Organic compound and organic light-emitting device comprising same

Abstract

The present invention relates to an organic light-emitting device which can operate at low voltages and has significantly improved light-emitting efficiency and lifespan due to having a plurality of types of host compounds in the light-emitting layer thereof while using a compound having a characteristic structure as one host material type. The organic light-emitting device can have high efficiency and long lifespan characteristics, and thus can be usefully employed throughout the industry for lighting devices and various display devices such as flat-panel, flexible, and wearable displays, vehicle and aviation displays, or virtual and augmented reality displays.

Description

Organic compounds and organic light-emitting devices containing the same

[0001] The present invention relates to an organic compound employed in a light-emitting layer in an organic light-emitting device and an organic light-emitting device comprising the same.

[0002] An organic light-emitting device is a self-luminous device in which electrons injected from an electron injection electrode (cathode electrode) and holes injected from a hole injection electrode (anode electrode) combine in a light-emitting layer to form excitons, and the excitons emit energy, thereby emitting light. Such an organic light-emitting device is attracting attention as a next-generation light source due to its advantages of low operating voltage, high brightness, wide viewing angle, and fast response speed, and its applicability to full-color flat panel light-emitting displays.

[0003] In order for these organic light-emitting devices to exhibit the above-described characteristics, the structure of the organic layers within the device must be optimized, and the materials that make up each organic layer, such as hole injection materials, hole transport materials, hole blocking materials, luminescent materials, electron transport materials, electron injection materials, and electron blocking materials, must first be supported by stable and efficient materials. However, the development of the structure of the organic layers and each material for stable and efficient organic light-emitting devices is still continuously necessary.

[0004] In particular, to obtain maximum efficiency in the light-emitting layer, the energy band gaps of the host and dopant must be appropriately combined so that holes and electrons can move to the dopant through stable electrochemical pathways to form excitons.

[0005] Accordingly, the present invention aims to provide a light-emitting layer host material having a characteristic structure and a high-efficiency, long-life organic light-emitting device including the same, which has low-voltage operation and significantly improved light-emitting efficiency and lifespan.

[0006] In order to solve the above problem, the present invention provides an organic light-emitting device comprising a first electrode; a second electrode facing the first electrode; and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises a light-emitting layer comprising a host and a dopant, the host comprises a first compound and a second compound, and the first compound comprises at least one organic compound represented by the following [Chemical Formula 1].

[0007] [Chemical Formula 1]

[0008]

[0009] The specific structure of the above [chemical formula 1] and the specific compound and definition of each substituent according to the present invention implemented accordingly will be described later.

[0010] The organic light-emitting device according to the present invention comprises a plurality of host compounds in the light-emitting layer, and employs a compound having a characteristic structure as one host material, thereby realizing high efficiency and long life characteristics with low voltage operation and significantly improved luminous efficiency and lifespan, and can be usefully utilized in various display devices such as lighting devices, flat panel, flexible, wearable, vehicle or aviation displays, and virtual or augmented reality displays.

[0011] Hereinafter, the present invention will be described in more detail.

[0012] The present invention relates to an organic light-emitting device comprising: a first electrode; a second electrode facing the first electrode; and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises a light-emitting layer comprising a host and a dopant, wherein the host comprises a first compound and a second compound, and wherein the first compound comprises at least one organic compound represented by the following [Chemical Formula 1].

[0013] At this time, the first compound represented by the following [chemical formula 1] is characterized by being an organic compound in which a benzene derivative skeleton containing structural nitrogen is substituted with two carbazoles and a silyl group substituted with a characteristic substituent, and by this characteristic, by configuring the host compound of the light-emitting layer with multiple types, and employing the compound of the following [chemical formula 1] having a characteristic structure as one type of host material, it is possible to implement a high-efficiency and long-life organic light-emitting device having low-voltage operation and significantly improved light-emitting efficiency and lifespan.

[0014] [Chemical Formula 1]

[0015]

[0016] In the above [chemical formula 1],

[0017] X1 to X3 are the same or different from each other, and are each independently N or CR, and at least one of X1 to X3 is N, and according to one embodiment of the present invention, X1 to X3 can each be all N.

[0018] Z is Si or Ge.

[0019] X is O, S, NR5, CR6R7, SiR8R9, and GeR 10 R 11 Any one of which is selected from, and according to one embodiment of the present invention, X may be O or S.

[0020] R1 and R2 are the same or different, and each independently represent one selected from a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, and a ring group in which a substituted or unsubstituted aliphatic ring having 3 to 30 carbon atoms and an aromatic ring having 5 to 30 carbon atoms are fused.

[0021] According to one embodiment of the present invention, R1 and R2 are the same as or different from each other, and can each independently be any one selected from a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms, and a ring group in which a substituted or unsubstituted aliphatic ring having 3 to 18 carbon atoms and an aromatic ring having 5 to 18 carbon atoms are fused.

[0022] m1 and m2 are each independently an integer from 1 to 3, and when each is an integer greater than or equal to 2, each of R1 and R2 is the same or different from each other.

[0023] R and R3 to R 11are the same or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a ring group in which a substituted or unsubstituted aliphatic ring having 3 to 30 carbon atoms and an aromatic ring having 5 to 30 carbon atoms are fused, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms Any one selected from an alkylthioxy group, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted amine group, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, a nitro group, a cyano group, and a halogen group.

[0024] m3 and m4 are each independently an integer of 8, and each of R3 and R4 is the same or different from each other, and according to one embodiment of the present invention, both R3 and R4 can be deuterium.

[0025] The above adjacent R3 and R4 may be linked to each other to additionally form an alicyclic or aromatic monocyclic or polycyclic ring.

[0026] Also, the above R6 and R7, R8 and R9 and R 10 and R 11 can be linked to each other to form additional alicyclic or aromatic monocyclic or polycyclic rings.

[0027]

[0028] L1 and L2 are the same or different, and each independently represent one selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and a divalent ring group in which a substituted or unsubstituted aliphatic ring having 3 to 24 carbon atoms and an aromatic ring having 5 to 24 carbon atoms are fused.

[0029] According to one embodiment of the present invention, L1 and L2 are the same as or different from each other, and can each independently be a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

[0030] n1 and n2 is an integer from 1 to 3, and when each is an integer greater than or equal to 2, each of L1 and L2 is the same or different from each other.

[0031]

[0032] A or B is the same as or different from each other, and is each independently selected from a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon ring having 3 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocycle having 2 to 30 carbon atoms, a substituted or unsubstituted aliphatic heterocycle having 2 to 30 carbon atoms, and a ring in which a substituted or unsubstituted aliphatic ring having 3 to 24 carbon atoms and an aromatic ring having 5 to 24 carbon atoms are fused.

[0033] According to one embodiment of the present invention, B may be a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 20 carbon atoms.

[0034]

[0035] In addition, the 'substitution' in 'substituted or unsubstituted' in the above [chemical formula 1] refers to a deuterium, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 2 to 30 carbon atoms, a ring group in which an aliphatic ring having 3 to 24 carbon atoms and an aromatic ring having 5 to 24 carbon atoms are fused, an alkoxy group having 1 to 24 carbon atoms, an alkyl group having 1 to It means being substituted with one or more substituents selected from the group consisting of an amine group having 30 carbon atoms, a silyl group having 1 to 30 carbon atoms, a germanium group having 1 to 30 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, an arylthionyl group having 6 to 24 carbon atoms, a cyano group, a halogen group, a hydroxy group and a nitro group, and in the case of two or more, they are the same or different, and at least one hydrogen in each substituent can be replaced with deuterium.

[0036]

[0037] In addition, the organic compound represented by the above-described [chemical formula 1] according to the present invention is characterized in that at least one deuterium is substituted in the above-described [chemical formula 1].

[0038]

[0039] In addition, according to one embodiment of the present invention, the organic compound represented by [Chemical Formula 1] may be represented by the following [Chemical Formula 1-1].

[0040] [Chemical Formula 1-1]

[0041]

[0042] In the above [chemical formula 1-1],

[0043] R 12are the same or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a ring group in which a substituted or unsubstituted aliphatic ring having 3 to 30 carbon atoms and an aromatic ring having 5 to 30 carbon atoms are fused, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms Any one selected from an alkylthioxy group, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted amine group, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, a nitro group, a cyano group, and a halogen group,

[0044] m5 is an integer of 3, and each R 12 are identical or different from each other.

[0045] The above adjacent multiple R 12 can be linked to each other to form additional alicyclic or aromatic monocyclic or polycyclic rings.

[0046] The above X, X1 to X3, Z, R1 to R4, L1, L2, n1, n2, m1 to m4 and B ring are the same as defined in the above [Chemical Formula 1].

[0047]

[0048] In addition, the light-emitting layer is a structure composed of a host and a dopant, and the light-emitting layer may further include a dopant material. At this time, the content of the dopant may be typically selected in a range of about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host, but is not limited thereto.

[0049]

[0050] In the present invention, the dopant compound included in the light-emitting layer is not a fluorescent dopant material that only transfers to a singlet state using the Förster energy transfer method in the existing Host-Dopant system, but a phosphorescent dopant material of a metal complex including at least one metal selected from Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Re, Pd, etc. that transfers without distinguishing between singlet and triplet states using the Dexter energy transfer method, and any known dopant material can be used without special limitation as long as it emits light from a triplet exciton.

[0051] As a metal complex, Ir, Pt and Pd can be preferably selected, and specific examples include Ir(ppy)3, Ir(ppy)2acac, Ir(Bt)2acac, Ir(MDQ)2acac, Ir(mppy)3, Ir(piq)3, Ir(piq)2acac, Ir(pq)2acac, Ir(mpp)2acac, F2Irpic, (F2ppy)2Ir(tmd), Ir(ppy)2tmd, Ir(pmi)3, Ir(pmb)3, FCNIr, FCNIrpic, FIr6, FIrN4, FIrpic, PtOEP, Ir(chpy)3,P0-01(C 31 H 23 IrN2O2S2), Ir(ppz)3, Ir(dfppz)3, PtNON, Pt-10, Pt-11, etc. can be used, but are not limited thereto.

[0052]

[0053] In addition, the light-emitting layer may additionally include various hosts and various dopant materials in addition to the host and dopant compounds according to the present invention, and accordingly, in the light-emitting layer, not only the host but also the dopant material may be used by mixing or laminating one or more different compounds.

[0054]

[0055] Here, in the case where at least one additional host compound is additionally included in addition to one compound represented by the above [Chemical Formula 1] and two or more host compounds are mixed or laminated and used, a compound having an electron donor moiety can be used as the additional host, and due to the HOMO / LUMO levels of the high hole injection and electron injection barrier resulting from mixing or laminating with [Chemical Formula 1] having an Azine moiety, which is a nitrogen-containing aromatic heterocycle as an electron acceptor moiety, the recombination region is limited to the interface of the two hosts, thereby minimizing current loss, etc., it is possible to implement a high-efficiency, long-life organic light-emitting device.

[0056] At this time, the compound having the electron donating moiety is a compound having a moiety that has an environment that is easy to donate electrons from the outside, such as a compound having an amine group in the molecule and a compound substituted with carbazole, and may preferably include a compound including an aromatic hydrocarbon ring including a tertiary amine in the molecule; or an aromatic hydrocarbon ring including carbazole and bicarbazole in the molecule.

[0057]

[0058] In addition, according to one embodiment of the present invention, the plurality of hosts in the light-emitting layer of the organic light-emitting device according to the present invention may be used by mixing one or more organic compounds represented by the following [Chemical Formula 3] in addition to the compound represented by the above [Chemical Formula 1], or by layering the compound represented by the following [Chemical Formula 3] on the upper or lower part of a layer including the compound represented by the above [Chemical Formula 1].

[0059] [Chemical Formula 3]

[0060]

[0061] In the above [chemical formula 3],

[0062] L 21 is independently a single bond, or any one selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and a divalent ring group in which a substituted or unsubstituted aliphatic ring having 3 to 24 carbon atoms and an aromatic ring having 5 to 24 carbon atoms are fused.

[0063] The above R 21 Inland R 23are the same or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a ring group in which a substituted or unsubstituted aliphatic ring having 3 to 30 carbon atoms and an aromatic ring having 5 to 30 carbon atoms are fused, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms Any one selected from an alkylthioxy group, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted amine group, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, a nitro group, a cyano group, and a halogen group.

[0064] m 21 is an integer from 1 to 2, but in the case of an integer of 2, each L 21 are identical or different from each other.

[0065] m 22 is an integer of 7 or 8, and each R 22 are identical or different from each other.

[0066] m 23 is an integer of 8, and each R 23 are identical or different from each other.

[0067] n is an integer of 0 or 1.

[0068] In the above [chemical formula 3], 'substitution' in 'substituted or unsubstituted' means deuterium, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 2 to 30 carbon atoms, a ring group in which an aliphatic ring having 3 to 24 carbon atoms and an aromatic ring having 5 to 24 carbon atoms are fused, an alkoxy group having 1 to 24 carbon atoms, an alkyl group having 1 to 30 carbon atoms. It means being substituted with one or more substituents selected from the group consisting of an amine group, a silyl group having 1 to 30 carbon atoms, a germanium group having 1 to 30 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, an arylthionyl group having 6 to 24 carbon atoms, a cyano group, a halogen group, a hydroxy group, and a nitro group, and in the case of two or more, they are the same or different, and at least one hydrogen in each substituent can be replaced with deuterium.

[0069]

[0070] In addition, the organic compound represented by [chemical formula 1] used in the above host is characterized in that it is used in a blue phosphorescent host.

[0071]

[0072] In addition, the organic layer of the organic light-emitting device according to the present invention may be formed as a single-layer structure, but may be formed as a multi-layer structure in which two or more organic layers are laminated. For example, it may have a structure including a hole injection layer, a hole transport layer, a hole blocking layer, a light-emitting layer, an electron blocking layer, an electron transport layer, an electron injection layer, etc. However, it is not limited thereto, and a smaller or larger number of organic layers may be included, and the organic layer structure of a preferred organic light-emitting device according to the present invention will be described in more detail in the following examples.

[0073]

[0074] In addition, according to one embodiment of the present invention, the dopant may include at least one organometallic compound, and may be used by mixing or layering a polycyclic ring compound represented by the following [chemical formula 2] in addition to the organometallic compound.

[0075] Accordingly, in an organic light-emitting device according to one embodiment of the present invention, the light-emitting layer may be configured to include a first compound, a second compound, an organometallic compound, and a polycyclic compound (boron thermally activated delayed fluorescent emitter) material of the following [chemical formula 2].

[0076] In this case, the organometallic compound functions as a sensitizer, and the polycyclic compound functions as a luminescent dopant, so that the sensitizer compound can receive excitons from the first compound and the second compound and transfer them to the luminescent dopant.

[0077] Accordingly, excitons from the sensitizer are transferred to the light-emitting dopant compound through the Dexter energy transfer (DET) or Forster resonance transfer (FRET) mechanism, and the exciton energy transferred to the light-emitting dopant compound can emit light while being transferred to the ground state. At this time, the excitons of the sensitizer can be transferred from the first compound and the second compound through the FRET mechanism, or can be formed by the transfer of excitons generated from the host through the DET mechanism.

[0078] Accordingly, energy transfer through FRET and DET mechanisms between the sensor and the light-emitting dopant is facilitated, and triplet-triplet annihilation is suppressed, enabling the production of a high-efficiency organic light-emitting device.

[0079]

[0080] The boron thermally activated delayed fluorescence emitter, which is a polycyclic compound represented by the following [chemical formula 2], enables Förster energy transfer from the triplet of the phosphorescence sensitizer to the singlet of the boron thermally activated delayed fluorescence emitter, thereby reducing the number of long-lived triplet excitons involved in device degradation and improving the lifetime. In addition, since it has a high molar extinction coefficient, the efficiency and lifetime can be improved due to effects such as an increase in the speed of fluorescence resonance energy transfer from the phosphorescence sensitizer to the emitter and a narrowing of the emission spectrum due to the multiple resonance effect, thereby increasing color purity.

[0081]

[0082] [Chemical Formula 2]

[0083]

[0084] In the above [chemical formula 2],

[0085] Y1 and Y2 are the same or different and are independently O, S, NR 13 , CR 14 R 15 , SiR 16 R 17 and GeR 18 R 19 One of the following is selected.

[0086] A1 to A3 are the same or different, and are each independently selected from a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon ring having 3 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocycle having 2 to 30 carbon atoms, a substituted or unsubstituted aliphatic heterocycle having 2 to 30 carbon atoms, and a ring in which a substituted or unsubstituted aliphatic ring having 3 to 24 carbon atoms and an aromatic ring having 5 to 24 carbon atoms are fused.

[0087] The above R 13 Inland R 19 are the same or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a ring group in which a substituted or unsubstituted aliphatic ring having 3 to 30 carbon atoms and an aromatic ring having 5 to 30 carbon atoms are fused, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms Any one selected from an alkylthioxy group, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted amine group, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, a nitro group, a cyano group, and a halogen group.

[0088] The above R 13 Inland R 19 It can be connected to the above A1 to A3 rings to additionally form an alicyclic or aromatic monocyclic or polycyclic ring.

[0089] The above R 14 Wow R 15 , R 16 and R 17 and R 18 and R 19 Each of them can be linked to each other to form an additional alicyclic or aromatic monocyclic or polycyclic ring.

[0090]

[0091] In addition, the 'substitution' in 'substituted or unsubstituted' in the above [chemical formula 2] refers to a deuterium, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 2 to 30 carbon atoms, a ring group in which an aliphatic ring having 3 to 24 carbon atoms and an aromatic ring having 5 to 24 carbon atoms are fused, an alkoxy group having 1 to 24 carbon atoms, an alkyl group having 1 to It means being substituted with one or more substituents selected from the group consisting of an amine group having 30 carbon atoms, a silyl group having 1 to 30 carbon atoms, a germanium group having 1 to 30 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, an arylthionyl group having 6 to 24 carbon atoms, a cyano group, a halogen group, a hydroxy group and a nitro group, and in the case of two or more, they are the same or different, and at least one hydrogen in each substituent can be replaced with deuterium.

[0092]

[0093] Meanwhile, in the present invention, the carbon number range of the alkyl group or aryl group in the 'substituted or unsubstituted alkyl group having 1 to 30 carbon atoms', 'substituted or unsubstituted aryl group having 6 to 50 carbon atoms', etc. means the total number of carbon atoms constituting the alkyl portion or aryl portion when the substituent is viewed as unsubstituted without considering the substituted portion. For example, a phenyl group substituted with a butyl group at the para-position means an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

[0094]

[0095] In addition, in the present invention, the meaning of forming an additional ring by being connected to each other or to adjacent groups means that among the specified substituents, adjacent substituents can be connected to each other, or a specified substituent and another adjacent group can be connected to each other to form a substituted or unsubstituted alicyclic or aromatic ring, and the 'adjacent group' can mean a substituent substituted on an atom directly connected to the atom substituted by the substituent, a substituent that is sterically closest to the substituent, or another substituent substituted on the atom substituted by the substituent. For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted on the same carbon in an aliphatic ring can be interpreted as 'adjacent groups', and a pair of connected substituents additionally form a ring by removing one hydrogen radical from each and connecting them, and the carbon atoms of the formed alicyclic or aromatic monocyclic or polycyclic ring can be replaced by heteroatoms such as N, O, S, Si, Ge, etc.

[0096]

[0097] In the present invention, the alkyl group may be straight-chain or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methyl-butyl group, a 1-ethyl-butyl group, a pentyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, an n-heptyl group, a 1-methylhexyl group, a cyclopentylmethyl group, a cyclohectylmethyl group, an octyl group, an n-octyl group, a tert-octyl group, a 1-methylheptyl group, Examples thereof include, but are not limited to, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, and 5-methylhexyl group.

[0098] In the present invention, specific examples of the arylalkyl group include, but are not limited to, phenylmethyl (benzyl), phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl, etc.

[0099] In the present invention, specific examples of the alkylaryl group include, but are not limited to, tolyl, xylenyl, dimethylnaphthyl, t-butylphenyl, t-butylnaphthyl, t-butylphenanthryl, etc.

[0100] In the present invention, the alkenyl group includes a straight chain or a branched chain, and may be further substituted by another substituent, and specifically, includes a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 3-methyl-1-butenyl group, a 1,3-butadienyl group, an allyl group, a 1-phenylvinyl-1-yl group, a 2-phenylvinyl-1-yl group, a 2,2-diphenylvinyl-1-yl group, a 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, a 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, a stilbenyl group, a styrenyl group, etc., but is not limited thereto.

[0101] In the present invention, the alkynyl group also includes a straight chain or branched chain, and may be further substituted by another substituent, and examples thereof include, but are not limited to, ethynyl and 2-propynyl.

[0102] In the present invention, a cycloalkenyl group is a cyclic unsaturated hydrocarbon group having one or more carbon double bonds and not an aromatic ring, and may include, but is not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 2,4-cycloheptadienyl, and 1,5-cyclooctadienyl groups.

[0103] In the present invention, the aromatic hydrocarbon ring or aryl group may be monocyclic or polycyclic, and polycyclic means a group directly connected to or condensed with another ring group, and the other ring group may be an aromatic hydrocarbon ring, but may also be another type of ring group, for example, an aliphatic heterocycle, an aliphatic hydrocarbon ring, an aromatic heterocycle, etc. Examples of monocyclic aryl groups include a phenyl group, a biphenyl group, a terphenyl group, etc., and examples of polycyclic aryl groups include a naphthyl group, anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a tetracenyl group, a chrysenyl group, a fluorenyl group, an acenaphthacenyl group, a triphenylene group, a fluoranthene group, etc., but the scope of the present invention is not limited to these examples.

[0104] In the present invention, the aromatic heterocycle or heteroaryl group is an aromatic ring containing at least one heteroatom, and includes a heteroatom such as O, S, N, P, Si or Ge, and examples thereof include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a pyrimidyl group, a triazine group, a triazole group, an acridyl group, a pyridazine group, a pyrazinyl group, a quinolinyl group, a quinazoline group, a quinoxalinyl group, a phthalazinyl group, a pyrido pyrimidinyl group, a pyrido pyrazinyl group, a pyrazino pyrazinyl group, an isoquinoline group, an indole group, a carbazole group, an indolocarbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, Examples thereof include, but are not limited to, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, and phenothiazinyl group.

[0105] In the present invention, an aliphatic hydrocarbon ring or cycloalkyl group means a ring that is not aromatic and is composed only of carbon and hydrogen atoms, and includes, for example, a monocyclic ring or a polycyclic ring, and may be further substituted by another substituent. A polycyclic ring means a group that is directly connected to or condensed with another ring group, and the other ring group may be an aliphatic hydrocarbon ring, but may also be another type of ring group, such as an aliphatic heterocycle, an aromatic hydrocarbon ring, an aromatic heterocycle, etc. Specifically, it includes, but is not limited to, cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, an adamantyl group, a bicycloheptanyl group, a 3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 3,4,5-trimethylcyclohexyl group, a 4-tert-butylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group, and cycloalkanes such as cyclohexane and cyclopentane, and cyclocycloalkenes such as cyclohexene and cyclobutene.

[0106] In the present invention, an aliphatic heterocycle or heterocycloalkyl group means an aliphatic ring containing at least one heteroatom, and includes a heteroatom such as O, S, Se, N, Si or Ge, and also includes a monocyclic ring or a polycyclic ring, and may be further substituted by another substituent, and a polycyclic ring means a group in which a heterocycloalkyl or a heterocycloalkane is directly connected to or condensed with another ring group, and the other ring group may be an aliphatic heterocycle, but may also be another type of ring group, for example, an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, an aromatic heterocycle, etc.

[0107] In the present invention, a ring (group) in which an aliphatic ring and an aromatic ring are fused is an aliphatic aromatic mixed ring (group), which means a ring in which two or more rings are connected and condensed with each other, and in which an aliphatic ring and an aromatic ring are condensed to have non-aromaticity as a whole, and more specifically, it means an aromatic hydrocarbon ring condensed with an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring condensed with an aliphatic heterocycle, an aromatic heterocycle condensed with an aliphatic heterocycle, an aromatic hydrocarbon ring condensed with an aliphatic hydrocarbon ring, an aromatic heterocycle condensed with an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring condensed with an aliphatic heterocycle, an aromatic heterocycle condensed with an aliphatic It can be a heterocyclic group, and specific examples include a tetrahydronaphthyl group, a tetrahydrobenzocycloheptene group, a tetrahydrophenanthrene group, a tetrahydroanthracenyl group, an octahydrotriphenylene group, a tetrahydrobenzothiophene group, a tetrahydrobenzofuranyl group, a tetrahydrocarbazole group, a tetrahydroquinoline group, etc. In addition, in a ring (group) in which an aliphatic ring and an aromatic ring are fused, it can be replaced with a heteroatom such as O, S, N, P, Si, or Ge other than carbon.

[0108]

[0109] In the present invention, the alkoxy group may be specifically methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, etc., but is not limited thereto.

[0110] In the present invention, the silyl group may include -SiH3, an alkylsilyl group, an arylsilyl group, an alkylarylsilyl group, an arylheteroarylsilyl group, a heteroarylsilyl group, etc., and the arylsilyl group means a silyl group in which one, two, or three hydrogens are substituted with an aryl group in -SiH3, and the alkylsilyl group means an amine in which one, two, or three hydrogens are substituted with alkyl in -SiH3, and the alkylarylsilyl group means a silyl group in which at least one hydrogen is substituted with an alkyl group and an aryl group, and includes one or two alkyl groups and two or one corresponding aryl groups, and the arylheteroarylsilyl group means a silyl group in which at least one hydrogen is substituted with an aryl group and a heteroaryl group, and includes one or two aryl groups and two or one corresponding heteroaryl groups, in -SiH3. It means, and the heteroarylsilyl group means a silyl group in which one, two, or three hydrogens in -SiH3 are substituted with a heteroaryl group, and examples of the arylsilyl group include a substituted or unsubstituted monoarylsilyl group, a substituted or unsubstituted diarylsilyl group, or a substituted or unsubstituted triarylsilyl group, and the alkylsilyl group and the heteroarylsilyl group are also the same.

[0111] Here, each aryl group in the arylsilyl group, heteroarylsilyl group, and arylheteroarylsilyl group may be a monocyclic aryl group or a polycyclic aryl group, and each heteroaryl group in the arylsilyl group, heteroarylsilyl group, and arylheteroarylsilyl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group.

[0112] In addition, specific examples of the silyl group include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl, etc., and at least one hydrogen atom of the silyl group can be substituted with a substituent similar to that of the aryl group.

[0113] In the present invention, the amine group may include -NH2, an alkylamine group, an arylamine group, an alkylarylamine group, an arylheteroarylamine group, a heteroarylamine group, etc., and the arylamine group means an amine in which one or two hydrogens in -NH2 are substituted with an aryl group, the alkylamine group means an amine in which one or two hydrogens in -NH2 are substituted with an alkyl group, the alkylarylamine group means an amine in which one hydrogen in -NH2 is substituted with an alkyl group and the other hydrogen in -NH2 is substituted with an aryl group, the arylheteroarylamine group means an amine in which one hydrogen in -NH2 is substituted with an aryl group and the other hydrogen in -NH2 is substituted with a heteroaryl group, and the heteroarylamine group means an amine in which one or two hydrogens in -NH2 are substituted with a heteroaryl group, and examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted There is a diarylamine group, or a substituted or unsubstituted triarylamine group, and the same applies to the alkylamine group and heteroarylamine group.

[0114] Here, each aryl group in the arylamine group, heteroarylamine group, and arylheteroarylamine group may be a monocyclic aryl group or a polycyclic aryl group, and each heteroaryl group in the arylamine group, heteroarylamine group, and arylheteroarylamine group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. Or, it may be a polycyclic aryl group, and each heteroaryl group in the arylamine group, heteroarylamine group, and arylheteroarylamine group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group.

[0115] In the present invention, the germanium group (or germane group) may include -GeH3, an alkylgermanium group, an arylgermanium group, a heteroarylgermanium group, an alkylarylgermanium group, an alkylheteroarylgermanium group, an arylheteroarylgermanium group, etc., and the definitions of these are as described for the silyl group, but may be applied to each substituent as a substituent obtained by substituting a germanium atom (Ge) for a silicon atom (Si) in the silyl group.

[0116] In addition, specific examples of the germanium group include trimethylgermane, triethylgermane, triphenylgermane, trimethoxygermane, dimethoxyphenylgermane, diphenylmethylgermane, diphenylvinylgermane, methylcyclobutylgermane, dimethylfurylgermane, etc., and one or more hydrogen atoms of the germanium group can be substituted with a substituent similar to that of the aryl group.

[0117] In the present invention, the cycloaryl group, aryl group, and heteroaryl group among the cycloalkyloxy group, aryloxy group, heteroaryloxy group, cycloalkylthio group, arylthio group, and heteroarylthio group are the same as the examples of the cycloaryl group, aryl group, and heteroaryl group described above, and specifically, as an example of the aryloxy group, a phenoxy group, a p-tolyloxy group, a m-tolyloxy group, a 3,5-dimethyl-phenoxy group, a 2,4,6-trimethylphenoxy group, a p-tert-butylphenoxy group, a 3-biphenyloxy group, a 4-biphenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methyl-1-naphthyloxy group, a 5-methyl-2-naphthyloxy group, a 1-anthryloxy group, a 2-anthryloxy group, a 9-anthryloxy group, Examples of arylthioxy groups include, but are not limited to, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, etc., and phenylthioxy group, 2-methylphenylthioxy group, 4-tert-butylphenylthioxy group, etc.

[0118] In the present invention, examples of halogen groups include fluorine, chlorine, bromine or iodine.

[0119]

[0120] According to one embodiment of the present invention, the compound represented by the above-described [chemical formula 1] may be any one selected from compounds represented by the following chemical formulas, but the scope thereof is not limited thereby.

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128] Hereinafter, one embodiment of an organic light-emitting device according to the present invention will be described in more detail.

[0129] The organic light-emitting device according to the present invention includes an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode. If necessary, a hole injection layer may be further included between the anode and the hole transport layer. In addition, an electron injection layer may be further included between the electron transport layer and the cathode. In addition, one or two intermediate layers may be further formed, a hole blocking layer or an electron blocking layer may be further formed, and as described above, an organic layer having various functions depending on the characteristics of the device, such as a capping layer, may be further included.

[0130]

[0131] Meanwhile, the specific structure of the organic light-emitting device according to one embodiment of the present invention, the manufacturing method thereof, and each organic layer material are as follows.

[0132] First, an anode is formed by coating an anode material on the upper surface of the substrate. Here, the substrate used is a substrate commonly used in organic light-emitting devices, but an organic substrate or transparent plastic substrate with excellent transparency, surface smoothness, ease of handling, and water resistance is preferred. In addition, the anode material used is indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity.

[0133] A hole injection layer is formed by vacuum thermal evaporation or spin coating of a hole injection layer material on top of the anode electrode, and then a hole transport layer is formed by vacuum thermal evaporation or spin coating of a hole transport layer material on top of the hole injection layer.

[0134] The above hole injection layer material can be used without particular limitation as long as it is commonly used in the art, and specific examples thereof include 2-TNATA [4,4',4"-tris(2-naphthylphenyl-phenylamino)-triphenylamine], NPD [N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine)], TPD [N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine], DNTPD [N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine], HAT-CN[1,4,5,8,9,11-Hexaazatriphenylenehexacarbonitrile], etc.

[0135] In addition, the hole transport layer material is not particularly limited as long as it is one commonly used in the art, and for example, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzidine (α-NPD) can be used.

[0136] Next, a hole-assisting layer and a light-emitting layer are successively stacked on top of the hole transport layer, and a hole-blocking layer can be selectively formed as a thin film on top of the light-emitting layer by a vacuum deposition method or a spin coating method. The hole-blocking layer prevents the lifespan and efficiency of the device from decreasing when holes pass through the organic light-emitting layer and flow into the cathode by using a material with a very low HOMO (Highest Occupied Molecular Orbital) level. The hole-blocking material used at this time is not particularly limited, but must have an electron transport ability and a higher ionization potential than the light-emitting compound, and representative examples thereof include BAlq, BCP, and TPBI.

[0137] As a material used in the above hole-blocking layer, BAlq, BCP, Bphen, TPBI, TAZ, BeBq2, OXD-7, Liq, etc. can be used, but are not limited thereto.

[0138] An electron transport layer is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, and then an electron injection layer is formed. A cathode electrode is formed by vacuum thermally depositing a metal for forming a cathode on top of the electron injection layer, thereby completing an organic light-emitting device according to one embodiment of the present invention.

[0139] Here, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), etc. can be used as the metal for forming the cathode, and a transparent cathode using ITO or IZO can be used to obtain a front-emitting element.

[0140] The above electron transport layer material has the function of stably transporting electrons injected from the cathode, and a known electron transport material can be used. Examples of known electron transport materials include quinoline derivatives, particularly tris(8-quinolinolate)aluminum (Alq3), TAZ, BAlq, beryllium bis(benzoquinolin-10-olate: Bebq2), and oxadiazole derivatives (PBD, BMD, BND, etc.).

[0141]

[0142] In addition, each of the above organic layers can be formed by a single molecule deposition method or a solution process, wherein the deposition method refers to a method of forming a thin film by evaporating a material used as a material for forming each layer through heating in a vacuum or low pressure state, and the solution process refers to a method of forming a thin film by mixing a material used as a material for forming each layer with a solvent and using a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, or spin coating.

[0143] In addition, the organic light-emitting device according to the present invention can be used in a device selected from a flat panel display device, a flexible display device, a flat panel lighting device of a single color or white color, a flexible lighting device of a single color or white color, a vehicle display device, a virtual or augmented reality display device, etc.

[0144] Hereinafter, to aid in understanding the present invention, synthetic examples of preferred compounds and device examples are presented. However, the following examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention.

[0145]

[0146] Synthesis Example 1: Synthesis of [ET-1]

[0147] Synthesis Example 1-1: Synthesis of A-1

[0148]

[0149] <a-1a> <a-1b> <a-1>

[0150] In a round bottom flask <a-1a>39.8 g and 398 mL of diethyl ether were added under nitrogen, cooled to -78°C, and 103.7 mL of 1.6 M n-butyl lithium was slowly added dropwise and stirred. After 1 hour <a-1b>20 g was added and stirred at room temperature for 12 hours. After completion of the reaction, the layers were separated with water and ethyl acetate, the organic layer was concentrated under reduced pressure, and then separated and purified by column chromatography. <a-1>(25.4 g, 65%) was obtained.

[0151]

[0152] Synthesis Example 1-2: Synthesis of A-2

[0153]

[0154] <a-1> <a-2a> <a-2>

[0155] In a round bottom flask <a-1> 25.4 g, <a-2a>11.8 g, (tetrakis(triphenylphosphine)palladium(0) 1.17 g, potassium carbonate 14 g, tetrahydrofuran 253 mL, water 40 mL) were added under nitrogen and refluxed for 12 hours. After completion of the reaction, the layers were separated and dried with MgSO4. The organic layer was concentrated under reduced pressure, separated and purified by column chromatography. <a-2>(18.2 g, 61%) was obtained

[0156]

[0157] Synthesis Example 1-3: Synthesis of A-3

[0158]

[0159] <a-2> <a-3>

[0160] In a round bottom flask <a-2>18.2 g of bis(pinacolato)diboron, 10.2 g of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) 2.26 g, 9.09 g of potassium acetate, and 180 mL of 1,4-dioxane were added under nitrogen and refluxed for 12 hours. After completion of the reaction, the layers were separated and dried over MgSO4. The organic layer was concentrated under reduced pressure, separated and purified by column chromatography. <a-3>(16 g, 91%) was obtained

[0161]

[0162] Synthesis Example 1-4: Synthesis of [ET-1]

[0163]

[0164] <a-4a> <a-3>[ET-1]

[0165] In a round bottom flask <a-4a> 11 g, <a-3>16 g, 1.38 g of tetrakis(triphenylphosphine)palladium(0), 8.23 ​​g of potassium carbonate, 150 mL of 1,4-dioxane, and 25 mL of water were added under nitrogen and refluxed for 12 hours. After completion of the reaction, the layers were separated and dried over MgSO4. The organic layer was concentrated under reduced pressure, separated and purified by column chromatography to obtain [ET-1]. (14.5 g, 65%)

[0166] MS (MALDI-TOF): m / z 935.46 [M + ]

[0167]

[0168] Synthesis Example 2: Synthesis of [ET-2]

[0169] Synthesis Example 2-1: Synthesis of B-1

[0170]

[0171] <b-1a> <b-1b> <b-1>

[0172] Used in the above synthesis example 1-4 <a-4a>instead <b-1b>Use , <a-3>instead <b-1a>Synthesized in the same way except that <b-1>was obtained. (Yield 80%)

[0173]

[0174] Synthesis Example 2-2: Synthesis of B-2

[0175]

[0176] <b-1> <b-2>

[0177] In a round bottom flask <b-1>50 g, 500 mL of dichloromethane was added under nitrogen, cooled to 0°C, 45 mL of boron tribromide was slowly added dropwise, and stirred at room temperature for 12 hours. After completion of the reaction, the layers were separated, dried with MgSO4, concentrated under reduced pressure, and separated and purified by column chromatography. <b-2>(36.9 g, 81%) was obtained.

[0178]

[0179] Synthesis Example 2-3: Synthesis of B-3

[0180]

[0181] <b-2> <b-3>

[0182] In a round bottom flask <b-2>36.9 g of potassium carbonate, 52.9 g of dimethylformamide, and 370 mL of sodium hydroxide were added under nitrogen and refluxed for 12 hours. After completion of the reaction, the layers were separated, dried with MgSO4, concentrated under reduced pressure, and separated and purified by column chromatography. <b-3>was obtained (29.2 g, 85%)

[0183]

[0184] Synthesis Example 2-4: Synthesis of B-4

[0185]

[0186] <b-3> <b-4a> <b-4>

[0187] Used in the above synthesis example 1-4 <a-4a>instead <b-3>Use , <a-3>instead <b-4a>Synthesized in the same way except that <b-4>was obtained. (Yield 82%)

[0188]

[0189] Synthesis Example 2-5: Synthesis of B-5

[0190]

[0191] <b-4> <b-5>

[0192] In a round bottom flask <b-4>25 g of pyridine and 10.9 g of pyridine were added under nitrogen atmosphere and cooled to -10 ℃. Then, 39 g of trifluoromethanesulfonic anhydride was slowly added dropwise and stirred at room temperature for 12 hours. After completion of the reaction, the layers were separated, dried with MgSO4, and separated and purified by column chromatography. <b-5>(31.2 g, 84%)

[0193]

[0194] Synthesis Example 2-6: Synthesis of B-6

[0195]

[0196] <b-5> <b-6>

[0197] Used in the above synthesis example 1-3 <a-2>instead <b-5>Synthesized in the same way except that <b-6>was obtained. (Yield 78%)

[0198]

[0199] Synthesis Example 2-7: Synthesis of B-7

[0200]

[0201] <a-1a> <b-7a> <b-7>

[0202] Used in the above synthesis example 1-1 <a-1b>instead <b-7a>Synthesized in the same way except that <b-7>was obtained. (Yield 63%)

[0203]

[0204] Synthesis Example 2-8: Synthesis of B-8

[0205]

[0206] <b-7> <b-6> <b-8>

[0207] Used in the above synthesis example 1-2 <a-1>instead <b-7>Use , <a-2a>instead <b-6>Synthesized in the same way except that <b-8>was obtained. (Yield 56%)

[0208]

[0209] Synthesis Example 2-9: Synthesis of B-9

[0210]

[0211] <b-8> <b-9>

[0212] Used in the above synthesis example 1-3 <a-2>instead <b-8>Synthesized in the same way except that <b-9>was obtained. (Yield 79%)

[0213]

[0214] Synthesis Example 2-10: Synthesis of ET-2

[0215]

[0216] <a-4a> <b-9>[ET-2]

[0217] Used in the above synthesis example 1-4 <a-3>instead <b-9>[ET-2] was obtained by the same method except that [ET-2] was used (yield 78%).

[0218] MS (MALDI-TOF): m / z 1032.62 [M + ]

[0219]

[0220] Synthesis Example 3: Synthesis of [ET-3]

[0221] Synthesis Example 3-1: Synthesis of C-1

[0222]

[0223] <c-1a> <b-4a> <c-1>

[0224] Used in the above synthesis example 1-2 <a-1>instead <c-1a>Use , <a-2a>instead <b-4a>Synthesized in the same way except that <c-1>was obtained. (Yield 60%)

[0225]

[0226] Synthesis Example 3-2: Synthesis of C-2

[0227]

[0228] <a-1a> <c-1> <c-2a> <c-2>

[0229] In a round bottom flask <a-1a>35.7 g, 360 mL of diethyl ether was cooled to -78°C under nitrogen atmosphere, and 102 mL of 1.6 M n-butyl lithium solution was slowly added dropwise, and placed in another round bottom flask. <c-1>24.9 g, 250 mL of diethyl ether was cooled to -78 °C under nitrogen atmosphere, 53.6 mL of 1.6 M n-butyl lithium solution was slowly added dropwise, and everything was stirred for 1 hour. The above two reaction solutions were dissolved in 75 mL of diethyl ether. <c-2a>The solution containing 15 g was added dropwise to a round bottom flask cooled to -78°C and stirred at room temperature for 12 hours. After completion of the reaction, the layers were separated, the organic layer was concentrated under reduced pressure, and then separated and purified by column chromatography. <c-2>(25.1 g, 60%) was obtained.

[0230]

[0231] Synthesis Example 3-3: Synthesis of C-3

[0232]

[0233] <c-2> <c-3a> <c-3>

[0234] Used in the above synthesis example 1-2 <a-1>instead <c-2>Use , <a-2a>instead <c-3a>Synthesized in the same way except that <c-3>was obtained. (Yield 58%)

[0235]

[0236] Synthesis Example 3-4: Synthesis of C-4

[0237]

[0238] <c-3> <c-4>

[0239] Used in the above synthesis example 1-3 <a-2>instead <c-3>Synthesized in the same way except that <c-4>was obtained. (Yield 80%)

[0240]

[0241] Synthesis Example 3-5: Synthesis of [ET-3]

[0242]

[0243] <a-4a> <c-4>[ET-3]

[0244] Used in the above synthesis example 1-4 <a-3>instead <c-4>[ET-3] was obtained by the same method except that [ET-3] was used (yield 69%).

[0245] MS (MALDI-TOF): m / z 1097.58 [M + ]

[0246]

[0247] Synthesis Example 4: Synthesis of [ET-4]

[0248] Synthesis Example 4-1: Synthesis of D-1

[0249]

[0250] <d-1a> <d-1b> <d-1>

[0251] Used in the above synthesis example 1-2 <a-2a>instead <d-1a>Use , <a-1>instead <d-1b>Synthesized in the same way except that <d-1>was obtained. (Yield 66%)

[0252]

[0253] Synthesis Example 4-2: Synthesis of D-2

[0254]

[0255] <d-1> <d-2>

[0256] Used in the above synthesis example 2-2 <b-1>instead <d-1>Synthesized in the same way except that <d-2>was obtained. (Yield 88%)

[0257]

[0258] Synthesis Example 4-3: Synthesis of D-3

[0259]

[0260] <d-2> <d-3>

[0261] Used in the above synthesis example 2-3 <b-2>instead <d-2>Synthesized in the same way except that <d-3>was obtained. (Yield 78%)

[0262]

[0263] Synthesis Example 4-4: Synthesis of D-4

[0264]

[0265] <d-3> <d-4>

[0266] Used in the above synthesis example 1-3 <a-2>instead <d-3>Synthesized in the same way except that <d-4>was obtained. (Yield 75%)

[0267]

[0268] Synthesis Example 4-5: Synthesis of D-5

[0269]

[0270] <a-1> <d-4> <d-5>

[0271] Used in the above synthesis example 1-2 <a-2a>instead <d-4>Synthesized in the same way except that <d-5>was obtained. (Yield 59%)

[0272]

[0273] Synthesis Example 4-6: Synthesis of D-6

[0274]

[0275] <d-5> <d-6>

[0276] Used in the above synthesis example 1-3 <a-2>instead <d-5>Synthesized in the same way except that <d-6>was obtained. (Yield 77%)

[0277]

[0278] Synthesis Example 4-7: Synthesis of [ET-4]

[0279]

[0280] <a-4a> <d-6>[ET-4]

[0281] Used in the above synthesis example 1-4 <a-3>instead <d-6>[ET-4] was obtained by the same method except that [ET-4] was used (yield 66%).

[0282] MS (MALDI-TOF): m / z 1051.52 [M + ]

[0283]

[0284] Synthesis Example 5: Synthesis of [ET-5]

[0285] Synthesis Example 5-1: Synthesis of E-1

[0286]

[0287] <a-1a> <e-1a> <e-1>

[0288] Used in the above synthesis example 1-1 <a-1b>instead <e-1a>Synthesized in the same way except that <e-1>was obtained. (Yield 65%)

[0289]

[0290] Synthesis Example 5-2: Synthesis of E-2

[0291]

[0292] <e-1> <b-4a> <e-2>

[0293] Used in the above synthesis example 1-2 <a-1>instead <e-1>Use , <a-2a>instead <b-4a>Synthesized in the same way except that <e-2>was obtained. (Yield 61%)

[0294]

[0295] Synthesis Example 5-3: Synthesis of E-3

[0296]

[0297] <e-2> <e-3a> <e-3>

[0298] Used in the above synthesis example 1-2 <a-1>instead <e-2>Use , <a-2a>instead <e-3a>Synthesized in the same way except that <e-3>was obtained. (Yield 57%)

[0299]

[0300] Synthesis Example 5-4: Synthesis of E-4

[0301]

[0302] <e-3> <e-4>

[0303] Used in the above synthesis example 1-3 <a-2>instead <e-3>Synthesized in the same way except that <e-4>was obtained. (Yield 78%)

[0304]

[0305] Synthesis Example 5-5: Synthesis of [ET-5]

[0306]

[0307] <a-4a> <e-4>[ET-5]

[0308] Used in the above synthesis example 1-4 <a-3>instead <e-4>[ET-5] was obtained by the same method except that [ET-5] was used (yield 68%).

[0309] MS (MALDI-TOF): m / z 1112.68 [M + ]

[0310]

[0311] Synthesis Example 6: Synthesis of [ET-6]

[0312] Synthesis Example 6-1: Synthesis of F-1

[0313]

[0314] <e-2> <f-1a> <f-1>

[0315] Used in the above synthesis example 1-2 <a-1>instead <e-2>Use , <a-2a>instead <f-1a>Synthesized in the same way except that <f-1>was obtained. (Yield 55%)

[0316]

[0317] Synthesis Example 6-2: Synthesis of F-2

[0318]

[0319] <f-1> <f-2>

[0320] Used in the above synthesis example 1-3 <a-2>instead <f-1>Synthesized in the same way except that <f-2>was obtained. (Yield 74%)

[0321]

[0322] Synthesis Example 6-3: Synthesis of [ET-6]

[0323]

[0324] <a-4a> <f-2>[ET-6]

[0325] Used in the above synthesis example 1-4 <a-3>instead <f-2>[ET-6] was obtained by the same method except that [ET-6] was used (yield 64%).

[0326] MS (MALDI-TOF): m / z 1121.61 [M + ]

[0327]

[0328] Synthesis Example 7: Synthesis of [ET-7]

[0329] Synthesis Example 7-1: Synthesis of G-1

[0330]

[0331] <a-1a> <g-1a> <g-1>

[0332] Used in the above synthesis example 1-1 <a-1b>instead <g-1a>Synthesized in the same way except that <g-1>was obtained. (Yield 64%)

[0333]

[0334] Synthesis Example 7-2: Synthesis of G-2

[0335]

[0336] <g-1> <e-3a> <g-2>

[0337] Used in the above synthesis example 1-2 <a-1>instead <g-1>Use , <a-2a>instead <e-3a>Synthesized in the same way except that <g-2>was obtained. (Yield 61%)

[0338]

[0339] Synthesis Example 7-3: Synthesis of G-3

[0340]

[0341] <g-2> <g-3>

[0342] Used in the above synthesis example 1-3 <a-2>instead <g-2>Synthesized in the same way except that <g-3>was obtained. (Yield 74%)

[0343]

[0344] Synthesis Example 7-4: Synthesis of [ET-7]

[0345]

[0346] <a-4a> <g-3>[ET-7]

[0347] Used in the above synthesis example 1-4 <a-3>instead <g-3>[ET-7] was obtained by the same method except that [ET-7] was used (yield 66%).

[0348] MS (MALDI-TOF): m / z 1124.64 [M + ]

[0349]

[0350] Synthesis Example 8: Synthesis of [ET-8]

[0351] Synthesis Example 8-1: Synthesis of H-1

[0352]

[0353] <a-1a> <h-1a> <c-2a> <h-1>

[0354] Used in the above synthesis example 3-2 <c-1>instead <h-1a>Synthesized in the same way except that <h-1>was obtained. (Yield 52%)

[0355]

[0356] Synthesis Example 8-2: Synthesis of H-2

[0357]

[0358] <h-1> <e-3a> <h-2>

[0359] Used in the above synthesis example 1-2 <a-1>instead <h-1>Use , <a-2a>instead <e-3a>Synthesized in the same way except that <h-2>was obtained. (Yield 63%)

[0360]

[0361] Synthesis Example 8-3: Synthesis of H-3

[0362]

[0363] <h-2> <h-3>

[0364] Used in the above synthesis example 1-3 <a-2>instead <h-2>Synthesized in the same way except that <h-3>(74%)

[0365]

[0366] Synthesis Example 8-4: Synthesis of [ET-8]

[0367]

[0368] <a-4a> <h-3>[ET-8]

[0369] Used in the above synthesis example 1-4 <a-3>instead <h-3>[ET-8] was obtained by the same method except that [ET-8] was used (yield 63%).

[0370] MS (MALDI-TOF): m / z 1119.64 [M + ]

[0371]

[0372] Synthesis Example 9: Synthesis of [ET-9]

[0373] Synthesis Example 9-1: Synthesis of I-1

[0374]

[0375] <i-1a> <b-4a> <i-1>

[0376] Used in the above synthesis example 1-2 <a-1>instead <i-1a>Use , <a-2a>instead <b-4a>Synthesized in the same way except that <i-1>was obtained. (Yield 59%)

[0377]

[0378] Synthesis Example 9-2: Synthesis of I-2

[0379]

[0380] <i-1> <i-2a> <i-2>

[0381] Used in the above synthesis example 1-2 <a-1>instead <i-1>Use , <a-2a>instead <i-2a>Synthesized in the same way except that <i-2>was obtained. (Yield 61%)

[0382]

[0383] Synthesis Example 9-3: Synthesis of I-3

[0384]

[0385] <a-1a> <h-1a> <i-2> <g-1a> <i-3>

[0386] In a round bottom flask <a-1a>16.6 g, 170 mL of ethyl ether was cooled to -78°C under nitrogen atmosphere, and 47.6 mL of 1.6 M n-butyllithium solution was slowly added dropwise, and transferred to another round-bottom flask. <h-1a>25.47 g, 250 mL of diethyl ether was cooled to -78°C under nitrogen atmosphere, and 166 mL of 1.6 M n-butyl lithium solution was slowly added dropwise, and placed in another round bottom flask. <i-2>31.57 g, 320 mL of diethyl ether was cooled to -78°C under nitrogen atmosphere, and 52.38 mL of 1.6 M n-butyl lithium solution was slowly added dropwise and stirred for 1 hour. The three reaction solutions above were dissolved in 75 mL of ether. <g-1a>The solution containing 15 g was added dropwise to a round bottom flask cooled to -78°C and stirred at room temperature for 12 hours. After completion of the reaction, the layers were separated, the organic layer was concentrated under reduced pressure, and then separated and purified by column chromatography. <i-3>(23.8 g, 50%) was obtained.

[0387]

[0388] Synthesis Example 9-4: Synthesis of I-4

[0389]

[0390] <i-3> <i-4>

[0391] Used in the above synthesis example 1-3 <a-2>instead <i-3>Synthesized in the same way except that <i-4>was obtained. (Yield 71%)

[0392]

[0393] Synthesis Example 9-5: Synthesis of [ET-9]

[0394]

[0395] <a-4a> <i-4>[ET-9]

[0396] Used in the above synthesis example 1-4 <a-3>instead <i-4>[ET-9] was obtained by the same method except that [ET-9] was used (yield 62%).

[0397] MS (MALDI-TOF): m / z 1204.72 [M + ]

[0398]

[0399] Synthesis Example 10: Synthesis of [ET-10]

[0400] Synthesis Example 10-1: Synthesis of J-1

[0401]

[0402] <j-1a> <j-1>

[0403] In a round bottom flask <j-1a>60 g of acetic acid, 4 g of palladium acetate, 10 g of tricyclohexylphosphine, and 600 mL of dimethylacetamide were added under nitrogen and refluxed for 12 hours. After completion of the reaction, the layers were separated, dried with MgSO4, concentrated under reduced pressure, and separated and purified by column chromatography. <j-1>(31.7 g, 70%) was obtained.

[0404]

[0405] Synthesis Example 10-2: Synthesis of J-2

[0406]

[0407] <j-1> <j-2>

[0408] In a round bottom flask <j-1>31.7 g, 320 mL of dimethylformamide were added under nitrogen atmosphere and cooled to -10 ℃, then 22.4 g of N-bromosuccinimide, 100 mL of dimethylformamide were slowly added dropwise and stirred at room temperature for 12 hours. After completion of the reaction, the layers were separated, dried with MgSO4, concentrated under reduced pressure, and separated and purified by column chromatography. <j-2>(33.2 g, 80%) was obtained.

[0409]

[0410] Synthesis Example 10-3: Synthesis of J-3

[0411]

[0412] <j-2> <j-3>

[0413] Used in the above synthesis example 1-3 <a-2>instead <j-2>Synthesized in the same way except that <j-3>was obtained. (Yield 71%)

[0414]

[0415] Synthesis Example 10-4: Synthesis of J-4

[0416]

[0417] <g-1> <j-3> <j-4>

[0418] Used in the above synthesis example 1-2 <a-1>instead <g-1>Use , <a-2a>instead <j-3>Synthesized in the same way except that <j-4>(Yield 50%)

[0419]

[0420] Synthesis Example 10-5: Synthesis of J-5

[0421]

[0422] <j-4> <i-2a> <j-5>

[0423] Used in the above synthesis example 1-2 <a-1>instead <j-4>Use , <a-2a>instead <i-2a>Synthesized in the same way except that <j-5>was obtained. (Yield 54%)

[0424]

[0425] Synthesis Example 10-6: Synthesis of J-6

[0426]

[0427] <j-5> <j-6>

[0428] Used in the above synthesis example 1-3 <a-2>instead <j-5>Synthesized in the same way except that <j-6>was obtained. (Yield 69%)

[0429]

[0430] Synthesis Example 10-7: Synthesis of [ET-10]

[0431]

[0432] <a-4a> <j-6>[ET-10]

[0433] Used in the above synthesis example 1-4 <a-3>instead <j-6>[ET-10] was obtained by the same method except that [ET-10] was used (yield 66%).

[0434] MS (MALDI-TOF): m / z 1200.70 [M + ]

[0435]

[0436] Synthesis Example 11: Synthesis of [ET-11]

[0437] Synthesis Example 11-1: Synthesis of K-1

[0438]

[0439] <k-1a> <c-3a> <k-1>

[0440] Used in the above synthesis example 1-2 <a-1>instead <k-1a>Use , <a-2a>instead <c-3a>Synthesized in the same way except that <k-1>was obtained. (Yield 68%)

[0441]

[0442] Synthesis Example 11-2: Synthesis of K-2

[0443]

[0444] <a-1a> <k-1> <a-1b> <k-2>

[0445] Used in the above synthesis example 3-2 <c-1>instead <k-1>Use , <c-1a>instead <a-1b>Synthesized in the same way except that <k-2>was obtained. (Yield 56%)

[0446]

[0447] Synthesis Example 11-3: Synthesis of K-3

[0448]

[0449] <k-2> <k-3>

[0450] Used in the above synthesis example 1-3 <a-2>instead <k-2>Synthesized in the same way except that <k-3>was obtained. (Yield 75%)

[0451]

[0452] Synthesis Example 11-4: Synthesis of [ET-11]

[0453]

[0454] <a-4a> <k-3>[ET-11]

[0455] Used in the above synthesis example 1-4 <a-3>instead <k-3>[ET-11] was obtained by the same method except that [ET-11] was used (yield 63%).

[0456] MS (MALDI-TOF): m / z 935.46 [M + ]

[0457]

[0458] Synthesis Example 12: Synthesis of [ET-12]

[0459] Synthesis Example 12-1: Synthesis of L-1

[0460]

[0461] <k-1a> <l-1a> <l-1>

[0462] Used in the above synthesis example 1-2 <a-1>instead <k-1a>Use , <a-2a>instead <l-1a>Synthesized in the same way except that <l-1>was obtained. (Yield 73%)

[0463]

[0464] Synthesis Example 12-2: Synthesis of L-2

[0465]

[0466] <a-1a> <l-1> <a-1b> <l-2>

[0467] Used in the above synthesis example 11-2 <k-1>instead <l-1>Synthesized in the same way except that <l-2>was obtained. (Yield 58%)

[0468]

[0469] Synthesis Example 12-3: Synthesis of L-3

[0470]

[0471] <l-2> <l-3>

[0472] Used in the above synthesis example 1-3 <a-2>instead <l-2>Synthesized in the same way except that <l-3>was obtained. (Yield 74%)

[0473]

[0474] Synthesis Example 12-4: Synthesis of [ET-12]

[0475]

[0476] <a-4a> <l-3>[ET-12]

[0477] Used in the above synthesis example 1-4 <a-3>instead <l-3>[ET-12] was obtained by the same method except that [ET-12] was used. (Yield: 65%)

[0478] MS (MALDI-TOF): m / z 958.48 [M + ]

[0479]

[0480] Synthesis Example 13: Synthesis of [ET-13]

[0481] Synthesis Example 13-1: Synthesis of M-1

[0482]

[0483] <a-1a> <a-2a> <m-1>

[0484] Used in the above synthesis example 1-2 <a-1>instead <a-1a>Synthesized in the same way except that <m-1>was obtained. (Yield 65%)

[0485]

[0486] Synthesis Example 13-2: Synthesis of M-2

[0487]

[0488] <i-1> <m-1> <m-2a> <m-2>

[0489] Used in the above synthesis example 11-2 <a-1a>instead <i-1>Use , <k-1>instead <m-1>, and use <a-1b>instead <m-2a>Synthesized in the same way except that <m-2>was obtained. (Yield 55%)

[0490]

[0491] Synthesis Example 13-3: Synthesis of M-3

[0492]

[0493] <m-2> <m-3>

[0494] Used in the above synthesis example 1-3 <a-2>instead <m-2>Synthesized in the same way except that <m-3>was obtained. (Yield 77%)

[0495]

[0496] Synthesis Example 13-4: Synthesis of [ET-13]

[0497]

[0498] <a-4a> <m-3>[ET-13]

[0499] Used in the above synthesis example 1-4 <a-3>instead <m-3>[ET-13] was obtained by the same method except that [ET-13] was used (yield 63%).

[0500] MS (MALDI-TOF): m / z 1061.46 [M + ]

[0501]

[0502] Synthesis Example 14: Synthesis of [ET-14]

[0503] Synthesis Example 14-1: Synthesis of N-1

[0504]

[0505] <a-1a> <c-3a> <n-1>

[0506] Used in the above synthesis example 1-2 <a-1>instead <a-1a>Use , <a-2a>instead <c-3a>Synthesized in the same way except that <n-1>was obtained. (Yield 62%)

[0507]

[0508] Synthesis Example 14-2: Synthesis of N-2

[0509]

[0510] <a-1a> <f-1a> <n-2>

[0511] Used in the above synthesis example 1-2 <a-1>instead <a-1a>Use , <a-2a>instead <f-1a>Synthesized in the same way except that <n-2>was obtained. (Yield 61%)

[0512]

[0513] Synthesis Example 14-3: Synthesis of N-3

[0514]

[0515] <n-1> <n-2> <m-2a> <n-3>

[0516] Used in the above synthesis example 11-2 <a-1a>instead <n-1>Use , <k-1>instead <n-2>, and use <a-1b>instead <m-2a>Synthesized in the same way except that <n-3>was obtained. (Yield 60%)

[0517]

[0518] Synthesis Example 14-4: Synthesis of N-4

[0519]

[0520] <n-3> <n-4>

[0521] Used in the above synthesis example 1-3 <a-2>instead <n-3>Synthesized in the same way except that <n-4>was obtained. (Yield 79%)

[0522]

[0523] Synthesis Example 14-5: Synthesis of [ET-14]

[0524]

[0525] <a-4a> <n-4>[ET-14]

[0526] Used in the above synthesis example 1-4 <a-3>instead <n-4>[ET-14] was obtained by the same method except that [ET-14] was used (yield 62%).

[0527] MS (MALDI-TOF): m / z 1162.42 [M + ]

[0528]

[0529] Synthesis Example 15: Synthesis of [ET-15]

[0530] Synthesis Example 15-1: Synthesis of O-1

[0531]

[0532] <a-1a> <o-1a> <o-1>

[0533] Used in the above synthesis example 1-1 <a-1b>instead <o-1a>Synthesized in the same way except that <o-1>(Yield 70%)

[0534]

[0535] Synthesis Example 15-2: Synthesis of O-2

[0536]

[0537] <o-1> <c-3a> <o-2>

[0538] Used in the above synthesis example 1-2 <a-1>instead <o-1>Use , <a-2a>instead <c-3a>Synthesized in the same way except that <o-2>was obtained. (Yield 53%)

[0539]

[0540] Synthesis Example 15-3: Synthesis of O-3

[0541]

[0542] <o-2> <o-3a> <o-3>

[0543] Used in the above synthesis example 1-2 <a-1>instead <o-2>Use , <a-2a>instead <o-3a>Synthesized in the same way except that <o-3>was obtained. (Yield 54%)

[0544]

[0545] Synthesis Example 15-4: Synthesis of O-4

[0546]

[0547] <o-3> <o-4>

[0548] Used in the above synthesis example 1-3 <a-2>instead <o-3>Synthesized in the same way except that <o-4>was obtained. (Yield 78%)

[0549]

[0550] Synthesis Example 15-5: Synthesis of [ET-15]

[0551]

[0552] <a-4a> <o-4>[ET-15]

[0553] Used in the above synthesis example 1-4 <a-3>instead <o-4>[ET-15] was obtained by the same method except that [ET-15] was used (yield 60%).

[0554] MS (MALDI-TOF): m / z 1211.51 [M + ]

[0555]

[0556] Examples 1 to 24: Manufacturing of organic light-emitting devices

[0557] After patterning the ITO glass to have a light-emitting area of ​​2 mm × 2 mm, it was cleaned. After mounting the ITO glass in a vacuum chamber, the base pressure was 1 × 10 -6 After making it torr, HATCN (50 Å) is deposited as a hole injection layer on the ITO, BCFN (600 Å) is deposited as a hole transport layer, and then PBCz (50 Å) is deposited as an electron blocking layer. The first and second compounds according to the present invention, which are host compounds in the light-emitting layer, and 12 wt% of the dopant compound PBD are mixed and deposited (350 Å), and then mSiTrz (50 Å) is deposited as a hole blocking layer, and mSiTrz: Liq (300 Å) is deposited as an electron injection and transport layer at a ratio of 1:1, and then Liq (10 Å) is sequentially deposited as an electron injection layer, and Al (1000 Å) is deposited as a cathode, thereby manufacturing an organic light-emitting device. The luminescence characteristics of the organic light-emitting device were measured at 0.4 mA.

[0558] [HATCN] [BCFN] [PBCz]

[0559]

[0560] [PBD] [mSiTrZ] [Liq]

[0561]

[0562] [HT-1] [HT-2]

[0563]

[0564]

[0565] Comparative Examples 1 to 12

[0566] For comparative examples, organic light-emitting devices were manufactured in the same manner as in the above-described examples, except that [RH-1] to [RH-6] were used instead of the compounds according to the present invention as host compounds in the device structure, and the luminescence characteristics of the organic light-emitting devices were measured at 0.4 mA. The structures of [RH-1] to [RH-6] are as follows.

[0567] [RH-1] [RH-2] [RH-3]

[0568]

[0569] [RH-4] [RH-5] [RH-6]

[0570]

[0571]

[0572] Classification Compound 1 Compound 2 Driving voltage (V) External quantum efficiency (EQE, %) Luminescence color Lifetime (T95, hr) Example 1 ET-1HT-14.5 16.6 Blue 128 Example 2 ET-2HT-14.5 16.8 Blue 155 Example 3 ET-3HT-14.4 17.0 Blue 128 Example 4 ET-4HT-14.5 16.6 Blue 120 Example 5 ET-5HT-14.6 16.7 Blue 157 Example 6 ET-6HT-14.6 16.5 Blue 150 Example 7 ET-7HT-14.6 17.3 Blue 158 Example 8 ET-8HT-14.5 16.8 Blue 150 Example 9ET-9HT-14.6 16.4 Blue 145 Example 10ET-10HT-14.6 16.5 Blue 146 Example 11ET-11HT-14.7 16.3 Blue 118 Example 12ET-12HT-14.8 16.3 Blue 117 Example 13ET-13HT-14.7 16.6 Blue 118 Example 14ET-14HT-14.7 16.7 Blue 116 Example 15ET-15HT-14.8 16.7 Blue 117 Example 16ET-2HT-24.6 16.7 Blue 159 Example 17ET-3HT-24.6 17.1 Blue 132 Example 18ET-4HT-24.5 16.7 Blue 124 Example 19ET-7HT-24.617.3Blue162Example 20ET-9HT-24.616.5Blue149Example 21ET-10HT-24.616.6Blue150Example 22ET-13HT-24.716.7Blue122Example 23ET-14HT-24.816.8Blue120Example 24ET-15HT-24.816.8Blue121ComparativeExample 1RH-1HT-15.013.0Blue56ComparativeExample 2RH-2HT-15.113.6Blue64ComparativeExample 3RH-3HT-15.213.6Blue66ComparativeExample 4RH-4HT-15.412.2Blue50ComparativeExample 5RH-5HT-15.2 13.5 Blue 52 Comparative Example 6RH-6HT-15.7 13.5 Blue 48 Comparative Example 7RH-1HT-25.4 13.1 Blue 60 Comparative Example 8RH-2HT-25.5 13.7 Blue 68 Comparative Example 9RH-3HT-25.5 13.9 Blue 70 Comparative Example 10RH-4HT-25.7 12.3 Blue 54 Comparative Example 11RH-5HT-25.4 13.5 Blue 56 Comparative Example 12RH-6HT-26.0 13.6 Blue 52

[0573]

[0574] As shown in the above [Table 1], a device employing a compound according to the present invention as a host compound of a light-emitting layer in an organic light-emitting device can realize a high-efficiency, long-life organic light-emitting device with excellent external quantum efficiency and lifespan characteristics at a low driving voltage compared to devices (Comparative Examples 1 to 12) employing a compound widely used in the past, which is in contrast to the characteristic structure of the compound according to the present invention.

[0575]

[0576] Examples 25 to 44: Manufacturing of organic light-emitting devices

[0577] The organic light-emitting device used in Examples 1 to 24 was manufactured in the same manner as in the above Examples 1 to 24, except that 0.5 wt% of the dopant compound TBD according to the present invention was additionally mixed and used, and the luminescence characteristics of the organic light-emitting device were measured at 0.4 mA.

[0578] [TBD]

[0579]

[0580]

[0581] Comparative examples 13 to 24

[0582] An organic light-emitting device for comparative example was manufactured in the same manner as the above-described example, except that [RH-1] to [RH-6] were used instead of the compound according to the present invention as a host compound in the device structure of the above-described example, and the luminescence characteristics of the organic light-emitting device were measured at 0.4 mA.

[0583] Classification Compound 1 Compound 2 Driving voltage (V) External quantum efficiency (EQE, %) Luminescence color Lifetime (T95, hr) Example 25 ET-1HT-14.4 17.1 Blue 138 Example 26 ET-2HT-14.4 17.3 Blue 165 Example 27 ET-3HT-14.3 17.5 Blue 138 Example 28 ET-4HT-14.4 17.1 Blue 130 Example 29 ET-5HT-14.5 17.2 Blue 167 Example 30 ET-6HT-14.6 17.0 Blue 160 Example 31 ET-7HT-14.5 17.8 Blue 168 Example 32 ET-8HT-14.4 17.5 Blue 160 Example 33ET-9HT-14.517.1 Blue 155 Example 34ET-10HT-14.617.5 Blue 156 Example 35ET-13HT-14.716.8 Blue 128 Example 36ET-14HT-14.817.1 Blue 126 Example 37ET-15HT-14.817.0 Blue 127 Example 38ET-2HT-24.617.2 Blue 169 Example 39ET-3HT-24.617.6 Blue 142 Example 40ET-4HT-24.517.1 Blue 134 Example 41ET-7HT-24.517.8 Blue 172 Example 42ET-9HT-24.517.0 Blue 159 Example 43ET-10HT-24.6 17.1 Blue 160 Example 44ET-14HT-24.8 17.0 Blue 130 Comparative Example 13RH-1HT-15.0 13.4 Blue 66 Comparative Example 14RH-2HT-15.0 13.9 Blue 74 Comparative Example 15RH-3HT-15.2 14.0 Blue 76 Comparative Example 16RH-4HT-15.3 12.5 Blue 60 Comparative Example 17RH-5HT-15.2 13.7 Blue 62 Comparative Example 18RH-6HT-15.7 13.7 Blue 58 Comparative Example 19RH-1HT-25.4 13.6 Blue 70 Comparative Example 20RH-2HT-25.4 14.1 Blue 78 Comparative Example 21RH-3HT-25.514.4Blue80Comparative Example 22RH-4HT-25.712.5Blue64Comparative Example 23RH-5HT-25.613.7Blue66Comparative Example 24RH-6HT-26.113.9Blue62

[0584]

[0585] As shown in the above [Table 2], a device employing a compound according to the present invention as a host compound of a light-emitting layer in an organic light-emitting device can realize a high-efficiency, long-life organic light-emitting device with excellent external quantum efficiency and lifespan characteristics at a low driving voltage, compared to devices (Comparative Examples 13 to 24) employing a compound widely used in the past, which is in contrast to the characteristic structure of the compound according to the present invention.

[0586] The organic light-emitting device according to the present invention comprises a plurality of host compounds in the light-emitting layer, and employs a compound having a characteristic structure as one host material, thereby realizing high efficiency and long life characteristics with low voltage operation and significantly improved luminous efficiency and lifespan, and thus can be industrially usefully utilized in various display devices such as lighting devices, flat panel, flexible, wearable, vehicle or aviation displays, and virtual or augmented reality displays. < / a-4a> < / o-3> < / o-3a> < / o-2> < / c-3a> < / o-1> < / o-1a> < / a-1a> < / a-4a> < / n-3> < / m-2a> < / n-2> < / n-1> < / f-1a> < / a-1a> < / c-3a> < / a-1a> < / a-4a> < / m-2> < / m-2a> < / m-1> < / i-1> < / a-2a> < / a-1a> < / a-4a> < / l-2> < / a-1b> < / l-1> < / a-1a> < / l-1a> < / k-1a> < / a-4a> < / k-2> < / a-1b> < / k-1> < / a-1a> < / c-3a> < / k-1a> < / a-4a> < / j-5> < / i-2a> < / j-4> < / j-3> < / g-1> < / j-2> < / j-1> < / j-1a> < / a-4a> < / i-3> < / g-1a> < / i-2> < / h-1a> < / a-1a> < / i-2a> < / i-1> < / b-4a> < / i-1a> < / a-4a> < / h-2> < / e-3a> < / h-1> < / c-2a> < / h-1a> < / a-1a> < / a-4a> < / g-2> < / e-3a> < / g-1> < / g-1a> < / a-1a> < / a-4a> < / f-1> < / f-1a> < / e-2> < / a-4a> < / e-3> < / e-3a> < / e-2> < / b-4a> < / e-1> < / e-1a> < / a-1a> < / a-4a> < / d-5> < / d-4> < / a-1> < / d-3> < / d-2> < / d-1> < / d-1b> < / d-1a> < / a-4a> < / c-3> < / c-3a> < / c-2> < / c-2a> < / c-1> < / a-1a> < / b-4a> < / c-1a> < / a-4a> < / b-8> < / b-6> < / b-7> < / b-7a> < / a-1a> < / b-5> < / b-4> < / b-4a> < / b-3> < / b-2> < / b-1> < / b-1b> < / b-1a> < / a-4a> < / a-4a> < / a-2> < / a-1> < / a-2a> < / a-1> < / a-1b> < / a-1a>

Claims

1. An organic light-emitting device comprising: a first electrode; a second electrode facing the first electrode; and an organic layer disposed between the first electrode and the second electrode; The organic layer includes a light-emitting layer including a host and a dopant; The above host comprises a first compound and a second compound; An organic light-emitting device characterized in that the first compound comprises at least one organic compound represented by the following [chemical formula 1]: [Chemical Formula 1] In the above [chemical formula 1], X1 to X3 are the same or different from each other, and are each independently N or CR, and at least one of X1 to X3 is N, Z is Si or Ge, X is O, S, NR5, CR6R7, SiR8R9, and GeR 10 R 11 One of the following is selected: R1 and R2 are the same or different, and each independently represent a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, and a ring group in which a substituted or unsubstituted aliphatic ring having 3 to 30 carbon atoms and an aromatic ring having 5 to 30 carbon atoms are fused, R and R3 to R 11 are the same or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a ring group in which a substituted or unsubstituted aliphatic ring having 3 to 30 carbon atoms and an aromatic ring having 5 to 30 carbon atoms are fused, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms Any one selected from among an alkylthioxy group, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted amine group, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, a nitro group, a cyano group, and a halogen group, L1 and L2 are the same or different from each other, and are each independently selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and a divalent ring group in which a substituted or unsubstituted aliphatic ring having 3 to 24 carbon atoms and an aromatic ring having 5 to 24 carbon atoms are fused, A or B are the same or different from each other, and are each independently selected from a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon ring having 3 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocycle having 2 to 30 carbon atoms, a substituted or unsubstituted aliphatic heterocycle having 2 to 30 carbon atoms, and a ring in which a substituted or unsubstituted aliphatic ring having 3 to 24 carbon atoms and an aromatic ring having 5 to 24 carbon atoms are fused, m1 and m2 are each independently an integer from 1 to 3, and when each is an integer greater than or equal to 2, each of R1 and R2 is the same or different from each other, m3 and m4 are each independently an integer of 8, and each of R3 and R4 is the same or different from each other, n1 and n2 is an integer from 1 to 3, and if each is an integer greater than or equal to 2, each of L1 and L2 is the same or different from each other. The above adjacent R3 and R4 may be connected to each other to additionally form an alicyclic or aromatic monocyclic or polycyclic ring, The above R6 and R7, R8 and R9 and R 10 and R 11 can be linked to each other to form additional alicyclic or aromatic monocyclic or polycyclic rings, In the above [Chemical Formula 1], 'substitution' in 'substituted or unsubstituted' means deuterium, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 2 to 30 carbon atoms, a ring group in which an aliphatic ring having 3 to 24 carbon atoms and an aromatic ring having 5 to 24 carbon atoms are fused, an alkoxy group having 1 to 24 carbon atoms, an alkyl group having 1 to 30 carbon atoms It means being substituted with one or more substituents selected from the group consisting of an amine group, a silyl group having 1 to 30 carbon atoms, a germanium group having 1 to 30 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, an arylthionyl group having 6 to 24 carbon atoms, a cyano group, a halogen group, a hydroxy group, and a nitro group, and in the case of two or more, they are the same or different, and at least one hydrogen in each substituent can be replaced with deuterium.

2. In paragraph 1, The organic compound represented by the above [chemical formula 1] is an organic light-emitting device characterized by being represented by the following [chemical formula 1-1]: [Chemical Formula 1-1] In the above [chemical formula 1-1], R 12 are the same or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a ring group in which a substituted or unsubstituted aliphatic ring having 3 to 30 carbon atoms and an aromatic ring having 5 to 30 carbon atoms are fused, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms Any one selected from among an alkylthioxy group, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted amine group, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, a nitro group, a cyano group, and a halogen group, m5 is an integer of 3, and each R 12 are identical or different from each other, The above adjacent multiple R 12 can be linked to each other to form additional alicyclic or aromatic monocyclic or polycyclic rings, The above X, X1 to X3, Z, R1 to R4, L1, L2, n1, n2, m1 to m4 and B ring are the same as the definition of [Chemical Formula 1] in the first paragraph.

3. In paragraph 1, An organic light-emitting device characterized in that the above L1 and L2 are the same or different from each other and are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

4. In paragraph 1, An organic light-emitting device characterized in that the above R1 and R2 are the same or different and are each independently selected from a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms, and a ring group in which a substituted or unsubstituted aliphatic ring having 3 to 18 carbon atoms and an aromatic ring having 5 to 18 carbon atoms are fused.

5. In paragraph 2, An organic light-emitting device characterized in that the above B is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 20 carbon atoms.

6. In paragraph 1, An organic light-emitting device characterized in that all of the above X1 to X3 are N.

7. In paragraph 1, An organic light-emitting device characterized in that at least one deuterium atom in the organic compound represented by the above [chemical formula 1] is substituted.

8. In paragraph 7, An organic light-emitting device characterized in that both R3 and R4 in the above [chemical formula 1] are deuterium.

9. In paragraph 1, An organic light-emitting device characterized in that X in the above [chemical formula 1] is O or S.

10. In paragraph 1, An organic light-emitting device characterized in that the above [chemical formula 1] is any one selected from compounds represented by the following chemical formula:

11. In paragraph 1, An organic light-emitting device characterized in that the second compound in the host is used by mixing or layering at least one compound other than the first compound represented by [Chemical Formula 1].

12. In paragraph 1, An organic light-emitting device characterized in that the organic compound represented by [chemical formula 1] used as the first compound in the host is used in a blue phosphorescent host.

13. In paragraph 1, An organic light-emitting device characterized in that the above dopant comprises at least one organometallic compound.

14. In paragraph 13, An organic light-emitting device characterized in that a polycyclic ring compound represented by the following [chemical formula 2] is mixed or layered in addition to the above organometallic compound: [Chemical Formula 2] In the above [chemical formula 2], Y1 and Y2 are the same or different and are independently O, S, NR 13 , CR 14 R 15 , SiR 16 R 17 and GeR 18 R 19 One of the following is selected: A1 to A3 are the same or different from each other, and are each independently selected from a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon ring having 3 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocycle having 2 to 30 carbon atoms, a substituted or unsubstituted aliphatic heterocycle having 2 to 30 carbon atoms, and a ring in which a substituted or unsubstituted aliphatic ring having 3 to 24 carbon atoms and an aromatic ring having 5 to 24 carbon atoms are fused, The above R 13 Inland R 19 are the same or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a ring group in which a substituted or unsubstituted aliphatic ring having 3 to 30 carbon atoms and an aromatic ring having 5 to 30 carbon atoms are fused, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 1 to 30 carbon atoms Any one selected from an alkylthioxy group, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted amine group, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, a nitro group, a cyano group, and a halogen group, The above R 13 Inland R 19 can be connected to the above A1 to A3 rings to additionally form an alicyclic or aromatic monocyclic or polycyclic ring, The above R 14 Wow R 15 , R 16 and R 17 and R 18 and R 19 Each of them can be linked to each other to form additional alicyclic or aromatic monocyclic or polycyclic rings, In the above [Chemical Formula 2], 'substitution' in 'substituted or unsubstituted' means deuterium, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 2 to 30 carbon atoms, a ring group in which an aliphatic ring having 3 to 24 carbon atoms and an aromatic ring having 5 to 24 carbon atoms are fused, an alkoxy group having 1 to 24 carbon atoms, an alkyl group having 1 to 30 carbon atoms It means being substituted with one or more substituents selected from the group consisting of an amine group, a silyl group having 1 to 30 carbon atoms, a germanium group having 1 to 30 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, an arylthionyl group having 6 to 24 carbon atoms, a cyano group, a halogen group, a hydroxy group, and a nitro group, and in the case of two or more, they are the same or different, and at least one hydrogen in each substituent can be replaced with deuterium.

15. In paragraph 10, The organic light-emitting device is an organic light-emitting device used in any one of a flat panel display device; a flexible display device; a flat panel lighting device of a single color or white color; a flexible lighting device of a single color or white color; a display device for vehicles and aircraft; and a display device for virtual or augmented reality.

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