Organic compound and organic electroluminescent device using same

Abstract

The present invention relates to: a novel compound having excellent carrier transport ability, light-emitting ability, and thermal stability; and an organic electroluminescent device comprising the novel compound in one or more organic layers and thus having improved properties such as improved luminous efficiency, driving voltage, lifespan, etc.

Description

Organic compounds and organic electroluminescent devices using the same

[0001] The present invention relates to a novel organic luminescent compound and an organic electroluminescent device using the same, and more particularly, to a compound having excellent electron transport ability, luminescent ability and thermal stability, and an organic electroluminescent device having improved characteristics such as luminescent efficiency, operating voltage and lifespan by including the compound in one or more organic layers.

[0002]

[0003] In organic electroluminescent devices, when a voltage is applied between two electrodes, holes are injected into the organic layer at the anode, and electrons are injected into the organic layer at the cathode. When the injected holes and electrons meet, excitons are formed, and when these excitons fall to the ground state, light is emitted. At this time, the materials used in the organic layer can be classified according to their function, such as luminescent materials, hole injection materials, hole transport materials, electron transport materials, and electron injection materials.

[0004] Luminescent materials can be categorized into blue, green, and red luminescent materials based on their luminescent color, as well as yellow and orange luminescent materials for better natural color reproduction. Furthermore, host / dopant systems can be used as luminescent materials to enhance color purity and luminescence efficiency through energy transfer.

[0005] Dopant materials can be divided into fluorescent dopants, which utilize organic materials, and phosphorescent dopants, which utilize metal complexes containing heavy atoms such as Ir and Pt. The development of phosphorescent materials can theoretically improve luminescence efficiency by up to four times compared to fluorescent materials, and therefore, extensive research is being conducted not only on phosphorescent dopants but also on phosphorescent host materials.

[0006] Currently, NPB, BCP, Alq3, etc. are widely known as materials for hole injection layers, hole transport layers, hole blocking layers, and electron transport layers, and anthracene derivatives have been reported as materials for light-emitting layers. In particular, among light-emitting layer materials, metal complex compounds containing Ir, such as Firpic, Ir(ppy)3, and (acac)Ir(btp)2, which have advantages in terms of improving efficiency, are being used as phosphorescent dopant materials for blue, green, and red, and 4,4-dicarbazolybiphenyl (CBP) is being used as a phosphorescent host material.

[0007] However, while conventional organic layer materials offer advantages in terms of luminescence properties, their low glass transition temperatures and poor thermal stability make them unsatisfactory in terms of the lifespan of organic electroluminescent devices. Therefore, the development of high-performance organic layer materials is urgently needed.

[0008]

[0009] The present invention has as its technical object the provision of a novel compound having excellent heat resistance, carrier transport ability, luminescence ability, etc., which can be used as an organic layer material of an organic electroluminescent device, specifically, as an electron transport layer, an electron transport auxiliary layer, or a luminescent layer.

[0010] In addition, another technical task of the present invention is to provide an organic electroluminescent device having a low driving voltage, high luminous efficiency, and improved lifespan, including the novel compound.

[0011] Other objects and advantages of the present invention can be more clearly explained by the detailed description of the invention and the claims below.

[0012]

[0013] To achieve the above-mentioned purpose, the present invention provides a compound represented by the following chemical formula 1.

[0014] [Chemical Formula 1]

[0015]

[0016] In the above chemical formula 1,

[0017] X1 to X3 are the same or different from each other, and are each independently CR2 or N, provided that at least one of X1 to X3 is N,

[0018] R1 and R2 are the same or different and each independently represent hydrogen, deuterium (D), halogen, cyano group, nitro group, C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group, C3~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group, C6~C 60 Arylamine group, C5~C 60 is selected from the group consisting of an arylheteroarylamine group and a heteroarylamine group having 5 to 60 nuclear atoms, or may be combined with any adjacent group to form a condensed ring;

[0019] Ar1 to Ar6 are the same or different from each other, and each independently represents hydrogen, deuterium (D), C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group, C3~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group, C6~C 60 Arylamine group, C5~C 60 Selected from the group consisting of an arylheteroarylamine group and a heteroarylamine group having 5 to 60 nuclear atoms,

[0020] L1 and L2 are the same or different, and each independently represents a single bond or C6~C 18 Selected from the group consisting of an arylene group and a heteroarylene group having 5 to 18 nuclear atoms,

[0021] o, p and q are each independently integers from 0 to 3,

[0022] The arylene group and heteroarylene group of the above L1~L2; the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphine oxide group and arylamine group of the above R1~R2 and Ar2~Ar6 are each independently hydrogen, deuterium (D), halogen, cyano group, nitro group, C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 A cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of, heteroaryl group of 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60Aryloxy group of C1~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group, C6~C 60 Arylamine group, C5~C 60 It may be substituted with one or more substituents selected from the group consisting of an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclear atoms, and in this case, when there are multiple substituents, they may be the same or different from each other.

[0023] In addition, the present invention provides an organic electroluminescent device comprising an anode, a cathode, and one or more organic layers interposed between the anode and the cathode, wherein at least one of the one or more organic layers comprises a compound represented by the chemical formula 1.

[0024] Here, the organic layer including the compound represented by the chemical formula 1 may be selected from the group consisting of a light-emitting layer, a light-emitting auxiliary layer, a hole injection layer, a hole transport layer, an electron injection layer, a life-span improvement layer, an electron transport layer, and an electron transport auxiliary layer. In this case, the compound represented by the chemical formula 1 may be included as at least one material among the phosphorescent host material of the light-emitting layer, the electron transport layer, and the electron transport auxiliary layer.

[0025]

[0026] As one embodiment of the present invention, the compound represented by the above chemical formula 1 can be used as an organic layer material of an organic electroluminescent device because it has excellent electron transport ability, luminescence ability, heat resistance, etc.

[0027] In particular, when the compound represented by the chemical formula 1 of the present invention is used as an electron transport layer or electron transport auxiliary layer material, it can exhibit high thermal stability, low driving voltage, fast mobility, high current efficiency, and long life characteristics compared to conventional host materials or electron transport materials.

[0028] Accordingly, the organic electroluminescent device including the compound of the above chemical formula 1 can be significantly improved in aspects such as excellent luminescence performance, low driving voltage, long life, and high efficiency, and thus can be effectively applied to full-color display panels, etc.

[0029] The effects according to the present invention are not limited to those exemplified above, and more diverse effects are included in this specification.

[0030]

[0031] Hereinafter, the present invention will be described in detail.

[0032] <New organic compounds>

[0033] The present invention provides a novel compound, for example a silane compound, which has excellent electron transport ability and thermal stability and can simultaneously exhibit low operating voltage, high luminous efficiency, and long life characteristics of a device.

[0034] Specifically, the novel organic compound according to the present invention comprises a silane group, a carbazole group, and an azine group (e.g., a nitrogen-containing heteroaromatic ring) as essential components, wherein the silane group and the azine group are both substituted on one phenyl ring of the carbazole group, and these form a basic skeleton in which they are directly connected or connected through a separate linker (e.g., L1 to L2).

[0035] The compound having the structure of the above chemical formula 1 forms an asymmetric structure with respect to the molecular long axis as different silane groups and azine groups are arranged on one phenyl ring constituting the carbazole group. The compound of the present invention not only has a high triplet (T1) energy level resulting from structural asymmetry and steric hindrance, but also has physicochemical properties more suitable for electron injection and electron transport by further enhancing the strong electron-withdrawing property (EWG) of the azine group. Accordingly, it exhibits the effect of simultaneously increasing the high-efficiency characteristics of the device.

[0036] In particular, when the structure is such that an azine group and a silane group are arranged on each of the phenyl rings on both sides of the carbazole, it is expected that only the donating influence of the carbazole group will be received, whereas when a silane group and an azine group are arranged simultaneously on one side of the carbazole group as in the present invention, the azine group acts as a relatively strong electron acceptor due to the donating influence of the two groups of the carbazole group and the silane group, and the lifespan and efficiency characteristics of an organic electroluminescent device including such a compound can be further improved.

[0037] In addition, since the compound has a structural feature in which a dibenzo moiety and a silane moiety with weak electron donating group (EDG) properties are combined with a nitrogen-containing aromatic ring (e.g., pyrazine, pyrimidine, triazine), which is a type of electron withdrawing group (EWG) with strong electron absorption, it can induce polarization within the material, thereby inducing a wide band gap, and has HOMO and LUMO orbitals widely distributed throughout the molecule. Accordingly, when the compound of the above chemical formula 1 is applied as a material for an electron transport layer or an electron transport auxiliary layer, it can well accept electrons from the cathode, so that electrons can be smoothly transferred to the light-emitting layer, and as a result, the operating voltage of the device can be lowered and high efficiency and long life characteristics can be induced.

[0038] In addition, since the compound of the above chemical formula 1 essentially has a silane (Si) moiety, it blocks electron conjugation and has a high triplet (T1) energy value through steric hindrance. This not only blocks holes, but also has the ability to quench when an excessive amount of excitons are generated, thereby preventing excitons generated in the light-emitting layer from diffusing to the electron transport layer or hole transport layer adjacent to the light-emitting layer. In addition, the number of excitons contributing to light emission within the light-emitting layer increases, thereby improving the light-emitting efficiency of the device, and enhancing the durability and stability of the device, thereby efficiently increasing the lifespan of the device.

[0039] Furthermore, the compound represented by the above chemical formula 1 is not only highly advantageous for electron transport, but also exhibits low operating voltage, high efficiency, and long life characteristics. The excellent electron transport ability of this compound can achieve high efficiency and fast mobility in organic electroluminescent devices, and the HOMO and LUMO energy levels can be easily controlled depending on the direction or position of the substituent. Therefore, organic electroluminescent devices using the above compound can exhibit high electron transport ability.

[0040] According to the present invention, a compound represented by chemical formula 1 has a basic skeletal structure including a silane group, a carbazole group, and an azine group (e.g., a nitrogen-containing heteroaromatic ring), wherein the silane group and the azine group are both substituted on one phenyl ring of the carbazole group, and these are directly connected or connected through a separate linker (e.g., L1 to L2).

[0041] The carbazole (e.g., Ar1-containing ring) group placed at the center of the compound represented by the above chemical formula 1 can use a conventional carbazole moiety known in the art without limitation. Different silane groups and azine groups are introduced into one phenyl ring of the carbazole group, and R1 can be substituted as a substituent on the other phenyl ring. R1 is hydrogen, deuterium (D), halogen, cyano group, nitro group, C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group, C3~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group, C6~C 60 Arylamine group, C5~C 60 is selected from the group consisting of an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclear atoms, or may be combined with any adjacent group to form a condensed ring. Specifically, R1 is hydrogen, deuterium (D), C1~C 40 Alkyl group of C6~C 60 An aryl group of , and a heteroaryl group having 5 to 60 nuclear atoms, or may be combined with any adjacent group to form a condensed ring, more specifically hydrogen, C6~C 40 It can be selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms.

[0042] At this time, the number of substitutions of R1 (e.g., q) can be an integer from 0 to 3. For example, when q is 0, R1 can be hydrogen. In addition, when q is greater than 0 and less than or equal to 3, multiple R1s are the same or different from each other, and can each independently be a substituent other than a single bond in the definition of the linker described above.

[0043] Ar1 substituted at the N position of the above carbazole group is hydrogen, deuterium (D), C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group, C3~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group, C6~C 60 Arylamine group, C5~C 60 is selected from the group consisting of an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclear atoms. Specifically, Ar1 is C6~C 60 An aryl group of , or a heteroaryl group having 5 to 60 nuclear atoms, more specifically C6~C 40 It is an aryl group or a heteroaryl group having 5 to 40 nuclear atoms.

[0044] For example, the carbazole group (e.g., Ar1-containing ring) may be embodied by any one of the following structural formulae, but is not limited thereto.

[0045]

[0046] In the above formula,

[0047] * indicates a part connected to the above chemical formula 1,

[0048] Ring A is a monocyclic or polycyclic hydrocarbon ring group containing or not containing a heteroatom,

[0049] Ar1, R1 and q are each as defined in chemical formula 1.

[0050] As a preferred specific example, the carbazole group (e.g., Ar1-containing ring) can be further specified as one selected from the following structural formulas.

[0051]

[0052] In the above formula,

[0053] * indicates a part connected to the above chemical formula 1,

[0054] Ar1, R1, and q are each as defined in Chemical Formula 1, and multiple Ar1s that are identically represented may be identical or different. In addition, although not indicated in the structural formula described above, at least one substituent known in the art (e.g., the same as the R1 definition part) may be substituted.

[0055] One of the two substituents introduced to one phenyl ring of the above carbazole group is a nitrogen-containing heteroaromatic ring (e.g., a ring containing X1 to X3), which is a monocyclic nitrogen-containing heteroaryl group containing at least one nitrogen atom. In one embodiment of the nitrogen-containing heteroaromatic ring, X1 to X3 are the same as or different from each other, and are each independently C(R2) or N, provided that at least one of X1 to X3 contains N. Preferably, it contains 2 to 3 Ns. By including a heterocycle containing 2 to 3 nitrogens in this way, it exhibits better electron absorption properties, which is advantageous for electron injection and transport.

[0056] Here, R2 is hydrogen, deuterium (D), halogen, cyano group, nitro group, C1~C40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group, C3~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group, C6~C 60 Arylamine group, C5~C 60 is selected from the group consisting of an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclear atoms. In this case, multiple R2s may be the same or different from each other. Specifically, R2 is hydrogen, deuterium, C1~C 40 Alkyl group of C6~C 60 It is preferably selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms.

[0057] For example, the nitrogen-containing heterocycle (e.g., X1 to X3-containing ring) can be further specified as one selected from the structural formula below, but is not limited thereto.

[0058]

[0059] In the above formula,

[0060] * indicates a part connected to the above chemical formula 1,

[0061] R2, Ar5 and Ar6 are each as defined in paragraph 1.

[0062] In the above nitrogen-containing heteroaromatic ring (e.g., X1~X3-containing ring), Ar5 and Ar6 can be substituted with various substituents. Ar5 and Ar6 can be the same or different from each other, and each independently represent hydrogen, deuterium (D), C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group, C3~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group, C6~C 60 Arylamine group, C5~C 60 is selected from the group consisting of an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclear atoms. Specifically, Ar5 and Ar6 may be the same or different from each other, and each independently represents C6~C 60 Selected from the group consisting of aryl group and heteroaryl group having 5 to 60 nuclear atoms, more specifically C6~C 40 It is preferable to select from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms.

[0063] For example, Ar5 and Ar6 may be the same or different from each other, and may be independently embodied as one selected from the following structural formulas. However, the present invention is not limited thereto.

[0064]

[0065] In the above formula,

[0066] * indicates a portion connected to the above chemical formula 1. In addition, although not indicated in the above structural formula, at least one substituent known in the art (e.g., the same as the R1 definition portion) may be substituted.

[0067] One of the two substituents introduced to one phenyl ring of the above carbazole group is a silane moiety (e.g., -SiAr2Ar3Ar4). These silane moieties may be substituted with Ar2 to Ar4 as substituents. Ar2 to Ar4 are the same or different from each other, and are each independently hydrogen, deuterium (D), C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group, C3~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group and C6~C 60 is selected from the group consisting of arylamine groups. Specifically, Ar2 to Ar4 are the same or different from each other, and are each independently C6~C 60 It can be selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms, and more specifically, C6~C 40 is an aryl group.

[0068] For example, Ar2 to Ar4 may be the same as the specific examples of Ar5 to Ar6 described above, and as a preferred specific example, may be selected from the group consisting of a phenyl group, a biphenyl group, and a terphenyl group.

[0069] The compound represented by chemical formula 1 according to the present invention has both a silane group and an azine group connected to one phenyl ring of a carbazole group, and these may be directly connected or may be bonded through a separate linker (e.g., L1 to L2). When a separate linker (L1 to L2) is present in this way, the HOMO region is expanded, which provides an advantage in the HOMO-LUMO distribution, and charge transfer efficiency can be increased through appropriate HOMO-LUMO overlap.

[0070] These linkers (L1~L2) may be linkers of common divalent groups known in the art. Specifically, L1~L2 are the same or different from each other, and each independently has a C6~C 18 It can be selected from the group consisting of an arylene group and a heteroarylene group having 5 to 18 nuclear atoms. More specifically, each independently C6~C 12 It can be selected from the group consisting of an arylene group and a heteroarylene group having 5 to 12 nuclear atoms.

[0071] Here, the number of linkers L1 and L2, o and p, are each independently integers from 0 to 3. Here, when o and p are each 0, L1 to L2 are single bonds (direct bonds), and when o or q are each 1 to 3, the remaining substituents excluding the single bonds in the above-described linker definition may have at least one selected from the group consisting of an arylene group and a heteroarylene group. In this case, when there are multiple L1 to L2, the multiple L1 to L2 may be the same or different from each other.

[0072] Specific examples of the above arylene linker and heteroarylene linker include a phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, an indenylene group, a pyranthrenylene group, a carbazolylene group, a thiophenylene group, an indoylene group, a purinylene group, a quinolinylene group, a pyrrolylene group, an imidazolylene group, an oxazolyl group, a thiazolyl group, a pyridinylene group, a pyrimidinylene group, a dibenzofuran-based moiety, a dibenzothiophene-based moiety, and / or a dibenzoselenophenone-based moiety. More specifically, a phenylene group, a biphenylene group, or a terphenylene group is preferable.

[0073] For example, L1 to L2 may be the same or different from each other, and may each be a linking group independently selected from the following structural formula.

[0074]

[0075] In the above formula,

[0076] * indicates a portion connected to the above chemical formula 1. In addition, although not indicated in the above structural formula, at least one substituent known in the art (e.g., the same as the definition of R1) may be substituted.

[0077] In the chemical formula 1 described above, the arylene group and heteroarylene group of L1 to L2; the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphine oxide group and arylamine group of R1 to R2 and Ar2 to Ar6 are each independently hydrogen, deuterium (D), halogen, cyano group, nitro group, C1 to C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 A cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of, heteroaryl group of 5 to 60 nuclear atoms, C1~C 40Alkyloxy group, C6~C 60 Aryloxy group of C1~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group, C6~C 60 Arylamine group, C5~C 60 It may be substituted with one or more substituents selected from the group consisting of an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclear atoms, and in this case, when there are multiple substituents, they may be the same or different from each other.

[0078] According to one embodiment of the present invention, the compound represented by the above chemical formula 1 can be further specified as one of the following chemical formulas 2 to 6 depending on the type of nitrogen-containing heteroaromatic ring (e.g., X1 to X3-containing ring). However, the present invention is not limited thereto.

[0079] [Chemical Formula 2]

[0080]

[0081] [Chemical Formula 3]

[0082]

[0083] [Chemical Formula 4]

[0084]

[0085] [Chemical Formula 5]

[0086]

[0087] [Chemical Formula 6]

[0088]

[0089] In the above chemical formulas 2 to 6,

[0090] Ar1~Ar6, L1~L2, R1, o, p and q are each as defined in chemical formula 1.

[0091] According to another embodiment of the present invention, the compound represented by the above chemical formula 1 can be further specified as one of the following chemical formulas 7 to 9, depending on the type of Ar5 to Ar6 substituents introduced into the nitrogen-containing heteroaromatic ring (e.g., X1 to X3-containing ring). However, the present invention is not limited thereto.

[0092] [Chemical Formula 7]

[0093]

[0094] [Chemical Formula 8]

[0095]

[0096] [Chemical Formula 9]

[0097]

[0098] In the above chemical formulas 7 to 9,

[0099] Z1 is O or S,

[0100] Z2 is N,

[0101] R 11 Silver hydrogen, deuterium (D), C1~C 40 Alkyl group of C6~C 60 is selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms, or may be combined with any adjacent group to form a condensed ring,

[0102] m is an integer from 0 to 3,

[0103] a and b are each independently integers from 1 to 3,

[0104] X1~X3, Ar1~Ar4, L1~L2, R1, o, p and q are each as defined in chemical formula 1.

[0105] According to another embodiment of the present invention, the compound represented by the above chemical formula 1 can be further specified as one of the following chemical formulas 10 to 13 depending on the bonding position of the R1 substituent introduced to the carbazole group. However, the present invention is not limited thereto.

[0106] [Chemical Formula 10]

[0107]

[0108] [Chemical Formula 11]

[0109]

[0110] [Chemical Formula 12]

[0111]

[0112] [Chemical Formula 13]

[0113]

[0114] In the above chemical formulas 10 to 13,

[0115] X1~X3, Ar1~Ar6, L1~L2, R1, o and p are each as defined in chemical formula 1.

[0116] According to another embodiment of the present invention, the compound represented by the above chemical formula 1 can be further specified as one of the following chemical formulas 14 to 16 depending on the bonding position of the condensed ring formed in the carbazole group. However, the present invention is not limited thereto.

[0117] [Chemical Formula 14]

[0118]

[0119] [Chemical Formula 15]

[0120]

[0121] [Chemical Formula 16]

[0122]

[0123] In the above chemical formulas 14 to 16,

[0124] Ring A is a monocyclic or polycyclic hydrocarbon ring group containing or not containing a heteroatom,

[0125] X1~X3, Ar1~Ar6, L1~L2, o and p are each as defined in chemical formula 1.

[0126] According to another embodiment of the present invention, the compound represented by the above chemical formula 1 can be further specified as the following chemical formula 17 or chemical formula 18 depending on the type of Ar1 substituent introduced to nitrogen (N) of the carbazole group. However, the present invention is not limited thereto.

[0127] [Chemical Formula 17]

[0128]

[0129] [Chemical Formula 18]

[0130]

[0131] In the above chemical formulas 17 to 18,

[0132] Y is O or S,

[0133] n is an integer from 1 to 3,

[0134] X1~X3, Ar2~Ar6, L1~L2, R1, o, p and q are each as defined in chemical formula 1.

[0135] According to another embodiment of the present invention, the compound represented by the above chemical formula 1 can be further specified as one of the following chemical formulas 19 to 26 depending on the bonding position of the silane group or azine group bonded to the carbazole group. However, the present invention is not limited thereto.

[0136] [Chemical Formula 19]

[0137]

[0138] [Chemical Formula 20]

[0139]

[0140] [Chemical Formula 21]

[0141]

[0142] [Chemical Formula 22]

[0143]

[0144] [Chemical Formula 23]

[0145]

[0146] [Chemical Formula 24]

[0147]

[0148] [Chemical Formula 25]

[0149]

[0150] [Chemical Formula 26]

[0151]

[0152] In the above chemical formulas 19 to 26,

[0153] X1~X3, Ar1~Ar6, L1~L2, R1, o, p and q are each as defined in chemical formula 1.

[0154] According to another embodiment of the present invention, the compound represented by the above chemical formula 1 can be further specified as one of the following chemical formulas 27 to 38, depending on the bonding positions of the silane group and the azine group simultaneously connected to one phenyl ring of the carbazole group. However, the present invention is not limited thereto.

[0155] [Chemical Formula 27]

[0156]

[0157] [Chemical Formula 28]

[0158]

[0159] [Chemical Formula 29]

[0160]

[0161] [Chemical Formula 30]

[0162]

[0163] [Chemical Formula 31]

[0164]

[0165] [Chemical Formula 32]

[0166]

[0167] [Chemical Formula 33]

[0168]

[0169] [Chemical Formula 34]

[0170]

[0171] [Chemical Formula 35]

[0172]

[0173] [Chemical Formula 36]

[0174]

[0175] [Chemical Formula 37]

[0176]

[0177] [Chemical Formula 38]

[0178]

[0179] In the above chemical formulas 27 to 38,

[0180] X1~X3, Ar1~Ar6, L1~L2, R1, o, p and q are each as defined in chemical formula 1.

[0181] The compound represented by chemical formula 1 according to the present invention described above can be further specified as a compound represented by any one of compounds 1 to 222 exemplified below. However, the compound represented by chemical formula 1 of the present invention is not limited to those exemplified below.

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189] In the present invention, the "number of nuclear atoms" refers to the number of ring atoms constituting a ring structure, and the nuclear atoms may be carbon or a heteroatom selected from the group consisting of N, O, S, and Se. For example, the number of nuclear atoms of pyridine refers to 6, including 5 C and 1 N constituting the pyridine ring.

[0190] In the present invention, "alkyl" means a monovalent substituent derived from a straight or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc.

[0191] In the present invention, "alkenyl" means a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

[0192] In the present invention, "alkynyl" means a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.

[0193] In the present invention, "aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms, which is a single ring or a combination of two or more rings. Furthermore, a form in which two or more rings are simply attached to each other (pendant) or condensed may also be included. Examples of such aryls include, but are not limited to, phenyl, naphthyl, phenanthryl, and anthryl.

[0194] In the present invention, "heteroaryl" refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. At this time, at least one carbon atom in the ring, preferably 1 to 3 carbon atom, is substituted with a heteroatom such as N, O, S, or Se. In addition, a form in which two or more rings are simply attached to each other (pendant) or condensed may be included, and a form condensed with an aryl group may also be included. Examples of such heteroaryls include, but are not limited to, 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, dibenzofuranyl, and dibendothophenyl.

[0195] In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, and diphenyloxy.

[0196] In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R' means alkyl having 1 to 40 carbon atoms, and may include a linear, branched, or cyclic structure. Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, and pentoxy.

[0197] In the present invention, “arylamine” means an amine substituted with an aryl having 6 to 40 carbon atoms.

[0198] In the present invention, "cycloalkyl" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

[0199] In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one carbon atom in the ring, preferably 1 to 3 carbon atom(s), is substituted with a heteroatom such as N, O, S or Se. Examples of such heterocycloalkyl include, but are not limited to, morpholine and piperazine.

[0200] In the present invention, “alkylsilyl” means silyl substituted with alkyl having 1 to 40 carbon atoms, and “arylsilyl” means silyl substituted with aryl having 5 to 40 carbon atoms.

[0201] In the present invention, “fused ring” means a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, a fused heteroaromatic ring, or a combination thereof.

[0202]

[0203] Electron transport layer material

[0204] The present invention provides an electron transport layer comprising a compound represented by the above chemical formula 1.

[0205] The above electron transport layer (ETL) plays a role in moving electrons injected from the cathode to an adjacent layer, specifically, the light-emitting layer.

[0206] The compound represented by the above chemical formula 1 can be used alone as an electron transport layer (ETL) material, or can be used in combination with an electron transport layer material known in the art. It is preferably used alone.

[0207] The electron transport layer material that can be mixed with the compound of the above chemical formula 1 includes an electron transport material commonly known in the art. Non-limiting examples of electron transport materials that can be used include oxazole compounds, isoxazole compounds, triazole compounds, isothiazole compounds, oxadiazole compounds, thiadiazole compounds, perylene compounds, aluminum complexes (e.g., Alq3(tris(8-quinolinolato)-aluminium) BAlq, SAlq, Almq3), gallium complexes (e.g., Gaq'2OPiv, Gaq'2OAc, 2(Gaq'2)), etc. These may be used alone or in combination of two or more.

[0208] In the present invention, when the compound of the above chemical formula 1 and the electron transport layer material are mixed, the mixing ratio thereof is not particularly limited and can be appropriately controlled within a range known in the art.

[0209]

[0210] <Electron transport auxiliary layer material>

[0211] In addition, the present invention provides an electron transport auxiliary layer comprising a compound represented by the above chemical formula 1.

[0212] The above electron transport auxiliary layer is positioned between the light-emitting layer and the electron transport layer, and serves to prevent excitons or holes generated in the light-emitting layer from diffusing into the electron transport layer.

[0213] The compound represented by the above chemical formula 1 may be used alone as an electron transport auxiliary layer material, or may be mixed with an electron transport auxiliary layer material known in the art. It is preferably used alone.

[0214] The electron transport auxiliary layer material that can be mixed with the compound of the above chemical formula 1 includes an electron transport material commonly known in the art. For example, the electron transport auxiliary layer material may include an oxadiazole derivative, a triazole derivative, a phenanthroline derivative (e.g., BCP), a nitrogen-containing heterocyclic derivative, and the like.

[0215] In the present invention, when the compound of the above chemical formula 1 and the electron transport auxiliary layer material are mixed, the mixing ratio thereof is not particularly limited and can be appropriately adjusted within a range known in the art.

[0216]

[0217] Organic electroluminescent devices

[0218] Meanwhile, another aspect of the present invention relates to an organic electroluminescent device (organic EL device) comprising a compound represented by the chemical formula 1 according to the present invention.

[0219] Specifically, the present invention is an organic electroluminescent device comprising an anode, a cathode, and one or more organic layers interposed between the anode and the cathode, wherein at least one of the one or more organic layers comprises a compound represented by the chemical formula 1. At this time, the compound may be used alone or in a mixture of two or more.

[0220] The organic layer of one or more layers may be at least one of a hole injection layer, a hole transport layer, a light-emitting layer, a light-emitting auxiliary layer, a life-span improvement layer, an electron transport layer, an electron transport auxiliary layer, and an electron injection layer, and at least one of the organic layers includes a compound represented by the chemical formula 1. Specifically, the organic layer including the compound of the chemical formula 1 may be a light-emitting layer, a light-emitting auxiliary layer, an electron transport layer, an electron transport auxiliary layer, and / or a life-span improvement layer, and more specifically, it is preferably an electron transport layer or an electron transport auxiliary layer.

[0221] The light-emitting layer of the organic electroluminescent device according to the present invention includes a host material and a dopant material, and may include the compound of the above chemical formula 1 as the host material. In addition, the light-emitting layer of the present invention may include a compound known in the art other than the compound of the above chemical formula 1 as the host.

[0222] When the compound represented by the above chemical formula 1 is included as a light-emitting layer material of an organic electroluminescent device, preferably as a blue, green, or red phosphorescent host material, the bonding force between holes and electrons in the light-emitting layer increases, thereby improving the efficiency (luminescent efficiency and power efficiency), lifespan, brightness, and driving voltage of the organic electroluminescent device. Specifically, the compound represented by the above chemical formula 1 is preferably included in the organic electroluminescent device as a green and / or red phosphorescent host, fluorescent host, or dopant material. In particular, the compound represented by the chemical formula 1 of the present invention is preferably a green phosphorescent exciplex N-type host material of a light-emitting layer having high efficiency.

[0223] The structure of the organic electroluminescent device of the present invention is not particularly limited, but may have a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, an electron transport layer, and a cathode are sequentially laminated. At this time, at least one of the hole injection layer, the hole transport layer, the light-emitting auxiliary layer, the light-emitting layer, the electron transport layer, and the electron injection layer may include a compound represented by the chemical formula 1, and preferably, the light-emitting layer, and more preferably, the phosphorescent host, may include a compound represented by the chemical formula 1. Meanwhile, an electron injection layer may be additionally laminated on the electron transport layer.

[0224] The structure of the organic electroluminescent device of the present invention may be a structure in which an insulating layer or an adhesive layer is inserted at the interface between the electrode and the organic layer.

[0225] The organic electroluminescent device of the present invention can be manufactured by forming an organic layer and an electrode using materials and methods known in the art, except that at least one of the organic layers described above includes a compound represented by the chemical formula 1.

[0226] The above organic layer can be formed by vacuum deposition or solution coating. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

[0227] The substrate used in manufacturing the organic electroluminescent device of the present invention is not particularly limited, and for example, a silicon wafer, quartz, glass plate, metal plate, plastic film and sheet, etc. can be used.

[0228] In addition, the cathode material may be any cathode material known in the art without limitation. Examples thereof include, but are not limited to, metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, or polyaniline; and carbon black.

[0229] In addition, the cathode material may be any cathode material known in the art without limitation. Examples thereof include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead, or alloys thereof; and multilayered materials such as LiF / Al or LiO2 / Al.

[0230] In addition, the hole injection layer, hole transport layer, electron injection layer, and electron transport layer are not particularly limited, and conventional materials known in the art can be used without limitation.

[0231]

[0232] Hereinafter, the present invention will be described in detail through examples. However, the following examples are only illustrative of the present invention, and the present invention is not limited to the following examples.

[0233]

[0234] [Preparation Example 1]

[0235] <Step 1> Synthesis of 4-chloro-9-phenyl-1-(triphenylsilyl)-9H-carbazole

[0236]

[0237] Dissolve 30 g (84.1 mmol) of 1-bromo-4-chloro-9-phenyl-9H-carbazole in 600 ml of THF and then -78 o 2.5 M n-BuLi (33.6 ml, 92.5 mmol) was added dropwise under C. After 30 minutes, chlorotriphenylsilane (27.3 g, 92.5 mmol) was added and stirred at room temperature for 5 hours. After completion of the reaction, H2O was added dropwise to quench, and the mixture was extracted with dichloromethane and H2O. The organic layer was anhydrous with MgSO4 and filtered. The filtered filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 37.0 g (yield 82%) of 4-chloro-9-phenyl-1-(triphenylsilyl)-9H-carbazole.

[0238] Mass: [(M+H) + ] : 535.15

[0239] <Step 2> Synthesis of intermediate 1

[0240]

[0241] 4-chloro-9-phenyl-1-(triphenylsilyl)-9H-carbazole 37.0 g (69.0 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 35.0 g (138.0 mmol), PdCl2(dppf) 2.5 g (3.5 mmol), Xphos 2.6 g (6.9 mmol), KOAc 16.5 g (207.0 mmol) were dissolved in 600 mL of 1,4-Dioxane and stirred under reflux for 8 hours to react. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 30.6 g (yield 87%) of intermediate 1.

[0242] Mass: [(M+H) + ] : 627.28

[0243]

[0244] [Preparation Example 2]

[0245] <Step 1> Synthesis of 4-chloro-9-phenyl-2-(triphenylsilyl)-9H-carbazole

[0246]

[0247] Dissolve 30 g (84.1 mmol) of 2-bromo-4-chloro-9-phenyl-9H-carbazole in 600 ml of THF and then -78 o 2.5 M n-BuLi (33.6 ml, 92.5 mmol) was added dropwise under C. After 30 minutes, chlorotriphenylsilane (27.3 g, 92.5 mmol) was added and stirred at room temperature for 5 hours. After completion of the reaction, H2O was added dropwise to quench, and the mixture was extracted with dichloromethane and H2O. The organic layer was anhydrous with MgSO4 and filtered. The filtered filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 38.3 g (yield 85%) of 4-chloro-9-phenyl-2-(triphenylsilyl)-9H-carbazole.

[0248] Mass: [(M+H) + ] : 535.15

[0249] <Step 2> Synthesis of intermediate 2

[0250]

[0251] 4-chloro-9-phenyl-2-(triphenylsilyl)-9H-carbazole 38.3 g (71.4 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 36.3 g (142.9 mmol), PdCl2(dppf) 2.6 g (3.6 mmol), Xphos 3.4 g (7.1 mmol), KOAc 21.0 g (214.3 mmol) were dissolved in 600 mL of 1,4-Dioxane and stirred under reflux for 8 hours to react. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 39.5 g (yield 88%) of intermediate 2.

[0252] Mass: [(M+H) + ] : 627.28

[0253]

[0254] [Preparation Example 3]

[0255] <Step 1> Synthesis of 4-chloro-9-phenyl-3-(triphenylsilyl)-9H-carbazole

[0256]

[0257] Dissolve 30 g (84.1 mmol) of 3-bromo-4-chloro-9-phenyl-9H-carbazole in 600 ml of THF and then -78 o2.5 M n-BuLi (33.6 ml, 92.5 mmol) was added dropwise under C. After 30 minutes, chlorotriphenylsilane (27.3 g, 92.5 mmol) was added and stirred at room temperature for 5 hours. After completion of the reaction, H2O was added dropwise to quench, and the mixture was extracted with dichloromethane and H2O. The organic layer was anhydrous with MgSO4 and filtered. The filtered filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 35.6 g (yield 79%) of 4-chloro-9-phenyl-3-(triphenylsilyl)-9H-carbazole.

[0258] Mass: [(M+H) + ] : 535.15

[0259] <Step 2> Synthesis of intermediate 3

[0260]

[0261] 4-chloro-9-phenyl-3-(triphenylsilyl)-9H-carbazole 35.6 g (66.4 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 33.7 g (132.8 mmol), PdCl2(dppf) 2.4 g (3.3 mmol), Xphos 3.2 g (6.6 mmol), KOAc 19.6 g (199.2 mmol) were dissolved in 600 mL of 1,4-Dioxane and stirred under reflux for 8 hours to react. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 33.3 g (yield 80%) of intermediate 3.

[0262] Mass: [(M+H) + ] : 627.28

[0263]

[0264] [Preparation Example 4]

[0265] <Step 1> Synthesis of 3-chloro-9-phenyl-1-(triphenylsilyl)-9H-carbazole

[0266]

[0267] Dissolve 30 g (84.1 mmol) of 1-bromo-3-chloro-9-phenyl-9H-carbazole in 600 ml of THF and then -78 o 2.5 M n-BuLi (33.6 ml, 92.5 mmol) was added dropwise under C. After 30 minutes, chlorotriphenylsilane (27.3 g, 92.5 mmol) was added and stirred at room temperature for 5 hours. After completion of the reaction, H2O was added dropwise to quench, and the mixture was extracted with dichloromethane and H2O. The organic layer was anhydrous with MgSO4 and filtered. The filtered filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 37.0 g (yield 82%) of 3-chloro-9-phenyl-1-(triphenylsilyl)-9H-carbazole.

[0268] Mass: [(M+H) + ] : 535.15

[0269] <Step 2> Synthesis of intermediate 4

[0270]

[0271] 3-chloro-9-phenyl-1-(triphenylsilyl)-9H-carbazole 37.0 g (69.0 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 35.0 g (138.0 mmol), PdCl2(dppf) 2.5 g (3.5 mmol), Xphos 3.3 g (6.9 mmol), KOAc 20.3 g (207.0 mmol) were dissolved in 600 mL of 1,4-Dioxane and stirred under reflux for 8 hours to react. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 35.1 g (yield 81%) of intermediate 4.

[0272] Mass: [(M+H) + ] : 627.28

[0273]

[0274] [Preparation Example 5]

[0275] <Step 1> Synthesis of 3-chloro-9-phenyl-2-(triphenylsilyl)-9H-carbazole

[0276]

[0277] Dissolve 30 g (84.1 mmol) of 2-bromo-3-chloro-9-phenyl-9H-carbazole in 600 ml of THF and then -78 o2.5 M n-BuLi (33.6 ml, 92.5 mmol) was added dropwise under C. After 30 minutes, chlorotriphenylsilane (27.3 g, 92.5 mmol) was added and stirred at room temperature for 5 hours. After completion of the reaction, H2O was added dropwise to quench, and the mixture was extracted with dichloromethane and H2O. The organic layer was anhydrous with MgSO4 and filtered. The filtered filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 33.8 g (yield 75%) of 3-chloro-9-phenyl-2-(triphenylsilyl)-9H-carbazole.

[0278] Mass: [(M+H) + ] : 535.15

[0279] <Step 2> Synthesis of intermediate 5

[0280]

[0281] 3-chloro-9-phenyl-2-(triphenylsilyl)-9H-carbazole 33.8 g (63.0 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 32.0 g (126.1 mmol), PdCl2(dppf) 2.3 g (3.2 mmol), Xphos 3.0 g (6.3 mmol), KOAc 18.6 g (189.1 mmol) were dissolved in 600 mL of 1,4-Dioxane and reacted by refluxing for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 30.5 g (yield 77%) of intermediate 5.

[0282] Mass: [(M+H) + ] : 627.28

[0283]

[0284] [Preparation Example 6]

[0285] <Step 1> Synthesis of 2-chloro-9-phenyl-1-(triphenylsilyl)-9,9a-dihydro-1H-carbazole

[0286]

[0287] Dissolve 30 g (84.1 mmol) of 1-bromo-2-chloro-9-phenyl-9H-carbazole in 600 ml of THF and then -78 o 2.5 M n-BuLi (33.6 ml, 92.5 mmol) was added dropwise under C. After 30 minutes, chlorotriphenylsilane (27.3 g, 92.5 mmol) was added and stirred at room temperature for 5 hours. After completion of the reaction, H2O was added dropwise to quench, and the mixture was extracted with dichloromethane and H2O. The organic layer was anhydrous with MgSO4 and filtered. The filtered filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 29.0 g (yield 64%) of 2-chloro-9-phenyl-1-(triphenylsilyl)-9,9a-dihydro-1H-carbazole.

[0288] Mass: [(M+H) + ] : 535.15

[0289] <Step 2> Synthesis of intermediate 6

[0290]

[0291] 29.0 g (53.9 mmol) of 2-chloro-9-phenyl-1-(triphenylsilyl)-9,9a-dihydro-1H-carbazole, 27.4 g (107.8 mmol) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.0 g (2.7 mmol) of PdCl2(dppf), 2.6 g (5.4 mmol) of Xphos, and 15.9 g (161.7 mmol) of KOAc were dissolved in 600 mL of 1,4-Dioxane and reacted by refluxing for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 24.1 g (yield 71%) of intermediate 6.

[0292] Mass: [(M+H) + ] : 627.28

[0293]

[0294] [Preparation Example 7]

[0295] <Step 1> Synthesis of 1-chloro-9-phenyl-4-(triphenylsilyl)-9,9a-dihydro-1H-carbazole

[0296]

[0297] Dissolve 30 g (84.1 mmol) of 4-bromo-1-chloro-9-phenyl-9H-carbazole in 600 ml of THF and then -78 o2.5 M n-BuLi (33.6 ml, 92.5 mmol) was added dropwise under C. After 30 minutes, chlorotriphenylsilane (27.3 g, 92.5 mmol) was added and stirred at room temperature for 5 hours. After completion of the reaction, H2O was added dropwise to quench, and the mixture was extracted with dichloromethane and H2O. The organic layer was anhydrous with MgSO4 and filtered. The filtered filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 34.0 g (yield 75%) of 1-chloro-9-phenyl-4-(triphenylsilyl)-9,9a-dihydro-1H-carbazole.

[0298] Mass: [(M+H) + ] : 535.15

[0299] <Step 2> Synthesis of intermediate 7

[0300]

[0301] 1-chloro-9-phenyl-4-(triphenylsilyl)-9,9a-dihydro-1H-carbazole 34.0 g (63.2 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 32.1 g (126.4 mmol), PdCl2(dppf) 2.3 g (3.2 mmol), Xphos 3.0 g (6.3 mmol), KOAc 18.6 g (189.5 mmol) were dissolved in 600 mL of 1,4-Dioxane and stirred under reflux for 8 hours to react. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 32.2 g (yield 81%) of intermediate 7.

[0302] Mass: [(M+H) + ] : 627.28

[0303]

[0304] [Preparation Example 8]

[0305] <Step 1> Synthesis of 2-chloro-9-phenyl-4-(triphenylsilyl)-9H-carbazole

[0306]

[0307] Dissolve 30 g (84.1 mmol) of 4-bromo-2-chloro-9-phenyl-9H-carbazole in 600 ml of THF and then -78 o 2.5 M n-BuLi (33.6 ml, 92.5 mmol) was added dropwise under C. After 30 minutes, chlorotriphenylsilane (27.3 g, 92.5 mmol) was added and stirred at room temperature for 5 hours. After completion of the reaction, H2O was added dropwise to quench, and the mixture was extracted with dichloromethane and H2O. The organic layer was anhydrous with MgSO4 and filtered. The filtered filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 36.5 g (yield 81%) of 2-chloro-9-phenyl-4-(triphenylsilyl)-9H-carbazole.

[0308] Mass: [(M+H) + ] : 535.15

[0309] <Step 2> Synthesis of intermediate 8

[0310]

[0311] 2-chloro-9-phenyl-4-(triphenylsilyl)-9H-carbazole 36.5 g (68.1 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 34.6 g (136.2 mmol), PdCl2(dppf) 2.5 g (3.4 mmol), Xphos 3.2 g (6.8 mmol), KOAc 20.0 g (204.2 mmol) were dissolved in 600 mL of 1,4-Dioxane and reacted by refluxing for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 35.0 g (yield 82%) of intermediate 8.

[0312] Mass: [(M+H) + ] : 627.28

[0313]

[0314] [Preparation Example 9]

[0315] <Step 1> Synthesis of 3-chloro-9-phenyl-4-(triphenylsilyl)-9H-carbazole

[0316]

[0317] Dissolve 30 g (84.1 mmol) of 4-bromo-3-chloro-9-phenyl-9H-carbazole in 600 ml of THF and then -78 o2.5 M n-BuLi (33.6 ml, 92.5 mmol) was added dropwise under C. After 30 minutes, chlorotriphenylsilane (27.3 g, 92.5 mmol) was added and stirred at room temperature for 5 hours. After completion of the reaction, H2O was added dropwise to quench, and the mixture was extracted with dichloromethane and H2O. The organic layer was anhydrous with MgSO4 and filtered. The filtered filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 29.0 g (yield 64%) of 3-chloro-9-phenyl-4-(triphenylsilyl)-9H-carbazole.

[0318] Mass: [(M+H) + ] : 535.15

[0319] <Step 2> Synthesis of intermediate 9

[0320]

[0321] 29.0 g (53.9 mmol) of 3-chloro-9-phenyl-4-(triphenylsilyl)-9H-carbazole, 27.4 g (107.8 mmol) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.0 g (2.7 mmol) of PdCl2(dppf), 2.6 g (5.4 mmol) of Xphos, and 15.9 g (161.7 mmol) of KOAc were dissolved in 600 mL of 1,4-Dioxane and stirred under reflux for 8 hours to react. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 24.1 g (yield 71%) of intermediate 6.

[0322] Mass: [(M+H) + ] : 627.28

[0323]

[0324] [Preparation Example 10]

[0325] <Step 1> Synthesis of 1-chloro-9-phenyl-3-(triphenylsilyl)-9H-carbazole

[0326]

[0327] Dissolve 30 g (84.1 mmol) of 3-bromo-1-chloro-9-phenyl-9H-carbazole in 600 ml of THF and then -78 o 2.5 M n-BuLi (33.6 ml, 92.5 mmol) was added dropwise under C. After 30 minutes, chlorotriphenylsilane (27.3 g, 92.5 mmol) was added and stirred at room temperature for 5 hours. After completion of the reaction, H2O was added dropwise to quench, and the mixture was extracted with dichloromethane and H2O. The organic layer was anhydrous with MgSO4 and filtered. The filtered filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 36.5 g (yield 81%) of 1-chloro-9-phenyl-3-(triphenylsilyl)-9H-carbazole.

[0328] Mass: [(M+H) + ] : 535.15

[0329] <Step 2> Synthesis of intermediate 10

[0330]

[0331] 1-chloro-9-phenyl-3-(triphenylsilyl)-9H-carbazole 36.5 g (68.1 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 34.6 g (136.2 mmol), PdCl2(dppf) 2.5 g (3.4 mmol), Xphos 3.2 g (6.8 mmol), KOAc 20.0 g (204.2 mmol) were dissolved in 600 mL of 1,4-Dioxane and reacted by refluxing for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 35.0 g (yield 82%) of intermediate 10.

[0332] Mass: [(M+H) + ] : 627.28

[0333]

[0334] [Preparation Example 11]

[0335] <Step 1> Synthesis of 3-chloro-9-phenyl-2-(triphenylsilyl)-9H-carbazole

[0336]

[0337] Dissolve 30 g (84.1 mmol) of 2-bromo-3-chloro-9-phenyl-9H-carbazole in 600 ml of THF and then -78 o2.5 M n-BuLi (33.6 ml, 92.5 mmol) was added dropwise under C. After 30 minutes, chlorotriphenylsilane (27.3 g, 92.5 mmol) was added and stirred at room temperature for 5 hours. After completion of the reaction, H2O was added dropwise to quench, and the mixture was extracted with dichloromethane and H2O. The organic layer was anhydrous with MgSO4 and filtered. The filtered filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 35.6 g (yield 79%) of 3-chloro-9-phenyl-2-(triphenylsilyl)-9H-carbazole.

[0338] Mass: [(M+H) + ] : 535.15

[0339] <Step 2> Synthesis of intermediate 11

[0340]

[0341] 3-chloro-9-phenyl-2-(triphenylsilyl)-9H-carbazole 35.6 g (66.4 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 33.7 g (132.8 mmol), PdCl2(dppf) 2.4 g (3.3 mmol), Xphos 3.2 g (6.6 mmol), KOAc 19.6 g (199.2 mmol) were dissolved in 600 mL of 1,4-Dioxane and stirred under reflux for 8 hours to react. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 33.3 g (yield 80%) of intermediate 11.

[0342] Mass: [(M+H) + ] : 627.28

[0343]

[0344] [Preparation Example 12]

[0345] <Step 1> Synthesis of 1-chloro-9-phenyl-2-(triphenylsilyl)-9H-carbazole

[0346]

[0347] Dissolve 30 g (84.1 mmol) of 2-bromo-1-chloro-9-phenyl-9H-carbazole in 600 ml of THF and then -78 o 2.5 M n-BuLi (33.6 ml, 92.5 mmol) was added dropwise under C. After 30 minutes, chlorotriphenylsilane (27.3 g, 92.5 mmol) was added and stirred at room temperature for 5 hours. After completion of the reaction, H2O was added dropwise to quench, and the mixture was extracted with dichloromethane and H2O. The organic layer was anhydrous with MgSO4 and filtered. The filtered filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 35.6 g (yield 79%) of 1-chloro-9-phenyl-2-(triphenylsilyl)-9H-carbazole.

[0348] Mass: [(M+H) + ] : 535.15

[0349] <Step 2> Synthesis of intermediate 12

[0350]

[0351] 1-chloro-9-phenyl-2-(triphenylsilyl)-9H-carbazole 35.6 g (66.4 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 33.7 g (132.8 mmol), PdCl2(dppf) 2.4 g (3.3 mmol), Xphos 3.2 g (6.6 mmol), KOAc 19.6 g (199.2 mmol) were dissolved in 600 mL of 1,4-Dioxane and stirred under reflux for 8 hours to react. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 33.3 g (yield 80%) of intermediate 12.

[0352] Mass: [(M+H) + ] : 627.28

[0353]

[0354] [Preparation Example 13]

[0355] <Step 1> Synthesis of 3-chloro-9-phenyl-1-(4-(triphenylsilyl)phenyl)-9H-carbazole

[0356]

[0357] 30 g (66.4 mmol) of 1-bromo-3-chloro-9-phenyl-9H-carbazole, 42.8 g (132.8 mmol) of triphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane, 44.9 g (3.3 mmol) of Pd(PPh3), and 23.3 g (199.2 mmol) of K2CO3 were dissolved in 600 mL of toluene, 125 mL of EtOH, and 125 mL of H2O, and the mixture was stirred under reflux for 8 hours to react. After the reaction was completed, the mixture was cooled to room temperature, extracted, and the organic layer was distilled under reduced pressure and purified by column chromatography to obtain 41.2 g (yield 80%) of 3-chloro-9-phenyl-1-(4-(triphenylsilyl)phenyl)-9H-carbazole.

[0358] Mass: [(M+H) + ] : 611.18

[0359] <Step 2> Synthesis of intermediate 13

[0360]

[0361] 41.2 g (67.3 mmol) of 3-chloro-9-phenyl-1-(4-(triphenylsilyl)phenyl)-9H-carbazole, 34.2 g (134.6 mmol) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.5 g (3.4 mmol) of PdCl2(dppf), 3.2 g (6.7 mmol) of Xphos, and 19.8 g (201.9 mmol) of KOAc were dissolved in 600 mL of 1,4-Dioxane and reacted by refluxing for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 38.8 g (yield 82%) of intermediate 13.

[0362] Mass: [(M+H) +] : 703.31

[0363]

[0364] [Preparation Example 14]

[0365] <Step 1> Synthesis of 3-chloro-9-phenyl-1-(3-(triphenylsilyl)phenyl)-9H-carbazole

[0366]

[0367] 30 g (66.4 mmol) of 1-bromo-3-chloro-9-phenyl-9H-carbazole, 42.8 g (132.8 mmol) of triphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane, 44.9 g (3.3 mmol) of Pd(PPh3), and 23.3 g (199.2 mmol) of K2CO3 were dissolved in 600 mL of toluene, 125 mL of EtOH, and 125 mL of H2O, and the mixture was stirred under reflux for 8 hours to react. After the reaction was completed, the mixture was cooled to room temperature, extracted, and the organic layer was distilled under reduced pressure and purified by column chromatography to obtain 41.2 g (yield 80%) of 3-chloro-9-phenyl-1-(3-(triphenylsilyl)phenyl)-9H-carbazole.

[0368] Mass: [(M+H) + ] : 611.18

[0369] <Step 2> Synthesis of intermediate 14

[0370]

[0371] 41.2 g (67.3 mmol) of 3-chloro-9-phenyl-1-(3-(triphenylsilyl)phenyl)-9H-carbazole, 34.2 g (134.6 mmol) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.5 g (3.4 mmol) of PdCl2(dppf), 3.2 g (6.7 mmol) of Xphos, and 19.8 g (201.9 mmol) of KOAc were dissolved in 600 mL of 1,4-Dioxane and reacted by refluxing for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and the solid (KOAc) was filtered. The filtered filtrate was distilled under reduced pressure and purified by column chromatography to obtain 38.8 g (yield 82%) of intermediate 14.

[0372] Mass: [(M+H) + ] : 703.31

[0373]

[0374] [Synthesis Example 1] Synthesis of Compound 1

[0375]

[0376] Intermediate 1 (25.8 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtration was performed. After removing the solvent from the filtered organic layer, the target compound 1 (21.1 g, yield 77%) was obtained using column chromatography.

[0377] Mass: [(M+H) + ] : 732.27

[0378]

[0379] [Synthesis Example 2] Synthesis of Compound 2

[0380]

[0381] Intermediate 2 (25.8 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtered. After removing the solvent from the filtered organic layer, the target compound 2 (20.5 g, yield 75%) was obtained using column chromatography.

[0382] Mass: [(M+H) + ] : 732.27

[0383]

[0384] [Synthesis Example 3] Synthesis of Compound 3

[0385]

[0386] Intermediate 3 (25.8 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), and K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtration was performed. After removing the solvent from the filtered organic layer, the target compound 3 (18.9 g, yield 69%) was obtained using column chromatography.

[0387] Mass: [(M+H) + ] : 732.27

[0388]

[0389] [Synthesis Example 4] Synthesis of Compound 4

[0390]

[0391] Intermediate 4 (25.8 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), and K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtration was performed. After removing the solvent from the filtered organic layer, the target compound 4 (20.9 g, yield 76%) was obtained using column chromatography.

[0392] Mass: [(M+H) + ] : 732.27

[0393]

[0394] [Synthesis Example 5] Synthesis of Compound 5

[0395]

[0396] Intermediate 5 (25.8 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), and K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtered. After removing the solvent from the filtered organic layer, the target compound 5 (17.8 g, yield 65%) was obtained using column chromatography.

[0397] Mass: [(M+H) + ] : 732.27

[0398]

[0399] [Synthesis Example 6] Synthesis of Compound 6

[0400]

[0401] Intermediate 6 (25.8 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), and K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtered. After removing the solvent from the filtered organic layer, the target compound 6 (18.3 g, yield 67%) was obtained using column chromatography.

[0402] Mass: [(M+H) + ] : 732.27

[0403]

[0404] [Synthesis Example 7] Synthesis of Compound 7

[0405]

[0406] Intermediate 7 (25.8 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), and K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtered. After removing the solvent from the filtered organic layer, the target compound 7 (21.4 g, yield 78%) was obtained using column chromatography.

[0407] Mass: [(M+H) + ] : 732.27

[0408]

[0409] [Synthesis Example 8] Synthesis of Compound 8

[0410]

[0411] Intermediate 8 (25.8 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), and K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtered. After removing the solvent from the filtered organic layer, the target compound 8 (20.3 g, yield 74%) was obtained using column chromatography.

[0412] Mass: [(M+H) + ] : 732.27

[0413]

[0414] [Synthesis Example 9] Synthesis of Compound 9

[0415]

[0416] Intermediate 9 (25.8 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), and K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtration was performed. After removing the solvent from the filtered organic layer, the target compound 9 (19.4 g, yield 71%) was obtained using column chromatography.

[0417] Mass: [(M+H) + ] : 732.27

[0418]

[0419] [Synthesis Example 10] Synthesis of Compound 10

[0420]

[0421] Intermediate 10 (25.8 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtered. After removing the solvent of the filtered organic layer, the target compound 10 (20.5 g, yield 75%) was obtained using column chromatography.

[0422] Mass: [(M+H) + ] : 732.27

[0423]

[0424] [Synthesis Example 11] Synthesis of Compound 11

[0425]

[0426] Intermediate 3 (25.8 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), and K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtration was performed. After removing the solvent from the filtered organic layer, the target compound 11 (18.3 g, yield 67%) was obtained using column chromatography.

[0427] Mass: [(M+H) + ] : 732.27

[0428]

[0429] [Synthesis Example 12] Synthesis of Compound 12

[0430]

[0431] Intermediate 3 (25.8 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), and K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtration was performed. After removing the solvent of the filtered organic layer, the target compound 12 (18.3 g, yield 67%) was obtained using column chromatography.

[0432] Mass: [(M+H) + ] : 732.27

[0433]

[0434] [Synthesis Example 13] Synthesis of Compound 13

[0435]

[0436] Intermediate 13 (28.9 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), and K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtration was performed. After removing the solvent from the filtered organic layer, the target compound 13 (22.3 g, yield 75%) was obtained using column chromatography.

[0437] Mass: [(M+H) + ] : 808.30

[0438]

[0439] [Synthesis Example 14] Synthesis of Compound 14

[0440]

[0441] Intermediate 14 (28.9 g, 41.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 37.4 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), and K2CO3 (10.3 g, 74.7 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtration was performed. After removing the solvent from the filtered organic layer, the target compound 14 (23.6 g, yield 78%) was obtained using column chromatography.

[0442] Mass: [(M+H) + ] : 808.30

[0443]

[0444] [Synthesis Example 15] Synthesis of Compound 28

[0445]

[0446] Intermediate 4 (25.9 g, 41.2 mmol), 4-chloro-2,6-diphenylpyrimidine (10 g, 37.5 mmol), Pd(PPh3)4 (2.2 g, 1.9 mmol), and K2CO3 (10.4 g, 75.0 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO4 was added, and filtered. After removing the solvent from the filtered organic layer, the target compound 28 (21.4 g, yield 78%) was obtained using column chromatography.

[0447] Mass: [(M+H) +] : 731.28

[0448]

[0449] [Synthesis Example 16] Synthesis of Compound 105

[0450]

[0451] Intermediate 4 (19.3 g, 30.7 mmol), 2-chloro-4-(dibenzo[b,d]furan-2-yl)-6-phenyl-1,3,5-triazine (10 g, 27.9 mmol), Pd(PPh3)4 (1.6 g, 1.4 mmol), and K2CO3 (7.7 g, 55.9 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtration was performed. After removing the solvent from the filtered organic layer, the target compound 105 (16.8 g, yield 73%) was obtained using column chromatography.

[0452] Mass: [(M+H) + ] : 822.28

[0453]

[0454] [Synthesis Example 17] Synthesis of Compound 131

[0455]

[0456] Intermediate 4 (18.5 g, 29.4 mmol), 2-chloro-4-(dibenzo[b,d]thiophen-2-yl)-6-phenyl-1,3,5-triazine (10 g, 26.7 mmol), Pd(PPh3)4 (1.5 g, 1.3 mmol), and K2CO3 (7.4 g, 53.5 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtration was performed. After removing the solvent from the filtered organic layer, the target compound 131 (16.2 g, yield 72%) was obtained using column chromatography.

[0457] Mass: [(M+H) + ] : 838.26

[0458]

[0459] [Synthesis Example 18] Synthesis of Compound 151

[0460]

[0461] Intermediate 4 (20.1 g, 32.0 mmol), 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine (10 g, 29.1 mmol), Pd(PPh3)4 (1.7 g, 1.5 mmol), K2CO3 (8.0 g, 58.2 mmol) were added to 200 ml of toluene / 50 ml of EtOH / 50 ml of H2O and stirred at 110°C for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, MgSO4 was added, and filtration was performed. After removing the solvent of the filtered organic layer, the target compound 151 (17.2 g, yield 73%) was obtained using column chromatography.

[0462] Mass: [(M+H) + ] : 807.31

[0463]

[0464] [Examples 1 to 18] Fabrication of blue organic electroluminescent devices

[0465] Compounds 1 to 151 synthesized in the above synthetic examples were purified by sublimation to high purity using a commonly known method, and then a blue organic electroluminescent device was manufactured as follows.

[0466] A glass substrate coated with a 1500 Å thick ITO (Indium Tin Oxide) film was ultrasonically cleaned in distilled water. After the distilled water cleaning, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and then transferred to a UV OZONE cleaner (Power Sonic 405, Hwasin Tech). The substrate was then cleaned for 5 minutes using UV and transferred to a vacuum deposition machine.

[0467] On the ITO transparent electrode prepared as above, an organic electroluminescent device was manufactured by stacking HT-1 + 2% HAT-CN (100 Å) / HT-1 (1400 Å) / HT-2 (50 Å) / BH + 2% BD (200 Å) / each compound 1-151 in Table 1 below: LiQ = 1:1 (300 Å) / LiF (10 Å) / Al (1000 Å) in that order.

[0468] The structures of the compounds HT-1, HAT-CN, HT-2, BH, BD, ET-1, ET-2 and LiQ used at this time are as follows.

[0469]

[0470]

[0471]

[0472]

[0473] [Comparative Example 1] Fabrication of a Blue Organic Electroluminescent Device

[0474] A blue organic electroluminescent device of Comparative Example 1 was manufactured in the same manner as in Example 1, except that ET-1 was deposited at 300 Å instead of Compound 1 as the electron transport layer material.

[0475]

[0476] [Evaluation Example 1]

[0477] For each blue organic electroluminescent device manufactured in Examples 1 to 18 and Comparative Example 1, the driving voltage, current efficiency, and luminescence peak at a current density of (10) mA / cm2 were measured, and the results are shown in Table 1 below.

[0478] Sample Electron Transport Layer Driving Voltage (V) EL Peak (nm) Current Efficiency (cd / A) Example 1 Compound 14.34606.2 Example 2 Compound 24.04596.4 Example 3 Compound 34.44625.9 Example 4 Compound 44.14596.1 Example 5 Compound 54.54615.9 Example 6 Compound 64.34606.1 Example 7 Compound 74.14586.2 Example 8 Compound 84.04596.3 Example 9 Compound 94.14615.9 Example 10 Compound 104.04606.3 Example 11 Compound 114.34606.2 Example 12 Compound 124.34616.2 Example 13 Compound 134.24595.9 Example 14 Compound 144.14606.1 Example 15 Compound 284.04606.1 Example 16 Compound 1054.24615.9 Example 17 Compound 1314.34595.9 Example 18 Compound 1514.44585.9 Comparative Example 1 ET-14.84605.4

[0479] As shown in Table 1 above, it was found that the blue organic electroluminescent devices of Examples 1 to 18 using the compound according to the present invention as an electron transport layer material exhibited superior performance in terms of driving voltage, emission peak, and current efficiency compared to the blue organic electroluminescent device of Comparative Example 1 using conventional ET-1 as an electron transport layer material.

[0480]

[0481] [Examples 19 to 36] Fabrication of blue organic electroluminescent devices

[0482] Compounds 1 to 151 synthesized above were purified by sublimation to high purity using a commonly known method, and then a blue organic electroluminescent device was manufactured as follows.

[0483] A glass substrate coated with a 1500 Å thick ITO (Indium Tin Oxide) film was ultrasonically cleaned in distilled water. After the distilled water cleaning, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and then transferred to a UV OZONE cleaner (Power Sonic 405, Hwasin Tech). The substrate was then cleaned for 5 minutes using UV and transferred to a vacuum deposition machine.

[0484] On the ITO transparent electrode prepared as above, an organic electroluminescent device was manufactured by stacking HT-1 + 2% HAT-CN (100 Å) / HT-1 (1400 Å) / HT-2 (50 Å) / BH + 2% BD (200 Å) / each compound 1 to 151 (50 Å) in Table 2 below / ET-1: LiQ = 1:1 (300 Å) / LiF (10 Å) / Al (1000 Å) in that order.

[0485] The structures of HT-1, HAT-CN, HT-2, BH, BD, ET-1, ET-2 and LiQ used at this time are as specified in Examples 1 to 17.

[0486]

[0487] [Comparative Example 2] Fabrication of a blue organic electroluminescent device

[0488] A blue organic electroluminescent device of Comparative Example 2 was manufactured in the same manner as in Example 19, except that the electron transport layer was deposited at 350 Å without using compound 1 used as an electron transport auxiliary layer material.

[0489]

[0490] [Comparative Examples 3 to 7] Fabrication of Blue Organic Electroluminescent Devices

[0491] Blue organic electroluminescent devices of Comparative Examples 3 to 7 were manufactured in the same manner as in Example 18, except that Compound 1 was not used as an electron transport auxiliary layer material and Compounds ET-2 to ET-6 were deposited at 50 Å.

[0492] The structures of compounds ET-2 to ET-6 used at this time are as follows.

[0493]

[0494]

[0495] [Evaluation Example 2]

[0496] For the organic electroluminescent devices manufactured in Examples 19 to 36 and Comparative Examples 2 to 7, the driving voltage, emission wavelength, current efficiency, and emission wavelength at a current density of 10 mA / cm2 were measured, and the results are shown in Table 2 below.

[0497] Sample Electron Transport Auxiliary Layer Driving Voltage (V) EL Peak (nm) Current Efficiency (cd / A) Example 19 Compound 14.34607.3 Example 20 Compound 24.14617.8 Example 21 Compound 34.44617.2 Example 22 Compound 43.74608.1 Example 23 Compound 54.04607.9 Example 24 Compound 64.34607.5 Example 25 Compound 73.94597.7 Example 26 Compound 83.74597.8 Example 27 Compound 94.14617.5 Example 28 Compound 103.94617.8 Example 29 Compound 114.14607.6 Example 30 Compound 123.94597.8 Example 31 Compound 133.74618.1 Example 32 Compound 143.74628.2 Example 33 Compound 284.14618.0 Example 34 Compound 1053.94607.9 Example 35 Compound 1313.94597.7 Example 36 Compound 1513.84608.0 Comparative Example 2-4.64606.0 Comparative Example 3 ET-24.44576.2 Comparative Example 4 ET-34.64615.9 Comparative Example 5 ET-44.64606.0 Comparative Example 6ET-54.84625.8Comparative example 7ET-65.04604.9

[0498] As shown in Table 2 above, it was found that the blue organic electroluminescent devices of Examples 19 to 36 including the compound of Chemical Formula 1 according to the present invention as an electron transport auxiliary layer material exhibited superior performance in terms of current efficiency and driving voltage compared to the organic electroluminescent devices of Comparative Example 2 not including an electron transport auxiliary layer and Comparative Examples 3 to 7 not including the compound of Chemical Formula 1 as an electron transport auxiliary layer material.

Claims

1. A compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, X 1 Inland X 3 are identical or different from each other, and each is independently CR 2 or N, and just X 1 Inland X 3 At least one of them is N, R 1 and R 2 are identical or different from each other, and each independently represents hydrogen, deuterium (D), halogen, cyano group, nitro group, C 1 ~C 40 Alkyl group of C 2 ~C 40 Alkenyl group of C 2 ~C 40 Alkynyl group of C 3 ~C 40 A cycloalkyl group of , a heterocycloalkyl group having 3 to 40 nuclear atoms, C 6 ~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C 1 ~C 40 Alkyloxy group of C 6 ~C 60 Aryloxy group of C 3 ~C 40 Alkylsilyl group of C 6 ~C 60 Arylsilyl group of C 1 ~C 40 Alkylboron group of C 6 ~C 60 Aryl boron group, C 6 ~C 60 Arylphosphine group of C 6 ~C 60 Arylphosphine oxide group of C 6 ~C 60 Arylamine group of C 5 ~C 60 is selected from the group consisting of an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclear atoms, or can form a condensed ring by combining with any adjacent group; Ar 1 Inland Ar 6 are identical or different from each other, and each independently represents hydrogen, deuterium (D), and C. 1 ~C 40 Alkyl group of C 2 ~C 40 Alkenyl group of C 2 ~C 40 Alkynyl group of C 3 ~C 40 A cycloalkyl group of , a heterocycloalkyl group having 3 to 40 nuclear atoms, C 6 ~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C 1 ~C 40 Alkyloxy group of C 6 ~C 60 Aryloxy group of C 3 ~C 40 Alkylsilyl group of C 6 ~C 60 Arylsilyl group of C 1 ~C 40 Alkylboron group of C 6 ~C 60 Aryl boron group, C 6 ~C 60 Arylphosphine group of C 6 ~C 60 Arylphosphine oxide group of C 6 ~C 60 Arylamine group of C 5 ~C 60 is selected from the group consisting of an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclear atoms, L 1 and L 2 are identical or different from each other, and each independently represents a single bond or C 6 ~C 18 is selected from the group consisting of an arylene group and a heteroarylene group having 5 to 18 nuclear atoms, o, p and q are each independently an integer from 0 to 3, Above L 1 ~L 2 An arylene group, a heteroarylene group; and the above R 1 ~R 2 and Ar 2 ~Ar 6 The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphine oxide group and arylamine group are each independently hydrogen, deuterium (D), halogen, cyano group, nitro group, C 1 ~C 40 Alkyl group of C 2 ~C 40 Alkenyl group of C 2 ~C 40 Alkynyl group of C 3 ~C 40 A cycloalkyl group of , a heterocycloalkyl group having 3 to 40 nuclear atoms, C 6 ~C 60 Aryl group of, heteroaryl group having 5 to 60 nuclear atoms, C 1 ~C 40 Alkyloxy group of C 6 ~C 60 Aryloxy group of C 1 ~C 40 Alkylsilyl group of C 6 ~C 60 Arylsilyl group of C 1 ~C 40 Alkylboron group of C 6 ~C 60 Aryl boron group, C 6 ~C 60 Arylphosphine group of C 6 ~C 60 Arylphosphine oxide group of C 6 ~C 60 Arylamine group of C 5 ~C 60 The compound may be substituted with at least one substituent selected from the group consisting of an aryl heteroarylamine group and a heteroarylamine group having 5 to 60 nuclear atoms, and when there are multiple substituents, they may be the same or different from each other.

2. In paragraph 1, Above X 1 Inland X 3 The containing ring is a compound selected from the group of substituents represented by the following chemical formula: In the above formula, * indicates a part connected to the chemical formula 1 above, R 2 , Ar 5 and Ar 6 are as defined in Article 1, respectively.

3. In paragraph 1, Above Ar 1 The containing ring is a compound selected from the group of substituents represented by the following chemical formula: In the above formula, * indicates a part connected to the chemical formula 1 above, Ring A is a monocyclic or polycyclic hydrocarbon ring group containing or not containing a heteroatom, Ar 1 , R 1 and q are as defined in paragraph 1, respectively.

4. In paragraph 1, Above Ar 1 The containing ring is a compound selected from the group of substituents represented by the following chemical formula: In the above formula, * indicates a part connected to the chemical formula 1 above, Ar 1 , R 1 and q are each as defined in clause 1, and a plurality of Ar 1 may be identical or different from each other.

5. In paragraph 1, Ar 1 Inland Ar 6 are identical or different from each other, and each is independently C 6 ~C 60 A compound selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms.

6. In paragraph 1, Ar 1 Inland Ar 6 are identical or different from each other, and each independently is a compound selected from the following structural formulas: In the above formula, * indicates a part connected to the above chemical formula 1.

7. In paragraph 1, L 1 and L 2 are identical or different from each other, and each independently is a compound selected from the following structural formulas: In the above formula, * indicates a part connected to the above chemical formula 1.

8. In paragraph 1, R 1 Silver hydrogen, deuterium (D), C 1 ~C 40 Alkyl group of C 6 ~C 60 A compound selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms, or capable of forming a condensed ring by combining with any adjacent group.

9. In paragraph 1, The compound represented by the above chemical formula 1 is a compound represented by any one of the following chemical formulas 2 to 6: [Chemical formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical formula 6] In the above chemical formulas 2 to 6, Ar 1 ~Ar 6 , L 1 ~L 2 , R 1 , o, p and q are as defined in paragraph 1, respectively.

10. In paragraph 1, The compound represented by the above chemical formula 1 is a compound represented by any one of the following chemical formulas 7 to 9: [Chemical formula 7] [Chemical formula 8] [Chemical formula 9] In the above chemical formulas 7 to 9, Z 1 is O or S, Z 2 is N, R 11 Silver hydrogen, deuterium (D), C 1 ~C 40 Alkyl group of C 6 ~C 60 is selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms, or may be combined with any adjacent group to form a condensed ring, m is an integer from 0 to 3, a and b are each independently an integer from 1 to 3, X 1 ~X 3 , Ar 1 ~Ar 4 , L 1 ~L 2 , R 1 , o, p and q are as defined in paragraph 1, respectively.

11. In paragraph 1, The compound represented by the above chemical formula 1 is a compound represented by any one of the following chemical formulas 10 to 13: [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] In the above chemical formulas 10 to 13, X 1 ~X 3 , Ar 1 ~Ar 6 , L 1 ~L 2 , R 1 , o and p are as defined in paragraph 1, respectively.

12. In paragraph 1, The compound represented by the above chemical formula 1 is a compound represented by any one of the following chemical formulas 14 to 16: [Chemical Formula 14] [Chemical Formula 15] [Chemical Formula 16] In the above chemical formulas 14 to 16, Ring A is a monocyclic or polycyclic hydrocarbon ring group containing or not containing a heteroatom, X 1 ~X 3 , Ar 1 ~Ar 6 , L 1 ~L 2 , o and p are as defined in paragraph 1, respectively.

13. In paragraph 1, The compound represented by the above chemical formula 1 is a compound represented by the following chemical formula 17 or chemical formula 18: [Chemical Formula 17] [Chemical Formula 18] In the above chemical formulas 17 to 18, Y is O or S, n is an integer from 1 to 3, X 1 ~X 3 , Ar 2 ~Ar 6 , L 1 ~L 2 , R 1 , o, p and q are as defined in paragraph 1, respectively.

14. In paragraph 1, The compound represented by the above chemical formula 1 is a compound represented by any one of the following chemical formulas 19 to 26: [Chemical Formula 19] [Chemical formula 20] [Chemical Formula 21] [Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 24] [Chemical Formula 25] [Chemical Formula 26] In the above chemical formulas 19 to 26, X 1 ~X 3 , Ar 1 ~Ar 6 , L 1 ~L 2 , R 1 , o, p and q are as defined in paragraph 1, respectively.

15. In paragraph 1, The compound represented by the above chemical formula 1 is a compound represented by any one of the following chemical formulas 27 to 38: [Chemical Formula 27] [Chemical Formula 28] [Chemical Formula 29] [Chemical formula 30] [Chemical Formula 31] [Chemical formula 32] [Chemical Formula 33] [Chemical Formula 34] [Chemical Formula 35] [Chemical formula 36] [Chemical Formula 37] [Chemical formula 38] In the above chemical formulas 27 to 38, X 1 ~X 3 , Ar 1 ~Ar 6 , L 1 ~L 2 , R 1 , o, p and q are as defined in paragraph 1, respectively.

16. In paragraph 1, The compound represented by the above chemical formula 1 is a compound represented by any one of the following chemical formulas 1 to 222.

17. In paragraph 1, The compound represented by the above chemical formula 1 is a compound that is a material for a light-emitting layer, an electron transport layer, or an electron transport auxiliary layer.

18. An organic electroluminescent device comprising an anode, a cathode, and one or more organic layers interposed between the anode and the cathode, wherein at least one of the one or more organic layers comprises a compound described in any one of claims 1 to 18.

19. In Article 18, An organic electroluminescent device, wherein the organic layer containing the compound is selected from the group consisting of a light-emitting layer, a light-emitting auxiliary layer, a life-span improvement layer, an electron transport layer, and an electron transport auxiliary layer.

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