrode EL2 may be connected to an auxiliary electrode. When the second electrode EL2 is connected to the auxiliary electrode, the resistance of the second electrode EL2 can be reduced.

[0193] In the organic electroluminescent device 10, when a voltage is applied to the first electrode EL1 and the second electrode EL2, holes injected from the first electrode EL1 move to the emission layer EML via the hole transport region HTR, and electrons injected from the second electrode EL2 move to the emission layer EML via the electron transport region ETR. The electrons and holes recombine in the emission layer EML to generate excitons, and the excitons emit light as they fall from the excited state to the ground state.

[0194] When the organic electroluminescent device 10 is a front emission type, the first electrode EL1 may be a reflective electrode, and the second electrode EL2 may be a transmissive electrode or a semi-transmissive electrode. When the organic electroluminescent device 10 is a back emission type, the first electrode EL1 may be a transmissive electrode or a semi-transmissive electrode, and the second electrode EL2 may be a reflective electrode.

[0195] The amine compound of the embodiment described above may be included as a material for the organic electroluminescent device 10 of the embodiment. The organic electroluminescent device 10 according to the embodiment of the present invention may include the amine compound in at least one organic layer disposed between the first electrode EL1 and the second electrode EL2 or in a cap layer (not shown) disposed on the second electrode EL2.

[0196] Specifically, the organic electroluminescent device 10 according to an embodiment of the present invention includes the above-mentioned amine compound in at least one organic layer disposed between the first electrode EL1 and the second electrode EL2, and thus exhibits excellent luminous efficiency and high reliability. In particular, the organic electroluminescent device 10 according to an embodiment of the present invention includes the above-mentioned amine compound in the hole transport region HTR, and thus exhibits high luminous efficiency and improved life characteristics.

[0197] Specifically, the organic electroluminescent device of the embodiment includes the amine compound of the embodiment in an organic layer adjacent to the light-emitting layer among a plurality of organic layers in the hole transport region, so that the hole transport region can suppress the movement of electrons while maintaining high hole transport capability, thereby exhibiting improved luminous efficiency.

[0198] In particular, in one embodiment, an amine compound including both a pyridoindole moiety and an arylamine moiety includes an amine compound including both a pyridoindole moiety and an arylamine moiety in a hole transport region, so that the amine compound has good reliability, and thus the organic electroluminescent device of the embodiment can exhibit good life characteristics. In addition, the nitrogen atom included in the pyridoindole moiety further improves the hole transport ability of the entire amine compound molecule, and increases the probability of recombination of holes and electrons in the light emitting layer of the organic electroluminescent device, so that the amine compound of the embodiment can exhibit improved luminous efficiency. EXAMPLES

[0199] Hereinafter, an amine compound according to an embodiment of the present invention and an organic electroluminescent device including the amine compound of the embodiment will be described in detail with reference to examples and comparative examples. Note that the following examples are merely illustrative examples for aiding understanding of the present invention, and the scope of the present invention is not limited thereto.

[0200] [Example] 1. Synthesis of amine compounds First, regarding the synthesis method of the amine compounds according to the present embodiment, the synthesis methods of Compound A1, Compound A28, Compound A57, Compound B36, Compound B46, Compound C47, Compound C87, Compound D47, Compound D60, Compound D74, Compound E6, Compound E25, Compound E55, Compound E73, Compound E89, Compound F21, Compound F63, and Compound F82 in Compound Group 1 will be illustrated and specifically described. Note that the synthesis method of the amine compounds described below is one embodiment, and the synthesis method of the amine compounds according to the embodiment of the present invention is not limited to the following embodiment.

[0201] (Synthesis of Compound A1) The amine compound A1 according to one embodiment can be synthesized, for example, according to the following reaction scheme 1.

[0202] [Reaction Scheme 1] [ka]

[0203] <Synthesis of intermediate IM-1> Under an argon (Ar) atmosphere, 20.00 g (103.5 mmol) of 3-phenyl-1H-indole and 345 mL (0.3 M) of THF were added to a 1000 mL three-neck flask, and 72 mL (1.1 equiv) of 1.6 mol / L nBuLi / n-hexane solution was added dropwise while stirring at -78 °C. After stirring for 1 hour under the same temperature conditions, 31.94 g (1.1 equiv, 113.8 mmol) of 2-(2-iodophenyl)acetyl chloride in THF solution (28.5 mL, 1 mol / L) was added dropwise and stirred at the same temperature for 30 minutes. The temperature was then raised to room temperature and further stirred. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was then removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in turn, and then washed with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-1 (31.68 g, 70% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 437, confirming that this was intermediate IM-1.

[0204] <Synthesis of intermediate IM-2> Under an argon atmosphere, 25.00 g (57.2 mmol) of intermediate IM-1, 8.42 g (1.5 equiv, 85.8 mmol) of potassium acetate, and Pd(PPh 3 ) 4 3.30g (0.05eq, 2.9mmol) and 228mL (0.25M) of N,N-dimethylamide were added in that order and heated and stirred at 80℃. After confirming the disappearance of the raw materials, the reaction solution was cooled to room temperature, water was added to the reaction solution, and it was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then MgSO 4 Dried with MgSO 4The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-2 (14.50 g, 82% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 309, confirming that this was intermediate IM-2.

[0205] <Synthesis of intermediate IM-3> Under an argon atmosphere, 10.00g (32.3mmol) of intermediate IM-2 and 108mL (0.3M) of THF were added to a 500mL three-neck flask, and 35.6mL (1.1 equiv) of 1.0mol / L KHMDS / THF solution was added dropwise while stirring at -78℃. After stirring for 1 hour at the same temperature, a THF solution (10.0mL, 1mol / L) of 13.86g (1.2 equiv, 38.8mmol) of N,N'-bis(trifluoromethanesulsonyl)aniline was added dropwise and stirred for 30 minutes at the same temperature. Then, the temperature was raised to room temperature and further stirred. Next, a 10% NaOH aqueous solution was added, and the reaction solution was extracted with AcOEt. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in turn, and then MgSO 4 Dried with MgSO 4 The crude product, intermediate IM-3 (11.27 g, 79% yield), was obtained by filtering the mixture and concentrating the organic layer, and was used directly in the next reaction. FAB-MS measurement revealed that the mass number m / z = 441 was a molecular ion peak, confirming that this was intermediate IM-3.

[0206] <Synthesis of Compound A1> Under an argon atmosphere, 10.00 g (22.7 mmol) of intermediate IM-3, 11.00 g (1.1 equiv, 24.9 mmol) of 4-{di[(1,1'-biphenyl)-4-yl]amino}phenylboronic acid, and K were added to a 500 mL three-neck flask. 2 CO 3 9.39g(3.0equiv, 68.0mmol), Pd(PPh 3 ) 41.31g (0.05eq, 1.1mmol) and 159mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain a white solid compound A1 (11.70 g, 75% yield). In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 688, confirming that it was compound A1.

[0207] (Synthesis of compound A28) The amine compound A28 according to one embodiment can be synthesized, for example, according to the following reaction scheme 2.

[0208] [Reaction Scheme 2] [ka]

[0209] <Synthesis of intermediate IM-4> Under an argon atmosphere, 20.00g (103.5mmol) of 3-phenyl-1H-indole and 345mL (0.3M) of THF were added to a 1000mL three-neck flask, and 72mL (1.1 equiv) of 1.6mol / L nBuLi / n-hexane solution was added dropwise while stirring at -78℃. After stirring at the same temperature for 1 hour, 31.94g (1.1 equiv, 113.8mmol) of 2-chloro-1-(2-iodophenyl)ethanone in THF solution (28.5mL, 1mol / L) was added dropwise and stirred at the same temperature for 30 minutes. The temperature was then raised to room temperature and stirred for another 2 hours. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in that order, and then MgSO 4 Dried with MgSO 4The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-4 (30.77 g, 68% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 437, confirming that this was intermediate IM-4.

[0210] <Synthesis of intermediate IM-5> Under an argon atmosphere, 25.00 g (57.2 mmol) of intermediate IM-4, 8.42 g (1.5 equiv, 85.8 mmol) of potassium acetate, and Pd(PPh 3 ) 4 3.30g (0.05eq, 2.9mmol) and 228mL (0.25M) of N,N-dimethylamide were added in that order and heated and stirred at 80℃. After confirming the disappearance of the raw materials, the reaction solution was cooled to room temperature, water was added to the reaction solution, and it was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-5 (15.03 g, 85% yield). FAB-MS measurement revealed a molecular ion peak at mass number m / z = 309, confirming that this was intermediate IM-5.

[0211] <Synthesis of intermediate IM-6> Under an argon atmosphere, 10.00g (32.3mmol) of intermediate IM-5 and 108mL (0.3M) of THF were added to a 500mL three-neck flask and stirred at -78℃, while 35.6mL (1.1equiv) of 1.0mol / L KHMDS / THF solution was added dropwise. After stirring at the same temperature for 1 hour, a THF solution (10.0mL, 1mol / L) of 13.86g (1.2equiv, 38.8mmol) of N,N'-bis(trifluoromethanesulsonyl)aniline was added dropwise and stirred at the same temperature for 30 minutes. After that, the temperature was raised to room temperature and further stirred. After adding a 10% NaOH aqueous solution, the reaction solution was extracted with AcOEt. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in turn, and then MgSO 4 Dried with MgSO 4 The crude product IM-6 (11.56 g, 81% yield) was obtained by filtering the mixture and concentrating the organic layer, and was used directly in the next reaction. The molecular ion peak at m / z=441 was observed by FAB-MS measurement, confirming that the product was intermediate IM-6.

[0212] <Synthesis of compound A28> Under an argon atmosphere, 10.00 g (18.5 mmol) of intermediate IM-6 and Pd(dba) were added to a 200 mL three-neck flask. 2 0.39g(0.03equiv, 0.7mmol), NaO t Bu 4.35g (2.0 equiv, 45.3mmol), toluene 113mL, N-[(1,1':4',1''-terphenyl)-4-yl]dibenzofuran-3-amine 10.25g (1.1 equiv, 24.9mmol) and t Bu 3 P 0.46g (0.1 equiv, 2.3mmol) was added in sequence, and the mixture was heated under reflux and stirred. After cooling to room temperature, water was added to the reaction solvent and the organic layer was separated. Toluene was added to the aqueous layer to further extract the organic layer, and the organic layers were then combined, washed with saline, and then with MgSO 4 Dried with MgSO 4The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain a white solid compound A28 (13.22 g, 83% yield). In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 702, confirming that this was compound A28.

[0213] (Synthesis of compound A57) The amine compound A57 according to one embodiment can be synthesized, for example, according to the following reaction scheme 3.

[0214] [Reaction Scheme 3] [ka]

[0215] <Synthesis of intermediate IM-7> In a 500 mL three-neck flask, 15.00 g (77.6 mmol) of 3-phenyl-1H-indole, 25.09 g (1.5 equiv, 116.4 mmol) of 1-bromo-4-chloro-2-ethynylbenzene, and K 3 PO 4 32.97g (2.0eq, 155.2mmol) and 215mL (0.2M) of DMSO were added in that order and heated and stirred at 120°C. After confirming the disappearance of the raw materials, the reaction solution was cooled to room temperature, water was added to the reaction solution, and the solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, followed by extraction with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-7 (19.03 g, 60% yield). FAB-MS measurement revealed that the mass number m / z = 408 was observed as a molecular ion peak, confirming that this was intermediate IM-7.

[0216] <Synthesis of intermediate IM-8> Under an argon atmosphere, 15.00 g (36.7 mmol) of intermediate IM-7, 5.40 g (1.5 equiv, 55.0 mmol) of potassium acetate, and Pd(PPh 3 ) 4 2.12g (0.05eq, 1.8mmol) and 146mL (0.25M) of N,N-dimethylamide were added in that order and heated and stirred at 80℃. After confirming the disappearance of the raw materials, the reaction solution was cooled to room temperature, water was added to the reaction solution, and it was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-8 (9.74 g, 81% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 327, confirming that this was intermediate IM-8.

[0217] <Synthesis of compound A57> In a 500 mL three-neck flask, 8.00 g (24.4 mmol) of intermediate IM-8, 9.80 g (1.1 equiv, 26.8 mmol) of [4'-(diphenylamino)-(1,1'-biphenyl)-4-yl]boronic acid, and K 2 CO 3 10.12g(3.0equiv, 73.2mmol), Pd(PPh 3 ) 4 1.41g (0.05eq, 1.2mmol) and 170mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in order and heated and stirred at 80℃. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain compound A57 (11.66 g, 78% yield) as a white solid. In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 612, confirming that this was compound A57.

[0218] (Synthesis of compound B36) The amine compound B36 according to one embodiment can be synthesized, for example, according to the following reaction scheme 4.

[0219] [Reaction Scheme 4] [ka]

[0220] <Synthesis of intermediate IM-9> Under an argon atmosphere, 20.00g (82.5mmol) of 3-bromo-7-chloroisoquinoline and 275mL (0.3M) of THF were added to a 500mL three-neck flask and stirred at -78℃, while 56.7mL (1.1equiv) of 1.6mol / L nBuLi / n-hexane solution was added dropwise. After stirring at the same temperature for 1 hour, 8.99g (1.1equiv, 90.7mmol) of ethyl cyanoformate in THF solution (23mL, 1mol / L) was added dropwise and stirred at the same temperature for 30 minutes. After that, the temperature was raised to room temperature and further stirred. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in turn, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-9 (17.10 g, 88% yield). FAB-MS measurement revealed that the mass number m / z = 235 was observed as a molecular ion peak, confirming that this was intermediate IM-9.

[0221] <Synthesis of intermediate IM-10> Under an argon atmosphere, 15.00 g (63.6 mmol) of intermediate IM-10 and 213 mL (0.3 M) of THF were added to a 500 mL three-neck flask and stirred at -78°C. 159 mL (2.5 equiv) of a 1.0 mol / L PhMgBr / THF solution was then added dropwise. After stirring at the same temperature for 1 hour, the temperature was raised to room temperature and further stirred. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in that order, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-10 (18.71 g, 85% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 345, confirming that this was intermediate IM-10.

[0222] <Synthesis of intermediate IM-11> Under an argon atmosphere, 15.00 g (43.4 mmol) of intermediate IM-10 and 145 mL (0.3 M) of formic acid were added to a 300 mL three-neck flask and heated and stirred at 120 °C. The reaction solution was cooled to room temperature, quenched with water, and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in that order, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-11 (11.23 g, 79% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 327, confirming that this was intermediate IM-11.

[0223] <Synthesis of compound B36> Under an argon atmosphere, 5.00 g (15.3 mmol) of intermediate IM-11 and Pd(dba) were added to a 200 mL three-neck flask.2 0.26g (0.03equiv, 0.5mmol), NaOtBu 2.93g (2.0equiv, 30.5mmol), toluene 76mL, N-[4-(naphthalen-1-yl)phenyl]dibenzothiophen-4-amine 6.74g (1.1equiv, 16.8mmol) t Bu 3 P 0.31g (0.1 equiv, 1.5mmol) was added in sequence and heated under reflux with stirring. After cooling to room temperature, water was added to the reaction solvent and the organic layer was separated. Toluene was added to the aqueous layer to further extract the organic layer, and the organic layers were combined and washed with saline, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain a white solid compound B36 (8.45 g, 80% yield). In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 692, confirming that this was compound B36.

[0224] (Synthesis of compound B46) The amine compound B46 according to one embodiment can be synthesized, for example, according to the following reaction scheme 5.

[0225] [Reaction Scheme 5] [ka]

[0226] <Synthesis of intermediate IM-12> Under an argon atmosphere, 20.00g (82.5mmol) of 3-bromo-6-chloroisoquinoline and 275mL (0.3M) of THF were added to a 500mL three-neck flask and stirred at -78℃, while 56.7mL (1.1equiv) of 1.6mol / L nBuLi / n-hexane solution was added dropwise. After stirring at the same temperature for 1 hour, 8.99g (1.1equiv, 90.7mmol) of ethyl cyanoformate in THF solution (23mL, 1mol / L) was added dropwise and stirred at the same temperature for 30 minutes. After that, the temperature was raised to room temperature and further stirred. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with aqueous sodium bicarbonate solution and saturated saline in turn, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-12 (16.72 g, 86% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 235, confirming that this was intermediate IM-12.

[0227] <Synthesis of intermediate IM-13> Under an argon atmosphere, 15.00 g (63.6 mmol) of intermediate IM-12 and 213 mL (0.3 M) of THF were added to a 500 mL three-neck flask and heated and stirred at -78°C, while 159 mL (2.5 equiv) of a 1.0 mol / L PhMgBr / THF solution was added dropwise. After stirring at the same temperature for 1 hour, the temperature was raised to room temperature and further stirred. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in that order, and then MgSO 4 Dried with MgSO 4The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-13 (19.15 g, 87% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 345, confirming that this was intermediate IM-13.

[0228] <Synthesis of intermediate IM-14> Under an argon atmosphere, 15.00 g (43.4 mmol) of intermediate IM-13 and 145 mL (0.3 M) of formic acid were added to a 300 mL three-neck flask and heated and stirred at 120 °C. The reaction solution was cooled to room temperature in air, quenched with water, and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in that order, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-14 (10.66 g, 75% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 327, confirming that this was intermediate IM-14.

[0229] <Synthesis of compound B46> Under an argon atmosphere, 5.00 g (15.3 mmol) of intermediate IM-14 and Pd(dba) were added to a 200 mL three-neck flask. 2 0.26g(0.03equiv, 0.5mmol), NaO t Bu 2.93g (2.0 equiv, 30.5mmol), toluene 76mL, bis[4-(naphthalen-1-yl)phenyl]amine 7.07g (1.1 equiv, 16.8mmol) and t Bu 3 P 0.31g (0.1 equiv, 1.5mmol) was added in sequence, and the mixture was heated under reflux and stirred. After cooling to room temperature, water was added to the reaction solvent to separate the organic layer. Toluene was added to the aqueous layer to further extract the organic layer, and the organic layers were combined, washed with saline, and then added with MgSO 4Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain a white solid compound B46 (9.03 g, 83% yield). By measuring FAB-MS, a molecular ion peak was observed at mass number m / z = 712, which confirmed that it was compound B46.

[0230] (Synthesis of compound C47) The amine compound C47 according to one embodiment can be synthesized, for example, according to the following reaction scheme 6.

[0231] [Reaction Scheme 6] [ka]

[0232] <Synthesis of intermediate IM-15> Under an argon atmosphere, 15.00 g (77.6 mmol) of 3-phenyl-1H-indole and Pd(dba) were placed in a 500 mL three-neck flask. 2 1.34g (0.03equiv, 2.3mmol), NaO t Bu 8.95g (1.2equiv, 93.1mmol), toluene 388mL, 2-bromo-1-chloro-3-iodobenzene 27.10g (1.1equiv, 85.4mmol) and t Bu 3 P 1.57g (0.1 equiv, 7.8mmol) was added in sequence, and the mixture was heated under reflux and stirred. After cooling to room temperature, water was added to the reaction solvent and the organic layer was separated. Toluene was added to the aqueous layer to further extract the organic layer, and the organic layers were combined and washed with saline, and then MgSO 4 Dried with MgSO 4The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-15 (25.55 g, 86% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 382, ​​confirming that this was intermediate IM-15.

[0233] <Synthesis of intermediate IM-16> Under an argon atmosphere, 15.00 g (39.2 mmol) of intermediate IM-15 and Pd(OAc) were added to a 500 mL three-neck flask. 2 0.88g(0.1equiv, 3.9mmol), Cs 2 CO 3 19.16g (1.5 equiv, 58.8mmol), 196mL of toluene, 14.45g (4.0 equiv, 156.8mmol) of norbornadiene, and 2.26g (0.22 equiv, 8.6mmol) of PPh3 were added in that order, and the mixture was refluxed and stirred at 120°C. After cooling to room temperature, water was added to the reaction solvent and the organic layer was separated. Toluene was added to the aqueous layer to further extract the organic layer, and the organic layers were combined and washed with saline, and then with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-16 (11.18 g, 87% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 327, confirming that this was intermediate IM-16.

[0234] <Synthesis of compound C47> Under an argon atmosphere, 8.00 g (24.4 mmol) of intermediate IM-16, 15.77 g (1.1 equiv, 26.8 mmol) of N-[4-(naphthalen-1-yl)phenyl]-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]dibenzofuran-1-amine, and K were added to a 500 mL three-neck flask. 2 CO3 10.12g(3.0equiv, 73.2mmol), Pd(PPh 3 ) 4 1.41g (0.05eq, 1.2mmol) and 170mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain a white solid compound C47 (13.78 g, 75% yield). In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 752, confirming that it was compound C47.

[0235] (Synthesis of compound C87) The amine compound C87 according to one embodiment can be synthesized, for example, according to the following reaction scheme 7.

[0236] [Reaction Scheme 7] [ka]

[0237] <Synthesis of intermediate IM-17> Under an argon atmosphere, 15.00 g (65.9 mmol) of 7-chloro-3-phenyl-1H-indole and Pd(dba) were placed in a 500 mL three-neck flask. 2 1.14g (0.03equiv, 2.0mmol), NaO t Bu 7.60g (1.2 equiv, 79.1mmol), toluene 388mL, 1-bromo-2-iodobenzene 20.50g (1.1 equiv, 72.5mmol) and t Bu 3P 1.33g (0.1 equiv, 6.6mmol) was added in sequence, and the mixture was heated under reflux and stirred. After cooling to room temperature, water was added to the reaction solvent and the organic layer was separated. Toluene was added to the aqueous layer to further extract the organic layer, and the organic layers were combined, washed with saline, and then diluted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-17 (20.92 g, 83% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 382, ​​confirming that this was intermediate IM-17.

[0238] <Synthesis of intermediate IM-18> Under an argon atmosphere, 15.00 g (39.2 mmol) of intermediate IM-17 and Pd(OAc) were added to a 500 mL three-neck flask. 2 0.88g(0.1equiv, 3.9mmol), Cs 2 CO 3 19.16g (1.5 equiv, 58.8mmol), toluene 196mL, norbornadiene 14.45g (4.0 equiv, 156.8mmol) and PPh 3 2.26g (0.22 equiv, 8.6mmol) were added in order and stirred under reflux at 120°C. After cooling to room temperature, water was added to the reaction solvent and the organic layer was separated. Toluene was added to the aqueous layer to further extract the organic layer, and the organic layers were combined and washed with saline, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-18 (10.15 g, 79% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 327, confirming that this was intermediate IM-18.

[0239] <Synthesis of compound C87> Under an argon atmosphere, 8.00 g (24.4 mmol) of intermediate IM-18, 14.80 g (1.1 equiv, 26.8 mmol) of N-(dibenzofuran-3-yl)-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]dibenzofuran-3-amine, and K were added to a 500 mL three-neck flask. 2 CO 3 10.12g(3.0equiv, 73.2mmol), Pd(PPh 3 ) 4 1.41g (0.05eq, 1.2mmol) and 170mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain a white solid compound C87 (12.25 g, 70% yield). In the FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 716, confirming that it was compound C87.

[0240] (Synthesis of compound D47) The amine compound D47 according to one embodiment can be synthesized, for example, according to the following reaction scheme 8.

[0241] [Reaction Scheme 8] [ka]

[0242] <Synthesis of intermediate IM-19> In a 500 mL three-neck flask, add 15.00 g (47.00 mmol) of 2-iodo-3-phenyl-1H-indole, 12.16 g (1.1 equiv, 51.7 mmol) of 2-bromo-3-chlorophenylboronic acid, and K2 CO 3 19.49g(3.0equiv, 141.0mmol), Pd(PPh 3 ) 4 2.72g (0.05eq, 2.3mmol) and 329mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-19 (12.41 g, 69% yield). FAB-MS measurement revealed that the mass number m / z = 382 was observed as a molecular ion peak, confirming that this was intermediate IM-19.

[0243] <Synthesis of intermediate IM-20> Under an argon atmosphere, 10.00 g (26.1 mmol) of intermediate IM-19, 5.86 g (1.1 equiv, 28.7 mmol), and K were added to a 500 mL three-neck flask. 2 CO 3 10.83g(3.0equiv, 78.4mmol), Pd(PPh 3 ) 4 3.02g (0.1eq, 2.6mmol), XPhos 1.25g (0.1eq, 2.6mmol), and DMF 105mL were added in that order, and the mixture was heated and stirred at 140°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-20 (6.91 g, 70% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 377, confirming that this was intermediate IM-20.

[0244] <Synthesis of compound D47> Under an argon atmosphere, 5.00 g (13.2 mmol) of intermediate IM-20, 9.66 g (1.1 equiv, 14.6 mmol) of N-[4-(naphthalen-1-yl)phenyl]-N-[4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-(1,1'-biphenyl)-4-yl]dibenzofuran-1-amine, and K were added to a 300 mL three-neck flask. 2 CO 3 5.49g(3.0equiv, 39.7mmol), Pd(PPh 3 ) 4 0.76g (0.05eq, 0.7mmol) and 93mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain compound D47 (8.38 g, 72% yield) as a white solid. In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 879, confirming that this was compound D47.

[0245] (Synthesis of compound D60) The amine compound D60 according to one embodiment can be synthesized, for example, according to the following reaction scheme 9.

[0246] [Reaction Scheme 9] [ka]

[0247] <Synthesis of intermediate IM-21> In a 500 mL three-neck flask, add 15.00 g (47.00 mmol) of 2-iodo-3-phenyl-1H-indole, 8.08 g (1.1 equiv, 51.7 mmol) of 3-chlorophenylboronic acid, and K 2 CO 3 19.49g(3.0equiv, 141.0mmol), Pd(PPh 3 ) 4 2.72g (0.05eq, 2.3mmol) and 329mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-21 (10.99 g, 77% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 303, confirming that this was intermediate IM-21.

[0248] <Synthesis of intermediate IM-22> Under an argon atmosphere, 10.00 g (32.9 mmol) of intermediate IM-21, 8.54 g (1.1 equiv, 36.2 mmol) of 1,2-dibromobenzene, and K were added to a 500 mL three-neck flask. 2 CO 3 13.65g(3.0equiv, 98.8mmol), Pd(PPh 3 ) 4 3.80g (0.1eq, 3.3mmol), XPhos 1.57g (0.1eq, 3.3mmol), and DMF 132mL were added in that order, and the mixture was heated and stirred at 140°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-22 (8.58 g, 69% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 377, confirming that this was intermediate IM-22.

[0249] <Synthesis of compound D60> Under an argon atmosphere, 5.00 g (13.2 mmol) of intermediate IM-22, 9.63 g (1.1 equiv, 14.6 mmol) of N-(naphthalen-2-yl)-9,9-diphenyl-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-9H-fluoren-2-amine, and K were added to a 300 mL three-neck flask. 2 CO 3 5.49g(3.0equiv, 39.7mmol), Pd(PPh 3 ) 4 0.76g (0.05eq, 0.7mmol) and 93mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain a white solid compound D60 (9.52 g, 82% yield). In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 877, confirming that it was compound D60.

[0250] (Synthesis of compound D74) The amine compound D74 according to one embodiment can be synthesized, for example, according to the following reaction scheme 10.

[0251] [Reaction Scheme 10] [ka]

[0252] <Synthesis of intermediate IM-23> In a 500 mL three-neck flask, 15.00 g (42.4 mmol) of 4-chloro-2-iodo-3-phenyl-1H-indole, 5.69 g (1.1 equiv, 46.7 mmol) of boronic acid, and K 2 CO 3 17.59g(3.0equiv, 127.3mmol), Pd(PPh 3 ) 4 2.45g (0.05eq, 2.1mmol) and 296mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-23 (10.70 g, 83% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 303, confirming that this was intermediate IM-23.

[0253] <Synthesis of intermediate IM-24> Under an argon atmosphere, 10.00 g (32.9 mmol) of intermediate IM-23, 8.54 g (1.1 equiv, 36.2 mmol) of 1,2-dibromobenzene, and K were added to a 500 mL three-neck flask. 2 CO 3 13.65g(3.0equiv, 98.8mmol), Pd(PPh 3 ) 4 3.80g (0.1eq, 3.3mmol), XPhos 1.57g (0.1eq, 3.3mmol), and DMF 132mL were added in that order, and the mixture was heated and stirred at 140°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-24 (9.33 g, 75% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 377, confirming that this was intermediate IM-24.

[0254] <Synthesis of compound D74> Under an argon atmosphere, 5.00 g (13.2 mmol) of intermediate IM-24, 9.83 g (1.1 equiv, 14.6 mmol) of N-[(1,1'-biphenyl)-4-yl]-N-[4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-(1,1'-biphenyl)-4-yl]-(1,1':2',1''-terphenyl)-4-amine, and K were added to a 300 mL three-neck flask. 2 CO 3 5.49g(3.0equiv, 39.7mmol), Pd(PPh 3 ) 4 0.76g (0.05eq, 0.7mmol) and 93mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain a white solid compound D74 (9.32 g, 79% yield). In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 891, confirming that it was compound D74.

[0255] (Synthesis of compound E6) The amine compound E6 according to one embodiment can be synthesized, for example, according to the following reaction scheme 11.

[0256] [Reaction Scheme 11] [ka]

[0257] <Synthesis of intermediate IM-25> Under an argon atmosphere, 25.00g (103.5mmol) of 1-bromo-7-chloronaphthalene and 345mL (0.3M) of THF were added to a 1000mL three-neck flask and stirred at -78℃. 71.2mL (1.1 equiv) of 1.6mol / L nBuLi / n-hexane solution was added dropwise. After stirring at the same temperature for 1 hour, 12.20g (1.1 equiv, 113.9mmol) of picolinaldehyde in THF solution (29mL, 1mol / L) was added dropwise and stirred at the same temperature for 30 minutes. After that, the temperature was raised to room temperature and further stirred. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in turn, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-25 (21.50 g, 77% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 269, confirming that this was intermediate IM-25.

[0258] <Synthesis of intermediate IM-26> Under an argon atmosphere, 20.00 g (74.1 mmol) of intermediate IM-25 and 247 mL (0.3 M) of formic acid were added to a 500 mL three-neck flask and heated with stirring at 120°C. The reaction solution was cooled to room temperature in air, quenched with water, and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in that order, and then extracted with MgSO 4 Dried with MgSO 4The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-26 (14.93 g, 80% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 251, confirming that this was intermediate IM-26.

[0259] <Synthesis of intermediate IM-27> Under an argon atmosphere, 12.00 g (47.7 mmol) of intermediate IM-26 and CH 2 C l2 239 mL and 10.18 g (1.2 equiv, 57.2 mmol) of N-bromosuccinimide were added in that order and stirred at room temperature. Water was added to the reaction solution, and then CHCl 3 The aqueous layer was removed, and the organic layer was washed with saturated saline and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-27 (12.92 g, 82% yield). FAB-MS measurement revealed a molecular ion peak at mass number m / z = 330, confirming that this was intermediate IM-27.

[0260] <Synthesis of intermediate IM-28> In a 500 mL three-neck flask, 10.00 g (30.2 mmol) of intermediate IM-27, 4.06 g (1.1 equiv, 33.3 mmol), and K 2 CO 3 12.54g(3.0equiv, 90.7mmol), Pd(PPh 3 ) 4 1.75g ​​(0.05eq, 1.5mmol) and 212mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-28 (7.44 g, 75% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 327, confirming that this was intermediate IM-28.

[0261] <Synthesis of compound E6> Under an argon atmosphere, 5.00 g (13.2 mmol) of intermediate IM-28, 8.90 g (1.1 equiv, 14.6 mmol) of N,9,9-triphenyl-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-9H-fluoren-2-amine, and K were added to a 300 mL three-neck flask. 2 CO 3 5.49g(3.0equiv, 39.7mmol), Pd(PPh 3 ) 4 0.76g (0.05eq, 0.7mmol) and 93mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain a white solid compound E6 (7.20 g, 70% yield). In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 776, confirming that it was compound E6.

[0262] (Synthesis of compound E25) The amine compound E25 according to one embodiment can be synthesized, for example, according to the following reaction scheme 12.

[0263] [Reaction scheme 12] [ka]

[0264] <Synthesis of intermediate IM-29> In a 500 mL three-neck flask, 10.00 g (30.2 mmol) of intermediate IM-27, 7.05 g (1.1 equiv, 33.3 mmol) of dibenzofuran-3-ylboronic acid, and K 2 CO 3 12.54g(3.0equiv, 90.7mmol), Pd(PPh 3 ) 4 1.75g ​​(0.05eq, 1.5mmol) and 212mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-29 (8.85 g, 70% yield). FAB-MS measurement revealed a molecular ion peak at mass number m / z = 417, confirming that this was compound IM-29.

[0265] <Synthesis of compound E25> Under an argon atmosphere, 5.00 g (12.0 mmol) of intermediate IM-29, 5.81 g (1.1 equiv, 13.2 mmol) of 4-di[(1,1'-biphenyl)-4-yl]aminophenylboronic acid, and K were added to a 300 mL three-neck flask. 2 CO 3 4.96g(3.0equiv, 35.9mmol), Pd(PPh 3 ) 40.69g (0.05eq, 0.6mmol) and 84mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain compound E25 (7.55 g, 81% yield) as a white solid. In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 778, confirming that it was compound E25.

[0266] (Synthesis of compound E55) The amine compound E55 according to one embodiment can be synthesized, for example, according to the following reaction scheme 13.

[0267] [Reaction Scheme 13] [ka]

[0268] <Synthesis of intermediate IM-30> Under an argon atmosphere, 25.00g (103.5mmol) of 1-bromo-3-chloronaphthalene and 345mL (0.3M) of THF were added to a 1000mL three-neck flask and stirred at -78℃, while 71.2mL (1.1 equiv) of 1.6mol / L nBuLi / n-hexane solution was added dropwise. After stirring at the same temperature for 1 hour, a THF solution (29mL, 1mol / L) of 12.20g (1.1 equiv, 113.9mmol) of picolinaldehyde was added dropwise and stirred at the same temperature for 30 minutes. Then, the temperature was raised to room temperature and further stirred. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in turn, and then MgSO 4 Dried with MgSO 4The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-30 (23.73 g, 85% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 269, confirming that this was intermediate IM-30.

[0269] <Synthesis of intermediate IM-31> Under an argon atmosphere, 20.00 g (74.1 mmol) of intermediate IM-30 and 247 mL (0.3 M) of formic acid were added to a 500 mL three-neck flask and heated with stirring at 120°C. The reaction solution was cooled to room temperature in air, quenched with water, and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in that order, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-31 (14.56 g, 78% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 251, confirming that this was intermediate IM-31.

[0270] <Synthesis of intermediate IM-32> Under an argon atmosphere, 12.00 g (47.7 mmol) of intermediate IM-31 and CH 2 Cl 2 239 mL and 10.18 g (1.2 equiv, 57.2 mmol) of N-bromosuccinimide were added in that order and stirred at room temperature. Water was added to the reaction solution, and then CHCl 3 The aqueous layer was removed, and the organic layer was washed with saturated saline and then extracted with MgSO 4 Dried with MgSO 4The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-32 (13.40 g, 85% yield). FAB-MS measurement revealed a molecular ion peak at mass number m / z = 330, confirming that this was intermediate IM-32.

[0271] <Synthesis of intermediate IM-33> In a 500 mL three-neck flask, 10.00 g (30.2 mmol) of intermediate IM-33, 4.06 g (1.1 equiv, 33.3 mmol), and K 2 CO 3 12.54g(3.0equiv, 90.7mmol), Pd(PPh 3 ) 4 1.75g ​​(0.05eq, 1.5mmol) and 212mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-33 (7.44 g, 75% yield). FAB-MS measurement revealed that the mass number m / z = 327 was observed as a molecular ion peak, confirming that this was intermediate IM-33.

[0272] <Synthesis of compound E55> Under an argon atmosphere, 5.00 g (13.2 mmol) of intermediate IM-33, 10.06 g (1.1 equiv, 14.6 mmol) of N,N-di[(1,1'-biphenyl)-4-yl]-4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-(1,1'-biphenyl)-4-amine, and K were added to a 300 mL three-neck flask. 2 CO 35.49g(3.0equiv, 39.7mmol), Pd(PPh 3 ) 4 0.76g (0.05eq, 0.7mmol) and 93mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain compound E55 (9.10 g, 78% yield) as a white solid. In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 764, confirming that it was compound E55.

[0273] (Synthesis of compound E73) The amine compound E73 according to one embodiment can be synthesized, for example, according to the following reaction scheme 14.

[0274] [Reaction Scheme 14] [ka]

[0275] <Synthesis of intermediate IM-34> Under an argon atmosphere, 20.00g (96.6mmol) of 1-bromonaphthalene and 322mL (0.3M) of THF were added to a 1000mL three-neck flask and stirred at -78℃, while 66.4mL (1.1 equiv) of 1.6mol / L nBuLi / n-hexane solution was added dropwise. After stirring at the same temperature for 1 hour, 15.04g (1.1 equiv, 106.2mmol) of 5-chloropicolinaldehyde in THF solution (27mL, 1mol / L) was added dropwise and stirred at the same temperature for 30 minutes. Then, the temperature was raised to room temperature and further stirred. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in turn, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-34 (22.93 g, 88% yield). FAB-MS measurement revealed a molecular ion peak at mass number m / z = 269, confirming that this was intermediate IM-34.

[0276] <Synthesis of intermediate IM-35> Under an argon atmosphere, 20.00 g (74.1 mmol) of IM-34 and 247 mL (0.3 M) of formic acid were added to a 500 mL three-neck flask and heated with stirring at 120°C. The reaction solution was cooled to room temperature in air, quenched with water, and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous solution of sodium bicarbonate and saturated saline in that order, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-35 (14.56 g, 78% yield). FAB-MS measurement revealed that the molecular ion peak was at mass number m / z = 251, confirming that this was intermediate IM-35.

[0277] <Synthesis of intermediate IM-36> Under an argon atmosphere, 12.00 g (47.7 mmol) of intermediate IM-35 and CH 2 Cl 2 239 mL and 10.18 g (1.2 equiv, 57.2 mmol) of N-bromosuccinimide were added in that order and stirred at room temperature. Water was added to the reaction solution, and then CHCl 3 The aqueous layer was removed, and the organic layer was washed with saturated saline and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-36 (12.77 g, 81% yield). FAB-MS measurement revealed a molecular ion peak at mass number m / z = 330, confirming that this was intermediate IM-36.

[0278] <Synthesis of intermediate IM-37> In a 500 mL three-neck flask, 10.00 g (30.2 mmol) of intermediate IM-36, 4.06 g (1.1 equiv, 33.3 mmol), and K 2 CO 3 12.54g(3.0equiv, 90.7mmol), Pd(PPh 3 ) 4 1.75g ​​(0.05eq, 1.5mmol) and 212mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-37 (7.73 g, 78% yield). FAB-MS measurement revealed a molecular ion peak at mass number m / z = 327, confirming that this was intermediate IM-37.

[0279] <Synthesis of compound E73> Under an argon atmosphere, 5.00 g (13.2 mmol) of intermediate IM-37, 10.06 g (1.1 equiv, 14.6 mmol) of N,9,9-triphenyl-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-9H-fluoren-2-amine, and K were added to a 300 mL three-neck flask. 2 CO 3 5.49g(3.0equiv, 39.7mmol), Pd(PPh 3 ) 4 0.76g (0.05eq, 0.7mmol) and 93mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain a white solid compound E73 (8.88 g, 75% yield). In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 776, confirming that it was compound E73.

[0280] (Synthesis of compound E89) The amine compound E89 according to one embodiment can be synthesized, for example, according to the following reaction scheme 15.

[0281] [Reaction Scheme 15] [ka]

[0282] <Synthesis of intermediate IM-38> Under an argon atmosphere, 20.00g (96.6mmol) of 1-bromonaphthalene and 322mL (0.3M) of THF were added to a 1000mL three-neck flask and stirred at -78℃, while 66.4mL (1.1equiv) of 1.6mol / L nBuLi / n-hexane solution was added dropwise. After stirring at the same temperature for 1 hour, 15.04g (1.1equiv, 106.2mmol) of 3-chloropicolinaldehyde in THF solution (27mL, 1mol / L) was added dropwise and stirred at the same temperature for 30 minutes. After that, the temperature was raised to room temperature and further stirred. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in turn, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-38 (19.80 g, 76% yield). FAB-MS measurement revealed that the mass number m / z = 269 was observed as a molecular ion peak, confirming that this was intermediate IM-38.

[0283] <Synthesis of intermediate IM-39> Under an argon atmosphere, 20.00 g (74.1 mmol) of intermediate IM-38 and 247 mL (0.3 M) of formic acid were added to a 500 mL three-neck flask and heated with stirring at 120°C. The reaction solution was cooled to room temperature in air, quenched with water, and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in that order, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-39 (14.74 g, 79% yield). FAB-MS measurement revealed that the mass number m / z = 251 was observed as a molecular ion peak, confirming that this was intermediate IM-39.

[0284] <Synthesis of intermediate IM-40> Under an argon atmosphere, 12.00 g (47.7 mmol) of intermediate IM-39 and CH 2 Cl 2 239 mL and 10.18 g (1.2 equiv, 57.2 mmol) of N-bromosuccinimide were added in that order and stirred at room temperature. Water was added to the reaction solution, and then CHCl 3 The aqueous layer was removed, and the organic layer was washed with saturated saline and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-40 (13.08 g, 83% yield). FAB-MS measurement revealed that the mass number m / z = 330 was observed as a molecular ion peak, confirming that this was intermediate IM-40.

[0285] <Synthesis of intermediate IM-41> In a 500 mL three-neck flask, 10.00 g (30.2 mmol) of intermediate IM-40, 4.06 g (1.1 equiv, 33.3 mmol), and K 2 CO 3 12.54g(3.0equiv, 90.7mmol), Pd(PPh 3 ) 4 1.75g ​​(0.05eq, 1.5mmol) and 212mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-41 (7.93 g, 80% yield). FAB-MS measurement revealed that the mass number m / z = 327 was observed as a molecular ion peak, confirming that this was intermediate IM-41.

[0286] <Synthesis of compound E89> Under an argon atmosphere, 5.00 g (13.2 mmol) of intermediate IM-41, 9.19 g (1.1 equiv, 14.6 mmol) of N-[(1,1'-biphenyl)-4-yl]-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]phenanthren-9-amine, and K were added to a 300 mL three-neck flask. 2 CO 3 5.49g(3.0equiv, 39.7mmol), Pd(PPh 3 ) 4 0.76g (0.05eq, 0.7mmol) and 93mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain compound E89 (9.24 g, 85% yield) as a white solid. In FAB-MS measurement, a molecular ion peak was observed at mass number m / z=712, confirming that the compound was compound E89.

[0287] (Synthesis of compound F21) The amine compound F21 according to one embodiment can be synthesized, for example, according to the following reaction scheme 16.

[0288] [Reaction Scheme 16] [ka]

[0289] <Synthesis of intermediate IM-42> Under an argon atmosphere, 25.00g (85.7mmol) of 10-bromo-2-chlorophenanthrene and 286mL (0.3M) of THF were added to a 1000mL three-neck flask and stirred at -78℃, while 59.0mL (1.1 equiv) of 1.6mol / L nBuLi / n-hexane solution was added dropwise. After stirring at the same temperature for 1 hour, a THF solution (24mL, 1mol / L) of 10.10g (1.1 equiv, 94.3mmol) of picolinaldehyde was added dropwise and stirred at the same temperature for 30 minutes. Then, the temperature was raised to room temperature and further stirred. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in turn, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-42 (20.57 g, 75% yield). FAB-MS measurement revealed that the mass number m / z = 319 was observed as a molecular ion peak, confirming that this was intermediate IM-42.

[0290] <Synthesis of intermediate IM-43> Under an argon atmosphere, 20.00 g (62.5 mmol) of intermediate IM-42 and 208 mL (0.3 M) of formic acid were added to a 500 mL three-neck flask and heated with stirring at 120°C. The reaction solution was cooled to room temperature in air, quenched with water, and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous solution of sodium bicarbonate and saturated saline in that order, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-43 (15.29 g, 81% yield). FAB-MS measurement revealed that the mass number m / z = 301 was observed as a molecular ion peak, confirming that this was intermediate IM-43.

[0291] <Synthesis of intermediate IM-44> Under an argon atmosphere, 12.00 g (39.8 mmol) of intermediate IM-43 and CH 2 Cl 2 199 mL of 1,000 mL of 1,000 mL of 1,000 mL of N-bromosuccinimide and 8.49 g (1.2 equiv, 47.7 mmol) of N-bromosuccinimide were added in that order and stirred at room temperature. Water was added to the reaction solution, and then CHCl 3 The aqueous layer was removed, and the organic layer was washed with saturated saline and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-44 (13.02 g, 86% yield). FAB-MS measurement revealed that the mass number m / z = 380 was observed as a molecular ion peak, confirming that this was intermediate IM-44.

[0292] <Synthesis of intermediate IM-45> In a 500 mL three-neck flask, 10.00 g (26.3 mmol) of intermediate IM-44, 3.52 g (1.1 equiv, 28.9 mmol), and K 2 CO 3 10.89g(3.0equiv, 78.8mmol), Pd(PPh 3 ) 4 1.52g (0.05eq, 1.3mmol) and 184mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-45 (8.54 g, 86% yield). FAB-MS measurement revealed that the mass number m / z = 377 was observed as a molecular ion peak, confirming that this was intermediate IM-45.

[0293] <Synthesis of compound F21> Under an argon atmosphere, 5.00 g (13.2 mmol) of intermediate IM-45 and Pd(dba) were added to a 200 mL three-neck flask. 2 0.23g(0.03equiv, 0.4mmol), NaO t Bu 2.54g (2.0 equiv, 26.5mmol), toluene 66mL, di[(1,1'-biphenyl)-4-yl]amine 4.68g (1.1 equiv, 14.6mmol) and t Bu 3 P 0.27g (0.1 equiv, 1.3mmol) was added in sequence, and the mixture was heated under reflux and stirred. After cooling to room temperature, water was added to the reaction solvent and the organic layer was separated. Toluene was added to the aqueous layer to further extract the organic layer, and the organic layers were combined, washed with saline, and then diluted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain compound F21 (7.01 g, 80% yield) as a white solid. In FAB-MS measurement, a molecular ion peak was observed at mass number m / z = 662, confirming that this was compound F21.

[0294] (Synthesis of compound F63) The amine compound F63 according to one embodiment can be synthesized, for example, according to the following reaction scheme 17.

[0295] [Reaction Scheme 17] [ka]

[0296] <Synthesis of intermediate IM-46> Under an argon atmosphere, 25.00g (97.2mmol) of 9-bromophenanthrene and 324mL (0.3M) of THF were added to a 1000mL three-neck flask and stirred at -78℃, while 66.8mL (1.1equiv) of 1.6mol / L nBuLi / n-hexane solution was added dropwise. After stirring at the same temperature for 1 hour, 15.14g (1.1equiv, 106.9mmol) of 6-chloropicolinaldehyde in THF solution (27mL, 1mol / L) was added dropwise and stirred at the same temperature for 30 minutes. After that, the temperature was raised to room temperature and further stirred. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with aqueous sodium bicarbonate solution and saturated saline in turn, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-46 (23.94 g, 77% yield). FAB-MS measurement revealed that the mass number m / z = 319 was observed as a molecular ion peak, confirming that this was intermediate IM-46.

[0297] <Synthesis of intermediate IM-47> Under an argon atmosphere, 20.00 g (62.5 mmol) of intermediate IM-46 and 208 mL (0.3 M) of formic acid were added to a 500 mL three-neck flask and heated with stirring at 120°C. The reaction solution was cooled to room temperature in air, quenched with water, and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous sodium bicarbonate solution and saturated saline in that order, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-47 (16.04 g, 85% yield). FAB-MS measurement revealed that the mass number m / z = 301 was observed as a molecular ion peak, confirming that this was intermediate IM-47.

[0298] <Synthesis of intermediate IM-48> Under an argon atmosphere, 12.00 g (39.8 mmol) of intermediate IM-47 and CH 2 Cl 2 199 mL of 1,000 mL of 1,000 mL of 1,000 mL of N-bromosuccinimide and 8.49 g (1.2 equiv, 47.7 mmol) of N-bromosuccinimide were added in that order and stirred at room temperature. Water was added to the reaction solution, and then CHCl 3 The aqueous layer was removed, and the organic layer was washed with saturated saline and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-48 (11.96 g, 79% yield). FAB-MS measurement revealed that the mass number m / z = 380 was observed as a molecular ion peak, confirming that this was intermediate IM-48.

[0299] <Synthesis of intermediate IM-49> In a 500 mL three-neck flask, 10.00 g (26.3 mmol) of intermediate IM-48, 3.52 g (1.1 equiv, 28.9 mmol), and K 2 CO 3 10.89g(3.0equiv, 78.8mmol), Pd(PPh 3 ) 4 1.52g (0.05eq, 1.3mmol) and 184mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-49 (8.34 g, 84% yield). FAB-MS measurement revealed that the mass number m / z = 377 was observed as a molecular ion peak, confirming that this was intermediate IM-49.

[0300] <Synthesis of compound F63> Under an argon atmosphere, 5.00 g (13.2 mmol) of intermediate IM-49, 7.62 g (1.1 equiv, 14.6 mmol) of N-phenyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1':3',1''-terphenyl]-5'-amine, and K were added to a 300 mL three-neck flask. 2 CO 3 5.49g(3.0equiv, 39.7mmol), Pd(PPh 3 ) 4 0.76g (0.05eq, 0.7mmol) and 93mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain compound F63 (8.31 g, 85% yield) as a white solid. In FAB-MS measurement, a molecular ion peak was observed at mass number m / z=738, confirming that this was compound F63.

[0301] (Synthesis of compound F82) The amine compound F82 according to one embodiment can be synthesized, for example, according to the following reaction scheme 18.

[0302] [Reaction Scheme 18] [ka]

[0303] <Synthesis of intermediate IM-50> Under an argon atmosphere, 25.00g (97.2mmol) of 9-bromophenanthrene and 324mL (0.3M) of THF were added to a 1000mL three-neck flask and stirred at -78℃, while 66.8mL (1.1equiv) of 1.6mol / L nBuLi / n-hexane solution was added dropwise. After stirring at the same temperature for 1 hour, 15.14g (1.1equiv, 106.9mmol) of 5-chloropicolinaldehyde in THF solution (27mL, 1mol / L) was added dropwise and stirred at the same temperature for 30 minutes. After that, the temperature was raised to room temperature and further stirred. After confirming the disappearance of the raw materials, the reaction solution was cooled with water and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with aqueous sodium bicarbonate solution and saturated saline in turn, and then MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-50 (25.18 g, 81% yield). FAB-MS measurement revealed that the mass number m / z = 319 was observed as a molecular ion peak, confirming that this was intermediate IM-50.

[0304] <Synthesis of intermediate IM-51> Under an argon atmosphere, 20.00 g (62.5 mmol) of intermediate IM-50 and 208 mL (0.3 M) of formic acid were added to a 500 mL three-neck flask and heated with stirring at 120°C. The reaction solution was cooled to room temperature in air, quenched with water, and extracted with toluene. The aqueous layer was removed, and the organic layer was washed with an aqueous solution of sodium bicarbonate and saturated saline in that order, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-51 (14.15 g, 75% yield). FAB-MS measurement revealed that the mass number m / z = 301 was observed as a molecular ion peak, confirming that this was intermediate IM-51.

[0305] <Synthesis of intermediate IM-52> Under an argon atmosphere, 12.00 g (39.8 mmol) of intermediate IM-51 and CH 2 Cl 2 199 mL of 1,000 mL of 1,000 mL of 1,000 mL of N-bromosuccinimide and 8.49 g (1.2 equiv, 47.7 mmol) of N-bromosuccinimide were added in that order and stirred at room temperature. Water was added to the reaction solution, and then CHCl 3 The aqueous layer was removed, and the organic layer was washed with saturated saline and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-52 (11.96 g, 79% yield). FAB-MS measurement revealed that the mass number m / z = 380 was observed as a molecular ion peak, confirming that this was intermediate IM-52.

[0306] <Synthesis of intermediate IM-53> In a 500 mL three-neck flask, 10.00 g (26.3 mmol) of intermediate IM-52, 3.52 g (1.1 equiv, 28.9 mmol), and K 2 CO 3 10.89g(3.0equiv, 78.8mmol), Pd(PPh 3 ) 4 1.52g (0.05eq, 1.3mmol) and 184mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtering and concentrating the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain intermediate IM-53 (8.34 g, 84% yield). FAB-MS measurement revealed that the mass number m / z = 377 was observed as a molecular ion peak, confirming that this was intermediate IM-53.

[0307] <Synthesis of compound F82> Under an argon atmosphere, 5.00 g (13.2 mmol) of intermediate IM-53, 6.51 g (1.1 equiv, 14.6 mmol) of N,N-diphenyl-4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-(1,1'-biphenyl)-4-amine, and K were added to a 300 mL three-neck flask. 2 CO 3 5.49g(3.0equiv, 39.7mmol), Pd(PPh 3 ) 4 0.76g (0.05eq, 0.7mmol) and 93mL of a mixed solution of toluene / ethanol (EtOH) / water (4 / 2 / 1) were added in that order, and the mixture was heated and stirred at 80°C. After cooling to room temperature, the reaction solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated saline, and then extracted with MgSO 4 Dried with MgSO 4 The crude product obtained by filtration and concentration of the organic layer was purified by silica gel column chromatography (using a mixed solvent of hexane and toluene as the developing layer) to obtain compound F82 (6.74 g, 77% yield) as a white solid. In FAB-MS measurement, a molecular ion peak was observed at mass number m / z=662, confirming that this was compound F82.

[0308] 2. Preparation and evaluation of organic electroluminescence devices containing amine compounds (Fabrication of Organic Electroluminescent Device) An organic electroluminescence device of an embodiment containing an amine compound of an embodiment in a hole transport layer was manufactured by the following method. The organic electroluminescence devices of Examples 1 to 18 were manufactured using the above-mentioned amine compounds A1, A28, A57, B36, B46, C47, C87, D47, D60, D74, E6, E25, E55, E73, E89, F21, F63, and F82 as materials for the hole transport layer. In Comparative Examples 1 to 6, organic electroluminescence devices were manufactured using the following Comparative Compounds R1 to R6 as materials for the hole transport layer.

[0309] The compounds used in the hole transport layer in Examples 1 to 18 and Comparative Examples 1 to 6 are shown in Table 1 below.

[0310] [Table 1] JPEG0007679171000139.jpg189154 JPEG0007679171000140.jpg208154 JPEG0007679171000141.jpg58154

[0311] After patterning ITO with a thickness of 150 nm on a glass substrate, it was washed with ultrapure water and subjected to UV ozone treatment for 10 minutes. Then, 2-TNATA was evaporated to a thickness of 60 nm to form a hole injection layer. Next, the example compound or the comparative compound was evaporated to a thickness of 30 nm to form a hole transport layer.

[0312] Then, a 25 nm thick light-emitting layer was formed by doping ADN with 3% TBP. 3 was evaporated to a thickness of 25 nm to form an electron transport layer, and LiF was evaporated to a thickness of 1 nm to form an electron injection layer.

[0313] Next, Al was applied to a thickness of 100 nm to form the second electrode.

[0314] In the examples, the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, the electron injection layer and the second electrode were formed using a vacuum deposition apparatus.

[0315] (Evaluation of the characteristics of organic electroluminescent devices) Table 2 shows the evaluation results of the organic electroluminescence devices of Examples 1 to 18 and Comparative Examples 1 to 6. Table 2 shows a comparison of the driving voltage, luminous efficiency, and device life of the produced organic electroluminescence devices. In the results of the characteristic evaluation of the Examples and Comparative Examples shown in Table 2, the luminous efficiency was 10 mA / cm 2 The efficiency value at a current density of 1.0 mA / cm is shown. 2 The half-life at

[0316] The current density, voltage, and luminous efficiency of the organic electroluminescent devices of the examples and comparative examples were measured in a dark room using a 2400 series source meter from Keithley Instruments, a colorimeter CS-200 from Konica Minolta, and a measuring PC program LabVIEW 2.0 from National Instruments Japan.

[0317] [Table 2]

[0318] Referring to the results in Table 2, it can be seen that the organic electroluminescent device using the amine compound of one embodiment of the present invention as a material for the hole transport layer exhibits low driving voltage, excellent device efficiency, and good device life.

[0319] It can be confirmed that Examples 1 to 18 exhibit lower driving voltages and higher luminous efficiencies than Comparative Examples 1 to 6, and that the half life is also improved in terms of life characteristics.

[0320] In Examples 1 to 10, an amine compound of compound group 1 was used as the material of the hole transport layer. In Examples 11 to 18, an amine compound of compound group 2 was used as the material of the hole transport layer. That is, in Examples 1 to 10, an amine compound of an Example in which an aromatic hydrocarbon ring is fused to the pyridine side of the pyridoindole moiety was used as the material of the hole transport layer, and in Examples 11 to 18, an amine compound of an Example in which an aromatic hydrocarbon ring is fused to the indole side of the pyridoindole moiety was used as the material of the hole transport layer. With reference to the results in Table 2, it can be confirmed that all of the cases in which the amine compounds of compound group 1 and compound group 2 were used showed superior luminous efficiency and improved life characteristics compared to the comparative example. In addition, with reference to the results of Examples 1 to 7, it can be seen that excellent luminous efficiency and life characteristics were shown regardless of the position where the hexagonal hydrocarbon ring group was fused.

[0321] In addition, in Examples 8 to 10 and Examples 16 to 18, an amine compound having two hexagonal hydrocarbon ring groups condensed to a pyridoindole moiety was used as a hole transport layer, and in this case, the luminescence lifetime was somewhat improved compared to other Examples. This is believed to be because the HOMO orbital of the substituent containing the arylamine moiety is widely extended to the pyridoindole moiety, which is a condensed ring, improving the stability in the radical state.

[0322] Comparative Example 1 is a case where an amine compound having a carbazole group instead of a pyridoindole moiety is used, and Comparative Example 2 is a case where an amine compound containing a pyridoindole moiety but not a condensed hexagonal ring is used, and the device life and luminous efficiency were lower than those of the Examples. This is believed to be because the expansion of the HOMO orbital of the substituent containing the arylamine moiety is smaller than that of the compounds of the Examples, resulting in a decrease in stability in the radical state.

[0323] Comparative Example 3 contains a pyridone indole moiety, but is different from the compounds of Examples in that an indole is further condensed to the pyridoindole. It can be confirmed that the structure of the compound of Comparative Example 3 causes carrier imbalance, resulting in a decrease in both the device efficiency and device life compared to the Examples.

[0324] Comparative Examples 4 and 5 have pyridoindole and arylamine moieties similar to the amine compounds of the Examples, but compared to the Examples, the device life was particularly reduced. This is presumably because the pyridoindole bonded to the arylamine moiety at a particularly highly reactive position in the pyridoindole moiety, reducing stability in the radical state. For reference, the bonding position of the arylamine moiety in Comparative Example 4 is the same as that of R in the "HT" of the present invention represented by the following chemical formula 2. 1 The bonding position of the arylamine moiety in Comparative Example 5 corresponds to the R 8 In the example compounds of the present invention, R 1 and R 8 does not bond to the arylamine moiety.

[0325] [ka]

[0326] In Comparative Example 6, the material had three nitrogen-containing heterocycles, and the molecular symmetry was too high, which induced molecular stacking and reduced the amorphous nature, resulting in lower element efficiency and element life compared to the Examples.

[0327] Therefore, referring to the results of Examples 1 to 18 and Comparative Examples 1 to 6, the amine compound of one Example contains both a pyridoindole portion and an arylamine portion fused with an aromatic hexagonal ring, and the bonding positions of the arylamine portion and the pyridoindole portion are optimized, thereby improving both the luminous efficiency and the device lifetime.

[0328] That is, the amine compound of the embodiment can be used in a hole transport region to improve the luminous efficiency of an organic electroluminescent device.

[0329] The amine compound of the embodiment includes a pyridoindole moiety having at least one condensed hexagonal hydrocarbon ring group and an arylamine moiety bonded to the pyridoindole moiety, and thereby improves hole transport capability and resistance to high heat and charge, thereby improving the luminous efficiency and device life of the organic electroluminescent device of the embodiment.

[0330] Although the present invention has been described above with reference to a preferred embodiment, it will be understood that a person skilled in the art or having ordinary knowledge in the art can modify and change the present invention in various ways without departing from the spirit and technical scope of the present invention as set forth in the appended claims.

[0331] Therefore, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be defined by the claims. [Explanation of symbols]

[0332] 10 Organic electroluminescent device EL1 First electrode EL2 2nd electrode HTR Hole Transport Region EML Light Emitting Layer ETR electron transport region

Claims

1. An amine compound represented by the following chemical formula 1: 【Chemistry 1】 In the above Chemical Formula 1, Ar １ and Ar ２ each independently represents a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, Ar １ and Ar ２ Those containing a pyridoindole moiety are excluded, L is a single bond, a substituted or unsubstituted arylene group having from 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having from 2 to 30 ring carbon atoms, HT is represented by any one of the following formulas 2-1a to 2-1d and 2-2a to 2-2d: 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 4】 【Chemistry 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 In the chemical formulae 2-1a to 2-1d and 2-2a to 2-2d, R １ ~R ９ each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, R １０ ~R １３ each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, When the HT is represented by the formula 2-1d, the Ar １ and the Ar ２ is not a structure represented by the above chemical formula 2-1d, and R １ , R ８ and R ２１ is not a single bond with L in Chemical Formula 1, In the chemical formulas 2-1a to 2-1c and 2-2a to 2-2c, R ２ ~R ７ and R ９ ~R １３ is a single bond to L; In the above formula 2-1d, R ６ , R ７ , R ９ , R ２０ , R ２２ , R ２３ and R ３０ ~R ３３ is a single bond to L; In the above formula 2-2d, R 2 to R 5, R ２０ ~R ２３ and R ３０ ~R ３３ is a single bond to L; In the above Chemical Formula 2-1d, R ２０ ~R ２３ , and R ３０ ~R ３３ each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms, In the above Chemical Formula 2-2d, R ２０ ~R ２３ , and R ３０ ~R ３３ are each independently a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a substituted or unsubstituted aryl group having from 6 to 40 ring carbon atoms, a substituted or unsubstituted heteroaryl group having from 2 to 40 ring carbon atoms, or a substituted or unsubstituted alkyl group having from 1 to 20 carbon atoms.

2. R １ is an unsubstituted phenyl group, an unsubstituted naphthyl group, an unsubstituted biphenylyl group, an unsubstituted dibenzofuranyl group, or an unsubstituted dibenzothiophenyl group.

3. 2. The amine compound according to claim 1, wherein L is a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylylene group, a substituted or unsubstituted terphenylylene group, a substituted or unsubstituted phenanthrenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted dibenzofuranylene group.

4. Ar １ and Ar ２ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted pyridinyl group.

5. Ar １ and Ar ２ are each independently an aryl group having 6 to 40 ring carbon atoms, which is substituted or unsubstituted with at least one substituent selected from the group consisting of a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a triarylsilyl group having 18 to 50 carbon atoms, and an adamantyl group; or The amine compound according to claim 1, which is a heteroaryl group having 2 to 40 ring carbon atoms and which is substituted or unsubstituted with at least one substituent selected from the group consisting of a halogen atom, a cyano group, an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, an aryloxy group having from 1 to 20 carbon atoms, an aryl group having from 6 to 30 carbon atoms, a triarylsilyl group having from 18 to 50 carbon atoms, and an adamantyl group.

6. The amine compound according to claim 1 , wherein the formula 1 is represented by any one of compounds in the following compound group 1 and compound group 2: [Compound group 1] 【Chemistry 12】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 [Compound group 2] 【Chemistry 13】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】

7. A first electrode; a second electrode disposed on the first electrode; a plurality of organic layers disposed between the first electrode and the second electrode; 10. An organic electroluminescent device, wherein at least one of the organic layers contains the amine compound according to claim 1.

8. The organic layer includes an emitting layer and a hole transport region disposed between the first electrode and the light emitting layer; The organic electroluminescent device of claim 7, wherein the hole transport region comprises an amine compound represented by Formula 1.

9. The organic electroluminescent device according to claim 8, wherein the light emitting layer emits blue or green light.

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