Compound for organic optoelectronic device, composition for organic optoelectronic device, organic optoelectronic device, and display device

Abstract

The present invention relates to a compound for an organic optoelectronic device represented by Chemical Formula 1, a composition for an organic optoelectronic device including the compound, an organic optoelectronic device, and a display device. Definitions in Chemical Formula 1 are the same as those defined in the specification.

Description

Technical Field

[0001] The present invention discloses a compound for an organic optoelectronic device, a composition for an organic optoelectronic device, an organic optoelectronic device, and a display device. Background Art

[0002] An organic optoelectronic diode is a device that converts electrical energy into light energy and vice versa.

[0003] Organic optoelectronic devices can be classified according to their driving principles as follows. One is a photoelectric device in which excitons are generated from light energy, separated into electrons and holes, and transferred to different electrodes to generate electrical energy, and the other is a light-emitting device in which a voltage or current is supplied to the electrodes to generate light energy from electrical energy.

[0004] Examples of organic optoelectronic devices may be organic photoelectric devices, organic light-emitting diodes, organic solar cells, and organic photo conductor drums.

[0005] Among them, organic light-emitting diodes (OLEDs) have recently attracted attention due to the increasing demand for flat panel display devices. An organic light-emitting diode converts electrical energy into light by applying a current to an organic light-emitting material, and the performance of an organic light-emitting diode may be affected by the organic materials disposed between the respective electrodes. Summary of the Invention

[0006] Technical Task

[0007] One embodiment provides a compound for an organic optoelectronic device, which can achieve an organic optoelectronic device with high efficiency and long life.

[0008] Another embodiment provides a composition for an organic optoelectronic device, which contains the compound for an organic optoelectronic device.

[0009] Still another embodiment provides an organic optoelectronic device containing the composition for an organic optoelectronic device.

[0010] Yet another embodiment provides a display device including the organic optoelectronic device.

[0011] Technical Solution

[0012] According to an embodiment, there is provided a compound for an organic optoelectronic device represented by Chemical Formula 1.

[0013] [Chemical Formula 1]

[0014]

[0015] In Chemical Formula 1,

[0016] Ar 1 and Ar 2 are independently a substituted or unsubstituted C6 - C12 aryl group,

[0017] Ar 3 and Ar 4 are independently a substituted or unsubstituted C6 - C30 aryl group,

[0018] L 1 is a single bond or a phenylene group,

[0019] L 2 to L 4 are independently a single bond or a substituted or unsubstituted C6 - C12 arylene group,

[0020] R 1 and R 2 are independently hydrogen, deuterium, cyano, or a substituted or unsubstituted C1 - C10 alkyl group.

[0021] According to another embodiment, a composition for an organic optoelectronic device includes a compound for an organic optoelectronic device as a first compound for an organic optoelectronic device, and a compound represented by Chemical Formula 2 as a second compound for an organic optoelectronic device.

[0022] [Chemical Formula 2]

[0023]

[0024] In Chemical Formula 2,

[0025] Z 1 to Z 3 are independently N or CR a ,

[0026] Z 1 to Z 3 at least two of which are N,

[0027] R a is hydrogen, deuterium, a substituted or unsubstituted C1 - C30 alkyl group, a substituted or unsubstituted C6 - C30 aryl group, a substituted or unsubstituted C3 - C30 heterocyclic group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amino group, a halogen, cyano, or a combination thereof,

[0028] L 5 to L 7Independently a single bond, a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C2-C20 heterocyclic group, or a combination thereof,

[0029] R 3 to R 5 Independently a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heterocyclic group, or a combination thereof,

[0030] R 3 to R 5 At least one of them is a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzocarbazolyl group, a substituted or unsubstituted dibenzocarbazolyl group, or a substituted or unsubstituted terphenylene group, and

[0031] R a and R 3 to R 5 Exist independently or their adjacent groups are connected to each other to form a substituted or unsubstituted aliphatic monocyclic or polycyclic ring, an aromatic monocyclic or polycyclic ring, or a heteroaromatic monocyclic or polycyclic ring.

[0032] According to another embodiment, an organic optoelectronic device includes an anode and a cathode facing each other and at least one organic layer disposed between the anode and the cathode, wherein the organic layer contains the compound or the composition for the organic optoelectronic device.

[0033] According to another embodiment, a display device including the organic optoelectronic device is provided.

[0034] Advantages of the Invention

[0035] An organic optoelectronic device with high efficiency and long life can be achieved. Description of the Drawings

[0036] Figure 1 and Figure 2 are cross-sectional views showing an organic light-emitting diode according to an embodiment.

[0037]

Reference Signs

[0038] 100, 200: Organic light-emitting diode

[0039] 105: Organic layer

[0040] 110: Cathode

[0041] 120: Anode

[0042] 130: Light-emitting layer

[0043] 140: Hole auxiliary layer Detailed implementation manners

[0044] Embodiments of the present invention are elaborated in detail below. However, these embodiments are exemplary, the present invention is not limited thereto, and the present invention is defined by the scope of the claims.

[0045] In this specification, when no other definition is provided, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by one of the following: deuterium, halogen, hydroxyl group, amino group, substituted or unsubstituted C1-C30 amino group, nitro group, substituted or unsubstituted C1-C40 silyl group, C1-C30 alkyl group, C1-C10 alkylsilyl group, C6-C30 arylsilyl group, C3-C30 cycloalkyl group, C3-C30 heterocycloalkyl group, C6-C30 aryl group, C2-C30 heteroaryl group, C1-C20 alkoxy group, C1-C10 trifluoroalkyl group, cyano group or a combination thereof.

[0046] In the examples of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, C1-C30 alkyl group, C1-C10 alkylsilyl group, C6-C30 arylsilyl group, C3-C30 cycloalkyl group, C3-C30 heterocycloalkyl group, C6-C30 aryl group or C2-C30 heteroaryl group. Additionally, in specific examples of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, C1-C20 alkyl group, C6-C30 aryl group or C2-C30 heteroaryl group. Additionally, in specific examples of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, C1-C5 alkyl group, C6-C18 aryl group, pyridyl group, quinolinyl group, isoquinolinyl group, dibenzofuranyl group, dibenzothiophenyl group or carbazolyl group. Additionally, in specific examples of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, C1-C5 alkyl group, C6-C18 aryl group, dibenzofuranyl group or dibenzothiophenyl group. Additionally, in specific examples of the present invention, "substituted" means that at least one hydrogen of a substituent or a compound is replaced by deuterium, methyl group, ethyl group, propyl group, butyl group, phenyl group, biphenyl group, terphenyl group, naphthyl group, triphenyl group, dibenzofuranyl group or dibenzothiophenyl group.

[0047] In this specification, when no other definition is provided, "hetero" means that a functional group contains 1 to 3 heteroatoms selected from N, O, S, P and Si and the rest are carbon.

[0048] In this specification, "aryl" refers to a group containing at least one hydrocarbon aromatic moiety, and all elements of the hydrocarbon aromatic moiety have conjugated p orbitals, such as phenyl, naphthyl, etc. Two or more hydrocarbon aromatic moieties can be connected by a σ bond and can be, for example, biphenyl, terphenyl, quaterphenyl, etc., and two or more hydrocarbon aromatic moieties are directly or indirectly fused to provide a non-aromatic fused ring, such as a fluorenyl group.

[0049] An aryl can contain a monocyclic, polycyclic or fused polycyclic (i.e., rings sharing adjacent carbon atom pairs) functional group.

[0050] In this specification, "heterocyclic group" is a general concept of heteroaryl and can contain at least one heteroatom selected from N, O, S, P and Si in place of carbon (C) in a cyclic compound (such as aryl, cycloalkyl, its fused ring or a combination thereof). When the heterocyclic group is a fused ring, the entire ring or each ring of the heterocyclic group can contain one or more heteroatoms.

[0051] For example, "heteroaryl" can refer to an aryl containing at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryls are directly connected by a σ bond, or when the heteroaryl contains two or more rings, the two or more rings can be fused. When the heteroaryl is a fused ring, each ring can contain 1 to 3 heteroatoms.

[0052] Heterocyclic groups can include, for example, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, etc.

[0053] More specifically, a substituted or unsubstituted C6-C30 aryl can be a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthracenyl, a substituted or unsubstituted phenanthrenyl, a substituted or unsubstituted fused tetraphenyl, a substituted or unsubstituted pyrenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted p-terphenyl, a substituted or unsubstituted m-terphenyl, a substituted or unsubstituted o-terphenyl, a substituted or unsubstituted chrysenyl group, substituted or unsubstituted terphenyl, substituted or unsubstituted perylenyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted indenyl group, or a combination thereof; the substituted or unsubstituted C2-C30 heterocyclic group may be a substituted or unsubstituted furyl group, substituted or unsubstituted thienyl group, substituted or unsubstituted pyrrolyl group, substituted or unsubstituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted thiazolyl group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazolyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted benzofuryl group, substituted or unsubstituted benzothienyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzothiazinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenazinyl group, substituted or unsubstituted phenothiazinyl group, substituted or unsubstituted phenoxazinyl group, substituted or unsubstituted dibenzofuryl group, substituted or unsubstituted dibenzothienyl group, or a combination thereof, but not limited thereto.

[0054] In this specification, "adjacent groups are connected to each other to form a substituted or unsubstituted aromatic monocyclic or polycyclic ring or a substituted or unsubstituted aromatic monocyclic or polycyclic heterocyclic ring" means that any two adjacent substituents directly substituting an aromatic ring or an aromatic heterocyclic ring are connected without a linking group by a single bond to form another ring.

[0055] For example, adjacent groups are connected to each other to form a substituted or unsubstituted aromatic monocyclic or polycyclic ring, and examples may be a substituted or unsubstituted aromatic monocyclic ring.

[0056] For example, any two substituents directly substituting a pyrimidine ring are connected to each other to form another ring, and thereby a substituted or unsubstituted quinazolinyl group may be formed together with the pyrimidine ring.

[0057] In this specification, the hole property refers to the ability to contribute electrons to form holes when an electric field is applied, and the holes formed in the anode can be easily injected into and transported in the light-emitting layer due to the conduction characteristics according to the HOMO (highest occupied molecular orbital) energy level.

[0058] In addition, the electron property refers to the ability to accept electrons when an electric field is applied, and the electrons formed in the cathode can be easily injected into and transported in the light-emitting layer due to the conduction characteristics according to the LUMO (lowest unoccupied molecular orbital) energy level.

[0059] Hereinafter, a compound for an organic optoelectronic device according to an embodiment will be described.

[0060] The compound for an organic optoelectronic device according to an embodiment is represented by Chemical Formula 1.

[0061] [Chemical Formula 1]

[0062]

[0063] In Chemical Formula 1,

[0064] Ar 1 and Ar 2 are independently a substituted or unsubstituted C6 - C12 aryl group,

[0065] Ar 3 and Ar 4 are independently a substituted or unsubstituted C6 - C30 aryl group,

[0066] L 1 is a single bond or a phenylene group,

[0067] L 2 to L 4 are independently a single bond or a substituted or unsubstituted C6 - C12 arylene group, and

[0068] R 1 and R 2 are independently hydrogen, deuterium, a cyano group, or a substituted or unsubstituted C1 - C10 alkyl group.

[0069] In the compound for an organic optoelectronic device according to an embodiment, one benzene ring of carbazole is substituted with an aryl group at the 2-position, the other benzene ring is directly substituted with an arylamino group at the 2-position, and carbazole is substituted with an aryl group having 18 or fewer carbon atoms in the N direction.

[0070] Compared with compounds aryl-substituted at other positions and unsubstituted compounds, a compound in which one benzene ring of carbazole is aryl-substituted at the 2-position can improve the lifetime of the device. Compared with compounds substituted at other positions additionally, a compound substituted only at the 2-position can improve the driving and lifetime of the device.

[0071] In addition, compared with a structure in which the other benzene ring of carbazole is arylamino-substituted at other positions and substituted by a linking group, a structure in which the other benzene ring is directly arylamino-substituted at the 2-position can achieve a device with improved driving characteristics and lifetime characteristics, and

[0072] In particular, when the aryl is amino-substituted, an appropriate HOMO energy level can be obtained, thereby achieving a device with improved driving characteristics and lifetime characteristics.

[0073] On the other hand, the HOMO energy level of a compound containing an aryl having 18 or fewer carbon atoms in the N direction of carbazole can be higher than that of a compound having a structure with more than 18 carbon atoms or a heteroaryl, and thus a device containing it can exhibit improved lifetime and driving.

[0074] Therefore, a device applying the compound according to the present invention can achieve improved long-lifetime characteristics.

[0075] For example, Ar 1 and Ar 2 can be independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, or a substituted or unsubstituted naphthyl.

[0076] For example, L 2 can be a single bond or a phenylene.

[0077] For a specific example, Ar 1 and Ar 2 can be independently a substituted or unsubstituted phenyl, and L 2 can be a single bond.

[0078] For example, Ar 3 and Ar 4 can be independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted anthryl, or a substituted or unsubstituted phenanthryl.

[0079] For example, L 3 and L 4 can be independently a single bond, a phenylene, or a naphthylene.

[0080] For a specific example, Ar 3and Ar 4 may each independently be a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, or a substituted or unsubstituted naphthyl, and L 3 and L 4 may each independently be a single bond or a phenylene group.

[0081] For example, R 1 and R 2 may each independently be hydrogen or a C1 to C5 alkyl group.

[0082] For a specific example, R 1 and R 2 may each independently be hydrogen.

[0083] For example, Chemical Formula 1 may be represented by Chemical Formula 1A.

[0084] [Chemical Formula 1A]

[0085]

[0086] In Chemical Formula 1A, Ar 1 to Ar 4 , L 1 to L 4 are defined as above.

[0087] Chemical Formula 1 may be, for example, one of the compounds in Group 1, but is not limited thereto.

[0088] [Group 1]

[0089]

[0090]

[0091] A composition for an organic optoelectronic device according to another embodiment includes a compound for an organic optoelectronic device (hereinafter, referred to as "the first compound for an organic optoelectronic device") and a second compound for an organic optoelectronic device.

[0092] The second compound for an organic optoelectronic device is represented by Chemical Formula 2 and is included together with the first compound for an organic optoelectronic device to exhibit good interfacial properties and hole and electron transport efficiencies, improve the lifetime characteristics of a device including the compound, increase the efficiency, and reduce the driving voltage.

[0093] [Chemical Formula 2]

[0094]

[0095] In Chemical Formula 2,

[0096] Z 1 to Z3 Independently N or CR a ,

[0097] Z 1 to Z 3 At least two of which are N,

[0098] R a is hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heterocyclic group, substituted or unsubstituted silyl, substituted or unsubstituted amino group, halogen, cyano or a combination thereof,

[0099] L 5 to L 7 Independently a single bond, substituted or unsubstituted C6-C20 arylene, substituted or unsubstituted C2-C20 heterocyclic group or a combination thereof,

[0100] R 3 to R 5 Independently substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heterocyclic group or a combination thereof,

[0101] R 3 to R 5 At least one of which is substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzocarbazolyl, substituted or unsubstituted dibenzocarbazolyl or substituted or unsubstituted terphenylene, and

[0102] R a and R 3 to R 5 Exist independently or adjacent groups are connected to each other to form a substituted or unsubstituted aliphatic monocyclic or polycyclic ring, aromatic monocyclic or polycyclic ring, or heteroaromatic monocyclic or polycyclic ring.

[0103] For example, Z 1 to Z 3 Two of which can be nitrogen (N), and one can be CR a .

[0104] For example, Z 1 and Z 2 can be nitrogen, and Z 3 can be CR a .

[0105] For example, Z 2 and Z 3 can be nitrogen, and Z 1 can be CRa .

[0106] For example, Z 1 and Z 3 can be nitrogen, and Z 2 can be CR a .

[0107] For example, Z 1 to Z 3 can be nitrogen (N).

[0108] For example, R a and R 3 to R 5 can exist independently or at least one of R 3 to R 5 can be a substituted or unsubstituted dibenzofuranyl or a substituted or unsubstituted dibenzothiophenyl.

[0109] For example, the second compound can be represented by one of Chemical Formulas 2B-1 to 2B-3.

[0110]

[0111] [Chemical Formula 2B-3]

[0112]

[0113] In Chemical Formulas 2B-1 to 2B-3, Z 1 to Z 3 , R 4 , R 5 and L 5 to L 7 are the same as above,

[0114] X 1 to X 3 are independently O or S, and

[0115] R b1 to R b3 , R c1 to R c3 , R d1 to R d3 and R e1 to R e3 are independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amino group, a halogen, a cyano group, or a combination thereof.

[0116] Another example, R a and R3 to R 5 The adjacent groups may be connected to each other to form a substituted or unsubstituted aliphatic monocyclic or polycyclic ring, an aromatic monocyclic or polycyclic ring, or a heteroaromatic monocyclic or polycyclic ring, and R that does not form a ring 3 to R 5 at least one of them may be a substituted or unsubstituted dibenzofuranyl or a substituted or unsubstituted dibenzothiophenyl group.

[0117] In this specification, "the adjacent groups are connected to each other to form a substituted or unsubstituted aliphatic monocyclic or polycyclic ring, an aromatic monocyclic or polycyclic ring, or a heteroaromatic monocyclic or polycyclic ring" means that any two adjacent substituents are fused to form a ring. For example, the adjacent R in Chemical Formula 2 a and R 3 , R a与 R 4 or R a and R 5 may be fused to each other to form a heteroaromatic polycyclic ring and a nitrogen-containing hexagon ring substituted therewith. Herein, examples of the formed heteroaromatic polycyclic ring may be a substituted or unsubstituted benzofuranylpyrimidinyl group, a substituted or unsubstituted benzothienylpyrimidinyl group, a substituted or unsubstituted quinazolinyl group, etc. For example, R in Chemical Formula 2 a and R 3 may be fused to form a substituted or unsubstituted benzofuranylpyrimidinyl group or a substituted or unsubstituted benzothienylpyrimidinyl group and a nitrogen-containing hexagon ring substituted therewith, thereby providing a compound represented by Chemical Formula 2B-4.

[0118] [Chemical Formula 2B-4]

[0119]

[0120] In Chemical Formula 2B-4, X 1 , Z 2 , Z 3 , L 6 , L 7 , R 5 , R b1 , R c1 , R d1 and R e1 are the same as above,

[0121] X 4 is O or S, and

[0122] R s and R tIndependently hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heterocyclic group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amino group, a halogen, a cyano group, or a combination thereof.

[0123] For example, in Chemical Formula 2B-2, X 1 and X 2 can be the same or different.

[0124] For example, in Chemical Formula 2B-2, X 1 and X 2 can be the same, and X 1 and X 2 can independently be O.

[0125] For example, in Chemical Formula 2B-2, X 1 and X 2 can be the same, and X 1 and X 2 can independently be S.

[0126] For example, in Chemical Formula 2B-2, X 1 and X 2 can be different, and X 1 can be S and X 2 can be O or X 1 can be O and X 2 can be S.

[0127] For example, in Chemical Formula 2B-3, X 1 to X 3 can be the same or different.

[0128] For example, in Chemical Formula 2B-3, X 1 to X 3 can be the same, and X 1 to X 3 can independently be O.

[0129] For example, in Chemical Formula 2B-3, X 1 to X 3 can be the same, and X 1 to X 3 can independently be S.

[0130] For example, in Chemical Formula 2B-3, one of X 1 to X 3 can be different, two of X 1 to X 3 can be S and one of X 1 to X 3 can be O or X1 to X 3 Both of them among to X 1 to X 3 One of them among to X may be S.

[0131] For example, in Chemical Formula 2B-1, Chemical Formula 2B-2 and Chemical Formula 2B-4, R 4 and R 5 may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted terrylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group or a substituted or unsubstituted triazinyl group.

[0132] For example, R 4 and R 5 in Chemical Formula 2B-1, Chemical Formula 2B-2 and Chemical Formula 2B-4 may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group or a substituted or unsubstituted carbazolyl group.

[0133] For example, R 4 and R 5 in Chemical Formula 2B-1, Chemical Formula 2B-2 and Chemical Formula 2B-4 may independently be one of the substituents in Group Ⅰ.

[0134] [Group Ⅰ]

[0135]

[0136] For example, in Chemical Formula 2B-1 to Chemical Formula 2B-4, L 5 to L 7 may independently be a single bond or a substituted or unsubstituted C6-C20 arylene group.

[0137] For example, L 5 to L 7 may independently be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group or a substituted or unsubstituted naphthylene group.

[0138] For example, L 5 to L 7 may independently be a single bond, a substituted or unsubstituted m-phenylene group or a substituted or unsubstituted p-phenylene group.

[0139] For example, in Chemical Formula 2B-1 to Chemical Formula 2B-4, R b1 to R b3 , R c1 to R c3 , R d1 to R d3 and R e1 to R e3 may each independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0140] For example, R b1 to R b3 , R c1 to R c3 , R d1 to R d3 and R e1 to R e3 may each independently be hydrogen or a substituted or unsubstituted phenyl group.

[0141] For a specific example, a dibenzofuranyl group or a dibenzothiophenyl group may be represented by one of Chemical Formula 2-1 to Chemical Formula 2-4 according to the bonding position.

[0142]

[0143] In Chemical Formula 2-1 to Chemical Formula 2-4, X is the same as X 1 and X 3 , and R b to R e is the same as R b1 to R b3 , R c1 to R c3 , R d1 to R d3 and R e1 to R e3 .

[0144] For example, a dibenzofuranyl group or a dibenzothiophenyl group may be represented by Chemical Formula 2-1 or Chemical Formula 2-3.

[0145] For example, the second compound for an organic optoelectronic device may be represented by Chemical Formula 2B-1 or Chemical Formula 2B-4.

[0146] For example, in Chemical Formula 2B-1, L 5 may be a single bond, and each of Z 1 to Z 3 may be N.

[0147] For example, Chemical Formula 2B-1 may be represented by Chemical Formula 2B-1-1 or Chemical Formula 2B-1-3.

[0148]

[0149] In Chemical Formulas 2B-1-1 and 2B-1-3,

[0150] X 1 , R 4 , R 5 , L 6 , L 7 , R b1 , R c1 , R d1 and R e1 are the same as described above.

[0151] The second compound for an organic optoelectronic device represented by Chemical Formulas 2B-1-1 and 2B-1-3 has an effectively extended LUMO energy band and an increased planarity of the molecular structure, and thus may have a structure that is prone to accepting electrons when an electric field is applied. Therefore, the driving voltage of an organic optoelectronic device including the second compound for an organic optoelectronic device can be reduced. In addition, such an extension of the LUMO and the fusion of the rings increase the stability of the electrons with respect to the triazine ring, and thus effectively improve the lifetime of an organic optoelectronic device manufactured by applying the second compound for an organic optoelectronic device.

[0152] For a specific example, in Chemical Formulas 2B-1-1 and 2B-1-3, X 1 may be O, L 6 and L 7 may independently be a single bond or a p-phenylene group, and R 4 and R 5 may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted naphthyl group.

[0153] For example, in Chemical Formula 2B-4, L 6 may be a single bond, and Z 2 and Z 3 may independently be N.

[0154] For example, Chemical Formula 2B-4 may be represented by Chemical Formula 2B-4-3.

[0155] [Chemical Formula 2B-4-3]

[0156]

[0157] In Chemical Formula 2B-4-3,

[0158] X 4 , R 5 , L 7 , R b1 , Rc1 , R d1 , R e1 , R s and R t are the same as above.

[0159] For a specific example, R in Chemical Formula 2B-4-3 5 can be a substituted or unsubstituted carbazolyl group and can be represented by Chemical Formula 2B-4-3a, for example.

[0160] [Chemical Formula 2B-4-3a]

[0161]

[0162] In Chemical Formula 2B-4-3a,

[0163] X 4 , L 7 , R b1 , R c1 , R d1 , R e1 , R s and R t are the same as above, and R u , R v , R w and R x are the same as R s and R t are the same.

[0164] For example, at least one of R 3 to R 5 can be a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzocarbazolyl group, or a substituted or unsubstituted dibenzocarbazolyl group, and for example, the second compound for an organic optoelectronic device can be represented by one of Chemical Formulas 2C-1 to 2C-12.

[0165]

[0166]

[0167] In Chemical Formulas 2C-1 to 2C-12, Z 1 to Z 3 , R 4 , R 5 and L 5 to L 7 are the same as above,

[0168] Z 4 to Z 6 are the same as Z 1 to Z 3 , R6 and R 7 with R 4 and R 5 is the same as R f , R g , R h , R i , R j , R k , R l and R m with R b1 to R b3 , R c1 to R c3 , R d1 to R d3 and R e1 to R e3 is the same, and L 8 to L 11 with L 5 to L 7 is the same.

[0169] Ar 5 is a substituted or unsubstituted C6 - C30 aryl group, a substituted or unsubstituted C2 - C30 heterocyclic group, or a combination thereof.

[0170] For example, Ar 5 can be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted terrylene group, or a substituted or unsubstituted fluorenyl group.

[0171] For example, Ar 5 can be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted fluorenyl group, but is not limited thereto.

[0172] For example, R from Chemical Formula 2C - 1 to Chemical Formula 2C - 12 4 to R 7 can exist independently, and can be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted terrylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0173] For example, R 4 to R 7 may exist independently and may be a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted quaterphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted phenanthryl, a substituted or unsubstituted pyrimidinyl, or a substituted or unsubstituted triazinyl.

[0174] For example, R 4 to R 7 adjacent to R a are connected to form a substituted or unsubstituted heteroaromatic monocyclic or polycyclic ring.

[0175] For specific examples, the substituted or unsubstituted heteroaromatic monocyclic or polycyclic ring may be a substituted or unsubstituted benzofuranylpyrimidinyl, a substituted or unsubstituted benzothienylpyrimidinyl, or a substituted or unsubstituted quinazolinyl, such as a substituted or unsubstituted quinazolinyl.

[0176] For example, L 5 to L 7 may independently be a single bond, a substituted or unsubstituted C6-C20 arylene, or a substituted or unsubstituted C2-C20 heteroarylene.

[0177] For example, L 5 to L 7 may independently be a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, or a substituted or unsubstituted naphthylene.

[0178] For example, R f 、R g 、R h 、R i 、R j 、R k 、R l and R m may independently be hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl, a substituted or unsubstituted C6-C20 aryl, or a substituted or unsubstituted C2-C20 heteroaryl.

[0179] For example, R f 、R g 、R h 、R i 、R j 、R k 、R l and Rm Independently hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0180] For specific examples, it can be represented by one of Chemical Formulas 2-5 to 2-8 according to the bonding position of the carbazolyl group of Chemical Formula 2C-1.

[0181]

[0182] In Chemical Formulas 2-5 to 2-8, Ar 5 , R f , R g , R h , R i and L 8 are the same as above.

[0183] For example, the second compound for an organic optoelectronic device can be represented by one of Chemical Formulas 2C-2 to 2C-6.

[0184] For example, the second compound for an organic optoelectronic device can be represented by Chemical Formula 2C-2 or Chemical Formula 2C-6.

[0185] For example, at least one of R 3 to R 5 can be a substituted or unsubstituted terphenyl group, and for example, the second compound for an organic optoelectronic device can be represented by one of Chemical Formulas 2D-1 or 2D-2.

[0186] [Chemical Formula 2D-1][Chemical Formula 2D-2]

[0187]

[0188] In Chemical Formulas 2D-1 and 2D-2, Z 1 to Z 3 , R 4 , R 5 and L 5 to L 7 are the same as above, and

[0189] R n , R o , R p , R q and R r are the same as R b1 to R b3 , R c1 to R c3 , R d1 to R d3and R e1 to R e3 are the same.

[0190] For example, R of Chemical Formula 2D-1 and Chemical Formula 2D-2 4 and R 5 can independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0191] For example, R 4 and R 5 can independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0192] For example, L of Chemical Formula 2D-1 and Chemical Formula 2D-2 5 to L 7 can independently be a single bond, a substituted or unsubstituted C6-C20 arylene group, or a substituted or unsubstituted C2-C20 heteroarylene group.

[0193] For example, L 5 to L 7 can independently be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

[0194] For example, R of Chemical Formula 2D-1 and Chemical Formula 2D-2 n 、R o 、R p 、R q and R r can independently be hydrogen, deuterium, cyano group, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C2-C20 heteroaryl group.

[0195] For example, R n 、R o 、R p 、R q and R r can independently be hydrogen, deuterium, cyano group, methyl group, or a substituted or unsubstituted phenyl group.

[0196] For example, the second compound for an organic optoelectronic device may be represented by Chemical Formula 2D-1, and L in Chemical Formula 2D-1 5 may be a single bond and Z 1 to Z 3 may be N. For example, it may be represented by Chemical Formula 2D-1-1.

[0197] [Chemical Formula 2D-1-1]

[0198]

[0199] In Chemical Formula 2D-1-1, R 4 , R 5 , L 5 to L 7 and R n , R o , R p , R q and R r are the same as those above.

[0200] In a specific exemplary embodiment, the second compound for an organic optoelectronic device may be represented by one of Chemical Formula 2B-1-1, Chemical Formula 2B-1-3, Chemical Formula 2B-4-3, and Chemical Formula 2D-1-1.

[0201] In particular, Chemical Formula 2B-4-3 may be represented by Chemical Formula 2B-4-3a.

[0202] The second compound for an organic optoelectronic device represented by Chemical Formula 2 may be, for example, one of the compounds in Group 2, but is not limited thereto.

[0203] [Group 2]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217] For example, it may contain a first compound for an organic optoelectronic device and a second compound for an organic optoelectronic device with a weight ratio of 1:99 to 99:1. Within this range, the electron transport ability of the first compound for an organic optoelectronic device and the hole transport ability of the second compound for an organic optoelectronic device can be used to adjust the desired weight ratio to achieve bipolar characteristics, thereby improving efficiency and lifespan. Within this range, it may contain, for example, a weight ratio of about 10:90 to 90:10, about 20:80 to 80:20, about 30:70 to 70:30, about 40:60 to 60:40, or about 50:50. For example, it may contain, for example, a weight ratio of 50:50 to 60:40 (for example, 60:40).

[0218] For example, the composition for an organic optoelectronic device according to an embodiment of the present invention may contain a compound represented by Chemical Formula 1A as the first compound for an organic optoelectronic device and a compound represented by Chemical Formula 2B-1, Chemical Formula 2B-4, or Chemical Formula 2D-1 as the second compound for an organic optoelectronic device.

[0219] For example, in Chemical Formula 1A, Ar 1 may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group, and Ar 2 may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, and L 1 to L 4 may independently be a single bond or a substituted or unsubstituted phenylene group, and Ar 3 and Ar 4 may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted naphthyl group.

[0220] For example, Chemical Formula 2B-1 may be represented by Chemical Formula 2B-1-1 or Chemical Formula 2B-1-3.

[0221] For example, Chemical Formula 2B-4 may be represented by Chemical Formula 2B-4-3, and for a specific example, it may be represented by Chemical Formula 2B-4-3a.

[0222] For example, Chemical Formula 2D-1 may be represented by Chemical Formula 2D-1-1.

[0223] The composition may further comprise at least one compound in addition to the first compound for an organic optoelectronic device and / or the second compound for an organic optoelectronic device.

[0224] The compound for an organic optoelectronic device or the composition for an organic optoelectronic device may further comprise a dopant. The dopant may be, for example, a phosphorescent dopant, such as a red, green or blue phosphorescent dopant, and may be, for example, a red phosphorescent dopant.

[0225] The dopant is a material mixed in a small amount with the compound for an organic optoelectronic device or the composition for an organic optoelectronic device to cause luminescence, and is generally a material such as a metal complex that emits light through multiple excitations to a triplet state or a higher state. The dopant may be, for example, an inorganic compound, an organic compound or an organic / inorganic compound, and one or more types thereof may be used.

[0226] Examples of the dopant may be phosphorescent dopants, and examples of the phosphorescent dopants may be organometallic compounds containing Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or a combination thereof. The phosphorescent dopant may be, for example, a compound represented by Chemical Formula Z, but is not limited thereto.

[0227] [Chemical Formula Z]

[0228] L 12 MX 5

[0229] In Chemical Formula Z, M is a metal, and L 12 and X 5 are the same or different and are ligands that form a complex compound with M.

[0230] M may be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or a combination thereof, and L 8 and X 4 may be, for example, bidentate ligands.

[0231] The compound for an organic optoelectronic device or the composition for an organic optoelectronic device may be formed by a dry film forming method such as chemical vapor deposition.

[0232] Hereinafter, an organic optoelectronic device comprising a compound for an organic optoelectronic device or a composition for an organic optoelectronic device will be described.

[0233] The organic optoelectronic device may be any device that converts electrical energy into light energy and vice versa, without particular limitation, and may be, for example, an organic optoelectronic device, an organic light-emitting diode, an organic solar cell, and an organic photoreceptor drum.

[0234] In this text, an organic light-emitting diode as an example of an organic optoelectronic device is described with reference to the drawings.

[0235] Figure 1 and Figure 2 is a cross-sectional view showing an organic light-emitting diode according to an embodiment.

[0236] Referring to Figure 1 , the organic light-emitting diode (100) according to an embodiment includes an anode 120 and a cathode 110 facing each other, and an organic layer 105 disposed between the anode 120 and the cathode 110.

[0237] The anode 120 may be made of a conductor having a large work function to assist hole injection, and may be, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 120 may be, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, etc., or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; a combination of a metal and an oxide such as ZnO and Al or SnO2 and Sb; a conductive polymer such as poly(3-methylthiophene), poly(3,4-(ethylenedioxy)thiophene) (PEDT), polypyrrole, and polyaniline, but is not limited thereto.

[0238] The cathode 110 may be made of a conductor having a small work function to assist electron injection, and may be, for example, a metal, a metal oxide, and / or a conductive polymer. The cathode 110 may be, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, etc., or an alloy thereof; a multilayer structure material such as LiF / Al, LiO2 / Al, LiF / Ca, LiF / Al, and BaF2 / Ca, but is not limited thereto.

[0239] The organic layer 105 includes a light-emitting layer 130, and the light-emitting layer 130 contains the compound or composition.

[0240] The light-emitting layer 130 may contain, for example, a composition.

[0241] The composition may be, for example, a red light-emitting composition.

[0242] The light-emitting layer 130 may contain, for example, a first compound for an organic optoelectronic device and a second compound for an organic optoelectronic device as a phosphorescent host, respectively.

[0243] Reference Figure 2 In addition to the light-emitting layer 130, the organic light-emitting diode 200 further includes a hole-assist layer 140. The hole-assist layer 140 further increases the hole injection and / or hole mobility between the anode 120 and the light-emitting layer 130 and blocks electrons.

[0244] The hole-assist layer 140 may include, for example, a compound for an organic optoelectronic device or a composition for an organic optoelectronic device, and may include at least one of a hole-transport layer, a hole-injection layer, and / or an electron-blocking layer.

[0245] More specifically, the hole-assist layer 140 may include a hole-transport layer located between the anode 120 and the light-emitting layer 130 and a hole-transport assist layer located between the light-emitting layer 130 and the hole-transport layer, and the hole-transport assist layer may include a compound for an organic optoelectronic device.

[0246] In an embodiment, in Figure 1 or Figure 2 , the organic light-emitting diode may further include an electron-transport layer, an electron-injection layer, a hole-injection layer, etc. as the organic layer 105.

[0247] The organic light-emitting diode 100 and the organic light-emitting diode 200 may be manufactured by the following method: forming an anode or a cathode on a substrate; forming an organic layer by a dry film-forming method such as a vacuum evaporation method, sputtering, plasma plating, and ion plating; and forming a cathode or an anode on the organic layer.

[0248] The organic light-emitting diode may be applied to an organic light-emitting display device.

[0249] Embodiment

[0250] Hereinafter, the embodiments will be described in more detail with reference to examples. However, these examples are exemplary, and the scope of the present invention is not limited thereto.

[0251] (Preparation of the First Compound for an Organic Optoelectronic Device)

[0252] Synthesis Example 1: Synthesis of Compound A-2

[0253] [Reaction Process 1]

[0254]

[0255] Step 1: Synthesis of Intermediate 1-a

[0256] 1 equivalent (30.3 g) of 1,4-dichloro-2-nitrobenzene, 1 equivalent (31.3 g) of 4-biphenylboronic acid, 5 mol% (9.1 g) of Pd(PPh3)4, and 2 equivalents (43.6 g) of K2CO3 were suspended in tetrahydrofuran (310 mL) and distilled water (220 mL), and then refluxed and stirred under a nitrogen stream for 12 hours. When the reaction was completed, the product was treated with tetrahydrofuran and distilled water to obtain an extract, the resulting organic layer was dried over magnesium sulfate (MgSO4) and filtered, and the resulting filtrate was concentrated under reduced pressure. The resulting solid was recrystallized from dichloromethane and hexane to obtain 37 g of intermediate 1-a (yield: 74%).

[0257] Step 2: Synthesis of intermediate 1-b

[0258] 37 g of intermediate 1-a and 100 g of triphenylphosphine were suspended in 400 mL of 1,2-dichlorobenzene, and then refluxed and stirred under a nitrogen stream for 18 hours. When the reaction was completed, the solvent was extracted therefrom, and the resulting organic layer was recrystallized from 200 mL of acetone to obtain 20 g of intermediate 1-b (yield: 61%).

[0259] Step 3: Synthesis of intermediate 1-c

[0260] 20 g of intermediate 1-b, 45 g of iodobenzene, 2.7 g of 1,10-phenanthroline, 2.8 g of CuI, and 15.2 g of K2CO3 were suspended in 250 mL of dimethylformamide, and then refluxed and stirred under a nitrogen stream. When the reaction was completed, the solid was precipitated therefrom in methanol, filtered, dissolved in monochlorobenzene, subjected to silica filtration and recrystallized to obtain 18 g of intermediate 1-c (yield: 69%).

[0261] Step 4: Synthesis of compound A-2

[0262] 1 equivalent (18 g) of intermediate 1-c, 1 equivalent (12.5 g) of phenyl-(4-biphenyl)-amine, 2 equivalents (9.7 g) of sodium tert-butoxide, and 0.03 equivalent (1.4 g) of Pd2(dba)3 were suspended in toluene (170 mL), 0.09 equivalent of tri-tert-butylphosphine was added thereto, and the resulting mixture was refluxed and stirred for 12 hours. When the reaction was completed, the product was treated with toluene and distilled water to obtain an extract, the resulting organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. After removing the organic solution therefrom, the concentrated product was subjected to silica column chromatography using hexane:dichloromethane = 8:2 (v / v, volume / volume), and the resulting solid was recrystallized from dichloromethane and acetone to obtain 21.2 g of compound A-2 (yield: 74%).

[0263] LC - Mass measurement (Theoretical value: 562.70 g / mol, Measured value: Mass: M = 562.92 g / mol)

[0264] Synthesis Example 2: Synthesis of Compound A - 3

[0265] 1 equivalent (16.6 g) of Intermediate 1 - c, 1 equivalent (15.1 g) of bis(4 - biphenyl) - amine, 2 equivalents (9.0 g) of sodium tert - butoxide, and 0.03 equivalent (1.3 g) of Pd2(dba)3 were suspended in 200 mL of toluene. 0.09 equivalent of tri - tert - butylphosphine was added thereto, and the mixture was refluxed and stirred for 12 hours. When the reaction was completed, the product was treated with toluene and distilled water to obtain an extract. The organic layer thus obtained was dried over magnesium sulfate and filtered, and the filtrate thus obtained was concentrated under reduced pressure. After removing the organic solution therefrom, the solid thus obtained was recrystallized from dichloromethane and acetone to obtain 24.3 g of Compound A - 3 (Yield: 84%).

[0266] LC - Mass measurement (Theoretical value: 638.80 g / mol, Measured value: M = 639.15 g / mol)

[0267] Synthesis Example 3: Synthesis of Compound A - 7

[0268] 1 equivalent of Intermediate 1 - c was reacted with 1 equivalent of phenyl - (4 - terphenyl) - amine according to the same method as in Synthesis Example 2 to obtain 23.5 g of Compound A - 7 (Yield: 78%).

[0269] LC - Mass measurement (Theoretical value: 638.80 g / mol, Measured value: M = 639.40 g / mol)

[0270] Synthesis Example 4: Synthesis of Compound A - 17

[0271] 17.3 g of Intermediate 1 - c was reacted with 14.5 g of 4 - (2 - naphthyl) - N - phenylaniline according to the same method as in Synthesis Example 2 to obtain 22.6 g of Compound A - 17 (Yield: 75%).

[0272] LC - Mass measurement (Theoretical value: 612.76 g / mol, Measured value: M = 613.76 g / mol)

[0273] Synthesis Example 5: Synthesis of Compound A - 23

[0274] [Reaction Scheme 2]

[0275]

[0276] Step 1: Synthesis of Intermediate 2-a

[0277] 1 equivalent (22.7 g) of phenyl-(4-biphenyl)-amine and 0.95 equivalent (15.7 g) of N-bromosuccinimide were dissolved in 300 mL of dichloromethane, and then refluxed and stirred at 0 °C for 8 hours. When the reaction was complete, the product was treated with distilled water to obtain an extract, and the resulting organic layer was dried over magnesium sulfate and filtered. The filtrate thus obtained was concentrated under reduced pressure and recrystallized from acetone to obtain 28.5 g of Intermediate 2-a (yield: 95%).

[0278] Step 2: Synthesis of Intermediate 2-b

[0279] 1 equivalent (26.2 g) of Intermediate 2-a, 1 equivalent (13.9 g) of naphthalene-2-bromonic acid, 5 mol% (9.1 g) of Pd(PPh3)4, and 2 equivalents (43.6 g) of K2CO3 were suspended in tetrahydrofuran (150 mL) and distilled water (80 mL), and then refluxed and stirred under a nitrogen stream for 12 hours. When the reaction was complete, the product was treated with tetrahydrofuran and distilled water to obtain an extract, the resulting organic layer was dried over magnesium sulfate (MgSO4) and filtered, and the filtrate was concentrated under reduced pressure. The solid thus obtained was recrystallized from dichloromethane and hexane to obtain 21 g of Intermediate 2-b (yield: 70%).

[0280] Step 3: Synthesis of Compound A-23

[0281] 1 equivalent (15.4 g) of Intermediate 1-c was reacted with 1 equivalent (16.2 g) of Intermediate 2-b in the same manner as in Synthesis Example 2 to obtain 23.0 g of Compound A-23 (yield: 77%).

[0282] LC-mass measurement (theoretical value: 688.86 g / mol, measured value: M = 689.86 g / mol)

[0283] Synthesis Example 6: Synthesis of Compound A-27

[0284] [Reaction Scheme 3]

[0285]

[0286] Step 1: Synthesis of Intermediate 3-a

[0287] 16.1 g of intermediate 1-b was suspended in 200 mL of dimethylformamide together with 41 g of 4-bromobiphenyl, 2.1 g of 1,10-phenanthroline, 2.2 g of CuI and 12.0 g of K2CO3, and then refluxed and stirred under a nitrogen stream. When the reaction was complete, the solid was precipitated in methanol, filtered, dissolved in monochlorobenzene, silica-filtered and recrystallized to obtain 15.7 g of intermediate 3-a (yield: 63%).

[0288] Step 2: Synthesis of compound A-27

[0289] 1 equivalent (15.5 g) of intermediate 3-a and 1 equivalent (8.8 g) of phenyl-(4-biphenyl)-amine were suspended in 200 mL of xylene together with 2 equivalents of sodium tert-butoxide and 0.03 equivalent of Pd2(dba)3. 0.09 equivalent of tri-tert-butylphosphine was added thereto, and the mixture was refluxed and stirred for 12 hours. When the reaction was complete, the product was treated with toluene and distilled water to obtain an extract. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. After removing the organic solution therefrom, the solid thus obtained was subjected to silica column chromatography using hexane:dichloromethane = 8:2 (v / v), and recrystallized using dichloromethane and acetone to obtain 17.5 g of compound A-27 (yield: 76%).

[0290] LC-mass measurement (theoretical value: 638.80 g / mol, measured value: M = 639.60 g / mol)

[0291] Synthesis Example 7: Synthesis of compound A-33

[0292] [Reaction Scheme 4]

[0293]

[0294] Step 1: Synthesis of intermediate 4-a

[0295] 17.2 g of intermediate 1-b, 38.5 g of 2-bromonaphthalene, 2.2 g of 1,10-phenanthroline, 2.4 g of CuI and 12.8 g of K2CO3 were suspended in 210 mL of dimethylformamide, and then refluxed and stirred under a nitrogen stream. When the reaction was complete, the solid was precipitated in methanol, filtered, dissolved in monochlorobenzene, silica-filtered and recrystallized to obtain 18.5 g of intermediate 4-a (yield: 74%).

[0296] Step 2: Synthesis of compound A-33

[0297] 1 equivalent (16.5 g) of intermediate 4-a and 1 equivalent (10.0 g) of phenyl-(4-biphenyl)-amine were suspended in xylene (180 mL) together with 2 equivalents of sodium tert-butoxide and 0.03 equivalent of Pd2(dba)3. 0.09 equivalent of tri-tert-butylphosphine was added thereto, and the mixture was refluxed and stirred for 12 hours. When the reaction was completed, the product was treated with toluene and distilled water to obtain an extract, and the organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. After removing the organic solution therefrom, the solid formed therein was subjected to silica gel column analysis using hexane:dichloromethane = 8:2 (v / v), and recrystallized using dichloromethane and acetone to obtain 20.1 g of compound A-33 (yield: 80%).

[0298] LC-mass measurement (theoretical value: 612.76 g / mol, measured value: M = 613.56 g / mol)

[0299] Synthesis Example 8: Synthesis of Compound A-47

[0300] [Reaction Scheme 5]

[0301]

[0302] Step 1: Synthesis of Intermediate 5-a

[0303] 1 equivalent (26.7 g) of 1,4-dichloro-2-nitrobenzene and 1 equivalent (34.5 g) of 4-(2-naphthyl)phenylboronic acid were suspended in tetrahydrofuran (340 mL) and distilled water (200 mL) together with 5 mol% (8.03 g) of Pd(PPh3)4 and 2 equivalents (38.4 g) of K2CO3, and then refluxed and stirred under a nitrogen stream for 12 hours. When the reaction was completed, the product was treated with tetrahydrofuran and distilled water to obtain an extract, the organic layer was dried over magnesium sulfate (MgSO4) and filtered, and the filtrate was concentrated under reduced pressure. The solid formed therein was recrystallized using dichloromethane and hexane to obtain 34 g of intermediate 5-a (yield: 68%).

[0304] Step 2: Synthesis of Intermediate 5-b

[0305] 34 g of intermediate 5-a and 100 g of triphenylphosphine were suspended in 300 mL of 1,2-dichlorobenzene, and then refluxed and stirred under a nitrogen stream for 18 hours. When the reaction was completed, the solvent was extracted, and then the organic layer thus obtained was recrystallized using 150 mL of acetone to obtain 17 g of intermediate 5-b (yield: 55%).

[0306] Step 3: Synthesis of Intermediate 5-c

[0307] 17 g of intermediate 5-b was suspended together with 36 g of iodobenzene, 1.9 g of 1,10-phenanthroline, 2.0 g of CuI and 10.7 g of K2CO3 in 180 mL of dimethylformamide, and then refluxed and stirred under a nitrogen stream. When the reaction was complete, the solid was precipitated in methanol and filtered, dissolved in monochlorobenzene, subjected to silica filtration and then recrystallized to obtain 16.4 g of intermediate 5-c (yield: 78%).

[0308] Step 4: Synthesis of Compound A-47

[0309] 1 equivalent (16.4 g) of intermediate 5-c, 1 equivalent (10.0 g) of phenyl-(4-biphenyl)-amine, 2 equivalents (7.8 g) of sodium tert-butoxide and 0.03 equivalent (1.12 g) of Pd2(dba)3 were suspended in xylene (150 mL), 0.09 equivalent of tri-tert-butylphosphine was added thereto, and the mixture was refluxed and stirred for 12 hours. When the reaction was complete, the product was treated with toluene and distilled water to obtain an extract, the organic layer thus obtained was dried over magnesium sulfate and filtered, and the filtrate thus obtained was concentrated under reduced pressure. After removing the organic solution, the solid formed therein was subjected to silica column chromatography using hexane:dichloromethane = 8:2 (v / v), and recrystallized using dichloromethane and acetone to obtain 19.6 g of Compound A-47 (yield: 78%).

[0310] LC-mass measurement (theoretical value: 612.76 g / mol, measured value: M = 613.77 g / mol)

[0311] Comparative Synthesis Example 1: Synthesis of Compound V-1

[0312] [Reaction Scheme 6]

[0313]

[0314] Step 1: Synthesis of Intermediate 11-a

[0315] 1 equivalent (43.6 g) of 2,7-dibromo-9H-carbazole, 1 equivalent (23.1 g) of 1-naphthylboronic acid, 5 mol% (7.8 g) of Pd(PPh3)4 and 2 equivalents (37.1 g) of K2CO3 were suspended in tetrahydrofuran (300 mL) and distilled water (150 mL), and then refluxed and stirred under a nitrogen stream for 12 hours. When the reaction was complete, the product was treated with tetrahydrofuran and distilled water to obtain an extract, the organic layer was dried over magnesium sulfate (MgSO4) and filtered, and the filtrate was concentrated under reduced pressure. The solid formed therein was recrystallized using dichloromethane and hexane to obtain 26.4 g of Intermediate 11-a (yield: 53%).

[0316] Step 2: Synthesis of Intermediate 11-b

[0317] 11.8 g of Intermediate 11-a, 28 g of 3-(4-chlorophenyl)dibenzothiophene, 1.14 g of 1,10-phenanthroline, 1.21 g of CuI, and 6.6 g of K2CO3 were suspended in 150 mL of dimethylformamide, and then refluxed and stirred under a nitrogen stream. When the reaction was completed, the solid was precipitated in methanol, filtered, dissolved in monochlorobenzene, filtered through silica gel, and recrystallized to obtain 14.7 g of Intermediate 11-b (yield: 74%).

[0318] Step 3: Synthesis of Compound V-1

[0319] 1 equivalent of Intermediate 11-b was reacted with 1 equivalent of diphenylamine according to the same method as in Synthesis Example 2 to obtain 11.9 g of Compound V-1 (yield: 79%).

[0320] LC-mass measurement (theoretical value: 718.9 g / mol, measured value: M = 719.60 g / mol)

[0321] Comparative Synthesis Example 2: Synthesis of Compound V-2

[0322] [Reaction Scheme 7]

[0323]

[0324] Step 1: Synthesis of Intermediate 12-a

[0325] 1 equivalent (30.3 g) of 1,3-dichloro-2-nitrobenzene, 1 equivalent (31.3 g) of 4-biphenylboronic acid, 5 mol% (9.1 g) of Pd(PPh3)4, and 2 equivalents (43.6 g) of K2CO3 were suspended in tetrahydrofuran (310 mL) and distilled water (220 mL), and then refluxed and stirred under a nitrogen stream for 12 hours. When the reaction was completed, the product was treated with tetrahydrofuran and distilled water to obtain an extract, the organic layer thus obtained was dried over magnesium sulfate (MgSO4) and filtered, and the filtrate thus obtained was concentrated under reduced pressure. The solid formed therein was recrystallized from dichloromethane and hexane to obtain 23.5 g of Intermediate 12-a (yield: 47%).

[0326] Step 2: Synthesis of Intermediate 12-b

[0327] 23.5 g of Intermediate 12-a and 60 g of triphenylphosphine were suspended in 250 mL of 1,2-dichlorobenzene, and then refluxed and stirred under a nitrogen stream for 24 hours. When the reaction was complete, the solvent was extracted therefrom, and the organic layer thus obtained was recrystallized with 120 mL of acetone to obtain 10.8 g of Intermediate 12-b (yield: 51%).

[0328] Step 3: Synthesis of Intermediate 12-c

[0329] 10.8 g of Intermediate 12-b, 24.4 g of iodobenzene, 1.4 g of 1,10-phenanthroline, 1.5 g of CuI, and 8.2 g of K2CO3 were suspended in 130 mL of dimethylformamide, and then refluxed and stirred under a nitrogen stream. When the reaction was complete, the solid was precipitated therefrom in methanol, filtered, dissolved in monochlorobenzene, subjected to silica filtration, and then recrystallized to obtain 9.4 g of Intermediate 12-c (yield: 67%).

[0330] Step 4: Synthesis of Compound V-2

[0331] 1 equivalent (9.4 g) of Intermediate 12-c, 1 equivalent (11.3 g) of 3-(diphenylamino)phenylboronic acid, 5 mol% (1.8 g) of Pd(PPh3)4, and 2 equivalents (8.8 g) of K2CO3 were suspended in 110 mL of tetrahydrofuran and 60 mL of distilled water, and then refluxed and stirred under a nitrogen stream for 12 hours. When the reaction was complete, the product was treated with tetrahydrofuran and distilled water to obtain an extract, the organic layer thus obtained was dried over magnesium sulfate (MgSO4) and filtered, and the filtrate thus obtained was concentrated under reduced pressure. The solid formed therein was recrystallized with dichloromethane and hexane to obtain 11.6 g of Compound V-2 (yield: 64%).

[0332] LC-mass measurement (theoretical value: 562.70 g / mol, measured value: M = 563.10 g / mol)

[0333] Comparative Synthesis Example 3: Synthesis of Compound V-3

[0334] 1 equivalent of 9H-phenyl-carbazole was reacted with 1 equivalent of 4-(2-naphthyl)-N-phenylaniline according to the same method as in Synthesis Example 2 to obtain 17.6 g of Compound V-3 (yield: 88%).

[0335] LC-mass measurement (theoretical value: 536.66 g / mol, measured value: M = 537.06 g / mol)

[0336]

[0337] Comparative Synthesis Example 4: Synthesis of Compound V-4

[0338] 1 equivalent of intermediate 1-c was reacted with 1 equivalent of 4-(3-dibenzothiophenyl)-2-naphthylamine according to the same method as in Synthesis Example 2 to obtain 18.2 g of Compound V-4 (yield: 92%).

[0339] LC-mass measurement (theoretical value: 718.90 g / mol, measured value: M = 719.30 g / mol)

[0340]

[0341] Comparative Synthesis Example 5: Synthesis of Compound V-5

[0342] [Reaction Scheme 8]

[0343]

[0344] Step 1: Synthesis of Intermediate 15-a

[0345] 1 equivalent (24.9 g) of 1,4-dichloro-2-nitrobenzene, 1 equivalent (35.5 g) of 2,4-(diphenyl)phenylboronic acid, 5 mol% (7.5 g) of Pd(PPh3)4, and 2 equivalents (35.8 g) of K2CO3 were suspended in tetrahydrofuran (310 mL) and distilled water (220 mL), and then refluxed and stirred under a nitrogen stream for 12 hours. When the reaction was complete, the product was treated with tetrahydrofuran and distilled water to obtain an extract, the organic layer thus obtained was dried over magnesium sulfate (MgSO4) and filtered, and the filtrate thus obtained was concentrated under reduced pressure. The solid formed therein was recrystallized from dichloromethane and hexane to obtain 30.4 g of Intermediate 15-a (yield: 61%).

[0346] Step 2: Synthesis of Intermediate 15-b

[0347] 30.4 g of Intermediate 15-a and 62 g of triphenylphosphine were suspended in 250 mL of 1,2-dichlorobenzene, and then refluxed and stirred under a nitrogen stream for 24 hours. When the reaction was complete, the solvent was extracted therefrom, and the organic layer thus obtained was recrystallized from 120 mL of acetone to obtain 18.1 g of Intermediate 15-b (yield: 65%).

[0348] Step 3: Synthesis of Intermediate 15-c

[0349] 16.5 g of intermediate 15-b, 28.5 g of iodobenzene, 1.7 g of 1,10-phenanthoroline, 1.8 g of CuI and 9.7 g of K2CO3 were suspended in 155 ml of dimethylformamide and then refluxed and stirred under a nitrogen stream. When the reaction was complete, the product was precipitated in methanol, and the solid was filtered therefrom, dissolved in monochlorobenzene, subjected to silica gel filtration and recrystallized to obtain 11.8 g of intermediate 15-c (yield: 59%).

[0350] Step 4: Synthesis of Compound V-5

[0351] 1 equivalent of intermediate 15-c, 1 equivalent of 4-biphenyl-aniline, 5 mol% of Pd(PPh3)4 and 2 equivalents of K2CO3 were suspended in tetrahydrofuran (110 ml) and distilled water (60 ml) and then refluxed and stirred under a nitrogen stream for 12 hours. When the reaction was complete, the product was treated with tetrahydrofuran and distilled water to obtain an extract, the organic layer thus obtained was dried over magnesium sulfate (MgSO4) and filtered, and the filtrate was concentrated under reduced pressure. After removing the organic solution, the residue was subjected to silica gel column chromatography using hexane:dichloromethane = 8:2 (v / v), and the solid therein was recrystallized from dichloromethane and acetone to obtain 16.0 g of Compound V-5 (yield: 89%).

[0352] LC-mass measurement (theoretical value: 638.80 g / mol, measured value: M = 639.8 g / mol)

[0353] (Preparation of a compound for a second organic optoelectronic device)

[0354] Synthesis Example 9: Synthesis of Compound B-17

[0355] [Reaction Scheme 9]

[0356]

[0357] Step 1: Synthesis of Intermediate B-17-1

[0358] 22.6 g (100 mmol) of 2,4-dichloro-6-phenyl-1,3,5-triazine was placed in a 500 mL round-bottom flask together with 100 mL of tetrahydrofuran, 100 mL of toluene, and 100 mL of distilled water. To this, 0.9 equivalent of dibenzofuran-3-boronic acid (CAS No.: 395087-89-5), 0.03 equivalent of tetrakis(triphenylphosphine)palladium, and 2 equivalents of potassium carbonate were added, and the resulting mixture was heated and refluxed under a nitrogen atmosphere. After 6 hours, the reaction solution was cooled, the aqueous layer was removed therefrom, and the organic layer therein was dried under reduced pressure. The solid obtained therefrom was washed with water and hexane and recrystallized with 200 mL of toluene to obtain 21.4 g of intermediate B-17-1 (yield: 60%).

[0359] Step 2: Synthesis of Compound B-17

[0360] Intermediate B-17-1 (56.9 mmol) was placed in a 500 mL round-bottom flask together with 200 mL of tetrahydrofuran and 100 mL of distilled water. To this, 1.1 equivalents of 3,5-diphenylbenzeneboronic acid (CAS No.: 128388-54-5), 0.03 equivalent of tetrakis(triphenylphosphine)palladium, and 2 equivalents of potassium carbonate were added, and the resulting mixture was heated and refluxed under a nitrogen atmosphere. After 18 hours, the reaction solution was cooled, the solid precipitated therein was filtered and washed with 500 mL of water. This solid was recrystallized with 500 mL of monochlorobenzene to obtain Compound B-17.

[0361] LC / MS measurement (C39H25N3O, theoretical value: 555.1998 g / mol, measured value: 556.21 g / mol)

[0362] Synthesis Example 10: Synthesis of Compound B-135

[0363] [Reaction Scheme 10]

[0364]

[0365] Step 1: Synthesis of Intermediate B-135-1

[0366] Intermediate B-135-1 was synthesized in the same manner as in Step 1 of Synthesis Example 9 using 1.0 equivalent amounts of 1-bromo-4-chlorobenzene and 2-naphthaleneboronic acid, respectively.

[0367] Step 2: Synthesis of Intermediate B-135-2

[0368] Intermediate B-135-1 and 250 mL of dimethylformamide (DMF) were placed in a 500 mL round-bottom flask. 0.05 equivalent of dichlorodiphenylphosphinoferrocenepalladium, 1.2 equivalents of bis(pinacolato)diboron, and 2 equivalents of potassium acetate were added thereto, and this mixture was heated and refluxed for 18 hours under a nitrogen atmosphere. The reaction solution was cooled and dropped into 1 L of water to obtain a solid. This solid was dissolved in boiling toluene to treat activated carbon and then filtered using silica gel, and the filtrate thus obtained was concentrated. The concentrated solid was stirred with a small amount of hexane and then filtered to synthesize Intermediate B-135-2.

[0369] Step 3: Synthesis of Compound B-135

[0370] Compound B-135 was synthesized using 1.0 equivalent amounts of Intermediate B-135-2 and Intermediate B-17-1 in Steps 2 of Synthesis Example 9, respectively.

[0371] LC / MS measurement (C37H23N3O, theoretical value: 525.18 g / mol, measured value: M = 525.22 g / mol)

[0372] Synthesis Example 11: Synthesis of Compound B-205

[0373] [Reaction Scheme 11]

[0374]

[0375] Step 1: Synthesis of Intermediate Int-1

[0376] 1-Bromo-4-chloro-2-fluorobenzene (61 g, 291 mmol), 2,6-dimethoxyphenylboronic acid (50.4 g, 277 mmol), K2CO3 (60.4 g, 437 mmol), and Pd(PPh3)4 (10.1 g, 8.7 mmol) were placed in a round-bottom flask and then dissolved in tetrahydrofuran (500 mL) (THF) and distilled water (200 mL), and refluxed and stirred at 60 °C for 12 hours. When the reaction was completed, the aqueous layer was removed, and the residue was treated by column chromatography using hexane:dichloromethane = 8:2 (v / v, volume / volume) to obtain 38 g of Intermediate Int-1 (yield: 51%).

[0377] Step 2: Synthesis of Intermediate Int-2

[0378] The intermediate Int-1 (38 g, 142 mmol) and pyridine hydrochloride (165 g, 1425 mmol) were placed in a round-bottom flask and then refluxed and stirred at 200 °C for 24 hours. When the reaction was complete, the product was cooled to room temperature and slowly poured into distilled water, and the mixture was stirred for one hour. The solid thus obtained was filtered to obtain 23 g of intermediate Int-2 (yield: 68%).

[0379] Step 3: Synthesis of intermediate Int-3

[0380] The intermediate Int-2 (23 g, 96 mmol) and K2CO3 (20 g, 144 mmol) were placed in a round-bottom flask and then dissolved in 100 mL of N-methylpyrrolidone and refluxed and stirred at 180 °C for 12 hours. When the reaction was complete, the mixture was poured into excess distilled water. The solid therein was filtered, dissolved in ethyl acetate, dried over MgSO4, and the organic layer was removed therefrom under reduced pressure. The product thus obtained was treated by column chromatography using hexane:ethyl acetate = 7:3 (v / v, volume / volume) to obtain 16 g of intermediate Int-3 (yield: 76%).

[0381] Step 4: Synthesis of intermediate Int-4

[0382] The intermediate Int-3 (16 g, 73 mmol) and pyridine (12 mL, 146 mmol) were placed in a round-bottom flask and dissolved in 200 mL of dichloromethane DCM. The solution was cooled to 0 °C, and trifluoromethanesulfonic anhydride (14.7 mL, 88 mmol) was slowly added dropwise thereto. The mixture was stirred for 6 hours, and when the reaction was complete, excess distilled water was added thereto, and the resulting mixture was stirred for 30 minutes and treated with DCM to obtain an extract. The organic solvent was removed under reduced pressure and vacuum dried to obtain 22.5 g of intermediate Int-4 (yield: 88%).

[0383] Step 5: Synthesis of intermediate Int-5

[0384] Using the same method as in Synthesis Example 1, 14.4 g of intermediate Int-5 (yield: 81%) was obtained using intermediate Int-4 (22.5 g, 64 mmol), phenylboronic acid (7.8 g, 64 mmol), K2CO3 (13.3 g, 96 mmol), and Pd(PPh3)4 (3.7 g, 3.2 mmol).

[0385] Step 6: Synthesis of intermediate Int-6

[0386] Intermediate Int-5 (22.5 g, 80 mmol), bis(pinacolato)diboron (24.6 g, 97 mmol), Pd(dppf)Cl2 (2 g, 2.4 mmol), tricyclohexylphosphine (3.9 g, 16 mmol), and potassium acetate (16 g, 161 mmol) were placed in a round-bottom flask and then dissolved in 320 mL of DMF. The solution was refluxed and stirred at 120 °C for 10 hours. When the reaction was completed, the product was poured into excess distilled water, and the resulting mixture was stirred for one hour. The solid formed therein was filtered and dissolved in DCM. After removing the moisture therefrom using MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid therein was recrystallized using ethyl acetate (EA) and hexane to obtain 26.9 g of Intermediate Int-6 (yield: 90%).

[0387] Step 7: Synthesis of Compound B-205

[0388] Intermediate B-23-2 (15 g, 35 mmol), Intermediate Int-6 (12.8 g, 35 mmol), K2CO3 (7.2 g, 52 mmol), and Pd(PPh3)4 (2 g, 1.7 mmol) were placed in a round-bottom flask under a nitrogen atmosphere and reacted according to the same method as in Step 2 of Synthesis Example 9 to obtain 15.5 g of Compound B-205 (yield: 70%).

[0389] LC / MS measurement (C45H27N3O2, theoretical value: 641.21 g / mol, measured value: M = 641.25 g / mol)

[0390] Synthesis Example 12: Synthesis of Compound B-183

[0391] [Reaction Scheme 12]

[0392]

[0393] Step 1: Synthesis of Intermediate B-183-1

[0394] Intermediate B-183-1 was synthesized according to the same method as in Step 1 of Synthesis Example 11 using 1.0 equivalent amounts of 2-bromo-1-chloro-3-fluorobenzene and 2-hydroxyphenylboronic acid, respectively.

[0395] Step 2: Synthesis of Intermediate B-183-2

[0396] Intermediate B-183-2 was synthesized according to the same method as in Step 3 of Synthesis Example 11 using Intermediate B-183-1 and K2CO3 in an equivalent ratio of 1:1.5.

[0397] Step 3: Synthesis of Intermediate B-183-3

[0398] Intermediate B-183-3 was synthesized according to the same method as in Step 6 of Synthesis Example 11 using Intermediate B-183-2 and bis(pinacolato)diboron at an equivalent ratio of 1:1.2.

[0399] Step 4: Synthesis of Compound B-183

[0400] Compound B-183 was synthesized according to the same method as in Step 2 of Synthesis Example 9 using 1.0 equivalent amount of Intermediate B-183-3 and 2,4-bis([1,1'-biphenyl]-4-yl)-6-chloro-1,3,5-triazine, respectively.

[0401] LC / MS measurement (C39H25N3O, theoretical value: 551.20 g / mol, measured value: M = 551.24 g / mol)

[0402] Synthesis Example 13: Synthesis of Compound B-209

[0403] [Reaction Scheme 13]

[0404]

[0405] Step 1: Synthesis of Intermediate B-209-1

[0406] 10.5 g of Intermediate A (refer to the synthesis method described in Korean Patent Publication No. 10-2017-0005637), 8.8 g of 3-dibenzofuranboronic acid, 11.4 g of potassium carbonate, and 2.4 g of tetrakis(triphenylphosphine)palladium(0) were added to 140 mL of 1,4-dioxane and 70 mL of water in a 500 mL flask, and then heated at 60 °C for 12 hours under a nitrogen stream. The mixture was added to 500 mL of methanol, the crystallized solid was filtered, dissolved in monochlorobenzene, filtered through silica gel / diatomaceous earth, and then recrystallized with methanol after removing an appropriate amount of organic solvent to obtain Intermediate B-209-1 (10.7 g, yield: 67%).

[0407] Step 2: Synthesis of Compound B-209

[0408] 10.4 g of Intermediate B-209-1, 7.8 g of 4-(9-carbazolyl)phenylboronic acid, 7.5 g of potassium carbonate, and 1.6 g of tetrakis(triphenylphosphine)palladium(0) were added to 90 mL of 1,4-dioxane and 45 mL of water in a 250 mL flask, and then heated at 70 °C for 12 hours under a nitrogen stream. The resulting mixture was added to 250 mL of methanol, and the crystallized solid was filtered, dissolved in 1,2-dichlorobenzene, filtered through silica gel / diatomaceous earth, and then recrystallized from methanol after removing an appropriate amount of the organic solvent to obtain Compound B-209 (13.0 g, yield: 74%).

[0409] LC / MS measurement (C40H23N3OS, theoretical value: 593.16 g / mol, measured value: M = 593.23 g / mol)

[0410] Synthesis Example 14: Synthesis of Compound C-25

[0411] [Reaction Scheme 14]

[0412]

[0413] Step 1: Synthesis of Intermediate C-25-1

[0414] 2-Bromocarbazole (35 g, 142 mmol) was dissolved in 0.5 L of tetrahydrofuran (THF), phenylboronic acid (17.3 g, 142 mmol) and tetrakis(triphenylphosphine)palladium (8.2 g, 7.1 mmol) were added thereto, and the mixture was stirred. Subsequently, a saturated aqueous solution of potassium carbonate (49.1 g, 356 mmol) was added thereto, and the resulting mixture was heated and refluxed at 80 °C for 12 hours. When the reaction was completed, water was added to the reaction solution, and an extract was obtained using dichloromethane (DCM), filtered through anhydrous magnesium sulfate after removing the moisture therefrom, and concentrated under reduced pressure. The resulting residue was separated and purified by flash column chromatography to obtain 22 g of Intermediate C-25-1 (yield: 63.6%).

[0415] Step 2: Synthesis of Intermediate C-25-2

[0416] Intermediate C-25-1 (22 g, 90.4 mmol), 1-bromo-4-chlorobenzene (25.96 g, 135.61 mmol), CuI (1.71 g, 9 mmol), K2CO3 (18.74 g, 135.61 mmol), and 1,10-phenanthroline (1.62 g, 9 mmol) were placed in a round-bottom flask and then dissolved in 700 mL of DMF. The solution was stirred at 180 °C for 18 h. When the reaction was complete, after removing the reaction solvent, the product thus obtained was dissolved in dichloromethane under reduced pressure and then subjected to silica gel filtration. The product was concentrated with dichloromethane and recrystallized with hexane to obtain 18 g of Intermediate C-25-2 (yield: 56.3%).

[0417] Step 3: Synthesis of Intermediate C-25-3

[0418] Intermediate C-25-2 (18 g, 51 mmol), bis(pinacolato)diboron (19.43 g, 76.5 mmol), Pd(dppf)Cl2 (2.24 g, 8.64 mmol), tricyclohexylphosphine (2.86 g, 10.2 mmol), and potassium acetate (15.02 g, 153.01 mmol) were placed in a round-bottom flask and then dissolved in 720 mL of DMF. The mixture was refluxed and stirred at 120 °C for 12 h. When the reaction was complete, the mixture was poured into excess distilled water, and the resulting mixture was stirred for one hour. The solid therein was filtered and dissolved in DCM. After removing the moisture therefrom with MgSO4, the organic solvent was filtered through a silica gel pad and removed under reduced pressure. The solid thus obtained was recrystallized with ethyl acetate and hexane to obtain 14.8 g of Intermediate C-25-3 (yield: 65.3%).

[0419] Step 4: Synthesis of Intermediate C-25-4

[0420] 31 g of Intermediate C-25-4 (yield: 65.1%) was synthesized according to the same method as Step 3 of Synthesis Example 12 using 3-bromo-dibenzofuran (40 g, 162 mmol) in place of Intermediate C-25-2.

[0421] Step 5: Synthesis of Intermediate C-25-5

[0422] The intermediate C-25-4 was dissolved in 0.3 L of tetrahydrofuran (THF), 2,4-chloro-6-phenyl-1,3,5-triazine (21 g, 93 mmol) and tetrakis(triphenylphosphine)palladium (5.38 g, 4.65 mmol) were added thereto, and the mixture was stirred. Subsequently, a saturated aqueous solution of potassium carbonate (32.14 g, 232 mmol) was added thereto, and the mixture was heated and refluxed at 80 °C for 12 hours. When the reaction was completed, water was added to the reaction solution, the obtained mixture was stirred for 30 minutes and filtered, the solid thus obtained was dissolved in monochlorobenzene at 133 °C, after removing water therefrom using anhydrous magnesium sulfate, the solution was filtered through silica gel, and the obtained filtrate was cooled to room temperature and filtered. The obtained solid was repeatedly purified using monochlorobenzene to obtain 15 g of intermediate C-25-5 (yield: 64.8%).

[0423] Step 6: Synthesis of Compound C-25

[0424] The intermediate C-25-5 (10.5 g, 29.3 mmol) was reacted with the intermediate C-25-3 (14.38 g, 32.28 mmol) according to the same method as in Step 4 of Synthesis Example 12 to obtain 12.7 g of Compound C-25 (yield: 67.5%).

[0425] LC / MS measurement (C45H28NO, theoretical value: 640.23 g / mol, measured value: M = 641.38 g / mol)

[0426] Synthesis Example 15: Synthesis of Compound C-23

[0427] [Reaction Scheme 15]

[0428]

[0429] Step 1: Synthesis of Intermediate C-23-1

[0430] 9H-carbazole (24.1 g, 144 mmol) was reacted with 1-bromo-3-chlorobenzene (27.6 g, 144 mmol) according to the same method as in Step 2 of Synthesis Example 14 to obtain 31.5 g of intermediate C-23-1 (yield: 79%).

[0431] Step 2: Synthesis of Intermediate C-23-2

[0432] Except for using intermediate C-23-1 (18 g, 65 mmol), 16.8 g of intermediate C-23-2 (yield: 70%) was obtained according to the same method as in Step 3 of Synthesis Example 14.

[0433] Step 3: Synthesis of Compound C-23

[0434] The intermediate C-23-2 (16.3 g, 44.3 mmol) was reacted with the intermediate C-25-3 (15.8 g, 44.3 mmol) according to the same method as in Step 6 of Synthesis Example 14 to obtain 16.4 g of Compound C-23 (yield: 66%).

[0435] LC / MS measurement (C39H24N4O, theoretical value: 564.20 g / mol, measured value: M = 565.36 g / mol)

[0436] Synthesis Example 16: Synthesis of Compound D-57

[0437] [Reaction Scheme 16]

[0438]

[0439] Compound D-57 was synthesized (yield: 88%) using Intermediate D-57-1 and Intermediate D-57-2 with reference to the synthesis method described in Korean Patent Publication No. 10-2014-0135524.

[0440] LC / MS measurement (C39H25N3, theoretical value: 535.20 g / mol, measured value: M = 535.83 g / mol)

[0441] (Manufacturing the hole auxiliary layer of the organic light-emitting diode Ⅰ)

[0442] Example 1

[0443] A glass substrate coated with ITO (indium tin oxide) to form a 1500 Å-thick film was washed with distilled water. After washing with distilled water, the glass substrate was ultrasonically washed with solvents such as isopropyl alcohol, acetone, methanol, etc. and dried, and then transferred to a plasma cleaner, cleaned with oxygen plasma for 10 minutes, and transferred to a vacuum evaporator. Using the obtained indium tin oxide transparent electrode as the anode, Compound A was vacuum deposited on the indium tin oxide substrate to form a 700 Å-thick hole injection layer, Compound B was deposited on the injection layer to a thickness of 50 Å, and Compound C was deposited to a thickness of 700 Å to form a hole transport layer. A 700 Å-thick hole transport auxiliary layer was formed on the hole transport layer by vacuum depositing Compound A-3. A 400 Å-thick light-emitting layer was formed on the hole transport auxiliary layer by vacuum depositing Compound E doped with [Ir(piq)2acac] as a dopant at 2 wt%. Subsequently, Compound D and Liq were co-vacuum deposited on the light-emitting layer at a ratio of 1:1 to form a 300 Å-thick electron transport layer, and a cathode was formed by sequentially vacuum depositing Liq to a thickness of 15 Å and Al to a thickness of 1200 Å on the electron transport layer, thereby manufacturing an organic light-emitting diode.

[0444] The organic light-emitting diode has the following five-layer organic thin-film structure:

[0445] ITO / Compound A (700 Å) / Compound B (50 Å) / Compound C (700 Å) / Compound A-3 (700 Å) / EML [Compound E: [Ir(piq)2acac] (2 wt%)] (400 Å) / Compound D: Liq (300 Å) / Liq (15 Å) / Al (1200 Å) structure.

[0446] Compound A: N4,N4'-diphenyl-N4,N4'-bis(9-phenyl-9H-carbazol-3-yl)biphenyl-4,4'-diamine

[0447] Compound B: 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT-CN)

[0448] Compound C: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine

[0449] Compound D: 8-(4-(4,6-bis(naphthalen-2-yl)-1,3,5-triazin-2-yl)phenyl)quinoline

[0450] Compound E: 9-phenyl-9'-(4-phenylquinazolin-2-yl)-9H,9'H-3,3'-bicarbazole

[0451] Examples 2 to 5

[0452] Except for using the compositions in Table 1, organic light-emitting diodes were respectively fabricated according to the same method as in Example 1.

[0453] Comparative Examples 1 to 5

[0454] Except for using the compositions in Table 1, organic light-emitting diodes were respectively fabricated according to the same method as in Example 1.

[0455] (Fabricating Organic Light-Emitting Diode Ⅱ - Host)

[0456] Example 6

[0457] A glass substrate coated with ITO (indium tin oxide) that forms a 1500 Å thick film was washed with distilled water. After washing with distilled water, the glass substrate was ultrasonically washed and dried with a solvent such as isopropyl alcohol, acetone, methanol, etc., and then transferred to a plasma cleaner, where it was cleaned with oxygen plasma for 10 minutes and then transferred to a vacuum deposition chamber. Using the obtained indium tin oxide transparent electrode as the anode, compound A was vacuum deposited on the indium tin oxide substrate to form a 700 Å thick hole injection layer, compound B was deposited on the injection layer to a thickness of 50 Å, and compound C was deposited to a thickness of 700 Å to form a hole transport layer. A 400 Å thick hole transport auxiliary layer was formed on the hole transport layer by vacuum depositing compound C-1. A 400 Å thick light-emitting layer was formed on the hole transport auxiliary layer by simultaneously vacuum depositing compound A-3 and B-135 doped with [Ir(piq)2acac] as a dopant at 2 wt%. A 400 Å thick light-emitting layer was formed on the hole transport auxiliary layer by vacuum depositing compound A-3 and compound B-135 at a weight ratio of 6:4, and their ratios in the following examples are described separately. Subsequently, compound D and Liq were simultaneously vacuum deposited on the light-emitting layer at a ratio of 1:1 to form a 300 Å thick electron transport layer, and a cathode was formed by sequentially vacuum depositing Liq to a thickness of 15 Å and Al to a thickness of 1200 Å on the electron transport layer, thereby fabricating an organic light-emitting diode.

[0458] The organic light-emitting diode has the following five-layer organic thin film structure:

[0459] ITO / Compound A (700 Å) / Compound B (50 Å) / Compound C (700 Å) / Compound C-1 (400 Å) / EML [Compound A-3:B-135:[Ir(piq)2acac] (2 wt%)] (400 Å) / Compound D:Liq (300 Å) / Liq (15 Å) / Al (1200 Å) structure.

[0460] Compound A: N4,N4'-diphenyl-N4,N4'-bis(9-phenyl-9H-carbazol-3-yl)-biphenyl-4,4'-diamine

[0461] Compound B: 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT-CN)

[0462] Compound C: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine

[0463] Compound C-1: N,N-bis([1,1'-biphenyl]-4-yl)-7,7-dimethyl-7H-fluoreno[4,3-b]benzofuran-10-amine

[0464] Compound D: 8-(4-(4,6-bis(naphthalen-2-yl)-1,3,5-triazin-2-yl)phenyl)quinoline

[0465] Examples 7 to 22

[0466] Except for using the compositions in Table 2, organic light-emitting diodes were manufactured separately according to the same method as in Example 6.

[0467] Comparative Examples 6 to 11

[0468] Except for using the compositions in Table 2, organic light-emitting diodes were manufactured separately according to the same method as in Examples 2 to 6.

[0469] Evaluation

[0470] The single properties of the materials were evaluated using the diodes according to Examples 1 to 5 and Comparative Examples 1 to 5, and

[0471] The power efficiency depending on the use of the host of the organic light-emitting diode was evaluated using the diodes according to Examples 6 to 22 and Comparative Examples 6 to 11.

[0472] The specific measurement methods are as follows, and the results are shown in Tables 1 and 2.

[0473] (1) Measuring the change in current density depending on the change in voltage

[0474] Regarding the current value flowing into the unit device, the obtained organic light-emitting diode was measured using a current-voltage meter (Keithley 2400) when the voltage was increased from 0 volts to 10 volts, and the measured current value was divided by the area to obtain the result.

[0475] (2) Measuring the change in brightness depending on the change in voltage

[0476] The brightness was measured using a luminance meter (Minolta Cs-1000A) when the voltage of the organic light-emitting diode was increased from 0 volts to 10 volts.

[0477] (3) Measuring the power efficiency

[0478] The power efficiency (candela / ampere) at the same current density (10 mA / cm²) was calculated by using the brightness, current density, and voltage (volts) from items (1) and (2).

[0479] (4) Measuring lifespan

[0480] The result is obtained by measuring the time when the current efficiency (candela / ampere) decreases to 97% while the luminance (candela per square meter) is maintained at 9000 candela per square meter.

[0481] (5) Measuring driving voltage

[0482] The driving voltage of each diode was measured using a current-voltage meter (Keithley 2400) at 15 milliamperes per square centimeter to obtain the result.

[0483] [Table 1]

[0484] Hole transport auxiliary layer Color Driving voltage (V) Lifetime (h) Example 1 A-3 Red 3.75 100 Example 2 A-17 Red 3.80 105 Example 3 A-23 Red 3.79 103 Example 4 A-27 Red 3.85 93 Example 5 A-47 Red 3.83 97 Comparative Example 1 V-1 Red 4.20 32 Comparative Example 2 V-2 Red 4.35 15 Comparative Example 3 V-3 Red 3.85 4 Comparative Example 4 V-4 Red 4.10 37 Comparative Example 5 V-5 Red 4.17 42

[0485] [Table 2]

[0486]

[0487] Referring to Table 1, compared with the organic light-emitting diodes according to Comparative Examples 1 to 5, the organic light-emitting diodes according to Examples 1 to 5 show significantly improved driving voltage and lifespan.

[0488] In addition, referring to Table 2, compared with the organic light-emitting diodes according to Comparative Examples 6 to 11, the organic light-emitting diodes according to Examples 6 to 22 show improved driving voltage, efficiency, and lifespan, and in particular, significant lifespan characteristics.

[0489] Although the present invention has been described in connection with exemplary embodiments that are currently considered practical, it should be understood that the present invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent configurations included within the spirit and scope of the appended claims.

Claims

1. A compound for an organic optoelectronic device, represented by Chemical Formula 1: [Chemical Formula 1] Among them, In Chemical Formula 1, Ar 1 is an unsubstituted C6-C12 aryl group, Ar 2 is a substituted or unsubstituted C6-C12 aryl group, Ar 3 and Ar 4 are each independently a substituted or unsubstituted C6-C30 aryl group, L 1 is a single bond or a phenylene group, L 2 is a single bond L 3 and L 4 are each independently a single bond or a substituted or unsubstituted C6-C12 arylene group, and R 1 and R 2 are independently hydrogen or deuterium, and "substituted" means that at least one hydrogen on the substituent is substituted by deuterium or a C1 - C5 alkyl group.

2. The compound for an organic optoelectronic device according to Claim 1, wherein Chemical Formula 1 is represented by Chemical Formula 1A: [Chemical Formula 1A] Among them, In Chemical Formula 1A, Ar 1 is an unsubstituted C6-C12 aryl group, Ar 2 is a substituted or unsubstituted C6-C12 aryl group, Ar 3 and Ar 4 each independently is a substituted or unsubstituted C6-C30 aryl group L 1 is a single bond, and L 2 is a single bond, and L 3 and L 4 each independently is a single bond or a substituted or unsubstituted C6-C12 arylene group, "substituted" means that at least one hydrogen on the substituent is substituted by deuterium or a C1 - C5 alkyl group.

3. The compound for an organic optoelectronic device according to claim 1, wherein Ar 1 is an unsubstituted phenyl, an unsubstituted biphenyl or an unsubstituted naphthyl and Ar 2 is a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl or a substituted or unsubstituted naphthyl.

4. The compound for an organic optoelectronic device according to claim 1, wherein Ar 3 and Ar 4 are independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted anthryl or a substituted or unsubstituted phenanthryl.

5. The compound for an organic optoelectronic device according to Claim 1, which is one of the compounds in Group 1: [Group 1] 6. A composition for an organic optoelectronic device, comprising: the compound for an organic optoelectronic device according to Claim 1 as the first compound, and a second compound for an organic optoelectronic device, represented by one of Chemical Formula 2B - 1, Chemical Formula 2B - 2, Chemical Formula 2B - 4, Chemical Formula 2C - 2, and Chemical Formula 2D - 1: [Chemical Formula 2B - 4] Among them, In Chemical Formula 2B - 1, Chemical Formula 2B - 2, and Chemical Formula 2B - 4, Z 1 to Z 3 is N, L 5 to L 7 independently is a single bond or a substituted or unsubstituted phenylene group, R 4 and R 5 are independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted carbazolyl group, X 1 、X 2 and X 4 are independently O or S, R b1 、R b2 、R c1 、R c2 、R d1 、R d2 、R e1 、R e2 、R s and R t are independently hydrogen or deuterium; [Chemical Formula 2C - 2] wherein, in Chemical Formula 2C - 2, Z 1 to Z 3 is N, R 4 and R 5 are independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted naphthyl or a substituted or unsubstituted dibenzofuranyl, R f 、R g 、R h and R i are independently hydrogen, deuterium or a substituted or unsubstituted phenyl group, L 5 to L 7 independently is a single bond or a substituted or unsubstituted phenylene group; [Chemical Formula 2D - 1] wherein, in Chemical Formula 2D - 1, Z 1 to Z 3 is N, R 4 and R 5 are independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl or a substituted or unsubstituted naphthyl, L 5 to L 7 independently is a single bond or a substituted or unsubstituted phenyl group, and R n 、R o 、R p 、R q and R r are independently hydrogen, deuterium or a substituted or unsubstituted phenyl group, and "substituted" means that at least one hydrogen on the substituent is substituted by deuterium or a C1 - C5 alkyl group.

7. The composition for an organic optoelectronic device according to Claim 6, wherein the second compound for an organic optoelectronic device is represented by one of Chemical Formula 2B - 1 - 1, Chemical Formula 2B - 1 - 3, Chemical Formula 2B - 4 - 3, and Chemical Formula 2D - 1 - 1: Among them, In Chemical Formula 2B - 1 - 1, Chemical Formula 2B - 1 - 3, and Chemical Formula 2B - 4 - 3, X 1 and X 4 is independently O or S, R 4 and R 5 are independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted naphthyl or a substituted or unsubstituted carbazolyl, L 6 and L 7 are each independently a single bond or a substituted or unsubstituted phenylene, and R b1 、R c1 、R d1 、R e1 、R s and R t are independently hydrogen or deuterium, wherein, in Chemical Formula 2D - 1 - 1, R 4 and R 5 are independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl or a substituted or unsubstituted naphthyl, L 6 and L 7 are each independently a single bond or a substituted or unsubstituted phenylene group, and R n 、R o 、R p 、R q 、R r are independently hydrogen, deuterium or a substituted or unsubstituted phenyl group, "substituted" means that at least one hydrogen on the substituent is substituted by deuterium or a C1 - C5 alkyl group.

8. The composition for an organic optoelectronic device according to Claim 7, wherein Chemical Formula 2B - 4 - 3 is represented by Chemical Formula 2B - 4 - 3a: [Chemical Formula 2B - 4 - 3a] Among them, In Chemical Formula 2B - 4 - 3a, X 1 and X 4 are independently O or S, L 7 independently a single bond or a substituted or unsubstituted phenylene, and R b1 、R c1 、R d1 、R e1 、R s 、R t 、R u 、R v 、R w and R x are independently hydrogen, deuterium or a substituted or unsubstituted phenyl group, "substituted" means that at least one hydrogen on the substituent is substituted by deuterium or a C1 - C5 alkyl group.

9. The composition for an organic optoelectronic device according to Claim 6, which further comprises a dopant.

10. An organic optoelectronic device, comprising: an anode and a cathode facing each other, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer comprises the compound for an organic optoelectronic device according to any one of Claims 1 to 5, or the composition for an organic optoelectronic device according to any one of Claims 6 to 9.

11. The organic optoelectronic device according to Claim 10, wherein the organic layer includes a light - emitting layer, and the light - emitting layer comprises the compound for an organic optoelectronic device or the composition for an organic optoelectronic device.

12. The organic optoelectronic device according to Claim 11, which comprises the first compound for an organic optoelectronic device and the second compound for an organic optoelectronic device as the phosphorescent host of the light - emitting layer.

13. The organic optoelectronic device according to claim 11, wherein the organic layer further comprises a hole transport auxiliary layer disposed between the anode and the light-emitting layer, and the hole transport auxiliary layer contains the compound for the organic optoelectronic device.

14. A display device comprising the organic optoelectronic device according to claim 10.

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