Organic light-emitting compound and organic electroluminescent device using same

Abstract

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

Description

Organic luminescent compounds and organic electroluminescent devices using the same

[0001] The present invention relates to a novel organic light-emitting compound and an organic electroluminescent device using the same, and more particularly, to a compound having excellent electron transport capability and an organic electroluminescent device having improved characteristics such as luminous efficiency, driving 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 aims to provide a novel organic 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, a luminescent layer material, a life-span improving layer material, a luminescent auxiliary layer material, an electron transport layer material, an electron transport auxiliary layer material, etc.

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

[0011]

[0012] To achieve the above-mentioned purpose, the present invention provides a compound represented by the following chemical formula 1.

[0013] [Chemical Formula 1]

[0014]

[0015] In the above chemical formula 1,

[0016] Ar1 to Ar3 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~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, but cases where at least two of Ar1 to Ar3 are hydrogen are excluded,

[0017] X1 to X5 are the same or different from each other, and are each independently C(R1) or N, provided that at least two of X1 to X5 are N,

[0018] When there are multiple R1s, the multiple R1s are the same or different, and each independently represents 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~C40 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, wherein two of the plurality of R1 are represented by B1 and B2,

[0019] A1 to A2 and B1 to B2 are the same or different from each other, and each independently represents hydrogen, deuterium (D), C1 to 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,

[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] d and e are each independently integers from 0 to 4,

[0022] The arylene group and heteroarylene group of the above L1 to L2, and the above Ar1 to Ar3, R1, The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkylboron group, arylborone group, phosphine group, phosphine oxide group, and arylamine group of A1 to A2, B1 to B2 are each independently selected from the group consisting of 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 40 Alkyloxy 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 and C6~C 60 It may be substituted with one or more substituents selected from the group consisting of arylamine groups, 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, electron transport auxiliary layer, or light emitting auxiliary layer material, it can exhibit characteristics such as a high low refractive index, thermal stability, low driving voltage, fast mobility, high current efficiency, and long lifespan 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 compound of chemical formula 1 according to the present invention has a basic skeleton in which two azine moieties (e.g., pyrazine group, pyrimidine / triazine group) having electron withdrawing group (EWG) ability exist at both terminals of the molecule, and a silane group is included between them, and these are directly connected or connected through a separate linker (e.g., L1 to L2).

[0034] The compound of chemical formula 1 having this structure has a dual EWG structure [e.g., triazine / pyrimidine group (EWG1) - silane group - pyrazine group (EWG2)] by including a triazine / pyrimidine group and a pyrazine group as functional groups having two strong electron-withdrawing abilities (EWG) in its molecular structure, thereby having advantageous properties in electron injection and transfer, and thus exhibiting an excellent effect in improving the initial driving voltage of the device by increasing the electron transfer ability to the light-emitting layer.

[0035] In addition, since different Dual EWG groups, such as triazine / pyrimidine groups and pyrazine groups, are arranged on both sides of the silane group, an asymmetric structure is formed based on the molecular long axis. The compound of the present invention has a high triplet (T1) energy level resulting from the structural asymmetry, and the low-voltage characteristic of the pyrazine group, which lowers the operating voltage of the device and at the same time further enhances the strong electron-withdrawing characteristic of the azine group such as triazine / pyrimidine, thereby simultaneously increasing the high efficiency characteristic of the device. 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. In particular, since the compound according to the present invention has an asymmetric structure, it has an advantageous aspect in terms of processability because it has no Tc (Crystallization Temp.) in thermal characteristics.

[0036] In addition, since the present invention uses an aromatic hydrocarbon group and a stable structure in a condensed form rather than a simple aliphatic ring group, the thermal stability of the material can be increased, and since the crystallization temperature (Tc) of the material does not exist, it is effective in improving the processability of the device as well as its lifespan.

[0037] In addition, the compound of the above chemical formula 1 has a silyl (Si) moiety at the center of the molecule, so 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 excitons are excessively generated, so that excitons generated in the light-emitting layer can be prevented 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, so that the lifespan of the device can be efficiently increased. In addition, the introduction of a silane moiety increases the molecular weight and secures a high glass transition temperature (Tg), so that heat resistance can be significantly improved.

[0038] 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.

[0039] According to the present invention, the compound represented by chemical formula 1 has a basic skeletal structure comprising two different nitrogen-containing heteroaromatic rings (e.g., pyrimidine / triazine, pyrazine) and a silane moiety, which are directly connected or connected via a separate linker (e.g., L1 to L2).

[0040] The silane moiety positioned at the center of the compound represented by the above chemical formula 1 can be a silyl / silane moiety (-SiA1A2-) of a common 4-valent group known in the art without limitation. In this silane moiety, A1 and A2 can be substituted as substituents. A1 to A2 are 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 and C6~C 60 is selected from the group consisting of arylamine groups. Specifically, A1 and A2 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 It can be an aryl group.

[0041] For example, A1 and A2 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.

[0042]

[0043]

[0044] In the above formula,

[0045] * indicates a part connected to the above chemical formula 1,

[0046] R2 is hydrogen, deuterium (D), C1~C 40 Alkyl group of C6~C 60 It is selected from the group consisting of an aryl group and a heteroarylene group having 5 to 18 nuclear atoms. In addition, although not shown 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.

[0047] Two different EWG groups (e.g., nitrogen-containing heterocycles) are substituted on one side and the other side of the above silane moiety, respectively, to form an asymmetric Dual EWG structure. Examples of these two EWG groups include a pyrazine group and a pyrimidine / triazine group (e.g., a ring containing X1 to X5).

[0048] The ring containing X1 to X5, which is a type of azine group, may be a monocyclic nitrogen-containing heteroaromatic ring containing at least two nitrogen atoms. In one embodiment of the nitrogen-containing heteroaromatic ring (e.g., the ring containing X1 to X5), X1 to X5 are the same or different, and are each independently C(R1) or N, provided that at least two of X1 to X5 are N, and specifically, 2 to 3 Ns are included. By including a heterocycle containing 2 to 3 nitrogens in this way, better electron absorption properties are exhibited, which is advantageous for electron injection and transport.

[0049] R1 located in the above nitrogen-containing heteroaromatic ring (e.g., X1~X5-containing ring) is the same or different from each other, and each independently represents hydrogen, deuterium, halogen group, cyano group, nitro group, amino 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 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, C1~C 40 Phosphine group, C1~C 40 Phosphine oxide group and C6~C 60 It can be selected from the group consisting of arylamine groups. Specifically, R1 is hydrogen, deuterium, halogen, cyano group, 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.

[0050] At this time, two of the multiple R1s located in the nitrogen-containing heteroaromatic ring (e.g., the ring containing X1 to X5) can be represented by B1 and B2. These B1 to B2 are the same or different from each other, and each independently represents hydrogen, deuterium (D), C1 to 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~C60 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, B1 and B2 are the same or different from each other, and each independently represents a non-hydrogen substituent, for example, 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 It can be an aryl group.

[0051] For example, the nitrogen-containing heteroaromatic ring (e.g., a ring containing X1 to X5) may be any one selected from the following structural formulas.

[0052]

[0053] In the above formula,

[0054] * indicates a part connected to the above chemical formula 1,

[0055] R1, B1 and B2 are each as defined in Chemical Formula 1. Specifically, R1 is hydrogen, deuterium, halogen, cyano group, C1~C 40 Alkyl group of C6~C 60 , and a heteroaryl group having 5 to 60 nuclear atoms, wherein B1 and B2 are each independently a non-hydrogen substituent, i.e., C6~C 60 It is preferable to select from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms.

[0056] For a more specific example, B1 and B2 may be the same or different, and may each be independently selected from the following structural formulas. However, the present invention is not limited thereto.

[0057]

[0058]

[0059] In the above formula,

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

[0061] R2 is hydrogen, deuterium (D), C1~C 40 Alkyl group of C6~C 60 It is selected from the group consisting of an aryl group and a heteroarylene group having 5 to 18 nuclear atoms. In addition, although not shown 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.

[0062] Meanwhile, the pyrazine group bonded to the other side of the silane moiety may be substituted with Ar1 to Ar3 as substituents. These Ar1 to Ar3 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~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~C60 is selected from the group consisting of arylamine groups, but the case where at least two of Ar1 to Ar3 are hydrogen is excluded. Specifically, Ar1 to Ar3 are the same or different from each other, and each independently represent hydrogen, deuterium (D), C1~C 40 Alkyl group of C6~C 60 aryl group, and a heteroaryl group having 5 to 60 nuclear atoms, more specifically C6~C 60 It may be an aryl group or a heteroaryl group having 5 to 60 nuclear atoms.

[0063] For example, Ar1 to Ar3 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 part connected to the above chemical formula 1,

[0067] R3 is hydrogen, deuterium (D), C1~C 40 Alkyl group of C6~C 60 It is selected from the group consisting of an aryl group and a heteroarylene group having 5 to 18 nuclear atoms. In addition, although not shown 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.

[0068] In the compound represented by chemical formula 1 according to the present invention, the pyrazine group and the pyrimidine / triazine group arranged at both ends with the silane moiety as the center are directly bonded or connected through a separate linker (e.g., L1 to L2). In this way, when the linker (e.g., L1 to L2) is present, the HOMO region is expanded, which provides an advantage in the HOMO-LUMO distribution, and the charge transfer efficiency can be increased through appropriate overlap of the HOMO-LUMO.

[0069] These linkers (e.g., L1 to L2) are not particularly limited and may be single bonds or linkers of common divalent groups known in the art. Specifically, L1 to L2 are the same or different from each other, and each independently represents a single bond (e.g., direct bond) or a C6 to C 18 It can be selected from the group consisting of an arylene group and a heteroarylene group having 5 to 18 nuclear atoms. Specific examples of the arylene group and the heteroarylene group include a phenylene group, a biphenylene group, a pyrrolylene group, an imidazolylene group, an oxazolyl group, a thiazolyl group, a triazolyl group, a pyridinylene group, a pyrimidinylene group, etc. More specifically, L1 to L2 are the same or different from each other, and each independently represents a single bond or 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.

[0070] At this time, the number of linkers (e.g., d, e) may be integers from 0 to 4, respectively. Specifically, d+e ≥ 1, and more specifically, d and e may be integers from 1 to 3, respectively. For example, when d and e are 0, L1 to L2 may each be a single bond. In addition, when d and e are greater than 0 and 4 or less, a plurality of L1 to L2 may be the same as or different from each other, and may each independently be a substituent excluding a single bond in the definition of the linker described above.

[0071] For example, L1 to L2 may be the same or different from each other, and may each independently be a single bond or a linking group selected from the following structural formula.

[0072]

[0073] In the above formula,

[0074] * 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.

[0075] In the chemical formula 1 described above, the arylene group and heteroarylene group of L1 to L2, and the Ar1 to Ar3, R 1, The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkylboron group, arylborone group, phosphine group, phosphine oxide group, and arylamine group of A1 to A2, B1 to B3 are each independently selected from the group consisting of 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 40 Alkyloxy 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 and C6~C 60 It may be substituted with one or more substituents selected from the group consisting of arylamine groups, and in this case, when there are multiple substituents, they may be the same or different from each other.

[0076] According to one embodiment of the present invention, the compound represented by the above chemical formula 1 can be embodied as the following chemical formula 2 depending on the type of linker (e.g., L1 to L2).

[0077] [Chemical Formula 2]

[0078]

[0079] In the above formula,

[0080] X1 to X5, Ar1 to Ar3, A1 to A2, B1 to B2, d and e are each as defined in chemical formula 1.

[0081] For example, in the chemical formula 2 above, and (When d and e are each 1 or more) are the same or different from each other, and can be independently selected from the structural formulas below.

[0082]

[0083] In the above formula,

[0084] * indicates a part connected to the above chemical formula 2.

[0085] 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 3 to 5, depending on the bonding position of the linker (e.g., L2) connected to the nitrogen-containing heterocycle (e.g., X1 to X5-containing ring). However, the present invention is not limited thereto.

[0086] [Chemical Formula 3]

[0087]

[0088] [Chemical Formula 4]

[0089]

[0090] [Chemical Formula 5]

[0091]

[0092] In the above formula,

[0093] X1 to X5, Ar1 to Ar3, A1 to A2, B1 to B2, d and e are each as defined in chemical formula 1.

[0094] 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 6a to 6l depending on the number (e = 1 to 2) of linkers positioned between the silane group and the nitrogen-containing heterocycle (e.g., X1 to X5-containing ring) and their bonding positions. However, the present invention is not limited thereto.

[0095] [Chemical Formula 6a]

[0096]

[0097] [Chemical Formula 6b]

[0098]

[0099] [Chemical formula 6c]

[0100]

[0101] [Chemical formula 6d]

[0102]

[0103] [Chemical Formula 6e]

[0104]

[0105] [Chemical formula 6f]

[0106]

[0107] [Chemical formula 6g]

[0108]

[0109] [Chemical formula 6h]

[0110]

[0111] [Chemical formula 6i]

[0112]

[0113] [Chemical formula 6j]

[0114]

[0115] [Chemical formula 6k]

[0116]

[0117] [Chemical formula 6l]

[0118]

[0119] In the above formula,

[0120] Ar1 to Ar3, A1 to A2, B1 to B2, R1, and d are each as defined in Chemical Formula 1.

[0121] 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 bonding position of the linker (e.g., L1) connected to the pyrazine (e.g., Ar1-Ar3 containing ring). However, the present invention is not limited thereto.

[0122] [Chemical Formula 7]

[0123]

[0124] [Chemical Formula 8]

[0125]

[0126] [Chemical Formula 9]

[0127]

[0128] In the above formula,

[0129] X1 to X5, Ar1 to Ar3, A1 to A2, B1 to B2, d and e are each as defined in chemical formula 1.

[0130] 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 10a to 101 depending on the number of linkers (d = 1 to 2) located between the pyrazine group and the silane group and their bonding positions. However, the present invention is not limited thereto.

[0131] [Chemical Formula 10a]

[0132]

[0133] [Chemical Formula 10b]

[0134]

[0135] [Chemical formula 10c]

[0136]

[0137] [Chemical Formula 10d]

[0138]

[0139] [Chemical Formula 10e]

[0140]

[0141] [Chemical formula 10f]

[0142]

[0143] [Chemical formula 10g]

[0144]

[0145] [Chemical formula 10h]

[0146]

[0147] [Chemical formula 10i]

[0148]

[0149] [Chemical formula 10j]

[0150]

[0151] [Chemical Formula 10k]

[0152]

[0153] [Chemical formula 10l]

[0154]

[0155] In the above formula,

[0156] X1 to X5, Ar1 to Ar3, A1 to A2, B1 to B2, and e are each as defined in chemical formula 1.

[0157] 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 11 to 14 depending on the type of linker (e.g., L1 to L2) and nitrogen-containing heterocycle (e.g., X1 to X5-containing ring). However, the present invention is not limited thereto.

[0158] [Chemical Formula 11]

[0159]

[0160] [Chemical Formula 12]

[0161]

[0162] [Chemical Formula 13]

[0163]

[0164] [Chemical Formula 14]

[0165]

[0166] In the above formula,

[0167] Ar1 to Ar3, A1 to A2, B1 to B2, d and e are each as defined in chemical formula 1.

[0168] 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 15 to 18 depending on the type of substituents Ar1 to Ar3 introduced to the pyrazine group. However, the present invention is not limited thereto.

[0169] [Chemical Formula 15]

[0170]

[0171] [Chemical Formula 16]

[0172]

[0173] [Chemical Formula 17]

[0174]

[0175] [Chemical Formula 18]

[0176]

[0177] In the above formula,

[0178] X1 to X5, Ar1 to Ar3, A1 to A2, B1 to B2, L1 to L2, d and e are each as defined in Chemical Formula 1, except when Ar1 to Ar3 are hydrogen.

[0179] The compounds represented by the above-described chemical formulas 15 to 18 can be further specified as one of the following chemical formulas 15a to 18a depending on the type of linker (e.g., L1 to L2).

[0180] [Chemical Formula 15a]

[0181]

[0182] [Chemical Formula 16a]

[0183]

[0184] [Chemical Formula 17a]

[0185]

[0186] [Chemical Formula 18a]

[0187]

[0188] In the above formula,

[0189] X1 to X5, Ar1 to Ar3, A1 to A2, B1 to B2, d and e are each as defined in Chemical Formula 1, except when Ar1 to Ar3 are hydrogen.

[0190] 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 128 exemplified below. However, the compound represented by chemical formula 1 of the present invention is not limited to those exemplified below.

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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.

[0202] 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.

[0203] 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, and 2-pyrimidinyl.

[0204] 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.

[0205] 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.

[0206] In the present invention, “arylamine” means an amine substituted with an aryl having 6 to 40 carbon atoms.

[0207] 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.

[0208] 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.

[0209] 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.

[0210] 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.

[0211] Electron transport layer material

[0212] The present invention provides an electron transport layer comprising a compound represented by the above chemical formula 1.

[0213] 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.

[0214] The compound represented by the above chemical formula 1 may be used alone as an electron transport layer (ETL) material, or may be mixed with an electron transport layer material known in the art. It is preferably used alone.

[0215] 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.

[0216] 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.

[0217] <Electron transport auxiliary layer material>

[0218] In addition, the present invention provides an electron transport auxiliary layer comprising a compound represented by the above chemical formula 1.

[0219] The electron transport 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.

[0220] 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 layer material known in the art. It is preferably used alone.

[0221] 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 may include an oxadiazole derivative, a triazole derivative, a phenanthroline derivative (e.g., BCP), a heterocyclic derivative containing nitrogen, etc.

[0222] 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.

[0223] Organic electroluminescent devices

[0224] 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.

[0225] 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.

[0226] 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, an electron transport auxiliary layer, or a light-emitting auxiliary layer.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] 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.

[0238] <Synthesis Examples 1 to 11>

[0239] [Synthesis Example 1] Synthesis of Compound 1

[0240]

[0241] [Synthesis Example 1-1] Synthesis of Compound 1-iii

[0242]

[0243]

[0244] 50 g (111.1 mmol, 1 eq) of (3-bromophenyl)(3-chlorophenyl)diphenylsilane and 33.9 g (133.4 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 3.3 g (4.4 mmol, 0.04 eq) of PdCl2(dppf), and 21.9 g (222.3 mmol, 2 eq) of KOAc were added to 750 ml of 1,4-dioxane and heated under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 1-iii, (3-chlorophenyl)diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (45.3 g, yield 82%).

[0245] Mass: [(M+H) + ] : 496.91

[0246] NMR( 1 H): σ= 7.85(1H, d), 7.61(1H, s), 7.55(1H, s), 7.50-7.32(15H, m), 1,20(12H, s)

[0247] [Synthesis Example 1-2] Synthesis of Compound 1-ii

[0248]

[0249] 45.3 g (91.1 mmol, 1 eq) of (3-chlorophenyl)diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane, 26.7 g (100.3 mmol, 1.1 eq) of 5-chloro-2,3-diphenylpyrazine, 3.2 g (2.7 mmol, 0.03 eq) of Pd(PPh3)4, and 25.2 g (182.3, 2 eq) of K2CO3 were added to 650 ml of toluene, 180 ml of EtOH, and 180 ml of H2O, and heated and stirred under reflux for 8 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, adsorbed onto silica gel, and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 1-ii, 5-(3-((3-chlorophenyl)diphenylsilyl)phenyl)-2,3-diphenylpyrazine (38.4 g, yield 70%).

[0250] Mass: [(M+H) + ] : 602.11

[0251] NMR( 1 H): σ= 8.79(1H, s), 8.50(1H, d), 8.44(1H, s), 8.03(2H, d), 7.68-7.59(5H, m), 7.46-7.32(19H, m)

[0252] [Synthesis Example 1-3] Synthesis of Compound 1-i

[0253]

[0254] 38.4 g (63.8 mmol, 1 eq) of 5-(3-((3-chlorophenyl)diphenylsilyl)phenyl)-2,3-diphenylpyrazine and 19.4 g (76.6 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.3 g (3.2 mmol, 0.04 eq) of PdCl2(dppf), 6.1 g (12.8 mmol, 0.2 eq) of Xphos, and 15.1 g (153.1 mmol, 2 eq) of KOAc were added to 570 ml of 1,4-dioxane and heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 1-i, 5-(3-(diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-2,3-diphenylpyrazine (34.0 g, yield 77%).

[0255] Mass: [(M+H) + ] : 692.74

[0256] NMR( 1 H): σ= 8.79(1H, s), 8.50(1H, d), 8.46(1H, s), 8.03(2H, d), 7.85(1H, d), 7.68-7.59(5H, m), 7.46-7.32(18H, m), 1.20(12H, s)

[0257] [Synthesis Example 1-4] Synthesis of Compound 1

[0258]

[0259] 34.0 g (49.1 mmol, 1 eq) of 5-(3-(diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-2,3-diphenylpyrazine and 14.5 g (54 mmol, 1.1 eq) of 2-chloro-4,6-diphenyl-1,3,5-triazine (intermediate A), 1.7 g (1.5 mmol, 0.03 eq) of Pd(PPh3)4, and 13.6 g (98.3 mmol, 2 eq) of K2CO3 were added to 500 ml of toluene, 150 ml of EtOH, and 150 ml of H2O, and heated and stirred under reflux for 8 hours. After the reaction was completed, the precipitated solid was filtered off with a sufficient amount of water and washed with sufficient water and MeOH. Next, it was adsorbed onto silica gel and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 1 (target compound B) as a white solid (33.3 g, yield 85%).

[0260] Mass: [(M+H) + ] : 798.04

[0261] [Synthesis Examples 2-11]

[0262] Except that the material of intermediate A in the above Synthesis Example 1 was changed as shown in Table 1 below, the same method as that for preparing compound 1 was performed to synthesize target compounds B of Synthesis Examples 2 to 11 as follows.

[0263] [Correction pursuant to Rule 91, 06.11.2024]

[0264] [Correction pursuant to Rule 91, 06.11.2024]

[0265] <Synthesis Examples 12-17>

[0266] [Synthesis Example 12] Synthesis of Compound 21

[0267]

[0268] [Synthesis Example 12-1] Synthesis of Compound 21-iii

[0269]

[0270] 50 g (111.1 mmol, 1 eq) of (4-bromophenyl)(3-chlorophenyl)diphenylsilane and 33.9 g (133.4 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 3.3 g (4.4 mmol, 0.04 eq) of PdCl2(dppf), and 21.9 g (222.3 mmol, 2 eq) of KOAc were added to 750 ml of 1,4-dioxane and heated under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 21-iii, ((3-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (44.2 g, yield 80%).

[0271] Mass: [(M+H) + ] : 496.91

[0272] NMR( 1 H): σ= 7.85(2H, d), 7.55(1H, s), 7.46-7.32(15H, m), 1,20(12H, s)

[0273] [Synthesis Example 12-2] Synthesis of Compound 21-ii

[0274]

[0275] 44.2 g (88.9 mmol, 1 eq) of (3-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane and 26.1 g (97.8 mmol, 1.1 eq) of 5-chloro-2,3-diphenylpyrazine, 3.1 g (2.7 mmol, 0.03 eq) of Pd(PPh3)4, and 24.6 g (177.8, 2 eq) of K2CO3 were added to 650 ml of toluene, 180 ml of EtOH, and 180 ml of H2O, and heated and stirred under reflux for 8 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, adsorbed onto silica gel, and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and Hexane was filtered to obtain compound 21-ii, 5-(4-((3-chlorophenyl)diphenylsilyl)phenyl)-2,3-diphenylpyrazine (37.4 g, yield 70%).

[0276] Mass: [(M+H) + ] : 602.11

[0277] NMR( 1 H): σ= 8.79(1H, s), 8.50(1H, d), 8.44(1H, s), 8.03(2H, d), 7.68-7.59(5H, m), 7.46-7.32(19H, m)

[0278] [Synthesis Example 12-3] Synthesis of Compound 21-i

[0279]

[0280] 37.4 g (62.2 mmol, 1 eq) of 5-(4-((3-chlorophenyl)diphenylsilyl)phenyl)-2,3-diphenylpyrazine and 19.0 g (74.7 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.3 g (3.1 mmol, 0.04 eq) of PdCl2(dppf), 5.9 g (12.4 mmol, 0.2 eq) of Xphos, and 14.7 g (149.4 mmol, 2 eq) of KOAc were added to 560 ml of 1,4-dioxane and heated and stirred under reflux for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 21-i, 5-(4-(diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-2,3-diphenylpyrazine (34.1 g, yield 79%).

[0281] Mass: [(M+H) + ] : 692.74

[0282] NMR( 1 H): σ= 8.79(1H, s), 8.43(2H, d), 8.03(2H, d), 7.85(1H, d), 7.69(2H, d), 7.61-7.59(3H, m), 7.45-7.32(18H, m), 1.20(12H, s)

[0283] [Synthesis Example 12-4] Synthesis of Compound 21

[0284]

[0285] 34.1 g (49.2 mmol, 1 eq) of 5-(4-(diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-2,3-diphenylpyrazine and 14.5 g (54.1 mmol, 1.1 eq) of 2-chloro-4,6-diphenyl-1,3,5-triazine (intermediate A), 1.7 g (1.5 mmol, 0.03 eq) of Pd(PPh3)4, and 13.6 g (98.3 mmol, 2 eq) of K2CO3 were added to 500 ml of toluene, 140 ml of EtOH, and 140 ml of H2O, and heated and stirred under reflux for 8 hours. After the reaction was completed, the precipitated solid was filtered off with a sufficient amount of water and washed with sufficient water and MeOH. Next, it was adsorbed onto silica gel and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 21 (target compound B) as a white solid (33.0 g, yield 84%).

[0286] Mass: [(M+H) + ] : 798.04

[0287] [Synthesis Examples 13-17]

[0288] Except that the material of intermediate A in the above Synthesis Example 12 was changed as shown in Table 2 below, the same method as that for preparing compound 21 was performed to synthesize target compounds B of Synthesis Examples 13 to 17 as follows.

[0289] [Correction pursuant to Rule 91, 06.11.2024]

[0290] [Correction pursuant to Rule 91, 06.11.2024]

[0291] <Synthesis Examples 18-22>

[0292] [Synthesis Example 18] Synthesis of Compound 41

[0293] [Correction pursuant to Rule 91, 06.11.2024]

[0294] [Synthesis Example 18-1] Synthesis of Compound 41-iii

[0295]

[0296] 50 g (111.1 mmol, 1 eq) of (4-bromophenyl)(4-chlorophenyl)diphenylsilane and 33.9 g (133.4 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 3.3 g (4.4 mmol, 0.04 eq) of PdCl2(dppf), and 21.9 g (222.3 mmol, 2 eq) of KOAc were added to 750 ml of 1,4-dioxane and heated under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 41-iii, (4-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (44.7 g, yield 81%).

[0297] Mass: [(M+H) + ] : 496.91

[0298] NMR( 1 H): σ= 7.85(2H, d), 7.52-7.38(16H, m), 1,20(12H, s)

[0299] [Synthesis Example 18-2] Synthesis of Compound 41-ii

[0300]

[0301] 44.7 g (90.0 mol, 1 eq) of (4-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane and 26.4 g (99.0 mmol, 1.1 eq) of 5-chloro-2,3-diphenylpyrazine, 3.1 g (2.7 mmol, 0.03 eq) of Pd(PPh3)4, and 24.6 g (180.1 ml, 2 eq) of K2CO3 were added to 650 ml of toluene, 180 ml of EtOH, and 180 ml of H2O, and heated and stirred under reflux for 8 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, adsorbed onto silica gel, and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and Hexane was filtered to obtain compound 41-ii, 5-(4-((4-chlorophenyl)diphenylsilyl)phenyl)-2,3-diphenylpyrazine (41.1 g, yield 76%).

[0302] Mass: [(M+H) + ] : 602.11

[0303] NMR( 1 H): σ= 8.79(1H, s), 8.43(2H, d), 8.03(2H, d), 7.69(2H, d), 7.59-7.32(22H, m)

[0304] [Synthesis Example 18-3] Synthesis of Compound 41-i

[0305]

[0306] 41.1 g (68.4 mmol, 1 eq) of 5-(4-((4-chlorophenyl)diphenylsilyl)phenyl)-2,3-diphenylpyrazine and 20.9 g (82.1 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.5 g (3.4 mmol, 0.04 eq) of PdCl2(dppf), 6.5 g (13.7 mmol, 0.2 eq) of Xphos, and 16.2 g (164.2 mmol, 2 eq) of KOAc were added to 620 ml of 1,4-dioxane and heated and stirred under reflux for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 41-i, 5-(4-(diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-2,3-diphenylpyrazine (38.9 g, yield 82%).

[0307] Mass: [(M+H) + ] : 692.74

[0308] NMR( 1 H): σ= 8.79(1H, s), 8.43(2H, d), 8.03(2H, d), 7.85(1H, d), 7.69(2H, d), 7.61-7.59(3H, m), 7.45-7.32(18H, m), 1.20(12H, s)

[0309] [Synthesis Example 18-4] Synthesis of Compound 41

[0310]

[0311] 38.9 g (56.1 mmol, 1 eq) of 5-(4-(diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-2,3-diphenylpyrazine and 16.5 g (61.7 mmol, 1.1 eq) of 2-chloro-4,6-diphenyl-1,3,5-triazine (intermediate A), 1.9 g (1.7 mmol, 0.03 eq) of Pd(PPh3)4, and 15.5 g (112.2 mmol, 2 eq) of K2CO3 were added to 600 ml of toluene, 150 ml of EtOH, and 150 ml of H2O, and heated and stirred under reflux for 8 hours. After the reaction was completed, the precipitated solid was filtered off with a sufficient amount of water and washed with sufficient water and MeOH. Next, it was adsorbed onto silica gel and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 41 (target compound B) as a white solid (37.2 g, yield 83%).

[0312] Mass: [(M+H) + ] : 874.14

[0313] [Synthesis Examples 19-22]

[0314] Except that the material of intermediate A in the above Synthesis Example 18 was changed as shown in Table 3 below, the same method as that for preparing compound 41 was performed to synthesize target compounds B of Synthesis Examples 19 to 22 as follows.

[0315] [Correction pursuant to Rule 91, 06.11.2024]

[0316] <Synthesis Examples 23-28>

[0317] [Synthesis Example 23] Synthesis of Compound 61

[0318] [Correction pursuant to Rule 91, 06.11.2024]

[0319] [Synthesis Example 23-1] Synthesis of Compound 61-iii

[0320]

[0321] 50 g (111.1 mmol, 1 eq) of (3-bromophenyl)(4-chlorophenyl)diphenylsilane and 33.9 g (133.4 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 3.3 g (4.4 mmol, 0.04 eq) of PdCl2(dppf), and 21.9 g (222.3 mmol, 2 eq) of KOAc were added to 750 ml of 1,4-dioxane and heated under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 61-iii, (4-chlorophenyl)diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (45.3 g, yield 82%).

[0322] Mass: [(M+H) + ] : 496.91

[0323] NMR( 1 H): σ= 7.85(1H, d), 7.61(1H, s), 7.52-7.32(16H, m), 1,20(12H, s)

[0324] [Synthesis Example 23-2] Synthesis of Compound 61-ii

[0325]

[0326] 45.3 g (91.1 mmol, 1 eq) of (4-chlorophenyl)diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane, 26.7 g (100.3 mmol, 1.1 eq) of 5-chloro-2,3-diphenylpyrazine, 3.2 g (2.7 mmol, 0.03 eq) of Pd(PPh3)4, and 25.2 g (182.3 mmol, 2 eq) of K2CO3 were added to 650 ml of toluene, 180 ml of EtOH, and 180 ml of H2O, and heated and stirred under reflux for 8 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, adsorbed onto silica gel, and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 61-ii, 5-(3-((4-chlorophenyl)diphenylsilyl)phenyl)-2,3-diphenylpyrazine (43.8 g, yield 80%).

[0327] Mass: [(M+H) + ] : 602.11

[0328] NMR( 1 H): σ= 8.79(1H, s), 8.50(1H, d), 8.46(1H, s), 8.03(2H, d), 7.68-7.32(24H, m)

[0329] [Synthesis Example 23-3] Synthesis of Compound 61-i

[0330]

[0331] 43.8 g (72.9 mmol, 1 eq) of 5-(3-((4-chlorophenyl)diphenylsilyl)phenyl)-2,3-diphenylpyrazine and 22.2 g (87.5 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.7 g (3.6 mmol, 0.04 eq) of PdCl2(dppf), 7.0 g (14.6 mmol, 0.2 eq) of Xphos, and 17.2 g (175.0 mmol, 2 eq) of KOAc were added to 640 ml of 1,4-dioxane and heated and stirred under reflux for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 61-i, 5-(3-(diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-2,3-diphenylpyrazine (38.4 g, yield 76%).

[0332] Mass: [(M+H) + ] : 692.74

[0333] NMR( 1 H): σ= = 8.79(1H, s), 8.50(1H, d), 8.46(1H, s), 8.03(2H, d), 7.85(2H, d), 7.68(2H, d), 7.59(2H, d), 7.46-7.32(18H, m), 1.20(12H, s)

[0334] [Synthesis Example 23-4] Synthesis of Compound 61

[0335]

[0336] 38.4 g (55.4 mmol, 1 eq) of 5-(3-(diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-2,3-diphenylpyrazine and 16.3 g (61.0 mmol, 1.1 eq) of 2-chloro-4,6-diphenyl-1,3,5-triazine (intermediate A), 1.9 g (1.7 mmol, 0.03 eq) of Pd(PPh3)4, and 15.3 g (110.8 mmol, 2 eq) of K2CO3 were added to 550 ml of toluene, 150 ml of EtOH, and 150 ml of H2O, and heated and stirred under reflux for 8 hours. After the reaction was completed, the precipitated solid was filtered off with a sufficient amount of water and washed with sufficient water and MeOH. Next, it was adsorbed onto silica gel and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 61 (target compound B) as a white solid (36.3 g, yield 82%).

[0337] Mass: [(M+H) + ] : 798.04

[0338] [Synthesis Examples 24-28]

[0339] Except that the material of intermediate A in Synthesis Example 23 was changed as shown in Table 4 below, the same method as that for preparing compound 61 was performed to synthesize target compounds B of Synthesis Examples 24 to 28 as follows.

[0340] [Correction pursuant to Rule 91, 06.11.2024]

[0341] [Synthesis Example 29] Synthesis of Compound 81

[0342] [Correction pursuant to Rule 91, 06.11.2024]

[0343] [Synthesis Example 29-1] Synthesis of Compound 81-iii

[0344] ((3-bromophenyl)(3-chlorophenyl)diphenylsilane 50g (111.1mmol, 1eq) and 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 33.9g (133.4mmol, 1.2eq), PdCl2(dppf) 3.3g (4.4mmol, 0.04eq), KOAc 21.9g (222.3mmol, 2eq) were added to 750ml of 1,4-dioxane and heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, adsorbed on silica gel, and purified by column chromatography to obtain compound 81-iii, (3-chlorophenyl)diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (45.3 g, yield 82%) was obtained.

[0345] Mass: [(M+H) + ] : 496.91

[0346] NMR( 1 H): σ= 7.85(1H, d), 7.61(1H, s), 7.55(1H, s), 7.50-7.32(15H, m), 1,20(12H, s)

[0347] [Synthesis Example 29-2] Synthesis of Compound 81-ii

[0348] 45.3 g (91.1 mmol, 1 eq) of (3-chlorophenyl)diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane and 34.4 g (100.3 mmol, 1.1 eq) of 2-chloro-3,5,6-triphenylpyrazine, 3.2 g (2.7 mmol, 0.03 eq) of Pd(PPh3)4, and 25.2 g (182.3 mmol, 2 eq) of K2CO3 were added to 650 ml of toluene, 180 ml of EtOH, and 180 ml of H2O, and heated and stirred under reflux for 9 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, adsorbed onto silica gel, and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 81-ii, 2-(3-((3-chlorophenyl)diphenylsilyl)phenyl)-3,5,6-triphenylpyrazine (46.3 g, yield 75%).

[0349] Mass: [(M+H) + ] : 677.32

[0350] NMR( 1 H): σ= 8.50(1H, d), 8.44(1H, d), 8.03(6H, s), 7.66-7.59(6H, m), 7.46-7.32(19H, m)

[0351] [Synthesis Example 29-3] Synthesis of Compound 81-i

[0352] 46.3 g (68.4 mmol, 1 eq) of 2-(3-((3-chlorophenyl)diphenylsilyl)phenyl)-3,5,6-triphenylpyrazine and 20.8 g (82.0 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.5 g (3.4 mmol, 0.04 eq) of PdCl2(dppf), 6.5 g (13.7 mmol, 0.2 eq) of Xphos, and 16.1 g (164.1 mmol, 2 eq) of KOAc were added to 700 ml of 1,4-dioxane and heated and stirred under reflux for 8 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 81-i, 2-(3-(diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-3,5,6-triphenylpyrazine (40.5 g, yield 77%).

[0353] Mass: [(M+H) + ] : 768.84

[0354] NMR( 1 H): σ= = 88.50(1H, d), 8.44(1H, s), 8.03(6H, m), 7.85(1H, d), 7.66-7.59(6H, m), 7.45-7.32(18H, m), 1.20(12H, s)

[0355] [Synthesis Example 29-4] Synthesis of Compound 81

[0356] 40.5 g (52.6 mmol, 1 eq) of 2-(3-(diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-3,5,6-triphenylpyrazine and 15.5 g (57.9 mmol, 1.1 eq) of 2-chloro-4,6-diphenyl-1,3,5-triazine (intermediate A), 1.8 g (1.6 mmol, 0.03 eq) of Pd(PPh3)4, and 14.5 g (105.3 mmol, 2 eq) of K2CO3 were added to 600 ml of toluene, 180 ml of EtOH, and 180 ml of H2O, and heated and stirred under reflux for 6 hours. After the reaction was completed, the precipitated solid was filtered off with a sufficient amount of water and washed with sufficient water and MeOH. Next, it was adsorbed onto silica gel and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 81 (target compound B) as a white solid (36.8 g, yield 80%).

[0357] Mass: [(M+H) + ] : 874.14

[0358] [Synthesis Example 30] Synthesis of Compound 82

[0359]

[0360] [Synthesis Example 30-1] Synthesis of Compound 81-iii

[0361] 50 g (111.1 mmol, 1 eq) of (4-bromophenyl)(3-chlorophenyl)diphenylsilane and 33.9 g (133.4 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 3.3 g (4.4 mmol, 0.04 eq) of PdCl2(dppf), and 21.9 g (222.3 mmol, 2 eq) of KOAc were added to 750 ml of 1,4-dioxane and heated under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 82-iii, (3-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (44.2 g, yield 80%).

[0362] Mass: [(M+H) + ] : 496.91

[0363] NMR( 1 H): σ= 7.85(2H, d), 7.55(1H, s), 7.46-7.32(15H, m), 1,20(12H, s)

[0364] [Synthesis Example 30-2] Synthesis of Compound 82-ii

[0365] 44.2 g (88.9 mmol, 1 eq) of (3-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane, 33.5 g (97.8 mmol, 1.1 eq) of 2-chloro-3,5,6-triphenylpyrazine, 3.1 g (2.7 mmol, 0.03 eq) of Pd(PPh3)4, and 24.6 g (177.8 mmol, 2 eq) of K2CO3 were added to 650 ml of toluene, 180 ml of EtOH, and 180 ml of H2O, and heated and stirred under reflux for 9 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, adsorbed onto silica gel, and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 82-ii, 2-(4-((3-chlorophenyl)diphenylsilyl)phenyl)-3,5,6-triphenylpyrazine (47.6 g, yield 75%).

[0366] Mass: [(M+H) + ] : 677.32

[0367] NMR( 1 H): σ= 8.43(2H, d), 8.03(6H, d), 7.69(2H, d), 7.59-7.55(4H, m), 7.46-7.32(19H,m)

[0368] [Synthesis Example 30-3] Synthesis of Compound 81-i

[0369] 47.6 g (70.2 mmol, 1 eq) of 2-(4-((3-chlorophenyl)diphenylsilyl)phenyl)-3,5,6-triphenylpyrazine and 21.4 g (84.3 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.6 g (3.5 mmol, 0.04 eq) of PdCl2(dppf), 6.7 g (14.0 mmol, 0.2 eq) of Xphos, and 16.6 g (168.6 mmol, 2 eq) of KOAc were added to 700 ml of 1,4-dioxane and heated and stirred under reflux for 8 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 82-i, 2-(4-(diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-3,5,6-triphenylpyrazine (41.6 g, yield 77%).

[0370] Mass: [(M+H) + ] : 768.84

[0371] NMR( 1 H): σ= = 8.43(2H, d), 8.03(6H,d), 7.85(1H, d), 7.69(2H, d), 7.61-7.59(4H, m), 7.46-7.32(18H, m), 1.20(12H, s)

[0372] [Synthesis Example 30-4] Synthesis of Compound 82

[0373] 41.6 g (54.1 mmol, 1 eq) of 2-(4-(diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-3,5,6-triphenylpyrazine and 25.0 g (59.5 mmol, 1.1 eq) of 2-([1,1'-biphenyl]-4-yl)-4-(3-chlorophenyl)-6-phenyl-1,3,5-triazine (intermediate A), 1.9 g (1.6 mmol, 0.03 eq) of Pd(PPh3)4, and 15.0 g (108.2 mmol, 2 eq) of K2CO3 were added to 600 ml of toluene, 180 ml of EtOH, and 180 ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After the reaction was completed, the precipitated solid was filtered off with a sufficient amount of water and washed with sufficient water and MeOH. Next, it was adsorbed onto silica gel and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 81 (target compound B) as a white solid (42.1 g, yield 82%).

[0374] Mass: [(M+H) + ] : 950.23

[0375] [Synthesis Example 31] Synthesis of Compound 85

[0376]

[0377] [Synthesis Example 31-1] Synthesis of Compound 85-iii

[0378] 50 g (111.1 mmol, 1 eq) of (4-bromophenyl)(4-chlorophenyl)diphenylsilane and 33.9 g (133.4 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 3.3 g (4.4 mmol, 0.04 eq) of PdCl2(dppf), and 21.9 g (222.3 mmol, 2 eq) of KOAc were added to 750 ml of 1,4-dioxane and heated under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 85-iii, (4-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (44.7 g, yield 81%).

[0379] Mass: [(M+H) + ] : 496.91

[0380] NMR( 1 H): σ= 7.85(2H, d), 7.52-7.38(16H, m), 1,20(12H, s)

[0381] [Synthesis Example 31-2] Synthesis of Compound 85-ii

[0382] 44.7 g (90.0 mol, 1 eq) of (4-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane and 34.0 g (99.0 mmol, 1.1 eq) of 2-chloro-3,5,6-triphenylpyrazine, 3.1 g (2.7 mmol, 0.03 eq) of Pd(PPh3)4, and 24.6 g (180.1 ml, 2 eq) of K2CO3 were added to 650 ml of toluene, 180 ml of EtOH, and 180 ml of H2O, and heated and stirred under reflux for 8 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, adsorbed onto silica gel, and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 85-ii, 2-(3-((4-chlorophenyl)diphenylsilyl)phenyl)-3,5,6-triphenylpyrazine (45.7 g, yield 75%).

[0383] Mass: [(M+H) + ] : 602.11

[0384] NMR( 1 H): σ= 8.50(1H, d), 8.44(1H, s), 8.03(6H, d), 7.66-7.32(25H, m)

[0385] [Synthesis Example 31-3] Synthesis of Compound 85-i

[0386] 45.7 g (67.5 mmol, 1 eq) of 2-(3-((4-chlorophenyl)diphenylsilyl)phenyl)-3,5,6-triphenylpyrazine and 20.6 g (81.0 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.5 g (3.4 mmol, 0.04 eq) of PdCl2(dppf), 6.4 g (13.5 mmol, 0.2 eq) of Xphos, and 15.9 g (162.1 mmol, 2 eq) of KOAc were added to 620 ml of 1,4-dioxane and heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 85-i, 2-(3-(diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-3,5,6-triphenylpyrazine (40.0 g, yield 77%).

[0387] Mass: [(M+H) + ] : 692.74

[0388] NMR( 1 H): σ=8.50(1H, d), 8.44(1H, s), 8.03(6H, d), 7.85(2H, d), 7.68-7.59(5H, m), 7.46-7.32(18H, m), 1.20(12H, s)

[0389] [Synthesis Example 31-4] Synthesis of Compound 85

[0390] 40.0 g (52.0 mmol, 1 eq) of 2-(3-(diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-3,5,6-triphenylpyrazine and 15.3 g (57.2 mmol, 1.1 eq) of 2-chloro-4,6-diphenyl-1,3,5-triazine (intermediate A), 1.8 g (1.6 mmol, 0.03 eq) of Pd(PPh3)4, and 14.4 g (104.0 mmol, 2 eq) of K2CO3 were added to 600 ml of toluene, 150 ml of EtOH, and 150 ml of H2O, and heated and stirred under reflux for 8 hours. After the reaction was completed, the precipitated solid was filtered off with a sufficient amount of water and washed with sufficient water and MeOH. Next, it was adsorbed onto silica gel and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 85 (target compound B) as a white solid (37.3 g, yield 82%).

[0391] Mass: [(M+H) + ] : 874.14

[0392] [Synthesis Example 32] Synthesis of Compound 89

[0393]

[0394] [Synthesis Example 32-1] Synthesis of Compound 89-iii

[0395] 50 g (111.1 mmol, 1 eq) of (4-bromophenyl)(3-chlorophenyl)diphenylsilane and 33.9 g (133.4 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 3.3 g (4.4 mmol, 0.04 eq) of PdCl2(dppf), and 21.9 g (222.3 mmol, 2 eq) of KOAc were added to 750 ml of 1,4-dioxane and heated under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 89-iii, (3-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (44.2 g, yield 80%).

[0396] Mass: [(M+H) + ] : 496.91

[0397] NMR( 1 H): σ= 7.85(2H, d), 7.55(1H, s), 7.46-7.32(15H, m), 1,20(12H, s)

[0398] [Synthesis Example 32-2] Synthesis of Compound 89-ii

[0399] 44.2 g (88.9 mmol, 1 eq) of (3-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane and 33.5 g (97.8 mmol, 1.1 eq) of 5-(3-chlorophenyl)-2,3-diphenylpyrazine, 3.1 g (2.7 mmol, 0.03 eq) of Pd(PPh3)4, and 24.6 g (177.8 mmol, 2 eq) of K2CO3 were added to 650 ml of toluene, 180 ml of EtOH, and 180 ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, adsorbed onto silica gel, and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 89-ii, 5-(4'-((3-chlorophenyl)diphenylsilyl)-[1,1'-biphenyl]-3-yl)-2,3-diphenylpyrazine (46.4 g, yield 77%).

[0400] Mass: [(M+H) + ] : 677.32

[0401] NMR( 1 H): σ= 8.79(1H, s), 8.50(2H, d), 8.03(2H, d), 7.87(2H, d), 7.77(1H, d), 7.71(1H, d), 7.65-7.55(5H, m), 7.48-7.32(19H, m)

[0402] [Synthesis Example 32-3] Synthesis of Compound 89-i

[0403] 46.4 g (68.5 mmol, 1 eq) of 5-(4'-((3-chlorophenyl)diphenylsilyl)-[1,1'-biphenyl]-3-yl)-2,3-diphenylpyrazine and 20.9 g (82.2 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.5 g (3.4 mmol, 0.04 eq) of PdCl2(dppf), 6.5 g (13.7 mmol, 0.2 eq) of Xphos, and 16.2 g (164.3 mmol, 2 eq) of KOAc were added to 700 ml of 1,4-dioxane and heated and stirred under reflux for 8 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 89-i, 5-(4'-(diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)-[1,1'-biphenyl]-3-yl)-2,3-diphenylpyrazine (39.0 g, yield 74%).

[0404] Mass: [(M+H) + ] : 768.84

[0405] NMR( 1 H): σ= = 8.79(1H, s), 8.50(2H, d), 8.03(2H, d), 7.87-7.85(3H, m), 7.77(1H, d), 7.71(1H, d), 7.65-7.55(5H, m), 7.48-7.32(18H, m), 1.20(12H, s)

[0406] [Synthesis Example 32-4] Synthesis of Compound 89

[0407] 39.0 g (50.7 mmol, 1 eq) of 5-(4'-(diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)-[1,1'-biphenyl]-3-yl)-2,3-diphenylpyrazine and 14.9 g (55.7 mmol, 1.1 eq) of 2-chloro-4,6-diphenyl-1,3,5-triazine (intermediate A), 1.8 g (1.5 mmol, 0.03 eq) of Pd(PPh3)4, and 14.0 g (101.3 mmol, 2 eq) of K2CO3 were added to 550 ml of toluene, 160 ml of EtOH, and 160 ml of H2O, and heated and stirred under reflux for 6 hours. After the reaction was completed, the precipitated solid was filtered off with a sufficient amount of water and washed with sufficient water and MeOH. Next, it was adsorbed onto silica gel and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 89 (target compound B) as a white solid (36.3 g, yield 82%).

[0408] Mass: [(M+H) + ] : 874.14

[0409] [Synthesis Example 33] Synthesis of Compound 90

[0410]

[0411] [Synthesis Example 33-1] Synthesis of Compound 90-iii

[0412] 50 g (111.1 mmol, 1 eq) of (4-bromophenyl)(4-chlorophenyl)diphenylsilane and 33.9 g (133.4 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 3.3 g (4.4 mmol, 0.04 eq) of PdCl2(dppf), and 21.9 g (222.3 mmol, 2 eq) of KOAc were added to 750 ml of 1,4-dioxane and heated under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 90-iii, (4-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (44.7 g, yield 81%).

[0413] Mass: [(M+H) + ] : 496.91

[0414] NMR( 1 H): σ= 7.85(2H, d), 7.52-7.38(16H, m), 1,20(12H, s)

[0415] [Synthesis Example 33-2] Synthesis of Compound 90-ii

[0416] 44.7 g (90.0 mol, 1 eq) of (4-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane and 34.0 g (99.0 mmol, 1.1 eq) of 5-(3-chlorophenyl)-2,3-diphenylpyrazine, 3.1 g (2.7 mmol, 0.03 eq) of Pd(PPh3)4, and 24.6 g (180.1 ml, 2 eq) of K2CO3 were added to 650 ml of toluene, 180 ml of EtOH, and 180 ml of H2O, and heated and stirred under reflux for 8 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, adsorbed onto silica gel, and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 90-ii, 5-(4'-((4-chlorophenyl)diphenylsilyl)-[1,1'-biphenyl]-3-yl)-2,3-diphenylpyrazine (45.7 g, yield 75%).

[0417] Mass: [(M+H) + ] : 677.32

[0418] NMR( 1 H): σ= 8.79(1H, d), 8.50(2H, d), 8.03(2H, d), 7.87-7.85(4H, m), 7.77(1H, d), 7.71(1H, s), 7.65-7.32(22H, m)

[0419] [Synthesis Example 33-3] Synthesis of Compound 90-i

[0420] 45.7 g (67.5 mmol, 1 eq) of 5-(4'-((4-chlorophenyl)diphenylsilyl)-[1,1'-biphenyl]-3-yl)-2,3-diphenylpyrazine and 20.6 g (81.0 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.5 g (3.4 mmol, 0.04 eq) of PdCl2(dppf), 6.4 g (13.5 mmol, 0.2 eq) of Xphos, and 15.9 g (162.1 mmol, 2 eq) of KOAc were added to 650 ml of 1,4-dioxane and heated and stirred under reflux for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 90-i, 5-(4'-(diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)-[1,1'-biphenyl]-3-yl)-2,3-diphenylpyrazine (40.0 g, yield 77%).

[0421] Mass: [(M+H) + ] : 768.84

[0422] NMR( 1 H): σ= 8.79(1H, s), 8.50(2H, d), 8.03(2H, d), 7.87-7.85(4H, m), 7.77-7.59(6H, m), 7.59-7.32(18H, m), 1.20(12H, s)

[0423] [Synthesis Example 33-4] Synthesis of Compound 90

[0424] 40.0 g (52.0 mmol, 1 eq) of 5-(4'-(diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)-[1,1'-biphenyl]-3-yl)-2,3-diphenylpyrazine and 15.3 g (57.2 mmol, 1.1 eq) of 2-chloro-4,6-diphenyl-1,3,5-triazine (intermediate A), 1.8 g (1.6 mmol, 0.03 eq) of Pd(PPh3)4, and 14.4 g (104.0 mmol, 2 eq) of K2CO3 were added to 600 ml of toluene, 150 ml of EtOH, and 150 ml of H2O, and the mixture was heated and stirred under reflux for 8 hours. After the reaction was completed, the precipitated solid was filtered off with a sufficient amount of water and washed with sufficient water and MeOH. Next, it was adsorbed onto silica gel and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 90 (target compound B) as a white solid (36.4 g, yield 80%).

[0425] Mass: [(M+H) + ] : 874.14

[0426] [Synthesis Example 34] Synthesis of Compound 118

[0427]

[0428] [Synthesis Example 34-1] Synthesis of Compound 118-iii

[0429] 50 g (111.1 mmol, 1 eq) of (4-bromophenyl)(3-chlorophenyl)diphenylsilane and 33.9 g (133.4 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 3.3 g (4.4 mmol, 0.04 eq) of PdCl2(dppf), and 21.9 g (222.3 mmol, 2 eq) of KOAc were added to 750 ml of 1,4-dioxane and heated under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 118-iii, ((3-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane (44.2 g, yield 80%).

[0430] Mass: [(M+H) + ] : 496.91

[0431] NMR( 1 H): σ= 7.85(2H, d), 7.55(1H, s), 7.46-7.32(15H, m), 1,20(12H, s)

[0432] [Synthesis Example 34-2] Synthesis of Compound 118-ii

[0433] 44.2 g (88.9 mmol, 1 eq) of (3-chlorophenyl)diphenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane and 31.0 g (97.8 mmol, 1.1 eq) of 5-chloro-2-(naphthalen-2-yl)-3-phenylpyrazine, 3.1 g (2.7 mmol, 0.03 eq) of Pd(PPh3)4, and 24.6 g (177.8, 2 eq) of K2CO3 were added to 650 ml of toluene, 180 ml of EtOH, and 180 ml of H2O, and heated and stirred under reflux for 8 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, adsorbed onto silica gel, and purified by column chromatography. After concentration, the solid obtained by stirring in a small amount of EA and hexane was filtered to obtain compound 118-ii, 5-(4-((3-chlorophenyl)diphenylsilyl)phenyl)-2-(naphthalen-2-yl)-3-phenylpyrazine (38.2 g, yield 66%).

[0434] Mass: [(M+H) + ] : 651.28

[0435] NMR( 1 H): σ= 9.02(1H, d), 8.79(1H, s), 8.54(1H, d), 8.43(2H, d), 8.10-8.00(5H, m), 7.69(2H, d), 7.61-7.32(19H, m)

[0436] [Synthesis Example 34-3] Synthesis of Compound 118-i

[0437] 38.2 g (58.7 mmol, 1 eq) of 5-(4-((3-chlorophenyl)diphenylsilyl)phenyl)-2-(naphthalen-2-yl)-3-phenylpyrazine and 17.9 g (70.4 mmol, 1.2 eq) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.1 g (2.9 mmol, 0.04 eq) of PdCl2(dppf), 5.6 g (11.7 mmol, 0.2 eq) of Xphos, and 13.9 g (140.8 mmol, 2 eq) of KOAc were added to 550 ml of 1,4-dioxane and heated and stirred under reflux for 8 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 118-i, 5-(4-(diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-2-(naphthalen-2-yl)-3-phenylpyrazine (33.1 g, yield 76%).

[0438] Mass: [(M+H) + ] : 742.80

[0439] NMR( 1 H): σ= 9.02(1H, s), 8.79(1H, s), 8.54(1H, d), 8.43(2H, d), 8.10-8.00(5H, m), 7.85(1H, d), 7.69(2H, d), 7.61-7.59(4H, m), 7.46-7.32(14H, m), 1.20(12H, s)

[0440] [Synthesis Example 34-4] Synthesis of Compound 118

[0441] 33.1 g (44.6 mmol, 1 eq) of 5-(4-(diphenyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silyl)phenyl)-2-(naphthalen-2-yl)-3-phenylpyrazine and 13.1 g (49.1 mmol, 1.1 eq) of 2-chloro-4,6-diphenyl-1,3,5-triazine (intermediate A), 1.5 g (1.3 mmol, 0.03 eq) of Pd(PPh3)4, and 12.3 g (89.2 mmol, 2 eq) of K2CO3 were added to 500 ml of toluene, 140 ml of EtOH, and 140 ml of H2O, and heated and stirred under reflux for 8 hours. After the reaction was completed, the precipitated solid was filtered off with a sufficient amount of water and washed with sufficient water and MeOH. Next, it was adsorbed onto silica gel and purified by column chromatography. After concentration, the solid obtained by stirring with a small amount of EA and hexane was filtered to obtain compound 118 (target compound B) as a white solid (29.1 g, yield 77%).

[0442] Mass: [(M+H) + ] : 848.10

[0443]

[0444] [Reference example]

[0445] The structures of compounds HI, HAT-CN6, EB, BH, BD, Liq, Alq3 E-1, E-2, E-3, E-4, and E-5 used in Examples 1 to 66 and Comparative Examples 1 to 12 are as follows, respectively.

[0446]

[0447]

[0448] [Examples 1 to 34] Fabrication of blue organic electroluminescent devices

[0449] After the compound synthesized in the above synthetic example was purified by high purity sublimation using a commonly known method, a blue organic electroluminescent device was manufactured using it as an electron transport layer material according to the process below.

[0450] First, a glass substrate coated with a 1200 Å thick ITO (Indium Tin Oxide) film was ultrasonically cleaned in distilled water. After the distilled water cleaning was completed, 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.

[0451] On the ITO transparent electrode prepared as above, an organic electroluminescent device was manufactured by stacking HI + 2% HAT-CN6 (10 nm) / HI (140 nm) / EB (5 nm) / BH + 2% BD (20 nm) / electron transport layer material of Table 1 + Liq (1:1) (30 nm) / LiF (1 nm) / Al (100 nm) in that order.

[0452]

[0453] [Comparative Examples 1 to 6] Manufacturing of blue organic electroluminescent devices

[0454] Blue organic electroluminescent devices of Comparative Examples 1 to 6 were manufactured in the same manner as in Example 1, except that Alq3, E-1, E-2, E-3, E-4, and E-5 were used instead of Compound 1 as the electron transport layer material.

[0455]

[0456] [Evaluation Example 1]

[0457] For the organic electroluminescent devices manufactured in Examples 1 to 34 and Comparative Examples 1 to 6, the driving voltage, emission wavelength, and current efficiency at a current density of 10 mA / cm2 were measured, and the results are shown in Table 5 below.

[0458] Sample Electron Transport Layer Material Driving Voltage (V) Luminescence Peak (nm) Current Efficiency (cd / A) Example 1 Compound 13.44548.0 Example 2 Compound 23.24558.1 Example 3 Compound 33.34558.3 ​​Example 4 Compound 53.44538.2 Example 5 Compound 83.34548.4 Example 6 Compound 93.44548.5 Example 7 Compound 113.24538.2 Example 8 Compound 123.34558.3 ​​Example 9 Compound 143.34548.2 Example 10 Compound 173.54557.9 Example 11 Compound 193.44548.3 Example 12 Compound 213.44557.9 Example 13 Compound 223.34568.0 Example 14 Compound 253.34548.1 Example 15 Compound 283.34538.2 Example 16 Compound 313.44538.1 Example 17 Compound 403.44548.3 Example 18 Compound 413.24557.8 Example 19 Compound 453.24547.9 Example 20 Compound 483.24558.1 Example 21 Compound 493.34568.1 Example 22 Compound 513.14538.3 Example 23 Compound 613.44538.0 Example 24 Compound 633.34548.3 Example 25 Compound 653.44548.2 Example 26 Compound 663.34538.2 Example 27 Compound 713.34568.4 Example 28 Compound 773.54558.4 Example 29 Compound 813.54538.2 Example 30 Compound 823.34538.4 Example 31 Compound 853.44558.1 Example 32 Compound 893.34538.3 Example 33 Compound 903.24548.3 Example 34 Compound 1183.34568.2Comparative Example 1Alq34.64575.6Comparative Example 2E-14.34576.6Comparative Example 3E-24.74607.0Comparative Example 4E-34.54596.2Comparative Example 5E-43.54557.5Comparative Example 6E-54.64557.7

[0459]

[0460] As shown in Table 5 above, it was confirmed that the organic electroluminescent devices of Examples 1 to 34 using the compounds according to the present invention as electron transport layer materials were far superior in terms of driving voltage, emission peak, and current efficiency compared to the blue organic electroluminescent devices of Comparative Examples 1 to 6 using compounds E-1 to E-4, which do not include the essential components of the present invention and conventional Alq3, as electron transport layer materials.

[0461]

[0462] [Examples 35 to 68] Fabrication of blue organic electroluminescent devices

[0463] After the compound synthesized in the above synthetic example was purified by high purity sublimation using a commonly known method, a blue organic electroluminescent device was manufactured using it as an electron transport auxiliary layer material according to the process below.

[0464] First, a glass substrate coated with a 1200 Å thick ITO (Indium Tin Oxide) film was ultrasonically cleaned in distilled water. After the distilled water cleaning was completed, 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.

[0465] On the ITO transparent electrode prepared as above, an organic electroluminescent device was manufactured by stacking HI + 2% HAT-CN6 (10 nm) / HI (140 nm) / EB (5 nm) / BH + 2% BD (20 nm) / electron transport auxiliary layer material (5 nm) of Table 1 / ET + Liq (1:1) (30 nm) / LiF (1 nm) / Al (100 nm) in that order.

[0466]

[0467] [Comparative Examples 7 to 12] Manufacturing of blue organic electroluminescent devices

[0468] Blue organic electroluminescent devices of Comparative Examples 7 to 12 were manufactured in the same manner as in Example 35, except that the electron transport auxiliary layer was not included instead of Compound 1 as the electron transport auxiliary layer material, or Compounds E-1 to E-5 were used.

[0469]

[0470] [Evaluation Example 2]

[0471] For the organic electroluminescent devices manufactured in Examples 35 to 68 and Comparative Examples 7 to 12, the driving voltage, emission wavelength, and current efficiency at a current density of 10 mA / cm2 were measured, and the results are shown in Table 6 below.

[0472] Sample Electron Transport Auxiliary Layer Material Driving Voltage (V) Luminescence Peak (nm) Current Efficiency (cd / A) Example 35 Compound 13.44538.2 Example 36 Compound 23.24528.3 Example 37 Compound 33.34538.5 Example 38 Compound 53.34518.3 Example 39 Compound 83.24538.5 Example 40 Compound 93.34538.6 Example 41 Compound 113.24528.3 Example 42 Compound 123.44548.3 Example 43 Compound 143.34538.3 Example 44 Compound 173.44548.1 Example 45 Compound 193.34538.4 Example 46 Compound 213.34527.9 Example 47 Compound 223.24548.1 Example 48 Compound 253.34538.2 Example 49 Compound 283.24538.3 Example 50 Compound 313.34548.3 Example 51 Compound 403.44538.4 Example 52 Compound 413.34537.9 Example 53 Compound 453.14558.0 Example 54 Compound 483.14538.2 Example 55 Compound 493.24558.1 Example 56 Compound 513.14518.4 Example 57 Compound 613.34538.1 Example 58 Compound 633.24538.3 Example 59 Compound 653.34558.3 ​​Example 60 Compound 663.44528.4 Example 61 Compound 713.44548.5 Example 62 Compound 773.34528.5 Example 63 Compound 813.44528.4 Example 64 Compound 823.24548.5 Example 65 Compound 853.34518.2 Example 66 Compound 893.34538.4 Example 67 Compound 903.44528.4 Example 68 Compound 1183.44538.3Comparative Example 7-4.94575.3Comparative Example 8E-14.34566.7Comparative Example 9E-24.84587.2Comparative Example 10E-34.64576.3Comparative Example 11E-43.54547.4Comparative Example 12E-54.94547.9

[0473]

[0474] As shown in Table 6 above, it was confirmed that the organic electroluminescent devices of Examples 35 to 68 using the compounds according to the present invention as electron transport auxiliary layer materials were superior in terms of driving voltage, emission peak, and current efficiency of the devices compared to the organic electroluminescent devices of Comparative Examples 7 to 12 using the compounds of conventional E-1 to E-5 which do not include an electron transport auxiliary layer or do not include the essential components of the present invention as electron transport auxiliary layer materials. Looking at the results of Tables 5 and 6 described above, it was confirmed that when the silane-based compound according to the present invention was used as an electron transport layer material, the driving voltage of the device was improved, and further, when the compound was used as an electron transport auxiliary layer material, the efficiency improvement range of the device was significantly increased.

[0475] More specifically, it was confirmed that the compounds according to the present invention, in which triazine and pyrazine are substituted as Dual EWG units, exhibited superior properties compared to compounds ET-1 to ET-5 used as comparative examples.

[0476] For example, it was confirmed that the device of the embodiment including a compound having Dual EWG groups on both sides of a silyl group according to the present invention has excellent driving voltage characteristics compared to the devices of Comparative Examples 2-4 and 8-10 using compounds of E-1 to E-3 as electron transport layer / electron transport auxiliary layer materials. This is presumed to be because the materials of the conventional E-1 to E-3 have an EWG group on one side of the silyl group formed of an SP3 orbital, and an arylene group, which increases the molecular size but does not increase electron mobility, is substituted on the other side, so that they do not have appropriate electron mobility.

[0477] Meanwhile, in Comparative Examples 5 and 11, where the compound of E-4 having two triazines as Dual EWG groups on both sides of the silyl group was used as an electron transport layer / electron transport auxiliary layer material, the device of the present invention exhibited similar operating voltage characteristics to the example, but poor efficiency characteristics. This is because the compound of the present invention has a high triplet (T1) energy level resulting from structural asymmetry due to the introduction of different Dual EWG groups, such as triazine and pyrazine, on both sides of the silyl group, and the low-voltage characteristics of pyrazine, thereby exerting the effect of lowering the operating voltage of the device, while at the same time further enhancing the strong electron-withdrawing characteristics of the azine group, thereby significantly improving the high-efficiency characteristics of the device. In particular, since the compound according to the present invention has an asymmetric structure, it has an advantageous aspect in terms of processability because it has no Tc (Crystallization Temp.) in thermal characteristics.

[0478] In addition, as a result of comparing Comparative Examples 2 and 6 and Comparative Examples 8 and 12 in which compounds of E-1 and E-5 were used as electron transport layer / electron transport auxiliary layer materials, it was confirmed that while the efficiency characteristics of the device can be improved when the number of silyl groups in the molecule increases, the volume of the structure increases, which hinders the flow of electrons and results in an unfavorable driving voltage.

[0479] In addition, as a result of comparing Comparative Examples 8 to 10 and 12 using compounds of E-1 to E-3 and E-5 as electron transport auxiliary layer materials, it was found that while the characteristics of the silyl group are helpful in improving the efficiency characteristics of the device as an electron transport auxiliary layer, they are disadvantageous in terms of driving voltage, and in the case of Comparative Example 11 using the compound of E-4 as an electron transport auxiliary layer material, it is judged that the symmetrical structure due to two triazines results in a low triplet energy level and unstable thermal characteristics, resulting in a lower overall efficiency of the device compared to the effect of improving the driving voltage of the device.

Claims

1. A compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, Ar1 to Ar3 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~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, but cases where at least two of Ar1 to Ar3 are hydrogen are excluded, X1 to X5 are the same or different from each other, and are each independently C(R1) or N, provided that at least two of X1 to X5 are N, When there are multiple R1s, the multiple R1s are the same or different, and each independently represents 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 and C6~C 60 is selected from the group consisting of arylamine groups, wherein two of the plurality of R1 are represented by B1 and B2, A1 to A2 and B1 to B2 are the same or different from each other, and each independently represents hydrogen, deuterium (D), C1 to 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, 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, d and e are each independently integers from 0 to 4, The arylene group and heteroarylene group of the above L1 to L2, and the above Ar1 to Ar3, R 1, The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkylboron group, arylborone group, phosphine group, phosphine oxide group, and arylamine group of A1 to A2, B1 to B2 are each independently selected from the group consisting of 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 40 Alkyloxy 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 and C6~C 60 It may be substituted with one or more substituents selected from the group consisting of arylamine groups, and in this case, when there are multiple substituents, they may be the same or different from each other.

2. In paragraph 1, The above X1 to X5 containing ring is a compound selected from the following structural formulas: In the above formula, * indicates a part connected to the above chemical formula 1, R1, B1 and B2 are each as defined in paragraph 1.

3. In paragraph 1, A1 to A2 and B1 to B2 are the same or different from each other, and are each independently C6 to C 60 A compound selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms.

4. In paragraph 1, A1 to A2 and B1 to B2 are the same or different from each other, and are each independently a compound selected from the following structural formulas: In the above formula, * indicates a part connected to the above chemical formula 1, R2 is hydrogen, deuterium (D), C1~C 40 Alkyl group of C6~C 60 It is selected from the group consisting of an aryl group and a heteroarylene group having 5 to 18 nuclear atoms.

5. In paragraph 1, Ar1 to Ar3 are the same or different from each other, and each independently represents hydrogen, deuterium (D), C1~C 40 Alkyl group of C6~C 60 A compound selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms, except that cases where at least two of Ar1 to Ar3 are hydrogen are excluded.

6. In paragraph 1, Ar1 to Ar3 are the same or different from each other, and are each independently a compound selected from the following structural formulas: In the above formula, * indicates a part connected to the above chemical formula 1, R3 is hydrogen, deuterium (D), C1~C 40 Alkyl group of C6~C 60 It is selected from the group consisting of an aryl group and a heteroarylene group having 5 to 18 nuclear atoms.

7. In paragraph 1, L1 and L2 are the same or different from each other, and are each independently 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, The compound represented by the above chemical formula 1 is a compound represented by the following chemical formula 2: [Chemical Formula 2] In the above formula, X1 to X5, Ar1 to Ar3, A1 to A2, B1 to B2, d and e are each as defined in paragraph 1.

9. In paragraph 8, In the above chemical formula 2 and are identical or different from each other, and each independently selected from the following structural formulae: In the above formula, * indicates a part connected to the above chemical formula 2.

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 3 to 5: [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] In the above formula, X1 to X5, Ar1 to Ar3, A1 to A2, B1 to B2, d and e are each as defined in paragraph 1.

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 6a to 6l: [Chemical Formula 6a] [Chemical Formula 6b] [Chemical formula 6c] [Chemical formula 6d] [Chemical Formula 6e] [Chemical formula 6f] [Chemical formula 6g] [Chemical formula 6h] [Chemical formula 6i] [Chemical formula 6j] [Chemical formula 6k] [Chemical formula 6l] In the above formula, Ar1 to Ar3, A1 to A2, B1 to B2, R1, and d are each as defined in paragraph 1.

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 7 to 9: [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] In the above formula, X1 to X5, Ar1 to Ar3, A1 to A2, B1 to B2, d and e are each as defined in paragraph 1.

13. In paragraph 1, The compound represented by the above chemical formula 1 is a compound represented by any one of the following chemical formulas 10a to 10l: [Chemical Formula 10a] [Chemical Formula 10b] [Chemical formula 10c] [Chemical Formula 10d] [Chemical Formula 10e] [Chemical formula 10f] [Chemical formula 10g] [Chemical formula 10h] [Chemical formula 10i] [Chemical formula 10j] [Chemical Formula 10k] [Chemical formula 10l] In the above formula, X1 to X5, Ar1 to Ar3, A1 to A2, B1 to B2, and e are each as defined in paragraph 1.

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 11 to 14: [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] In the above formula, Ar1 to Ar3, A1 to A2, B1 to B2, d and e are each as defined in paragraph 1.

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 15 to 18: [Chemical Formula 15] [Chemical Formula 16] [Chemical Formula 17] [Chemical Formula 18] In the above formula, X1 to X5, Ar1 to Ar3, A1 to A2, B1 to B2, L1 to L2, d and e are each as defined in paragraph 1, except that the case where Ar1 to Ar3 are hydrogen is excluded.

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 128.

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, a light-emitting auxiliary 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 17.

19. In paragraph 18, An organic electroluminescent device, wherein the organic layer including 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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