Composition, organic optoelectronic device and display device

Abstract

The present invention relates to a composition, an organic photoelectric device, and a display device comprising a first compound represented by a combination of Chemical Formula 1 and Chemical Formula 2 and a second compound represented by Chemical Formula 3. Chemical Formulas 1 to 3 are the same as those defined in the specification.

Description

Technical Field

[0001] Disclosed are a composition, an organic optoelectronic device (optoelectronic device, optoelectronic device, optoelectronic device, optoelectronic device) and a display device (display device, display device). Background Art

[0002] Organic optoelectronic devices are devices that convert electrical energy into light energy and vice versa.

[0003] Organic photoelectric devices can be classified according to their driving principles as follows: one is an optoelectronic 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 voltage or current is supplied to electrodes to generate light energy from electrical energy.

[0004] Examples of the organic optoelectronic device may be an organic optoelectronic device, an organic light emitting diode, an organic solar cell, and an organic photoconductor.

[0005] Among them, organic light emitting diodes (OLEDs) have recently attracted attention due to an increase in demand for flat panel displays. Organic light emitting diodes convert electrical energy into light by applying current to organic light emitting materials, and the performance of organic light emitting diodes may be affected by organic materials disposed between electrodes. Summary of the invention

[0006] [Technical issues]

[0007] One embodiment provides a composition capable of realizing an organic photoelectric device having high efficiency and long lifespan.

[0008] Another embodiment provides an organic optoelectronic device including the composition.

[0009] Yet another embodiment provides a display device including the organic photoelectric device.

[0010] [Technical solution]

[0011] According to one embodiment, the composition includes a first compound represented by a combination of Chemical Formula 1 and Chemical Formula 2 and a second compound represented by Chemical Formula 3.

[0012]

[0013]

[0014] In Chemical Formula 1 and Chemical Formula 2,

[0015] Ar 1is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

[0016] a 1 * to a 4 The two adjacent ones in * are 1 * and b 2 *connect,

[0017] a 1 * to a 4 *Not with b 1 * and b 2 * The remaining two connected independently for CL a -R a ,

[0018] L a and L 1 To L 4 are independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0019] R a and R 1 To R 4 are independently hydrogen, deuterium, cyano, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, or a combination thereof, and

[0020] R a and R 1 To R 4 At least one of them is a group represented by chemical formula A,

[0021] [Chemical formula A]

[0022]

[0023] Wherein, in chemical formula A,

[0024] R b and R c are independently substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, or a combination thereof, and

[0025] * is with L a and L 1 To L 4 The connection point;

[0026] [Chemical formula 3]

[0027]

[0028] Among them, in chemical formula 3,

[0029] L 5 To L 9 are independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0030] Ar 2 is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

[0031] R 5 To R 8 are independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof,

[0032] R 5 To R 8 exist independently or their adjacent groups are connected to each other to form a substituted or unsubstituted aromatic monocyclic or polycyclic ring, and

[0033] Ar 2 and R 5 To R 8 At least one of them is a group represented by chemical formula B,

[0034] [Chemical formula B]

[0035]

[0036] Among them, in chemical formula B,

[0037] Z 1 To Z 5 N or CL independently b -R d ,

[0038] Z 1 To Z 5 At least one of them is N,

[0039] Where L b are independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0040] R dare independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof,

[0041] R d exist independently or their 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, and

[0042] * Yes and L 5 To L 9 connection point.

[0043] According to another embodiment, an organic photoelectric 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 includes the composition.

[0044] According to another embodiment, a display device including an organic photoelectric device is provided.

[0045] [Beneficial Effects]

[0046] Organic optoelectronic devices with high efficiency and long lifetime can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 and Figure 2 is a cross-sectional view showing an organic light emitting diode according to an embodiment.

[0048] <Description of symbols>

[0049] 100, 200: Organic light-emitting diodes

[0050] 105: Organic layer

[0051] 110: cathode

[0052] 120: Anode

[0053] 130: Luminous layer

[0054] 140: Hole auxiliary layer DETAILED DESCRIPTION

[0055] [Best Mode]

[0056] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the present invention is not limited thereto, and the present invention is defined by the scope of the claims.

[0057] In the present specification, when no definition is otherwise provided, "substituted" means that at least one hydrogen of the substituent or the compound is replaced by deuterium, halogen, hydroxyl, amino, substituted or unsubstituted C1 to C30 amine, nitro, substituted or unsubstituted C1 to C40 silyl (silyl), C1 to C30 alkyl, C1 to C10 alkylsilyl (alkylsilyl), C6 to C30 arylsilyl (arylsilyl), C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, C1 to C20 alkoxy, C1 to C10 trifluoroalkyl, cyano or a combination thereof.

[0058] In one example of the present invention, "substituted" means that at least one hydrogen in the substituent or compound is replaced by deuterium, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl or C2 to C30 heteroaryl. In addition, in a specific example of the present invention, "substituted" means that at least one hydrogen in the substituent or compound is replaced by deuterium, C1 to C20 alkyl, C6 to C30 aryl or C2 to C30 heteroaryl. In addition, in a specific example of the present invention, "substituted" means that at least one hydrogen in the substituent or compound is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl, pyridyl, quinolyl, isoquinolyl, dibenzofuranyl, dibenzothienyl or carbazolyl. In addition, in the specific examples of the present invention, "substituted" means that at least one hydrogen in the substituent or compound is replaced by deuterium, C1 to C5 alkyl, C6 to C18 aryl, dibenzofuranyl or dibenzothienyl. In addition, in the specific examples of the present invention, "substituted" means that at least one hydrogen in the substituent or compound is replaced by deuterium, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl, naphthyl, triphenylene group (triphenylene group, triphenylene group), dibenzofuranyl or dibenzothienyl.

[0059] In the present specification, when a definition is not otherwise provided, "hetero" means a group containing one to three hetero atoms selected from N, O, S, P and Si in one functional group and the rest being carbon.

[0060] In the present specification, "aryl" refers to a group containing at least one hydrocarbon aromatic portion, and all elements of the hydrocarbon aromatic portion have p-orbitals forming conjugation, such as phenyl, naphthyl, etc., two or more hydrocarbon aromatic portions may be connected by a σ bond, and may be, for example, biphenyl, terphenyl, quaterphenyl, etc., and two or more hydrocarbon aromatic portions are directly or indirectly fused to provide a non-aromatic fused ring, such as fluorenyl, etc.

[0061] Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (ie, rings which share adjacent pairs of carbon atoms) functional groups.

[0062] In this specification, "heterocyclic group" is a general concept of heteroaryl, and may include at least one heteroatom selected from N, O, S, P and Si to replace carbon (C) in a cyclic compound, such as an aryl group, a cycloalkyl group, a condensed ring thereof or a combination thereof. When the heterocyclic group is a condensed ring, the entire ring or each ring of the heterocyclic group may include one or more heteroatoms.

[0063] For example, "heteroaryl" may refer to an aryl group including at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryls may be directly connected by a sigma bond, or when the heteroaryl group includes two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

[0064] More specifically, the substituted or unsubstituted C6 to C30 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted The invention may include, but is not limited to, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof.

[0065] More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted furyl, a substituted or unsubstituted thienyl, a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted oxazolyl, a substituted or unsubstituted thiazolyl, a substituted or unsubstituted oxadiazolyl, a substituted or unsubstituted thiadiazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted The invention may include, but is not limited to, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted quinazolyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, but is not limited thereto.

[0066] In this specification, hole characteristics refer to the ability to provide electrons to form holes when an electric field is applied, and the holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to the conductive characteristics according to the highest occupied molecular orbital (HOMO) level.

[0067] In addition, the electronic property refers to the ability to accept electrons when an electric field is applied according to the lowest unoccupied molecular orbital (LUMO) level, and the electrons formed in the cathode are easily injected into the light-emitting layer and transported in the light-emitting layer due to the conductive property.

[0068] Hereinafter, a composition for an organic photoelectric device according to one embodiment is described.

[0069] A composition for an organic photoelectric device according to one embodiment includes a first compound having hole characteristics and a second compound having electron characteristics.

[0070] The first compound is represented by a combination of Chemical Formula 1 and Chemical Formula 2.

[0071]

[0072] In Chemical Formula 1 and Chemical Formula 2,

[0073] Ar 1 is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

[0074] a 1 * to a 4 The two adjacent ones in * are 1 * and b 2 *connect,

[0075] a 1 * to a 4 *Not with b 1 * and b 2 * The remaining two connected independently for CL a -R a ,

[0076] L a and L 1 To L 4 are independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0077] R a and R 1 To R 4are independently hydrogen, deuterium, cyano, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, or a combination thereof, and

[0078] R a and R 1 To R 4 At least one of them is a group represented by chemical formula A,

[0079] [Chemical formula A]

[0080]

[0081] Wherein, in chemical formula A,

[0082] R b and R c are independently substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, or a combination thereof, and

[0083] * is with L a and L 1 To L 4 connection point.

[0084] The first compound has a structure in which benzocarbazole is substituted with amine, whereby the HOMO electron cloud is extended from the amine to the benzocarbazole, and thus hole injection and transport characteristics may be improved due to high HOMO energy.

[0085] In addition, since benzocarbazole has a relatively high HOMO energy compared to bicarbazole and indolecarbazole, a device having a low driving voltage may be realized due to a structure in which benzocarbazole is substituted with amine.

[0086] In addition, bicarbazole and indolecarbazole are not suitable as red hosts due to high T1 energy, but the structure in which benzocarbazole is substituted by amine has a desired T1 energy as a red host. Therefore, a device including the compound according to the present invention can achieve high efficiency / long life characteristics.

[0087] Meanwhile, it may be included together with the second compound to balance holes and electrons, so that the driving voltage including them may be reduced.

[0088] For example, R b and R c The group may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

[0089] For example, R b and R c It may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted fluorenyl group, wherein the substituent may be phenyl, naphthyl, anthracenyl, phenanthryl, triphenylene, carbazolyl, dibenzofuranyl or dibenzothiophenyl.

[0090] For example, Ar 1 They may independently be a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heterocyclic group.

[0091] For example, Ar 1 It may 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 phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, or a combination thereof.

[0092] For example, Ar 1 The group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group, but is not limited thereto.

[0093] For example, L a and L 1 To L 4 and may independently be a single bond or a substituted or unsubstituted C6 to C20 arylene group.

[0094] For example, L a and L 1 To L 4 and 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.

[0095] For example, L a and L 1 To L 4It may be independently a single bond, a substituted or unsubstituted m-phenylene, a substituted or unsubstituted p-phenylene, a substituted or unsubstituted o-phenylene, a substituted or unsubstituted m-biphenylene, a substituted or unsubstituted p-biphenylene, a substituted or unsubstituted o-biphenylene, a substituted or unsubstituted m-terphenylene, a substituted or unsubstituted p-terphenylene, or a substituted or unsubstituted o-terphenylene. Herein, "substituted" may refer to, for example, replacement of at least one hydrogen by deuterium, a C1 to C20 alkyl group, a C6 to C20 aryl group, a halogen, a cyano group, or a combination thereof, but is not limited thereto.

[0096] For example, R a and R 1 To R 4 They may independently be hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C2 to C20 heterocyclic group, or a group represented by Chemical Formula A.

[0097] For example, R a and R 1 To R 4 They may independently be hydrogen or a group represented by Chemical Formula A, but are not limited thereto.

[0098] For example, according to the fusion position of Chemical Formula 1 and Chemical Formula 2, the first compound may be represented by one of Chemical Formula 1A to Chemical Formula 1C.

[0099]

[0100] In Chemical Formulae 1A to 1C, Ar 1 , L a and L 1 To L 4 and R a and R 1 To R 4 Same as above.

[0101] For example, according to the substitution position of the group represented by Chemical Formula A, Chemical Formula 1A may be represented by one of Chemical Formulae 1A-1 to Chemical Formulae 1A-3.

[0102]

[0103] In Chemical Formulae 1A-1 to 1A-3, Ar 1 , L a , L 1 To L 4 , R a , R 1 To R 4 , R b and R c Same as above.

[0104] For example, depending on a specific substitution position of the group represented by Chemical Formula A, Chemical Formula 1A-1 may be represented by one of Chemical Formulae 1A-1-a to Chemical Formulae 1A-1-d.

[0105]

[0106]

[0107] In Chemical Formulae 1A-1-a to 1A-1-d, Ar 1 , L a , L 1 To L 4 , R a , R 1 To R 4 , R b and R c Same as above.

[0108] In one exemplary embodiment, Chemical Formula 1A-1 may be represented by Chemical Formula 1A-1-b or Chemical Formula 1A-1-c.

[0109] For example, depending on a specific substitution position of the group represented by Chemical Formula A, Chemical Formula 1A-2 may be represented by Chemical Formula 1A-2-a or Chemical Formula 1A-2-b.

[0110]

[0111] In the chemical formula 1A-2-a and the chemical formula 1A-2-b, Ar 1 , L a and L 1 To L 4 and R 1 To R 4 and R b and R c Same as above.

[0112] In one exemplary embodiment, Chemical Formula 1A-2 may be represented by Chemical Formula 1A-2-a.

[0113] For example, depending on a specific substitution position of the group represented by Chemical Formula A, Chemical Formula 1A-3 may be represented by one of Chemical Formulas 1A-3-a to 1A-3-d.

[0114]

[0115]

[0116] In Chemical Formulae 1A-3-a to 1A-3-d, Ar 1 , L a , L1 To L 4 , R a , R 1 To R 4 , R b and R c Same as above.

[0117] In one exemplary embodiment, Chemical Formula 1A-3 may be represented by Chemical Formula 1A-3-b or Chemical Formula 1A-3-c.

[0118] For example, according to the substitution position of the group represented by Chemical Formula A, Chemical Formula 1B may be represented by one of Chemical Formulae 1B-1 to 1B-3.

[0119]

[0120] In Chemical Formulae 1B-1 to 1B-3, Ar 1 , L a , L 1 To L 4 , R a , R 1 To R 4 , R b and R c Same as above.

[0121] For example, depending on a specific substitution position of the group represented by Chemical Formula A, Chemical Formula 1B-1 may be represented by one of Chemical Formulas 1B-1-a to 1B-1-d.

[0122]

[0123]

[0124] In Chemical Formula 1B-1-a to Chemical Formula 1B-1-d, Ar 1 , L a , L 1 To L 4 , R a , R 1 To R 4 , R b and R c Same as above.

[0125] For example, depending on a specific substitution position of the group represented by Chemical Formula A, Chemical Formula 1B-2 may be represented by Chemical Formula 1B-2-a or Chemical Formula 1B-2-b.

[0126]

[0127] In the chemical formula 1B-2-a and the chemical formula 1B-2-b, Ar1 , L a , L 1 To L 4 , R 1 To R 4 , R b and R c Same as above.

[0128] For example, according to a specific substitution position of the group represented by Chemical Formula A, Chemical Formula 1B-3 may be represented by one of Chemical Formulas 1B-3-a to 1B-3-d.

[0129]

[0130]

[0131] In Chemical Formula 1B-3-a to Chemical Formula 1B-3-d, Ar 1 , L a , L 1 To L 4 , R a , R 1 To R 4 , R b and R c Same as above.

[0132] In one embodiment, Chemical Formula 1B-3 may be represented by Chemical Formula 1B-3-b.

[0133] For example, according to the substitution position of the group represented by Chemical Formula A, Chemical Formula 1C may be represented by one of Chemical Formulae 1C-1 to 1C-3.

[0134]

[0135] In Chemical Formulae 1C-1 to 1C-3, Ar 1 , L a , L 1 To L 4 , R a , R 1 To R 4 , R b and R c Same as above.

[0136] For example, depending on a specific substitution position of the group represented by Chemical Formula A, Chemical Formula 1C-1 may be represented by one of Chemical Formulae 1C-1-a to 1C-1-d.

[0137]

[0138]

[0139] In Chemical Formulae 1C-1-a to 1C-1-d, Ar 1 , L a , L 1 To L 4 , R a , R 1 To R 4 , R b and R c Same as above.

[0140] In one embodiment, Chemical Formula 1C-1 may be represented by Chemical Formula 1C-1-b.

[0141] For example, depending on a specific substitution position of the group represented by Chemical Formula A, Chemical Formula 1C-2 may be represented by one of Chemical Formula 1C-2-a or Chemical Formula 1C-2-b.

[0142]

[0143] In the chemical formula 1C-2-a and the chemical formula 1C-2-b, Ar 1 , L a , L 1 To L 4 , R 1 To R 4 , R b and R c Same as above.

[0144] For example, according to a specific substitution position of the group represented by Chemical Formula A, Chemical Formula 1C-3 is represented by one of Chemical Formulae 1C-3-a to 1C-3-d.

[0145]

[0146] In Chemical Formulae 1C-3-a to 1C-3-d, Ar 1 , L a , L 1 To L 4 , R a , R 1 To R 4 , R b and R c Same as above.

[0147] In one embodiment, Chemical Formula 1C-3 may be represented by Chemical Formula 1C-3-b.

[0148] In one embodiment of the present invention, the first compound can be represented by Chemical Formula 1A, particularly Chemical Formula 1A-1, such as Chemical Formula 1A-1-b.

[0149] The first compound may be, for example, one of the compounds of Group 1, but is not limited thereto.

[0150] [Group 1]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156] The second compound is represented by Chemical Formula 3.

[0157] [Chemical formula 3]

[0158]

[0159] In chemical formula 3,

[0160] L 5 To L 9 are independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0161] Ar 2 is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

[0162] R 5 To R 8 are independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof,

[0163] R 5 To R 8 They exist independently or their adjacent groups are connected to each other to form a substituted or unsubstituted aromatic monocyclic or polycyclic ring,

[0164] Ar 2 and R 5 To R 8 At least one of them is a group represented by chemical formula B,

[0165] [Chemical formula B]

[0166]

[0167] Among them, in chemical formula B,

[0168] Z 1 To Z 5 N or CL independently b -R d ,

[0169] Z 1 To Z 5 At least one of them is N,

[0170] Where L b are independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0171] R d are independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof,

[0172] R d exist independently or their 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, and

[0173] * Yes and L 5 To L 9 connection point.

[0174] The second compound is a compound that can accept both holes and electrons when an electric field is applied, that is, a compound having bipolar properties, and specifically, due to the carbazole core represented by Formula 3 substituted with a ring containing at least one nitrogen (such as pyrimidine or triazine), it can have the effect of increasing the glass transition temperature relative to the molecular weight and ensuring heat resistance.

[0175] In addition, the second compound has fast and stable electron transport characteristics, and thus can match the balance of holes and electrons by being included together with the first compound having fast and stable hole transport characteristics, and can reduce the driving voltage of an organic photoelectric device including the compound.

[0176] For example, L 5 To L 9 and may independently be a single bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heterocyclic group.

[0177] For example, L 5 To L 9It may independently be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted fused dibenzofuranyl group, a substituted or unsubstituted fused dibenzothienyl group, or a combination thereof.

[0178] For example, L 5 To L 9 and may independently be a single bond, a substituted or unsubstituted m-phenylene group, a substituted or unsubstituted p-phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted terphenylene group.

[0179] For example, Ar 2 The group may 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 phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a group represented by Chemical Formula B, or a combination thereof.

[0180] For example, Ar 2 The group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, or a group represented by Chemical Formula B, but is not limited thereto.

[0181] For example, R 5 To R 8 It may independently be hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, a group represented by Chemical Formula B, or a combination thereof.

[0182] For example, R 5 To R 8 It may independently be hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl or a group represented by Chemical Formula B, but is not limited thereto.

[0183] For example, according to the bonding position of the group represented by Chemical Formula B, the second compound may be represented by, for example, one of Chemical Formulae 2A to 2L.

[0184]

[0185]

[0186] In Formulae 2A to 2L, L 5 To L 9 ,Ar 2 , R 5 To R 8 and Z 1 To Z 5 Same as above.

[0187] R e , R f , R g , R h , R i and R j With R 5 To R 8 same,

[0188] Z 1a To Z 5a With Z 1 To Z 5 The same, and

[0189] Z 1b To Z 5b With Z 1 To Z 5 same.

[0190] For example, L b may independently be a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

[0191] For example, L b The groups may independently be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted dibenzofuranylene group, or a substituted or unsubstituted dibenzothiophenylene group.

[0192] For example, L b They may independently be a single bond, a substituted or unsubstituted m-phenylene group, or a substituted or unsubstituted p-phenylene group, but are not limited thereto.

[0193] For example, R d and may independently be hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof.

[0194] For example, R dThe radicals may independently be hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiophenyl.

[0195] For example, R d The radicals may independently be hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted m-biphenyl, substituted or unsubstituted p-biphenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiophenyl, but are not limited thereto.

[0196] R d The groups exist independently or their adjacent groups are linked to each other to form a substituted or unsubstituted monocyclic or polycyclic, or a substituted or unsubstituted aromatic monocyclic or polycyclic heterocyclic ring.

[0197] For example, in the group represented by chemical formula B, Z 1 To Z 5 At least two of them can be N, and R d Can exist independently.

[0198] For example, the group represented by Chemical Formula B may be a substituted or unsubstituted pyrimidinyl group or a substituted or unsubstituted triazine group.

[0199] For example, Z 1 and Z 3 Can be N, and Z 2 , Z 4 and Z 5 Can be independently CL b -R d ; Z 3 and Z 5 Can be N, and Z 1 , Z 2 and Z 4 Can be independently CL b -R d ; or Z 2 and Z 4 Can be N, and Z 1 , Z 3 and Z 5 Can be independently CL b -R d In this case, L b and R d Same as above.

[0200] For example, Z 1, Z 3 and Z 5 Can be N, and Z 2 and Z 4 Can be independently CL b -R d In this case, L b and R d Same as above.

[0201] For example, in the group represented by chemical formula B, Z 1 To Z 5 At least one of may be N, and R d are connected to each other to form a substituted or unsubstituted aromatic monocyclic ring or a substituted or unsubstituted aromatic monocyclic heterocyclic ring.

[0202] In this case, the group represented by Chemical Formula B may be a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted quinazolinyl group, or a substituted or unsubstituted naphthyridinyl group.

[0203] For example, Z 3 and Z 4 Can be independently CR d , adjacent R d are connected to each other to form a benzene ring, and Z 1 , Z 2 and Z 5 One of them can be N.

[0204] For example, Z 3 and Z 4 Can be independently CR d , adjacent R d are connected to each other to form a benzene ring, and Z 1 , Z 2 and Z 5 Two of them can be N.

[0205] For example, Z 3 and Z 4 Can be independently CR d , adjacent R d are connected to each other to form a benzene ring, and Z 1 , Z 2 and Z 5 Each of can be N.

[0206] For example, Chemical Formula B may be represented by one of Chemical Formulas B-1 to B-7, but is not limited thereto.

[0207]

[0208] In Chemical Formula B-1 to Chemical Formula B-7,

[0209] L b1 To L b5 and L c1 and L c2 With L b The same, and

[0210] R d1 To R d5 , R k1 and R k2 With R d same.

[0211] * Yes and L 5 To L 9 connection point.

[0212] For specific examples, the group represented by Chemical Formula B may be a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted quinazolinyl group, or a substituted or unsubstituted naphthyridinyl group.

[0213] For a more specific example, the chemical formula B can be one of the substituents of Group I.

[0214] [Group I]

[0215]

[0216] For example, according to a specific bonding position of the group represented by Chemical Formula B, Chemical Formula 2A may be represented by one of Chemical Formulae 2A-1 to 2A-4.

[0217]

[0218] In Chemical Formulae 2A-1 to 2A-4, L 5 To L 9 ,Ar 2 , R 5 To R 8 and Z 1 To Z 5 Same as above.

[0219] For example, according to a specific bonding position of the group represented by Chemical Formula B, Chemical Formula 2C may be represented by one of Chemical Formulae 2C-1 to 2C-4.

[0220]

[0221]

[0222] In Chemical Formulae 2C-1 to 2C-4, L 5 To L9 , R 6 To R 8 , Z 1a To Z 5a and Z 1b To Z 5b Same as above.

[0223] In one embodiment of the present invention, the second compound may be represented by one of Chemical Formula 2B, Chemical Formula 2C, Chemical Formula 2D, Chemical Formula 2E, and Chemical Formula 2F, for example, Chemical Formula 2B or Chemical Formula 2F.

[0224] The second compound may be, for example, one of the compounds of Group 2, but is not limited thereto.

[0225] [Group 2]

[0226]

[0227]

[0228]

[0229]

[0230] The first compound and the second compound may be included, for example, in a weight ratio of 1:99 to 99:1. Within this range, the hole transport ability of the first compound and the electron transport ability of the second compound may be used to adjust the desired weight ratio to achieve bipolar characteristics, thereby improving efficiency and lifespan. Within this range, they may be included, for example, in 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, they may be included in a weight ratio of about 50:50 to 60:40, such as about 50:50 or about 60:40.

[0231] For example, the composition according to the exemplary embodiment of the present invention may include a compound represented by Chemical Formula 1A-1-b as a first compound and a compound represented by Chemical Formula 2B or Chemical Formula 2F as a second compound.

[0232] For example, in Chemical Formula 1A-1-b, Ar 1 It 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 phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted carbazolyl group or a combination thereof, L a and L 1To L 4 R 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, a , R 1 , R 2 and R 4 may independently be hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof, and R b and R c are independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl, and

[0233] In Formula 2B and Formula 2F, L 5 To L 9 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, and R 5 To R 8 , R e , R f and R g They may independently be hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano or a combination thereof.

[0234] In addition, Z 1 To Z 5 Can be N or CL independently b -R d , Z 1 To Z 5 At least two of them can be N, L b may independently be a single bond, or a substituted or unsubstituted C6 to C20 arylene group, and R d The group 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 anthracenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothiophenyl group.

[0235] The composition may further include at least one compound in addition to the first compound and the second compound.

[0236] The composition may further comprise a dopant. The dopant may be, for example, a phosphorescent dopant, such as a red, green or blue phosphorescent dopant, such as a red phosphorescent dopant.

[0237] The dopant is a material mixed with the first compound and the second compound in a small amount to cause luminescence, and is generally a material such as a metal complex that emits light by multiple excitations to a triplet state or a multiplet state. The dopant may be, for example, an inorganic, organic, or organic / inorganic compound, and one or more types thereof may be used.

[0238] Examples of the dopant may be a phosphorescent dopant, and examples of the phosphorescent dopant may be an organic metal compound including 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 the chemical formula Z, but is not limited thereto.

[0239] [Chemical formula Z]

[0240] L 10 MX

[0241] In the chemical formula Z, M is a metal and L 10 is the same as or different from X and is a ligand that forms a complex with M.

[0242] M can be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof, and L 10 and X may be, for example, a bidentate ligand.

[0243] The composition may be formed by a dry film forming method such as chemical vapor deposition (CVD).

[0244] Hereinafter, an organic photoelectric device including the composition is described.

[0245] The organic photoelectric 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 photoconductor.

[0246] Herein, an organic light emitting diode as one example of an organic photoelectric device is described with reference to the accompanying drawings.

[0247] Figure 1 and Figure 2 is a cross-sectional view showing an organic light emitting diode according to an embodiment.

[0248] refer to Figure 1 According to one embodiment, an organic photoelectric device (100) 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).

[0249] The anode (120) may be made of a conductor with a large work function to facilitate 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, or the like, or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or the like; a combination of a metal and an oxide such as ZnO and Al or SnO 2 and Sb; conductive polymers such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (PEDT), polypyrrole, and polyaniline, but not limited thereto.

[0250] The cathode (110) may be made of a conductor with a small work function to facilitate 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, LiO 2 / Al, LiF / Ca, LiF / Al and BaF 2 / Ca, but not limited thereto.

[0251] The organic layer (105) includes a light emitting layer (130) including a composition.

[0252] The light emitting layer (130) may include, for example, a composition.

[0253] The composition may be, for example, a red-luminescent composition.

[0254] The light emitting layer (130) may include, for example, a first compound and a second compound as phosphorescent hosts.

[0255] refer to Figure 2 In addition to the light-emitting layer (130), the organic light-emitting diode (200) further includes a hole auxiliary layer (140). The hole auxiliary layer (140) can further increase hole injection and / or hole mobility while blocking electrons between the anode (120) and the light-emitting layer (130). The hole auxiliary layer (140) can include, for example, at least one of a hole transport layer, a hole injection layer, and / or an electron blocking layer.

[0256] The hole assisting layer (140) may include, for example, at least one of the compounds of group D.

[0257] Specifically, the hole auxiliary layer (140) may include a hole transport layer between the anode (120) and the light-emitting layer (130) and a hole transport auxiliary layer between the light-emitting layer (130) and the hole transport layer, and at least one of the compounds of group D may be included in the hole transport auxiliary layer.

[0258] [Group D]

[0259]

[0260]

[0261]

[0262] In the hole transport auxiliary layer, in addition to the compound, known compounds disclosed in US5061569A, JP1993-009471A, WO1995-009147A1, JP1995-126615A, JP1998-095973A, etc. and compounds similar thereto can be used.

[0263] In one embodiment of the present invention, Figure 1 or Figure 2 In the embodiment, the organic light emitting diode may further include an electron transport layer, an electron injection layer or a hole injection layer as the organic layer (105).

[0264] The organic light emitting diode (100, 200) can be manufactured by forming an anode or a cathode on a substrate, forming an organic layer using a dry film forming method such as a vacuum deposition method (evaporation), sputtering, plasma plating and ion plating, and forming a cathode or an anode thereon.

[0265] Organic light emitting diodes can be applied to organic light emitting display devices.

[0266] [Invention Mode]

[0267] Hereinafter, the embodiments will be described in more detail with reference to Examples. However, these Examples are exemplary, and the present scope is not limited thereto.

[0268] (Preparation of the First Compound)

[0269] Synthesis Example 1: Synthesis of Compound A-2

[0270] [Reaction Scheme 1]

[0271]

[0272] a) Synthesis of intermediate A-2-1

[0273] Phenylhydrazine hydrochloride (70.0 g, 484.1 mmol) and 7-bromo-3,4-dihydro-2H-naphthalene-1-one (108.9 g, 484.1 mmol) were placed in a round-bottom flask and then dissolved in ethanol (1200 ml). At room temperature, 60 mL of hydrochloric acid was slowly added thereto in a dropwise manner, and the resulting mixture was stirred at 90 ° C for 12 hours. When the reaction was completed, the solvent was removed therefrom under reduced pressure, and an extract was obtained therefrom by using an excess of EA. After removing the organic solvent under reduced pressure, the extract was stirred in a small amount of methanol and then filtered to obtain 95.2 g of intermediate A-2-1 (66%).

[0274] b) Synthesis of intermediate A-2-2

[0275] Intermediate A-2-1 (95.2 g, 319.3 mmol) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (108.7 g, 478.9 mmol) were placed in a round-bottom flask and dissolved in 600 ml of toluene. The solution was stirred at 80 ° C for 12 hours. When the reaction was completed, the reaction solvent was removed and the remaining portion was processed by column chromatography to obtain 41.3 g of intermediate A-2-2 (44%).

[0276] c) Synthesis of intermediate A-2-3

[0277] Intermediate A-2-2 (41.3 g, 139.0 mmol), iodobenzene (199.2 g, 976.0 mmol), CuI (5.31 g, 28.0 mmol), K 2 CO 3 (28.9g, 209.0mmol) and 1,10-phenanthroline (5.03g, 28.0mmol) were placed in a round-bottom flask and dissolved in 500ml of DMF. The solution was stirred at 180°C for 12 hours. When the reaction was completed, the reaction solvent was removed therefrom under reduced pressure, and then the product was dissolved in dichloromethane and filtered with silica gel. After dichloromethane was concentrated, the filtered product was recrystallized with hexane to obtain 39.0g of intermediate A-2-3 (75%).

[0278] d) Synthesis of Compound A-2

[0279] Intermediate A-2-3 (23.2 g, 62.5 mmol), bis(biphenyl-4-ylamine) (21.1 g, 65.6 mmol), sodium tert-butoxide (NaOtBu) (9.0 g, 93.8 mmol), Pd 2 (dba) 3 (3.4 g, 3.7 mmol) and tri-tert-butylphosphine (P(tBu) 3) (4.5 g, 50% toluene solution) was placed in xylene (300 mL), then heated and refluxed under nitrogen flow for 12 hours. After removing xylene, 200 mL of methanol was added thereto to crystallize the solid, which was filtered, dissolved in toluene, and filtered with silica gel / celite, and then an appropriate amount of organic solvent was concentrated to obtain 29 g of compound A-2 (76%).

[0280] LC / MS calculated value: C46H32N2 exact mass: 612.26, found value 612.32 [M+H] +

[0281] Synthesis Example 2: Synthesis of Compound A-3

[0282] [Reaction Scheme 2]

[0283]

[0284] a) Synthesis of intermediate A-3-1

[0285] According to the same method as a) of Synthesis Example 1, Intermediate A-3-1 was synthesized by using 1.0 equivalent of phenylhydrazine hydrochloride and 6-bromo-3,4-dihydro-2H-naphthalen-1-one, respectively.

[0286] b) Synthesis of intermediate A-3-2

[0287] According to the same method as b) of Synthesis Example 1, Intermediate A-3-2 was synthesized by using Intermediate A-3-1 and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in an equivalent ratio of 1:1.5.

[0288] c) Synthesis of intermediate A-3-3

[0289] According to the same method as c) of Synthesis Example 1, Intermediate A-3-3 was synthesized by using Intermediate A-3-2 and iodobenzene in an equivalent ratio of 1:3.

[0290] d) Synthesis of Compound A-3

[0291] According to the same method as d) of Synthesis Example 1, compound A-3 was synthesized by using intermediate A-3-3 and bisbiphenyl-4-ylamine in an equivalent ratio of 1:1.

[0292] LC / MS calculated value: C46H32N2 exact mass: 612.26, found value 612.28 [M+H] +

[0293] Synthesis Example 3: Synthesis of Compound A-5

[0294] [Reaction Scheme 3]

[0295]

[0296] a) Synthesis of intermediate A-5-1

[0297] According to the same method as a) of Synthesis Example 1, Intermediate A-5-1 was synthesized by using 1.0 equivalent of phenylhydrazine hydrochloride and 3,4-dihydro-2H-naphthalen-1-one, respectively.

[0298] b) Synthesis of intermediate A-5-2

[0299] According to the same method as b) of Synthesis Example 1, Intermediate A-5-2 was synthesized by using Intermediate A-5-1 and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone at an equivalent ratio of 1:1.5, respectively.

[0300] c) Synthesis of intermediate A-5-3

[0301] According to the same method as c) of Synthesis Example 1, Intermediate A-5-3 was synthesized by using Intermediate A-5-2 and iodobenzene in an equivalent ratio of 1:3.

[0302] d) Synthesis of intermediate A-5-4

[0303] Intermediate A-5-3 (23.6 g, 80.6 mmol) was placed in a round-bottom flask and then dissolved in 300 mL of dichloromethane. Subsequently, N-bromosuccinimide (NBS) (14.1 g, 79.0 mmol) was dissolved in 100 mL of DMF, the solution was slowly added dropwise to the above solution, and the mixed solution was stirred at room temperature for 2 hours. When the reaction was completed, the reaction solvent was removed and the product was treated by column chromatography to obtain 25 g of intermediate A-5-4 (83%).

[0304] e) Synthesis of Compound A-5

[0305] According to the same method as d) of Synthesis Example 1, compound A-5 was synthesized by using intermediate A-5-4 and bisbiphenyl-4-ylamine in an equivalent ratio of 1:1.

[0306] LC / MS calculated value: C46H32N2 exact mass: 612.26, found value 612.33 [M+H] +

[0307] Synthesis Example 4: Synthesis of Compound A-7

[0308] [Reaction Scheme 4]

[0309]

[0310] a) Synthesis of intermediate A-7-1

[0311] According to the same method as a) of Synthesis Example 1, Intermediate A-7-1 was synthesized by using 1.0 equivalent of 4-bromophenylhydrazine hydrochloride and 3,4-dihydro-2H-naphthalen-1-one, respectively.

[0312] b) Synthesis of intermediate A-7-2

[0313] According to the same method as b) of Synthesis Example 1, Intermediate A-7-2 was synthesized by using Intermediate A-7-1 and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in an equivalent ratio of 1:1.5.

[0314] c) Synthesis of intermediate A-7-3

[0315] According to the same method as c) of Synthesis Example 1, Intermediate A-7-3 was synthesized by using Intermediate A-7-2 and iodobenzene in an equivalent ratio of 1:3.

[0316] d) Synthesis of Compound A-7

[0317] According to the same method as d) of Synthesis Example 1, compound A-7 was synthesized by using intermediate A-7-3 and bisbiphenyl-4-ylamine in an equivalent ratio of 1:1.

[0318] LC / MS calculated value: C46H32N2 exact mass: 612.26, found value 612.30 [M+H] +

[0319] Synthesis Example 5: Synthesis of Compound A-8

[0320] [Reaction Scheme 5]

[0321]

[0322] a) Synthesis of intermediate A-8-1

[0323] According to the same method as a) of Synthesis Example 1, Intermediate A-8-1 was synthesized by using 1.0 equivalent of 3-bromophenylhydrazine hydrochloride and 3,4-dihydro-2H-naphthalen-1-one, respectively.

[0324] b) Synthesis of intermediate A-8-2

[0325] According to the same method as b) of Synthesis Example 1, Intermediate A-8-2 was synthesized by using Intermediate A-8-1 and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in an equivalent ratio of 1:1.5.

[0326] c) Synthesis of intermediate A-8-3

[0327] According to the same method as in c) of Synthesis Example 1, Intermediate A-8-3 was synthesized by using Intermediate A-8-2 and iodobenzene in an equivalent ratio of 1:3.

[0328] d) Synthesis of Compound A-8

[0329] According to the same method as d) of Synthesis Example 1, compound A-8 was synthesized by using intermediate A-8-3 and bisbiphenyl-4-ylamine in an equivalent ratio of 1:1.

[0330] LC / MS calculated value: C46H32N2 exact mass: 612.26, found value 612.33 [M+H] +

[0331] Synthesis Example 6: Synthesis of Compound A-11

[0332] [Reaction Scheme 6]

[0333]

[0334] a) Synthesis of intermediate A-11-1

[0335] 4-Bromo-aniline (50.0 g, 290.7 mmol), 2-naphthaleneboronic acid (59.9 g, 171.9 mmol), K 2 CO 3 (80.4 g, 581.3 mmol) and Pd(PPh 3 ) 4 (10.1 g, 8.7 mmol) was placed in a round-bottom flask and dissolved in 800 ml of toluene and 400 ml of distilled water, and the solution was stirred at 80° C. for 12 hours. When the reaction was completed, the water layer was removed therefrom, and the remainder thereof was treated by column chromatography to obtain 40.0 g of intermediate A-11-1 (63%).

[0336] b) Synthesis of intermediate A-11-2

[0337] Intermediate A-11-1 (17.7 g, 80.8 mmol), 4-bromobiphenyl (18.8 g, 80.8 mmol), sodium tert-butoxide (NaOtBu) (11.6 g, 121.1 mmol), Pd 2 (dba) 3 (4.4 g, 4.8 mmol) and tri-tert-butylphosphine (P(tBu) 3) (5.9 g, 50% toluene solution) was added to xylene (400 mL), and then heated and refluxed together under a nitrogen stream for 12 hours. After removing xylene, the remaining part was treated by column chromatography to obtain 20.0 g of intermediate A-11-2 (67%).

[0338] c) Synthesis of Compound A-11

[0339] According to the same method as d) of Synthesis Example 1, Compound A-11 was synthesized by using Intermediate A-11-2 and Intermediate A-2-3 in an equivalent ratio of 1:1.

[0340] LC / MS calculated value: C50H34N2 exact mass: 662.27, found value 662.31 [M+H] +

[0341] Synthesis Example 7: Synthesis of Compound A-12

[0342] [Reaction Scheme 7]

[0343]

[0344] According to the same method as d) of Synthesis Example 1, compound A-12 was synthesized by using intermediate A-3-3 and intermediate A-11-2 in an equivalent ratio of 1:1.

[0345] LC / MS calculated value: C50H34N2 exact mass: 662.27, found value 662.30 [M+H]

[0346] Synthesis Example 8: Synthesis of Compound A-29

[0347] [Reaction Scheme 8]

[0348]

[0349] a) Synthesis of intermediate A-29-1

[0350] Aniline (8.3 g, 89.5 mmol), 4-(4-bromo-phenyl)-dibenzofuran (23.1 g, 71.5 mmol), sodium tert-butoxide (NaOtBu) (12.9 g, 134.2 mmol), Pd 2 (dba) 3 (4.9 g, 5.4 mmol) and tri-tert-butylphosphine (P(tBu) 3 ) (6.5 g, 50% toluene solution) was added to xylene (400 mL), and then heated and refluxed together under nitrogen flow for 12 hours. After removing xylene, the remaining part was treated by column chromatography to obtain 20.0 g of intermediate A-29-1 (67%).

[0351] b) Synthesis of Compound A-29

[0352] According to the same method as d) of Synthesis Example 1, compound A-29 was synthesized by using intermediate A-29-1 and intermediate A-2-3 in an equivalent ratio of 1:1.

[0353] LC / MS calculated value: C46H30N2O exact mass: 626.24, found value 626.28 [M+H] +

[0354] Synthesis Example 9: Synthesis of Compound A-38

[0355] [Reaction Scheme 9]

[0356]

[0357] a) Synthesis of intermediate A-38-1

[0358] 9,9-dimethyl-9H-fluoren-2-ylamine (17.4 g, 83.0 mmol), 4-bromo-biphenyl (15.5 g, 66.4 mmol), sodium tert-butoxide (NaOtBu) (12.0 g, 124.5 mmol), Pd 2 (dba) 3 (4.6 g, 5.0 mmol) and tri-tert-butylphosphine (P(tBu) 3 ) (6.0 g, 50% toluene solution) was placed in xylene (400 mL), and then heated and refluxed under nitrogen flow for 12 hours. After removing xylene, the remaining part was treated by column chromatography to obtain 18.0 g of intermediate A-38-1 (60%).

[0359] b) Synthesis of Compound A-38

[0360] According to the same method as d) of Synthesis Example 1, compound A-38 was synthesized by using intermediate A-38-1 and intermediate A-3-3 in an equivalent ratio of 1:1.

[0361] LC / MS calculated value: C49H36N2 exact mass: 652.29, found value 652.33 [M+H] +

[0362] Synthesis Example 10: Synthesis of Compound A-51

[0363] [Reaction Scheme 10]

[0364]

[0365] a) Synthesis of intermediate A-51-1

[0366] Intermediate A-3-3 (30.0 g, 80.6 mmol), 4-chlorophenylboronic acid (15.1 g, 96.7 mmol), K 2 CO 3 (22.3 g, 161.2 mmol) and Pd(PPh 3 ) 4 (2.8 g, 2.4 mmol) was placed in a round-bottom flask and then dissolved in 200 ml of tetrahydrofuran and 100 ml of distilled water, and the solution was stirred at 80° C. for 12 hours. When the reaction was completed, the water layer was removed therefrom, and the remainder thereof was treated by column chromatography to obtain 27.0 g of intermediate A-51-1 (83%).

[0367] b) Synthesis of Compound A-51

[0368] According to the same method as d) of Synthesis Example 1, compound A-51 was synthesized by using intermediate A-51-1 and bisbiphenyl-4-ylamine in an equivalent ratio of 1:1.

[0369] LC / MS calculated value: C52H36N2 exact mass: 688.29, found value 688.34 [M+H] +

[0370] Synthesis Example 11: Synthesis of Compound A-65

[0371] [Reaction Scheme 11]

[0372]

[0373] a) Synthesis of intermediate A-65-1

[0374] 1,4-dibromo-2-nitrobenzene (30.0 g, 106.8 mmol), 2-naphthaleneboronic acid (18.4 g, 106.8 mmol), K 2 CO 3 (29.5 g, 213.6 mmol) and Pd(PPh 3 ) 4 (3.7 g, 3.2 mmol) was placed in a round-bottom flask, then dissolved in 300 mL of tetrahydrofuran and 150 mL of distilled water, and the solution was stirred at 80° C. for 12 hours. When the reaction was completed, the water layer was removed therefrom, and the remainder thereof was processed by column chromatography to obtain 27.0 g of intermediate A-65-1 (77%).

[0375] b) Synthesis of intermediate A-65-2

[0376] Intermediate A-65-1 (27.0 g, 82.3 mmol) and triphenylphosphine (86.3 g, 329.1 mmol) were placed in a round-bottom flask and then dissolved in 300 mL of 1,2-dichlorobenzene, and the solution was stirred at 180° C. for 12 hours. When the reaction was completed, the solvent was removed therefrom, and the remaining portion thereof was processed by column chromatography to obtain 18.0 g of intermediate A-65-2 (74%).

[0377] c) Synthesis of intermediate A-65-3

[0378] According to the same method as c) of Synthesis Example 1, Intermediate A-65-3 was synthesized by using Intermediate A-65-2 and iodobenzene in an equivalent ratio of 1:3.

[0379] d) Synthesis of Compound A-65

[0380] According to the same method as d) of Synthesis Example 1, Intermediate A-65 was synthesized by using Intermediate A-65-3 and bisbiphenyl-4-ylamine in an equivalent ratio of 1:1.

[0381] LC / MS calculated value: C46H32N2 exact mass: 612.26, found value 612.30 [M+H] +

[0382] Synthesis Example 12: Synthesis of Compound A-72

[0383] [Reaction Scheme 12]

[0384]

[0385] a) Synthesis of intermediate A-72-1

[0386] According to the same method as a) of Synthesis Example 1, Intermediate A-72-1 was synthesized by using 1.0 equivalent of phenylhydrazine hydrochloride and 6-bromo-3,4-dihydro-1H-naphthalen-2-one.

[0387] b) Synthesis of intermediate A-72-2

[0388] According to the same method as b) of Synthesis Example 1, Intermediate A-72-2 was synthesized by using Intermediate A-72-1 and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in an equivalent ratio of 1:1.5.

[0389] c) Synthesis of intermediate A-72-3

[0390] According to the same method as in c) of Synthesis Example 1, Intermediate A-72-3 was synthesized by using Intermediate A-72-2 and iodobenzene in an equivalent ratio of 1:3.

[0391] d) Synthesis of Compound A-72

[0392] According to the same method as d) of Synthesis Example 1, Intermediate A-72 was synthesized by using Intermediate A-72-3 and bisbiphenyl-4-ylamine in an equivalent ratio of 1:1.

[0393] LC / MS calculated value: C46H32N2 exact mass: 612.26, found value 612.31 [M+H] +

[0394] Synthesis Example 13: Synthesis of Compound A-77

[0395] [Reaction Scheme 13]

[0396]

[0397] a) Synthesis of intermediate A-77-1

[0398] According to the same method as a) of Synthesis Example 11, Intermediate A-77-1 was synthesized by using 1.0 equivalent of 1,4-dibromo-2-nitrobenzene and 1-naphthaleneboric acid.

[0399] b) Synthesis of intermediate A-77-2

[0400] According to the same method as b) of Synthesis Example 11, Intermediate A-77-2 was synthesized by using Intermediate A-77-1 and triphenylphosphine in an equivalent ratio of 1:4.

[0401] c) Synthesis of intermediate A-77-3

[0402] According to the same method as in c) of Synthesis Example 1, Intermediate A-77-3 was synthesized by using Intermediate A-77-2 and iodobenzene in an equivalent ratio of 1:3.

[0403] d) Synthesis of Compound A-77

[0404] According to the same method as d) of Synthesis Example 1, compound A-77 was synthesized by using intermediate A-77-3 and bisbiphenyl-4-ylamine in an equivalent ratio of 1:1.

[0405] LC / MS calculated value: C46H32N2 exact mass: 612.26, found value 612.29 [M+H] +

[0406] (Preparation of Second Compound)

[0407] Synthesis Example 14: Synthesis of Compound B-8

[0408] [Reaction Scheme 14]

[0409]

[0410] a) Synthesis of intermediate B-8-1

[0411] In a 1L round-bottom flask, 3-bromocarbazole (35g, 142mmol) was dissolved in 0.5L of tetrahydrofuran (THF), and phenylboric acid (17.3g, 142mmol) and tetrakis (triphenylphosphine) palladium (8.2g, 7.1mmol) were added thereto, and the mixture was stirred. Subsequently, potassium carbonate (49.1g, 356mmol) saturated in water was added thereto, and the resulting mixture was heated and refluxed at 80°C for 12 hours. When the reaction was complete, water was poured into the reaction solution, and then an extract was obtained from it by using dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture therefrom, filtered and concentrated under reduced pressure. The residue obtained was separated and purified by flash column chromatography to obtain 22.0g of intermediate B-8-1.

[0412] b) Synthesis of intermediate B-8-2

[0413] In a 1L round-bottom flask, intermediate B-8-1 (40g, 164mmol) was dissolved in 0.5L of tetrahydrofuran (THF), and 2-chloro-4,6-diphenyl-1,3,5-triazine (40g, 149mmol) and tetrakis (triphenylphosphine) palladium (8.63g, 7.5mmol) were added thereto, and the mixture was stirred. Subsequently, potassium carbonate (51.6g, 374mmol) saturated in water was added thereto, and the resulting mixture was heated and refluxed at 80°C for 12 hours. When the reaction was complete, water was poured into the reaction solution, and then an extract was obtained from it by using dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture therefrom, filtered and concentrated under reduced pressure. The residue obtained was separated and purified by flash column chromatography to obtain 32.1g of intermediate B-8-2.

[0414] c) Synthesis of Compound B-8

[0415] Intermediate B-8-1 (22.0 g, 90.4 mmol), intermediate B-8-2 (31.1 g, 90.4 mmol), sodium tert-butoxide (NaOtBu) (13.01 g, 135.6 mmol), Pd2(dba)3 (2.48 g, 2.7 mmol) and tri-tert-butylphosphine (P(tBu) 3) (5.49 g, 50% toluene solution) was added to xylene (300 mL), and the mixture was heated and refluxed under a nitrogen stream for 12 hours. After removing xylene therefrom, 200 mL of methanol was added thereto, the crystallized solid therein was filtered, dissolved in monochlorobenzene (MCB), and filtered with silica gel / diatomaceous earth, and an appropriate amount of organic solvent was concentrated therefrom to obtain compound B-8 (32 g, 64.3%).

[0416] Synthesis Example 15: Synthesis of Compound B-12

[0417] [Reaction Scheme 15]

[0418]

[0419] a) Synthesis of intermediate B-12-1

[0420] Carbazole (35 g, 209.3 mmol), 1-bromo-4-chlorobenzene (60.11 g, 313.98 mmol), CuI (3.99 g, 20.9 mmol), K 2 CO 3 (43.39 g, 313.98 mmol) and 1,10-phenanthroline (3.77 g, 20.9 mmol) were placed in a round-bottom flask and dissolved in 700 ml of DMF. The solution was stirred at 180 ° C for 18 hours. When the reaction was completed, the reaction solvent was removed therefrom under reduced pressure, and then the product was dissolved in dichloromethane and filtered with silica gel. After the dichloromethane was concentrated, the filtered product was recrystallized with hexane to obtain 40.0 g of intermediate B-12-1 (68.8%).

[0421] b) Synthesis of intermediate B-12-2

[0422] Intermediate B-12-1 (40 g, 144 mmol), bis(pinacol)diboron (54.86 g, 216 mmol), Pd(dppf)Cl 2 (7.1 g, 8.64 mmol), tricyclohexylphosphine (8.08 g, 28.8 mmol) and potassium acetate (42.4 g, 432.04 mmol) were placed in a round-bottom flask and dissolved in 720 ml of DMF. The mixture was refluxed at 120 ° C and stirred for 12 hours. When the reaction was completed, the mixture was poured into an excess of distilled water, and then the obtained mixture was stirred for 1 hour. The solid was filtered and dissolved in DCM. MgSO 4 The moisture was removed, and the organic solvent was filtered using a silica gel pad and removed under reduced pressure. The solid was recrystallized with EA and hexane to obtain 31.3 g of Intermediate B-12-2 (58.9%).

[0423] c) Synthesis of Compound B-12

[0424] In a 1L round-bottom flask, intermediate B-12-2 (31g, 83.95mmol) was dissolved in 0.3L of tetrahydrofuran (THF), and intermediate B-8-2 (28.86g, 83.95mmol) and tetrakis (triphenylphosphine) palladium (4.85g, 4.2mmol) were added thereto, and the mixture was stirred. Subsequently, potassium carbonate (29.01g, 209.9mmol) saturated in water was added thereto, and the resulting mixture was heated and refluxed at 80°C for 12 hours. When the reaction was complete, water was poured into the reaction solution, the obtained mixture was stirred for 30 minutes, filtered to obtain a solid, the solid was dissolved in monochlorobenzene at 133°C, treated with anhydrous magnesium sulfate to remove the moisture therein, filtered using silica gel, the filtrate therein was cooled to room temperature, and filtered. The solid obtained was purified repeatedly using monochlorobenzene to obtain 31.0g (67.1%) of compound B-12.

[0425] Synthesis Example 16: Synthesis of Compound B-25

[0426] [Reaction Scheme 16]

[0427]

[0428] a) Synthesis of intermediate B-25-1

[0429] By using 2-bromocarbazole (35 g, 142 mmol), 22 g (63.6%) of Intermediate B-25-1 was synthesized according to the same method as method a) of Synthesis Example 14.

[0430] b) Synthesis of intermediate B-25-2

[0431] By using Intermediate B-25-1 (22 g, 90.4 mmol), 18 g (56.3%) of Intermediate B-25-2 was synthesized according to the same method as method a) of Synthesis Example 15.

[0432] c) Synthesis of intermediate B-25-3

[0433] By using Intermediate B-25-2 (18 g, 51 mmol), 14.8 g (65.3%) of Intermediate B-25-3 was synthesized according to the same method as method b) of Synthesis Example 15.

[0434] d) Synthesis of intermediate B-25-4

[0435] By using 3-bromodibenzofuran (40 g, 162 mmol), 31 g (65.1%) of Intermediate B-25-4 was synthesized according to the same method as method b) of Synthesis Example 15.

[0436] e) Synthesis of intermediate B-25-5

[0437] By using 2,4-chloro-6-phenyl-1,3,5-triazine (21 g, 93 mmol) and intermediate B-25-4, 15 g (64.8%) of intermediate B-25-5 was synthesized according to the same method as in c) of Synthesis Example 15.

[0438] f) Synthesis of Compound B-25

[0439] By using intermediate B-25-5 (10.5 g 29.3 mmol) and intermediate B-25-3 (14.38 g, 32.28 mmol), according to the same method as c) of Synthesis Example 15, 12.7 g (67.5%) of compound B-25 was synthesized.

[0440] Synthesis Example 17: Synthesis of Compound B-42

[0441] [Reaction Scheme 17]

[0442]

[0443] a) Synthesis of intermediate B-42-1

[0444] Mg (3.44 g, 142 mmol) and I2 (0.36 g, 1.41 mmol) were stirred under nitrogen. Subsequently, a solution prepared by dissolving 3-bromo-dibenzofuran (35 g, 142 mmol) in 236 ml of anhydrous THF was slowly added dropwise thereto to obtain 3-Mgbr-dibenzofuran. A mixed solution of 3-Mgbr-dibenzofuran and THF was slowly added dropwise to another solution prepared by dissolving cyanuric chloride (13.06 g, 70.8 mmol) in 118 ml of anhydrous THF under nitrogen, while maintaining at 0 ° C, and the obtained mixture was reacted at room temperature for 2 hours. When the reaction was completed, water and ice were added thereto to cool it, and ethyl acetate was added thereto to extract and separate the aqueous layer and the organic layer. The extracted organic layer was subjected to silica filtration, and the solvent thus obtained was completely evaporated and distilled. Then, the solid therein was recrystallized by using n-hexane and paper filtered. The solid was dried. By this method, 21 g (66.2%) of intermediate B-42-1 was obtained.

[0445] b) Synthesis of Compound B-42

[0446] By using intermediate B-42-1 (21 g, 46.89 mmol) and carbazole (7.84 g, 46.89 mmol), according to the same method as c) of Synthesis Example 14, 18.7 g (68.9%) of compound B-42 was synthesized.

[0447] Synthesis Example 18: Synthesis of Compound B-55

[0448] [Reaction Scheme 18]

[0449]

[0450] a) Synthesis of intermediate B-55-1

[0451] By using 1-bromo-2-nitrobenzene (35 g, 173.2 mmol) and 1-naphthalene-boric acid (32.78 g, 190.6 mmol), 28 g (64.8%) of Intermediate B-55-1 was synthesized according to the same method as a) of Synthesis Example 14.

[0452] b) Synthesis of intermediate B-55-2

[0453] In a round-bottom flask, intermediate B-55-1 (28.0 g, 112 mmol) and triphenylphosphine (88.4 g, 337 mmol) were dissolved in 300 mL of 1,2-dichlorobenzene and then stirred at 180° C. for 24 hours. When the reaction was completed, the resultant was treated by column chromatography to remove the solvent, obtaining 17.7 g (72.5%) of intermediate B-55-2.

[0454] c) Synthesis of compound B-55-3

[0455] Intermediate B-55-3 was synthesized according to the same method as in Synthesis Example 14 b).

[0456] d) Synthesis of Compound B-55

[0457] By using intermediate B-55-3 (22 g, 63.9 mmol) and intermediate B-55-2 (13.9 g, 63.9 mmol), according to the same method as c) of Synthesis Example 14, 21.0 g (62.6%) of compound B-55 was synthesized.

[0458] Comparative Synthesis Example 1: Synthesis of Comparative Compound 1

[0459] [Reaction Scheme 19]

[0460]

[0461] a) Synthesis of intermediate 1-2

[0462] In a 500 mL flask, intermediate 1-1 (30 g, 121.9 mmol), 1 equivalent of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane), 2 equivalents of potassium acetate, 0.03 equivalents of 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) and 0.2 equivalents of tricyclohexylphosphine were mixed with 300 mL of N,N-dimethylformamide, and the mixture was stirred at 130° C. for 12 hours. When the reaction was completed, the organic layer obtained by extracting the reaction solution with water and EA was concentrated after removing the moisture therein using magnesium sulfate, and then purified by column chromatography to obtain intermediate 1-2 as a white solid (29.66 g, yield: 83%).

[0463] b) Synthesis of Intermediate 1-3

[0464] In a 500 mL flask, 29.66 g (0.4 mol) of intermediate 1-2, 2 equivalents of 1-bromo-2-nitrobenzene, 2 equivalents of potassium carbonate and 0.02 equivalents of tetrakis(triphenylphosphine)palladium(0) were mixed with 200 mL of 1,4-dioxane and 100 mL of water, and the mixture was heated at 90° C. for 16 hours under a nitrogen stream. After removing the reaction solvent therein, the resulting product was dissolved in dichloromethane, filtered with silica gel / diatomaceous earth, and after removing an appropriate amount of organic solvent, recrystallized with methanol to obtain intermediate 1-3 in solid form (16.92 g, yield: 58%).

[0465] c) Synthesis of Intermediates 1-4

[0466] In a 500 mL flask, 8.7 g (30.2 mmol) of intermediate 1-3, 7.5 g (36.2 mmol) of 2-bromonaphthalene, 4.3 g (45.3 mmol) of sodium tert-butoxide (NaOtBu), 1.0 g (1.8 mmol) of Pd(dba) 2 and 2.2 g of tri-tert-butylphosphine (P(tBu) 3 ) (50% toluene solution) was added to 150 mL of xylene, and then heated and refluxed for 12 hours under a nitrogen stream. After removing the xylene therein, 200 mL of methanol was added thereto to crystallize the solid, which was filtered, dissolved in dichloromethane, filtered with silica gel / diatomaceous earth, and then recrystallized with acetone after removing an appropriate amount of organic solvent therefrom to obtain intermediate 1-4 (9.83 g, yield: 77%).

[0467] d) Synthesis of Intermediate 1-5

[0468] Intermediate 1-4 (211.37 g, 0.51 mol) and triethyl phosphite (528 ml, 3.08 mol) were placed in a 1000 ml flask, and after replacing with nitrogen, stirred at 160 ° C for 12 hours. When the reaction was completed, 3 L of MeOH was added thereto, the resulting mixture was stirred and filtered, and the filtrate was evaporated. The resulting residue was purified by column chromatography with hexane to obtain Intermediate 1-5 (152.14 g, yield: 78%).

[0469] e) Synthesis of Comparative Compound 1

[0470] According to Comparative Synthesis Example c), Comparative Compound 1 was synthesized by using Intermediate 1-5 and an intermediate of 1-(4-bromophenyl)-4-phenylbenzene.

[0471] Comparative Synthesis Example 2: Synthesis of Comparative Compound 2

[0472] [Reaction Scheme 20]

[0473]

[0474] a) Synthesis of Comparative Compound 2

[0475] According to e) of Comparative Synthesis Example 1, Comparative Compound 2 was synthesized by using Intermediate 2-1 and Intermediate 2-2.

[0476] Comparative Synthesis Example 3: Synthesis of Comparative Compound 3

[0477] [Reaction Scheme 21]

[0478]

[0479] a) Synthesis of Intermediate 3-1

[0480] According to c) of Comparative Synthesis Example 1, Intermediate 3-1 was synthesized by using bromobenzene instead of 2-bromonaphthalene.

[0481] b) Synthesis of Intermediate 3-2

[0482] Intermediate 3-2 was synthesized according to the same method as in Comparative Synthesis Example 1 (d).

[0483] c) Synthesis of Comparative Compound 3

[0484] According to the same method as e) of Comparative Synthesis Example 1, Comparative Compound 3 was synthesized by using Intermediate 3-2 and 2-(4-chlorophenyl)naphthalene.

[0485] (Manufacturing of organic light-emitting diodes)

[0486] Example 1

[0487] Wash the ITO (indium tin oxide) coated After washing with distilled water, the glass substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc. and dried, then moved to a plasma cleaner, cleaned by using oxygen plasma for 10 minutes, and moved to a vacuum depositor. The obtained ITO transparent electrode was used as an anode, and compound A was vacuum deposited on the ITO substrate to form The compound B is deposited on the injection layer to form a hole injection layer. Thickness, and compound C is deposited to On the hole transport layer, a hole transport layer is formed by depositing compound C-1 On the hole transport auxiliary layer, the compound A-2 and B-42 as the host and 2 wt % of [Ir(piq) 2 acac] as a dopant to form Herein, compound A-2 and compound B-42 are used in a weight ratio of 6:4, and their ratios in the following examples are provided respectively. Subsequently, on the light-emitting layer, compound D and Liq are simultaneously vacuum deposited in a ratio of 1:1 to form A thick electron transport layer is formed, and on the electron transport layer, Liq and Al are vacuum-deposited in sequence. Thick and harmonious Thick, making organic light emitting diodes.

[0488] The organic light emitting diode has five organic thin layers, and has the following specific structure.

[0489] ITO / Compound A / Compound B / Compound C / Compound C-1 / EML[Compound A-2:B-42:[Ir(piq) 2 acac](2wt%)] / Compound D: Liq / Liq / Al structure.

[0490] Compound A: N4,N4'-diphenyl-N4,N4'-bis(9-phenyl-9H-carbazole-3-yl)biphenyl-4,4'-diamine

[0491] Compound B: 1,4,5,8,9,11-hexaazatriphenylene-hexanitrile (HAT-CN)

[0492] Compound C: N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine

[0493] Compound C-1: N,N-di([1,1'-biphenyl]-4-yl)-7,7-dimethyl-7H-fluoro[4,3-b]benzofuran-10-amine

[0494] Compound D: 8-(4-(4,6-di(naphthalen-2-yl)-1,3,5-triazine-2-yl)phenyl)quinoline

[0495] Examples 2 to 6 and Comparative Examples 1 to 5

[0496] Each organic light emitting diode was manufactured according to the same method as Example 1, except that the composition was changed as shown in Tables 1 to 5.

[0497] evaluate

[0498] The power efficiency of the organic light emitting diodes according to Examples 1 to 6 and Comparative Examples 1 and 5 was evaluated.

[0499] The specific measurement method is as follows, and the results are shown in Tables 1 to 5.

[0500] (1) Measuring the change in current density based on the change in voltage

[0501] The obtained organic light emitting diode was measured with respect to a current value flowing in a unit device while increasing a voltage from 0 V to 10 V using a current-voltage meter (Keithley 2400), and the measured current value was divided by an area to provide a result.

[0502] (2) Measuring brightness changes based on voltage changes

[0503] The luminance was measured by using a luminance meter (Minolta Cs-1000A) while the voltage of the organic light emitting diode was increased from 0V to 10V.

[0504] (3) Power efficiency measurement

[0505] By using the luminance, current density and voltage from items (1) and (2), the same current density (10 mA / cm 2 ) under power efficiency (cd / A).

[0506] (4) Life measurement

[0507] By measuring the current efficiency (cd / A) reduced to 97%, the brightness (cd / m 2 ) remains at 9000cd / m 2time to get results.

[0508] (5) Calculation of T97 life ratio (%)

[0509] The relative T97(h) comparison values ​​of Examples (using the first compound as the first host) and Comparative Examples (using the comparative compound as the first host) using the same second host were calculated.

[0510] T97 life ratio (%) = {[T97(h) of Example (when the first compound is used as the first host)] / [T97(h) of Comparative Example (when the comparative compound is used as the first host)]}×100

[0511] (6) Determination of driving voltage

[0512] An ampere-voltmeter (Keithley 2400) was used to measure the 2 Measure the drive voltage of each diode.

[0513] (7) Calculation of driving voltage ratio (%)

[0514] Relative comparison values ​​of Examples (using the first compound as the first host) and Comparative Examples (using the comparative compound as the first host) to which the same second host is applied are calculated.

[0515] Driving voltage ratio (%) = {[driving voltage (V) of the example (using the first compound as the first host)] / [driving voltage (V) of the comparative example (using the comparative compound as the first host)]} × 100 [Table 1]

[0516]

[0517] [Table 2]

[0518]

[0519] [Table 3]

[0520]

[0521] [Table 4]

[0522]

[0523] [Table 5]

[0524]

[0525] Referring to Tables 1 to 5, the organic light emitting diodes according to Examples 1 to 6 exhibited significantly improved driving voltage and lifespan compared to the organic light emitting diodes of Comparative Examples 1 to 5.

[0526] While the invention has been described in connection with what are presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A composition comprising a first compound represented by Chemical Formula 1A, and The second compound represented by Chemical Formula 2B or Chemical Formula 2F: [Chemical Formula 1A] in, In Chemical Formula 1A, Ar 1 is a substituted or unsubstituted C6 to C30 aryl group, L a and L 1 To L 4 is a single bond, R 3 To R 4 is a group represented by chemical formula A, and R 3 To R 4 Another one in R a , R 1 and R 2 are independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof, [Chemical formula A] Wherein, in chemical formula A, R b and R c are independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, or a combination thereof, and * is with L 3 or L 4 The connection point; Wherein, in Chemical Formula 2B and Chemical Formula 2F, L 5 To L 8 All are single bonds, L 9 is a single bond or a substituted or unsubstituted C6 to C20 arylene group, R 5 and R 6 are independently hydrogen, deuterium, cyano or substituted or unsubstituted phenyl, R 7 To R 8 , R e , R f and R g are independently hydrogen, deuterium or cyano, and Z 2 and Z 4 Independently for CL b -R d , Z 1 , Z 3 and Z 5 For N, Among them, L b is a single bond, R d are independently substituted or unsubstituted phenyl or substituted or unsubstituted dibenzofuranyl, and "Substituted" means that at least one hydrogen of the substituent is replaced with deuterium or a C1 to C20 alkyl group.

2. The composition according to claim 1, wherein The first compound is represented by Chemical Formula 1A-1: [Chemical Formula 1A-1] Wherein, in Chemical Formula 1A-1, Ar 1 , R 1 , R 2 , R 4 , R a To R c , L a and L 1 To L 4 Same as defined in claim 1.

3. The composition according to claim 1, wherein The first compound is represented by chemical formula 1A-1-b: [Chemical formula 1A-1-b] Wherein, in Chemical Formula 1A-1-b, Ar 1 , R 1 , R 2 , R 4 , R a To R c , L a and L 1 To L 4 Same as defined in claim 1.

4. The composition according to claim 1, wherein is one of the substituents selected from Group I: [Group I] Among them, in group I, * It is the connection point.

5. The composition according to claim 1, wherein Ar in Formula 1A 1 is a substituted or unsubstituted phenyl group, Among them, L in Formula 2B and Formula 2F 9 and are independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group. The composition of claim 1 , further comprising a dopant.

7. An organic optoelectronic device comprising The anode and cathode face each other, at least one organic layer disposed between the anode and the cathode, in, The organic layer comprises the composition of any one of claims 1 to 6.

8. The organic optoelectronic device according to claim 7, wherein The organic layer includes a light-emitting layer, and The light-emitting layer includes the composition.

9. The organic optoelectronic device according to claim 8, wherein: The first compound and the second compound are included as phosphorescent hosts of the light-emitting layer, respectively.

10. The organic optoelectronic device according to claim 8, wherein: The composition is a red light emitting composition.

11. A display device comprising the organic photoelectric device according to claim 7.

Images