Organic light-emitting compound and organic electroluminescent device comprising same

Abstract

The present invention relates to a novel compound having excellent carrier transport capability, light emission capability, and thermal stability, and an organic electroluminescent device having improved characteristics such as light emission efficiency, driving voltage, and lifespan by including the compound in one or more organic material layers, and to an organic electroluminescent device.

Description

Technical Field

[0001] The present invention relates to a novel organic compound and an organic electroluminescent device using the same, and more particularly, to a novel compound and an organic electroluminescent device. The novel compound has excellent carrier transport capability, luminescence capability and heat resistance. The organic electroluminescent device improves luminescence efficiency, driving voltage, life and other characteristics by including the compound in more than one organic layer. Background Art

[0002] Starting from Bernanose's observation of organic thin film luminescence in the 1950s, the research on organic electroluminescent devices using blue electroluminescence of anthracene single crystals developed in 1965, and Tang proposed an organic electroluminescent device with a stacked structure of functional layers divided into a hole layer and a light-emitting layer in 1987. Then, in order to prepare high-efficiency and long-life organic electroluminescent devices, it developed into a form of introducing various characteristic organic layers into the device, thereby developing special substances for this purpose.

[0003] For an organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground state, light is emitted. In this case, the substances used as the organic layer can be divided into luminescent substances, hole injection substances, hole transport substances, electron transport substances, electron injection substances, etc. according to their functions.

[0004] The light-emitting layer materials of organic electroluminescent devices can be divided into blue, green, and red light-emitting materials according to the light-emitting color. In addition, yellow and orange light-emitting substances are also used as light-emitting materials to achieve better natural colors. In addition, in order to increase the color purity and the luminescence efficiency through energy transfer, a host / dopant system can be used as a light-emitting material. The above-mentioned doping substances can be divided into fluorescent dopants using organic substances and phosphorescent dopants using metal coordination compounds containing heavy atoms (heavy atoms) such as Ir and Pt. Compared with fluorescence, the development of such phosphorescent materials can theoretically increase the luminescence efficiency by up to 4 times, so not only phosphorescent dopants but also phosphorescent host materials have attracted much attention. So far, it is well known that NPB, BCP, Alq 3 As materials used in hole injection layer, hole transport layer, hole group separation layer, electron transport layer, and as luminescent materials, anthracene derivatives have been reported as fluorescent dopants / host materials. In particular, Firpic, Ir(ppy) 3 、(acac)Ir(btp) 2Metal complexes containing Ir are used as phosphorescent materials with great advantages in improving efficiency among luminescent materials as blue, green, and red dopant materials. So far, CBP has shown excellent characteristics as a phosphorescent host material.

[0005] However, existing luminescent materials have advantages in luminescent properties, but due to low glass transition temperature and very poor thermal stability, they cannot achieve a satisfactory level in terms of the life of organic electroluminescent devices. Therefore, it is necessary to develop luminescent materials with excellent properties.

[0006] On the other hand, the natural abundance of deuterium is about 0.015%. It is well known that the deuterium concentration of deuterated compounds is abundant. Deuterated aromatic compounds are used to study chemical reactions and metabolic pathways, and are also used as raw materials for drugs, agricultural chemicals, functional substances and analytical tracers. It is reported that compared with undeuterated isomers, some deuterated electroluminescent materials show improved performance (efficiency, lifespan) (for example, with reference to Tong, et al. J. Phys. Chem. C 2007, 111, 3490-4). At present, the method for synthesizing deuterated compounds may require multiple treatments to achieve a high level of deuteration. Since this method requires high cost or consumes time, it is not suitable in terms of cost and efficiency. Therefore, there is a constant need for an improved preparation method for synthesizing deuterated aromatic compounds. Summary of the invention

[0007] Technical issues

[0008] The present invention is proposed to solve the above-mentioned problems. More specifically, its technical problem is to provide a new type of compound which has excellent carrier transport ability, luminescence ability, heat resistance, etc., and can therefore be used as an organic layer material of an organic electroluminescent device, specifically, as a main material of the light-emitting layer.

[0009] Furthermore, another technical problem of the present invention is to provide an organic electroluminescent device, which comprises the novel compound and thus has low driving voltage, high luminous efficiency and improved lifespan.

[0010] Other objects and advantages of the present invention will be more clearly described through the following detailed description of the invention and the scope of protection claimed in the invention.

[0011] Technical Solution

[0012] In order to solve the above technical problems, the present invention provides a compound represented by the following chemical formula 1, specifically a deuterated tris carbazole compound.

[0013] Chemical formula 1:

[0014]

[0015] In the above chemical formula 1,

[0016] Ar 1 and Ar 2 are the same as or different from each other and are independently selected from C 1 ~C 40 Alkyl, C 2 ~C 40 The alkenyl group, C 2 ~C 40 Alkynyl, C 6 ~C 40 aryl, heteroaryl having 5 to 40 nuclear atoms, C 6 ~C 40 The aryloxy group, C 1 ~C 40 Alkoxy, C 6 ~C 40 The aromatic amine group, C 3 ~C 40 Cycloalkyl, heterocycloalkyl having 3 to 40 nuclear atoms, C 1 ~C 40 Alkylsilyl, C 1 ~C 40 Alkylboryl, C 6 ~C 40 Arylboryl, C 6 ~C 40 Arylphosphino, C 6 ~C 40 Arylphosphine oxide group and C 6 ~C 40 In the group consisting of arylsilyl groups,

[0017] a, d and f are each independently 1 to 3,

[0018] b, c, e are each independently 1 to 4, but a+b+c+d+e+f≥15,

[0019] The hydrogen on the benzene ring of the deuterium (D) unsubstituted carbazole can be selected from C 1 ~C 40 Alkyl, C 6 ~C 40 substituted with a substituent selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms,

[0020] The above Ar 1 ~Ar 2The alkyl, alkenyl, alkynyl, aryl, heteroaryl, aryloxy, alkoxy, arylamine, cycloalkyl, heterocycloalkyl, alkylsilyl, alkylboryl, arylboryl, arylphosphino, arylphosphine oxide and arylsilyl groups are each independently selected from deuterium (D), halogen, cyano, nitro, C 1 ~C 40 Alkyl, C 2 ~C 40 The alkenyl group, C 2 ~C 40 Alkynyl, C 3 ~C 40 Cycloalkyl, heterocycloalkyl having 3 to 40 nuclear atoms, C 6 ~C 40 aryl, heteroaryl having 5 to 40 nuclear atoms, C 1 ~C 40 Alkoxy, C 6 ~C 60 The aryloxy group, C 1 ~C 40 Alkylsilyl, C 6 ~C 40 Arylsilyl, C 1 ~C 40 Alkylboryl, C 6 ~C 40 Arylboryl, C 6 ~C 40 Arylphosphino, C 6 ~C 40 Arylphosphine oxide group and C 6 ~C 40 The aromatic amine group may be substituted or unsubstituted with one or more substituents. When a plurality of such substituents are present, they may be the same as or different from each other.

[0021] Furthermore, the present invention provides an organic electroluminescent device, which includes an anode, a cathode, and one or more organic layers between the anode and the cathode, wherein at least one of the one or more organic layers contains the compound represented by the above Chemical Formula 1.

[0022] In one embodiment, the above-mentioned one or more organic layers may include at least one 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, an electron transport layer and an electron transport auxiliary layer, and the above-mentioned light-emitting layer may contain the above-mentioned compound represented by Chemical Formula 1 as a main body.

[0023] In one embodiment, the electron transport layer may include an electron transport compound having at least two electron withdrawing groups (EWG).

[0024] Effects of the Invention

[0025] In one embodiment of the present invention, since the compound represented by the above Chemical Formula 1 has excellent carrier transport capability, luminescence capability, heat resistance, etc., it can be used as an organic layer material of an organic electroluminescent device.

[0026] In particular, when the compound represented by Chemical Formula 1 of the present invention is used as a host of a light-emitting layer, it can exhibit high thermal stability, low driving voltage, fast mobility, high current efficiency, and long life characteristics compared to conventionally known host materials.

[0027] Therefore, the organic electroluminescent device including the compound represented by the above Chemical Formula 1 can be significantly improved in terms of excellent luminescent properties, low driving voltage, long life, and high efficiency, and thus can be effectively applied to full-color display panels.

[0028] The effects of the present invention are not limited to the contents of the above-mentioned examples, and more various effects are included in this specification. DETAILED DESCRIPTION

[0029] Hereinafter, the present invention will be described in detail.

[0030] <Organic compounds>

[0031] The present invention aims to provide a novel electroluminescent material comprising at least three carbazole groups (Cz), and improving the carrier transport capability, luminescence capability and chemical structure stability by deuterium (D) substitution of the carbazole groups, thereby simultaneously achieving device characteristics, such as low voltage, high efficiency and long life characteristics of the device.

[0032] Specifically, the compound represented by Chemical Formula 1 of the present invention has a basic skeleton structure that must contain at least 3 carbazole groups (Cz) and at least 15 substituted deuteriums (D) in the above carbazole groups. This compound is a new type of P-type host composed of triscarbazole, which has a stronger hole character than the existing host material, so the performance of the N-type host can be maximized. Moreover, compared with the existing P-type host material, it has excellent hole stability, so it can continue to maintain stable life characteristics even in the initial characteristics of the device. Therefore, when having a P-type host composed of at least 3 carbazole groups, a high-performance OLED device can be prepared by improving the hole stability of the device itself.

[0033] On the other hand, in terms of potential energy, compared with hydrogen (H), deuterium (Deuterium, D) has higher molecular mass and lower zero-point energy, making the dissociation of deuterium in the reaction relatively more difficult. Due to this low zero-point energy, bond dissociation energy increases and as reactivity decreases, so that the stability of the molecule comprising deuterium increases (Molecules 2014, 19Chem.Commun., 2014, 50, 14870-14872J.Org.Chem.2004, 69, 7212-7219). Therefore, compared with the compound of the same structure not comprising deuterium, comprising at least 3 carbazolyls, and substituted with at least 15 deuteriums (D) in the above-mentioned carbazolyls The compound represented by Chemical Formula 1 of the present invention can maximize the color purity of green, further increase the intramolecular bonding force between the weakened carbon-hydrogen, and enhance the stability of the material, so that the life characteristics of the device can be significantly improved.

[0034] Moreover, in the present invention, a dual electron withdrawing group type (dual EWG type) electron transport layer having high electron transport ability due to at least two EWG groups is used in combination while constituting the light-emitting layer including the compound represented by Chemical Formula 1, thereby optimizing the performance of the organic electroluminescent device by enhancing the hole stability of the light-emitting layer (EML) and maximizing the electron transport ability of the electron transport layer (ETL).

[0035] Specifically, the compound represented by Chemical Formula 1 of the present invention has a basic skeleton structure that must contain at least 3 carbazole groups (Cz) and at least 15 substituted deuteriums (D) in such carbazole groups. For example, the number of deuteriums (D) contained in the above basic skeleton structure is 15 or more. As another expression, a, d and f of Chemical Formula 1 are each independently 1 to 3, b, c, e are each independently 1 to 4, but a+b+c+d+e+f≥15. Preferably, in Chemical Formula 1, a=d=f=3, b=c=e=4, and the number of deuteriums (D) is 21 or more.

[0036] In this case, the hydrogen atoms of the benzene ring in the deuterium (D) unsubstituted carbazole group can be independently selected from C 1 ~C 40 Alkyl, C 6 ~C 40 The substituent is substituted by a substituent selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms.

[0037] In the above chemical formula 1, Ar 1 and Ar 2 Various substituents are introduced as N positions of two carbazolyl groups located at both ends of at least three carbazolyl groups (Cz). 1 and Ar 2may be the same as or different from each other and may be independently selected from C 1 ~C 40 Alkyl, C 2 ~C 40 The alkenyl group, C 2 ~C 40 Alkynyl, C 6 ~C 40 aryl, heteroaryl having 5 to 40 nuclear atoms, C 6 ~C 40 The aryloxy group, C 1 ~C 40 Alkoxy, C 6 ~C 40 The aromatic amine group, C 3 ~C 40 Cycloalkyl, heterocycloalkyl having 3 to 40 nuclear atoms, C 1 ~C 40 Alkylsilyl, C 1 ~C 40 Alkylboryl, C 6 ~C 40 Arylboryl, C 6 ~C 40 Arylphosphino, C 6 ~C 40 Arylphosphine oxide group and C 6 ~C 40 Specifically, Ar 1 and Ar 2 may be the same as or different from each other and may be independently selected from C 6 ~C 40 and a heteroaryl group having 5 to 40 nuclear atoms. More specifically, Ar 1 and Ar 2 Can be independently C 6 ~C 40 The aryl group, the above Ar 1 ~Ar 2 The aryl groups can be independently selected from deuterium (D), C 6 ~C 40 The Ar is substituted or unsubstituted with one or more substituents selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms. When there are a plurality of such substituents, they may be the same or different from each other. 1 ~Ar 2 The aryl group may not be substituted by deuterium (D) or may be partially substituted by one or more deuterium (D), but Ar may be excluded. 1 ~Ar 2 The case where all the aromatic groups are substituted by deuterium (D).

[0038] In particular, it is preferred that the compound represented by Chemical Formula 1 secures a deuterium substitution rate of at least 67% to confirm a deuteration substitution effect, and in this case, the upper limit value is not particularly limited.

[0039] In one specific example, Ar 1 and Ar 2 The substituents S1 to S5 may be the same as or different from each other, and may each independently be represented by any one selected from the group consisting of the following substituents S1 to S5. However, it is not limited thereto.

[0040]

[0041]

[0042] In the above formula,

[0043] * indicates a site of connection with Chemical Formula 1. Also, although not shown in the above structural formula, it may be substituted with at least one deuterium (D). Also, it may be substituted with at least one substituent known in the art (e.g., R in Chemical Formula 18 described later). 1 The definition part is the same).

[0044] In the above chemical formula 1, the above Ar 1 ~Ar 2 The alkyl, alkenyl, alkynyl, aryl, heteroaryl, aryloxy, alkoxy, arylamine, cycloalkyl, heterocycloalkyl, alkylsilyl, alkylboryl, arylboryl, arylphosphino, arylphosphine oxide and arylsilyl groups can be independently selected from deuterium (D), halogen, cyano, nitro, C 1 ~C 40 Alkyl, C 2 ~C 40 The alkenyl group, C 2 ~C 40 Alkynyl, C 3 ~C 40 Cycloalkyl, heterocycloalkyl having 3 to 40 nuclear atoms, C 6 ~C 40 aryl, heteroaryl having 5 to 40 nuclear atoms, C 1 ~C 40 Alkoxy, C 6 ~C 60 The aryloxy group, C 1 ~C 40 Alkylsilyl, C 6 ~C 40 Arylsilyl, C 1 ~C 40 Alkylboryl, C 6 ~C40 Arylboryl, C 6 ~C 40 Arylphosphino, C 6 ~C 40 Arylphosphine oxide group and C 6 ~C 40 The aromatic amine group may be substituted or unsubstituted with one or more substituents. When a plurality of such substituents are present, they may be the same as or different from each other.

[0045] In one embodiment of the present invention, the compound represented by the above Chemical Formula 1 can be embodied as any one of the following Chemical Formulas 2 to 17 according to the binding sites between at least three carbazole groups.

[0046] Chemical formula 2:

[0048] Chemical formula 3:

[0049] Chemical formula 4:

[0050] Chemical formula 5:

[0051] Chemical formula 6:

[0052] Chemical formula 7:

[0053] Chemical formula 8:

[0054] Chemical formula 9:

[0055] Chemical formula 10:

[0056] Chemical formula 11:

[0057] Chemical formula 12:

[0058] Chemical formula 13:

[0059] Chemical formula 14:

[0060] Chemical formula 15:

[0061] Chemical formula 16:

[0062] Chemical formula 17:

[0064] In the above formula,

[0065] Ar 1 ,Ar 2 , a, b, c, d, e and f are as defined in Chemical Formula 1, respectively.

[0066] The compounds represented by chemical formula 2 to chemical formula 17 of the present invention are tris carbazole type materials in which one carbazole is added to the existing bis type carbazole. Compared with the existing bis type materials, the hole stability can be maximized due to the further combined carbazole. This helps to optimize the performance of the expression device. In addition, the thermal stability of the material itself can be maximized by deuterating the main skeleton of the material. The compounds represented by chemical formula 2 to chemical formula 17 above all achieve the above-mentioned hole stability improvement effect. Preferably, the compounds represented by chemical formula 6 to chemical formula 9 can ensure better hole stability in terms of structure. More preferably, it can be a compound represented by chemical formula 8, in which at least 3 carbazole groups are combined, but combined to the third position as the active site of the above-mentioned carbazole group.

[0067] The compound represented by Chemical Formula 1 of the present invention described above can be further embodied as any one of Compounds A-1 to U-1 exemplified below. However, the compound represented by Chemical Formula 1 of the present invention is not limited to the compounds exemplified below.

[0068]

[0069]

[0070]

[0071]

[0072] In the present invention, "alkyl" refers to a monovalent substituent derived from a straight or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples of such alkyl groups include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, and the like.

[0073] In the present invention, "alkenyl" refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples of such alkenyl groups include vinyl, allyl, isopropenyl, 2-butenyl, etc., but are not limited thereto.

[0074] In the present invention, "alkynyl" refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. Examples of such alkynyl groups include, but are not limited to, ethynyl, 2-propynyl, and the like.

[0075] In the present invention, "cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl may include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, etc., but are not limited thereto.

[0076] In the present invention, "heterocycloalkyl" refers to a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 core atoms, wherein one or more carbons in the ring, preferably 1 to 3 carbons, are substituted by heteroatoms such as N, O, S or Se. Examples of such heterocycloalkyl may include morpholine, piperazine, etc., but are not limited thereto.

[0077] In the present invention, "aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having a single ring or a combination of two or more rings and having 6 to 60 carbon atoms. In addition, it may include a form in which two or more rings are simply attached (pendant) or fused to each other. Examples of such aryl groups include phenyl, naphthyl, phenanthrenyl, anthracenyl, etc., but are not limited thereto.

[0078] In the present invention, "heteroaryl" refers to a monovalent substituent derived from a monocyclic or polycyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. In this case, one or more carbons in the ring, preferably 1 to 3 carbons, are substituted by heteroatoms such as N, O, S or Se. In addition, it may include a form in which two or more rings are simply attached (pendant) or fused to each other, and further, it may include a form fused with an aromatic group. Examples of such heteroaryl groups include: 6-membered monocyclic rings, such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings, such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, dibenzofuranyl, dibenzothiophenyl, and the like; and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidinyl, and the like, but are not limited thereto.

[0079] In the present invention, "alkoxy" is a monovalent substituent represented by R'O-, where R' refers to an alkyl group having 1 to 40 carbon atoms. Such alkoxy groups may include linear, branched or cyclic structures. Examples of such alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, tert-butoxy, n-butoxy, pentoxy, etc.

[0080] In the present invention, "aryloxy" is a monovalent substituent represented by RO-, where R is an aryl group having 6 to 60 carbon atoms. Examples of such aryloxy groups include phenoxy, naphthoxy, diphenoxy, etc., but are not limited thereto.

[0081] In the present invention, an "alkylsilyl group" refers to a silyl group substituted by an alkyl group having 1 to 40 carbon atoms, and an "arylsilyl group" refers to a silyl group substituted by an aryl group having 6 to 60 carbon atoms.

[0082] In the present invention, "alkyl boron" refers to boron substituted by an alkyl group having 1 to 40 carbon atoms, and "aryl boron" refers to boron substituted by an aryl group having 6 to 60 carbon atoms.

[0083] In the present invention, the “arylphosphine” refers to a phosphine substituted by an aryl group having 6 to 60 carbon atoms, and the “arylphosphine oxide group” refers to a phosphine substituted by an aryl group having 6 to 60 carbon atoms, including O.

[0084] In the present invention, the "fused ring" refers to a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, a fused heteroaromatic ring or a combination thereof.

[0085] In the present invention, the "arylamine group" refers to an amine group substituted with an aryl group having 6 to 60 carbon atoms.

[0086] The compound represented by Chemical Formula 1 of the present invention as described above can be prepared by methods known in the art without limitation. For example, it can be synthesized in various ways with reference to the synthesis process of the following examples.

[0087] <Organic electroluminescent device>

[0088] The present invention provides an organic electroluminescent device comprising the compound represented by the above Chemical Formula 1.

[0089] Specifically, the organic electroluminescent device of the present invention includes an anode, a cathode, and one or more organic layers between the anode and the cathode, and at least one of the one or more organic layers contains the compound represented by the above Chemical Formula 1.

[0090] The one or more organic layers include at least one 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, an electron transport layer, and an electron transport auxiliary layer, wherein at least one organic layer contains the compound represented by the above Chemical Formula 1. More specifically, the organic layer containing the compound represented by the above Chemical Formula 1 is a light-emitting layer, and in this case, contains the compound represented by Chemical Formula 1 as a host material.

[0091] This light-emitting layer includes a host material and / or a dopant material, in which case the compound represented by Chemical Formula 1 can be used as a P-type host material. In addition to the host material of the above Chemical Formula 1, the above-mentioned light-emitting layer may also include at least one of a conventional P-type host and an N-type host known in the art. In addition, a dopant known in the art may also be included without restriction. There is no particular restriction on their content ratio (mixing ratio), and they can be appropriately adjusted within the content range known in the art. For example, relative to the total weight of the above-mentioned light-emitting layer, the light-emitting layer may include 70 to 99.9 parts by weight of the host and 0.1 to 30 parts by weight of the dopant.

[0092] The dopant contained in the above-mentioned light-emitting layer is not particularly limited as long as it is well known in the art. For example, it can contain at least one of a fluorescent light-emitting dopant and a phosphorescent light-emitting dopant. As non-limiting examples of usable dopants, anthracene derivatives, pyrene derivatives, aromatic amine derivatives, and metal coordination compounds containing iridium (Ir) or platinum (Pt) can be included. Such dopants can be divided into red dopants, green dopants, and blue dopants, and red dopants, green dopants, and blue dopants generally known in the art can be used without restriction.

[0093] On the other hand, the organic electroluminescent device of the present invention may include an emitting layer (EML) containing the compound represented by Chemical Formula 1 as a main body and a dual electron withdrawing group type (dual EWG type) electron transport layer (ETL) having high electron transport capability due to the inclusion of at least two EWG groups. In this case, the performance of the organic electroluminescent device can be optimized by enhancing the hole stability of the emitting layer (EML) and maximizing the electron transport capability of the electron transport layer (ETL).

[0094] The electron transport layer is not particularly limited as long as it is a compound including at least two EWG (electron withdrawing group) groups. Specifically, it may include a compound represented by the following Chemical Formula 18.

[0095] Chemical formula 18:

[0096]

[0097] In the above chemical formula 18,

[0098] L chooses from C 6 ~C 40 In the group consisting of an arylene group and a heteroarylene group having 5 to 40 nuclear atoms, X 1 To X 10 Each independently is N or C(R 1 ),

[0099] When there are multiple C(R 1 ), multiple R 1 are the same as or different from each other and are independently selected from C 1 ~C 40 Alkyl, C 2 ~C 40 The alkenyl group, C 2 ~C 40 Alkynyl, C 6 ~C 40 aryl, heteroaryl having 5 to 40 nuclear atoms, C 6 ~C40 The aryloxy group, C 1 ~C 40 Alkoxy, C 6 ~C 40 The aromatic amine group, C 3 ~C 40 Cycloalkyl, heterocycloalkyl having 3 to 40 nuclear atoms, C 1 ~C 40 Alkylsilyl, C 1 ~C 40 Alkylboryl, C 6 ~C 40 Arylboryl, C 6 ~C 40 Arylphosphino, C 6 ~C 40 Arylphosphine oxide group and C 6 ~C 40 In the group consisting of arylsilyl groups,

[0100] The arylene group and heteroarylene group of the above L and the above R 1 The alkyl, alkenyl, alkynyl, aryl, heteroaryl, aryloxy, alkoxy, arylamine, cycloalkyl, heterocycloalkyl, alkylsilyl, alkylboryl, arylboryl, arylphosphino, arylphosphine oxide and arylsilyl groups can be independently selected from deuterium (D), halogen, cyano, nitro, C 1 ~C 40 Alkyl, C 2 ~C 40 The alkenyl group, C 2 ~C 40 Alkynyl, C 3 ~C 40 Cycloalkyl, heterocycloalkyl having 3 to 40 nuclear atoms, C 6 ~C 60 aryl, heteroaryl having 5 to 60 nuclear atoms, C 1 ~C 40 Alkoxy, C 6 ~C 60 The aryloxy group, C 1 ~C 40 Alkylsilyl, C 6 ~C 60 Arylsilyl, C 1 ~C 40 Alkylboryl, C 6 ~C 60 Arylboryl, C 6 ~C 60 Arylphosphino, C 6 ~C 60 Arylphosphine oxide group and C6 ~C 60 The substituents may be substituted with one or more substituents selected from the group consisting of an aromatic amine group and, in this case, when a plurality of the substituents are present, they may be the same as or different from each other.

[0101] In the above chemical formula 18, each of the 1 To X 5 The ring and the ring containing X 6 To X 10 The ring containing X 1 To X 5 The ring and the ring containing X 6 To X 10 The rings may be the same as or different from each other, and may each independently be embodied as any one selected from the group consisting of substituents A-1 to A-5 described below.

[0102]

[0103] In the above formula,

[0104] * indicates the site of connection with Chemical Formula 18.

[0105] Z 1 and Z 2 are the same as or different from each other and are independently selected from C 6 ~C 40 The group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms,

[0106] R 1 Each independently selected from hydrogen, C 1 ~C 40 Alkyl, C 6 ~C 40 The group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms,

[0107] The above Z 1 To Z 2 The aryl and heteroaryl groups and the above R 1 The alkyl, aryl and heteroaryl groups can be independently selected from deuterium (D), halogen, cyano, C 6 ~C 40 The substituent may be substituted by one or more substituents selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms. In this case, when a plurality of the substituents are present, they may be the same as or different from each other.

[0108] In one specific example, Z 1 and Z 2 They may be the same as or different from each other, and may each be independently embodied as any one selected from the following structural formulae.

[0109]

[0110] The two EWG groups are connected by a linker (L). Such a linker is a conventional divalent group linker known in the art, and specifically, can be selected from C 6 ~C 25 The arylene group and the heteroarylene group having 5 to 18 nuclear atoms.

[0111] In one specific example, L can be further embodied as a linker selected from the following structural formulas. However, it is not limited thereto.

[0112]

[0113] In the above formula,

[0114] * indicates a site of connection with Chemical Formula 18. Also, although not shown in the above structural formula, it may be replaced by at least one substituent known in the art (e.g., 1 ) are replaced by the same definition as .

[0115] The structure of the organic electroluminescent device of the present invention including the above-mentioned structure is not particularly limited, and may have a structure known in the art. As a non-limiting example, it may be a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a luminescence auxiliary layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode are sequentially stacked. In this case, 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.

[0116] Except that at least one of the organic layers contains the compound represented by Chemical Formula 1, the organic electroluminescent device of the present invention can be prepared by forming the organic layers and electrodes using materials and methods known in the art.

[0117] The organic layer may be formed by vacuum deposition or solution coating, examples of which include spin coating, dip coating, tape casting, inkjet printing, thermal transfer, etc., but are not limited thereto.

[0118] The substrate used in preparing the organic electroluminescent device of the present invention is not particularly limited, and silicon wafers, quartz, glass plates, metal plates, plastic films and sheets, etc. can be used.

[0119] Furthermore, the anode material may include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or ZnO:Al or SnO 2: Combinations of metals such as Sb and oxides; polythiophene, poly(3-methylthiophene), such as poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole or polyaniline and other conductive polymers; and carbon black, etc., but not limited thereto.

[0120] Furthermore, the cathode material may include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; and 2 / Al and other multi-layer structure materials, but not limited to these.

[0121] Furthermore, the hole injection layer, the hole transport layer, and the electron injection layer are not particularly limited, and conventional materials known in the art may be used.

[0122] Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are only for illustrating the present invention, and the present invention is not limited to the following examples.

[0123] Preparation Example 1-1: Synthesis of Cz-D1

[0124]

[0125] Under nitrogen flow, 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7 (134.3 g, 530.6 mmol), iodobenzene (130.0 g, 636.7 mmol), Cu (16.8 g, 265.3 mmol), K 2 CO 3 (146.7 g, 1061.3 mmol) and toluene (1000 ml) were mixed and stirred at 110° C. for 12 hours.

[0126] After the reaction was completed, it was extracted with ethyl acetate and then with MgSO 4 The water was removed and purified by column chromatography (Hexane:EA=5:1 (v / v)) to obtain Cz-D1 (125.7 g, yield 72%).

[0127] Mass (theoretical value: 329.25, measured value: 329 g / mol)

[0128] Preparation Example 1-2: Synthesis of Cz-D2

[0129]

[0130] The same process as in Preparation Example 1-1 was carried out except that 4-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain Cz-D2 (135.5 g, yield 63%) as the target compound.

[0131] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0132] Preparation Example 1-3: Synthesis of Cz-D3

[0133]

[0134] The same process as in Preparation Example 1-1 was carried out except that 3-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain Cz-D3 (148.4 g, yield 69%) as the target compound.

[0135] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0136] Preparation Example 1-4: Synthesis of Cz-D4

[0137]

[0138] The same process as in Preparation Example 1-1 was carried out except that 2-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain Cz-D4 (96.8 g, 45% yield) as the target compound.

[0139] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0140] Preparation Example 2-1: Synthesis of Cz-D5

[0141]

[0142] The same process as in Preparation Example 1-1 was carried out to obtain the target compound Cz-D5 (117.1 g, 67% yield), except that 4-bromo-9H-carbazole-1,2,3,5,6,7,8-d7 (134.3 g, 530.6 mmol) was used instead of 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7 (3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7).

[0143] Mass (theoretical value: 329.25, measured value: 329 g / mol)

[0144] Preparation Example 2-2: Synthesis of Cz-D6

[0145]

[0146] The same process as in Preparation Example 2-1 was carried out except that 4-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain Cz-D6 (139.8 g, 65% yield) as the target compound.

[0147] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0148] Preparation Example 2-3: Synthesis of Cz-D7

[0149]

[0150] The same process as in Preparation Example 2-1 was carried out except that 3-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain Cz-D7 (152.7 g, yield 71%) as the target compound.

[0151] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0152] Preparation Example 2-4: Synthesis of Cz-D8

[0153]

[0154] The same process as in Preparation Example 2-1 was carried out except that 2-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain Cz-D8 (75.2 g, 35% yield) as the target compound.

[0155] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0156] Preparation Example 3-1: Synthesis of Cz-D9

[0157]

[0158] The same process as in Preparation Example 1-1 was carried out to obtain the target compound Cz-D9 (134.5 g, 77% yield), except that 2-bromo-9H-carbazole-1,3,4,5,6,7,8-d7 (134.3 g, 530.6 mmol) was used instead of 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7 (3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7).

[0159] Mass (theoretical value: 329.25, measured value: 329 g / mol)

[0160] Preparation Example 3-2: Synthesis of Cz-D10

[0161]

[0162] The same process as in Preparation Example 3-1 was carried out except that 4-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain the target compound Cz-D10 (159.1 g, yield 74%).

[0163] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0164] Preparation Example 3-3: Synthesis of Cz-D11

[0165]

[0166] The same process as in Preparation Example 3-1 was carried out except that 3-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain the target compound Cz-D11 (163.4 g, yield 76%).

[0167] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0168] Preparation Example 3-4: Synthesis of Cz-D12

[0169]

[0170] The same process as in Preparation Example 3-1 was carried out except that 2-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain Cz-D12 (92.4 g, 43% yield) as the target compound.

[0171] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0172] Preparation Example 4-1: Synthesis of Cz-D13

[0173]

[0174] The same process as in Preparation Example 1-1 was carried out to obtain the target compound Cz-D13 (94.3 g, 54% yield), except that 1-bromo-9H-carbazole-2,3,4,5,6,7,8-d7 (134.3 g, 530.6 mmol) was used instead of 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7 (3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7).

[0175] Mass (theoretical value: 329.25, measured value: 329 g / mol)

[0176] Preparation Example 4-2: Synthesis of Cz-D14

[0177]

[0178] The same process as in Preparation Example 4-1 was carried out except that 4-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain the target compound Cz-D14 (122.6 g, yield 57%).

[0179] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0180] Preparation Example 4-3: Synthesis of Cz-D15

[0181]

[0182] The same process as in Preparation Example 4-1 was carried out except that 3-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain the target compound Cz-D15 (111.8 g, yield 52%).

[0183] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0184] Preparation Example 4-4: Synthesis of Cz-D16

[0185]

[0186] The same process as in Preparation Example 4-1 was carried out except that 2-iodo-1,1'-biphenyl (178.3 g, 636.7 mmol) was used instead of iodobenzene to obtain the target compound Cz-D16 (68.8 g, yield 32%).

[0187] Mass (theoretical value: 405.35, measured value: 405 g / mol)

[0188] Preparation Example 5-1: Synthesis of BCz-D1

[0189] Step 5-1-1: 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1, 2,4,5,6,7,8-d7

[0190] (9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H- Synthesis of carbazole-1,2,4,5,6,7,8-d7)

[0191]

[0192] Under nitrogen flow, Cz-D1 (100.0 g, 303.7 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (84.8 g, 334.1 mmol), Pd(dppf)Cl 2 (26.6 g, 30.3 mmol), KOAc (85.8 g, 911.1 mmol) and 1,4-dioxane (1000 ml) were mixed and stirred at 130 °C for 12 hours. After the reaction was completed, it was extracted with ethyl acetate and then with MgSO 4 The water was removed and purified by column chromatography (Hexane:EA=8:1 (v / v)) to obtain 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,2,4,5,6,7,8-d7 (96.0 g, 84% yield).

[0193] Mass (theoretical value: 376.3, measured value: 376 g / mol)

[0194] Step 5-1-2: Synthesis of BCz-D1

[0195]

[0196] Under nitrogen flow, 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,2,4,5,6,7,8-d7

[0197] (9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,2,4,5,6,7,8-d7)(96.0g, 25 5.1mmol), 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7(3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7) (77.5g, 306.1mmol), Pd(PPh 3 ) 4 (14.7 g, 12.7 mmol), K2 CO 3 (88.1 g, 637.8 mmol), 1,4-dioxane / H 2 O (1000 ml / 250 ml) and stirred at 120°C for 4 hours.

[0198] After the reaction was complete, it was extracted with dichloromethane and MgSO 4 The organic layer was filtered and the solvent was removed, followed by purification by column chromatography (Hexane:EA=7:1 (v / v)) to obtain BCz-D1 (71.1 g, yield 66%).

[0199] Mass (theoretical value: 422.59, measured value: 422 g / mol)

[0200] Preparation Example 5-2: Synthesis of BCz-D2

[0201]

[0202] The same process as in Preparation Example 5-1 was carried out except that Cz-D2 (100 g, 246.7 mmol) was used instead of Cz-D1 to obtain BCz-D2 (66.4 g, final yield 54.0%) as the target compound.

[0203] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0204] Preparation Example 5-3: Synthesis of BCz-D3

[0205]

[0206] The same process as in Preparation Example 5-1 was carried out except that Cz-D3 (100 g, 246.7 mmol) was used instead of Cz-D1 to obtain BCz-D3 (59.7 g, final yield 48.5%) as the target compound.

[0207] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0208] Preparation Example 5-4: Synthesis of BCz-D4

[0209]

[0210] The same process as in Preparation Example 5-1 was carried out except that Cz-D4 (100 g, 246.7 mmol) was used instead of Cz-D1 to obtain BCz-D4 (59.4 g, final yield 48.3%) as the target compound.

[0211] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0212] Preparation Example 6-1: Synthesis of BCz-D5

[0213] Step 6-1-1: 9-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1, 2,3,5,6,7,8-d7

[0214] (9-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H- Synthesis of carbazole-1,2,3,5,6,7,8-d7)

[0215]

[0216] Under nitrogen flow, Cz-D5 (100.0 g, 303.7 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (84.8 g, 334.1 mmol), Pd(dppf)Cl 2 (26.6 g, 30.3 mmol), KOAc (85.8 g, 911.1 mmol) and 1,4-dioxane (1000 ml) were mixed and stirred at 130° C. for 12 hours.

[0217] After the reaction was completed, it was extracted with ethyl acetate and then with MgSO 4 The water was removed and purified by column chromatography (Hexane:EA=8:1 (v / v)) to obtain 9-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,2,3,5,6,7,8-d7 (74.3 g, 65% yield).

[0218] Mass (theoretical value: 376.3, measured value: 376 g / mol)

[0219] Step 6-1-2: Synthesis of BCz-D5

[0220]

[0221] Under nitrogen flow, 9-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,2,3,5,6,7,8-d7

[0222] (9-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,2,3,5,6,7,8-d7) (74.3g, 19 7.4mmol), 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7(3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7) (60.0g, 236.9mmol), Pd(PPh 3 ) 4 (11.4 g, 9.9 mmol), K 2 CO 3 (68.2 g, 493.5 mmol), 1,4-dioxane / H 2 O (1000 ml / 250 ml) and stirred at 120°C for 4 hours.

[0223] After the reaction was complete, it was extracted with dichloromethane and MgSO 4 The organic layer was filtered and the solvent was removed, followed by purification by column chromatography (Hexane:EA=7:1 (v / v)) to obtain BCz-D5 (63.4 g, yield 76%).

[0224] Mass (theoretical value: 422.59, measured value: 422 g / mol)

[0225] Preparation Example 6-2: Synthesis of BCz-D6

[0226]

[0227] The same process as in Preparation Example 6-1 was carried out except that Cz-D6 (100 g, 246.7 mmol) was used instead of Cz-D5 to obtain BCz-D6 (55.4 g, final yield 45.1%) as the target compound.

[0228] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0229] Preparation Example 6-3: Synthesis of BCz-D7

[0230]

[0231] The same process as in Preparation Example 6-1 was carried out except that Cz-D7 (100 g, 246.7 mmol) was used instead of Cz-D5 to obtain BCz-D7 (43.1 g, final yield 35.1%) as the target compound.

[0232] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0233] Preparation Example 6-4: Synthesis of BCz-D8

[0234]

[0235] The same process as in Preparation Example 6-1 was carried out except that Cz-D8 (100 g, 246.7 mmol) was used instead of Cz-D5 to obtain BCz-D8 (28.2 g, final yield 22.9%) as the target compound.

[0236] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0237] Preparation Example 7-1: Synthesis of BCz-D9

[0238] Step 7-1-1: 9-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1, 3,4,5,6,7,8-d7

[0239] (9-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H- Synthesis of carbazole-1,3,4,5,6,7,8-d7)

[0240]

[0241] Under nitrogen flow, Cz-D9 (100.0 g, 303.7 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (84.8 g, 334.1 mmol), Pd(dppf)Cl 2 (26.6 g, 30.3 mmol), KOAc (85.8 g, 911.1 mmol) and 1,4-dioxane (1000 ml) were mixed and stirred at 130° C. for 12 hours.

[0242] After the reaction was completed, it was extracted with ethyl acetate and then with MgSO 4The water was removed and purified by column chromatography (Hexane:EA=8:1 (v / v)) to obtain 9-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,3,4,5,6,7,8-d7 (81.1 g, 71% yield).

[0243] Mass (theoretical value: 376.3, measured value: 376 g / mol)

[0244] Step 7-1-2: Synthesis of BCz-D9

[0245]

[0246] Under nitrogen flow, 9-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,3,4,5,6,7,8-d7

[0247] (9-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,3,4,5,6,7,8-d7) (81.1g, 21 5.6mmol), 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7(3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7) (65.5g, 258.8mmol), Pd(PPh 3 ) 4 (12.5 g, 10.8 mmol), K 2 CO 3 (74.5 g, 539.1 mmol), 1,4-dioxane / H 2 O (1000 ml / 250 ml) and stirred at 120°C for 4 hours.

[0248] After the reaction was complete, it was extracted with dichloromethane and MgSO 4 The organic layer was filtered and the solvent was removed, followed by purification by column chromatography (Hexane:EA=7:1 (v / v)) to obtain BCz-D9 (67.4 g, yield 74%).

[0249] Mass (theoretical value: 422.59, measured value: 422 g / mol)

[0250] Preparation Example 7-2: Synthesis of BCz-D10

[0251]

[0252] The same process as in Preparation Example 7-1 was carried out except that Cz-D10 (100 g, 246.7 mmol) was used instead of Cz-D9 to obtain BCz-D10 (65.2 g, final yield 53.0%) as the target compound.

[0253] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0254] Preparation Example 7-3: Synthesis of BCz-D11

[0255]

[0256] The same procedure as in Preparation Example 7-1 was performed except that Cz-D11 (100 g, 246.7 mmol) was used instead of Cz-D9 to obtain BCz-D11 (68.2 g, final yield 55.4%) as the target compound.

[0257] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0258] Preparation Example 7-4: Synthesis of BCz-D12

[0259]

[0260] The same process as in Preparation Example 7-1 was carried out except that Cz-D12 (100 g, 246.7 mmol) was used instead of Cz-D9 to obtain BCz-D12 (51.1 g, final yield 41.6%) as the target compound.

[0261] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0262] Preparation Example 8-1: Synthesis of BCz-D13

[0263] Step 8-1-1: 9-phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-2, 3,4,5,6,7,8-d7

[0264] (9-phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H- Synthesis of carbazole-2,3,4,5,6,7,8-d7)

[0265]

[0266] Under nitrogen flow, Cz-D9 (100.0 g, 303.7 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (84.8 g, 334.1 mmol), Pd(dppf)Cl 2 (26.6 g, 30.3 mmol), KOAc (85.8 g, 911.1 mmol) and 1,4-dioxane (1000 ml) were mixed and stirred at 130° C. for 12 hours.

[0267] After the reaction was completed, it was extracted with ethyl acetate and then with MgSO 4 The water was removed and purified by column chromatography (Hexane:EA=8:1 (v / v)) to obtain 9-phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-2,3,4,5,6,7,8-d7 (64.0 g, 56% yield).

[0268] Mass (theoretical value: 376.3, measured value: 376 g / mol)

[0269] Step 8-1-2: Synthesis of BCz-D13

[0270]

[0271] Under nitrogen flow, 9-phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-2,3,4,5,6,7,8-d7

[0272] (9-phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-2,3,4,5,6,7,8-d7)(64.0g, 17 0.0mmol), 3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7(3-bromo-9H-carbazole-1,2,4,5,6,7,8-d7) (51.7g, 204.1mmol), Pd(PPh 3 ) 4(9.8 g, 8.5 mmol), K 2 CO 3 (58.8 g, 425.2 mmol), 1,4-dioxane / H 2 O (1000 ml / 250 ml) and stirred at 120°C for 4 hours.

[0273] After the reaction was complete, it was extracted with dichloromethane and MgSO 4 The organic layer was filtered and the solvent was removed, followed by purification by column chromatography (Hexane:EA=7:1 (v / v)) to obtain BCz-D13 (37.3 g, yield 52%).

[0274] Mass (theoretical value: 422.59, measured value: 422 g / mol)

[0275] Preparation Example 8-2: Synthesis of BCz-D14

[0276]

[0277] The same process as in Preparation Example 8-1 was carried out except that Cz-D14 (100 g, 246.7 mmol) was used instead of Cz-D13 to obtain BCz-D14 (33.2 g, final yield 27.0%) as the target compound.

[0278] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0279] Preparation Example 8-3: Synthesis of BCz-D15

[0280]

[0281] The same process as in Preparation Example 8-1 was carried out except that Cz-D15 (100 g, 246.7 mmol) was used instead of Cz-D13 to obtain BCz-D15 (32.2 g, final yield 26.2%) as the target compound.

[0282] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0283] Preparation Example 8-4: Synthesis of BCz-D16

[0284]

[0285] The same process as in Preparation Example 8-1 was carried out except that Cz-D16 (100 g, 246.7 mmol) was used instead of Cz-D13 to obtain BCz-D16 (27.0 g, final yield 21.9%) as the target compound.

[0286] Mass (theoretical value: 498.69, measured value: 498 g / mol)

[0287] Preparation Example 9-1: Synthesis of BCz-D17

[0288]

[0289] Under nitrogen flow, 9-phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-2,3,4,5,6,7,8-d7

[0290] (9-phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-2,3,4,5,6,7,8-d7)(100.0g, 17 0.0mmol), 1-bromo-9H-carbazole-2,3,4,5,6,7,8-d7 (1-bromo-9H-carbazole-2,3,4,5,6,7,8-d7) (80.7g, 318.8mmol), Pd (PPh 3 ) 4 (15.3 g, 13.2 mmol), K 2 CO 3 (91.8 g, 664.2 mmol), 1,4-dioxane / H 2 O (1000 ml / 250 ml) and stirred at 120°C for 4 hours.

[0291] After the reaction was complete, it was extracted with dichloromethane and MgSO 4 The organic layer was filtered and the solvent was removed, followed by purification by column chromatography (Hexane:EA=7:1 (v / v)) to obtain BCz-D17 (50.5 g, yield 45%).

[0292] Mass (theoretical value: 422.59, measured value: 422 g / mol)

[0293] Preparation Example 9-2: Synthesis of BCz-D18

[0294]

[0295] Under nitrogen flow, 9-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,3,4,5,6,7,8-d7

[0296] (9-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,3,4,5,6,7,8-d7)(100.0g, 17 0.0mmol), 2-bromo-9H-carbazole-1,3,4,5,6,7,8-d7 (2-bromo-9H-carbazole-1,3,4,5,6,7,8-d7) (80.7g, 318.8mmol), Pd (PPh 3 ) 4 (15.3 g, 13.2 mmol), K 2 CO 3 (91.8 g, 664.2 mmol), 1,4-dioxane / H 2 O (1000 ml / 250 ml) and stirred at 120°C for 4 hours.

[0297] After the reaction was complete, it was extracted with dichloromethane and MgSO 4 The organic layer was filtered and the solvent was removed, followed by purification by column chromatography (Hexane:EA=7:1 (v / v)) to obtain BCz-D18 (70.7 g, yield 63%).

[0298] Mass (theoretical value: 422.59, measured value: 422 g / mol)

[0299] Preparation Example 9-3: Synthesis of BCz-D19

[0300]

[0301] Under nitrogen flow, 9-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,2,3,5,6,7,8-d7

[0302] (9-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole-1,2,3,5,6,7,8-d7)(100.0g, 17 0.0mmol), 4-bromo-9H-carbazole-1,2,3,5,6,7,8-d7(4-bromo-9H-carbazole-1,2,3,5,6,7,8-d7) (80.7g, 318.8mmol), Pd(PPh 3 ) 4 (15.3 g, 13.2 mmol), K 2 CO 3 (91.8 g, 664.2 mmol), 1,4-dioxane / H 2 O (1000 ml / 250 ml) and stirred at 120°C for 4 hours.

[0303] After the reaction was complete, it was extracted with dichloromethane and MgSO 4 The organic layer was filtered and the solvent was removed, followed by purification by column chromatography (Hexane:EA=7:1 (v / v)) to obtain BCz-D19 (59.5 g, yield 53%).

[0304] Mass (theoretical value: 422.59, measured value: 422 g / mol)

[0305] Synthesis Example 1: Synthesis of A-1

[0306]

[0307] Under nitrogen flow, BCz-D1 (10.0 g, 23.6 mmol), Cz-D1 (9.3 g, 28.3 mmol), Pd(OAc) 2 (1.36 g, 1.18 mmol), P(t-Bu) 3 (0.57 ml, 2.36 mmol), NaO(t-Bu) (4.55 g, 47.3 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain the target compound A-1 (13.0 g, yield 82%).

[0308] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0309] Synthesis Example 2: Synthesis of A-2

[0310]

[0311] The same process as in Synthesis Example 1 was carried out except that Cz-D2 (10.0 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-2 (13.8 g, yield 78%).

[0312] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0313] Synthesis Example 3: Synthesis of A-3

[0314]

[0315] The same process as in Synthesis Example 1 was carried out except that Cz-D3 (10.0 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-3 (13.2 g, yield 75%).

[0316] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0317] Synthesis Example 4: Synthesis of A-4

[0318]

[0319] The same process as in Synthesis Example 1 was carried out except that Cz-D4 (10.0 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-4 (12.2 g, yield 69%).

[0320] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0321] Synthesis Example 5: Synthesis of A-5

[0322]

[0323] The same process as in Synthesis Example 1 was carried out except that Cz-D5 (9.3 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-5 (8.73 g, yield 55%).

[0324] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0325] Synthesis Example 6: Synthesis of A-6

[0326]

[0327] The same process as in Synthesis Example 1 was carried out except that Cz-D6 (10.0 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-6 (7.42 g, yield 42%).

[0328] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0329] Synthesis Example 7: Synthesis of A-7

[0330]

[0331] The same process as in Synthesis Example 1 was performed except that Cz-D7 (10.0 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-7 (8.83 g, yield 50%).

[0332] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0333] Synthesis Example 8: Synthesis of A-8

[0334]

[0335] The same process as in Synthesis Example 1 was performed except that Cz-D8 (10.0 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-8 (9.89 g, yield 56%).

[0336] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0337] Synthesis Example 9: Synthesis of A-9

[0338]

[0339] The same process as in Synthesis Example 1 was performed except that Cz-D9 (9.3 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-9 (8.41 g, yield 53%).

[0340] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0341] Synthesis Example 10: Synthesis of A-10

[0342]

[0343] The same process as in Synthesis Example 1 was carried out except that Cz-D10 (10.0 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-10 (8.66 g, yield 49%).

[0344] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0345] Synthesis Example 11: Synthesis of A-11

[0346]

[0347] The same process as in Synthesis Example 1 was carried out except that Cz-D11 (10.0 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-11 (9.01 g, yield 51%).

[0348] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0349] Synthesis Example 12: Synthesis of A-12

[0350]

[0351] The same process as in Synthesis Example 1 was carried out except that Cz-D12 (10.0 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-12 (9.19 g, yield 52%).

[0352] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0353] Synthesis Example 13: Synthesis of A-13

[0354]

[0355] The same process as in Synthesis Example 1 was carried out except that Cz-D13 (9.3 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-13 (9.52 g, yield 60%).

[0356] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0357] Synthesis Example 14: Synthesis of A-14

[0358]

[0359] The same process as in Synthesis Example 1 was carried out except that Cz-D14 (10.0 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-14 (10.78 g, yield 61%).

[0360] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0361] Synthesis Example 15: Synthesis of A-15

[0362]

[0363] The same process as in Synthesis Example 1 was performed except that Cz-D15 (10.0 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-15 (11.13 g, yield 63%).

[0364] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0365] Synthesis Example 16: Synthesis of A-16

[0366]

[0367] The same process as in Synthesis Example 1 was carried out except that Cz-D16 (10.0 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound A-16 (9.02 g, yield 51%).

[0368] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0369] Synthesis Example 17: Synthesis of B-1

[0370]

[0371] Under nitrogen flow, BCz-D2 (10.0 g, 20.1 mmol), Cz-D1 (7.9 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain B-1 (10.2 g, yield 62%) as the target compound.

[0372] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0373] Synthesis Example 18: Synthesis of B-2

[0374]

[0375] The same process as in Synthesis Example 5 was carried out except that Cz-D2 (9.75 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound B-2 (11.9 g, yield 72%).

[0376] Mass (theoretical value: 823.12, measured value: 823 g / mol)

[0377] Synthesis Example 19: Synthesis of B-3

[0378]

[0379] The same process as in Synthesis Example 5 was carried out except that Cz-D3 (9.75 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound B-3 (10.9 g, yield 66%).

[0380] Mass (theoretical value: 823.12, measured value: 823 g / mol)

[0381] Synthesis Example 20: Synthesis of B-4

[0382]

[0383] The same process as in Synthesis Example 5 was carried out except that Cz-D4 (9.75 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound B-4 (9.6 g, yield 58%).

[0384] Mass (theoretical value: 823.12, measured value: 823 g / mol)

[0385] Synthesis Example 21: Synthesis of B-5

[0386]

[0387] Except for using Cz-D5 (7.9 g, 24.1 mmol) instead of Cz-D1, the same process as the above-mentioned Synthesis Example 17 was carried out to obtain B-5 (8.5 g, yield 48%) as the target compound.

[0388] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0389] Synthesis Example 22: Synthesis of B-6

[0390]

[0391] Except for using Cz-D9 (7.9 g, 24.1 mmol) instead of Cz-D1, the same process as the above-mentioned Synthesis Example 17 was carried out to obtain B-6 (11.1 g, yield 63%) as the target compound.

[0392] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0393] Synthesis Example 23: Synthesis of B-7

[0394]

[0395] The same process as in Synthesis Example 17 was carried out except that Cz-D13 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound B-7 (7.42 g, yield 42%).

[0396] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0397] Synthesis Example 24: Synthesis of C-1

[0398]

[0399] Under nitrogen flow, BCz-D3 (10.0 g, 20.1 mmol), Cz-D1 (7.9 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain C-1 (9.4 g, yield 63%) as the target compound.

[0400] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0401] Synthesis Example 25: Synthesis of C-2

[0402]

[0403] The same process as in Synthesis Example 24 was carried out except that Cz-D2 (9.75 g, 24.1 mmol) was used instead of Cz-D1 to obtain C-2 (12.2 g, yield 74%) as the target compound.

[0404] Mass (theoretical value: 823.12, measured value: 823 g / mol)

[0405] Synthesis Example 26: Synthesis of C-3

[0406]

[0407] The same process as in Synthesis Example 24 was carried out except that Cz-D3 (9.75 g, 24.1 mmol) was used instead of Cz-D1 to obtain C-3 (12.9 g, yield 78%) as the target compound.

[0408] Mass (theoretical value: 823.12, measured value: 823 g / mol)

[0409] Synthesis Example 27: Synthesis of C-4

[0410]

[0411] The same process as in Synthesis Example 24 was carried out except that Cz-D4 (9.75 g, 24.1 mmol) was used instead of Cz-D1 to obtain C-4 (10.1 g, yield 61%) as the target compound.

[0412] Mass (theoretical value: 823.12, measured value: 823 g / mol)

[0413] Synthesis Example 28: Synthesis of C-5

[0414]

[0415] The same process as in Synthesis Example 24 was carried out except that Cz-D5 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain C-5 (7.78 g, yield 44%) as the target compound.

[0416] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0417] Synthesis Example 29: Synthesis of C-6

[0418]

[0419] The same process as in Synthesis Example 24 was carried out except that Cz-D9 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain C-6 (11.67 g, yield 66%) as the target compound.

[0420] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0421] Synthesis Example 30: Synthesis of C-7

[0422]

[0423] The same process as in Synthesis Example 24 was carried out except that Cz-D13 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain C-7 (6.89 g, yield 39%) as the target compound.

[0424] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0425] Synthesis Example 31: Synthesis of D-1

[0426]

[0427] Under nitrogen flow, BCz-D4 (10.0 g, 20.1 mmol), Cz-D1 (7.9 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain D-1 (8.1 g, yield 54%) as the target compound.

[0428] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0429] Synthesis Example 32: Synthesis of D-2

[0430]

[0431] The same process as in Synthesis Example 31 was carried out except that Cz-D2 (9.75 g, 24.1 mmol) was used instead of Cz-D1 to obtain D-2 (10.9 g, yield 66%) as the target compound.

[0432] Mass (theoretical value: 823.12, measured value: 823 g / mol)

[0433] Synthesis Example 33: Synthesis of D-3

[0434]

[0435] The same process as in Synthesis Example 31 was carried out except that Cz-D3 (9.75 g, 24.1 mmol) was used instead of Cz-D1 to obtain D-3 (9.1 g, yield 55%) as the target compound.

[0436] Mass (theoretical value: 823.12, measured value: 823 g / mol)

[0437] Synthesis Example 34: Synthesis of D-4

[0438]

[0439] The same process as in Synthesis Example 31 was carried out except that Cz-D4 (9.75 g, 24.1 mmol) was used instead of Cz-D1 to obtain D-4 (7.1 g, yield 43%) as the target compound.

[0440] Mass (theoretical value: 823.12, measured value: 823 g / mol)

[0441] Synthesis Example 35: Synthesis of D-5

[0442]

[0443] The same process as in Synthesis Example 31 was carried out except that Cz-D5 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain D-5 (7.24 g, yield 41%) as the target compound.

[0444] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0445] Synthesis Example 36: Synthesis of D-6

[0446]

[0447] Except for using Cz-D9 (7.9 g, 24.1 mmol) instead of Cz-D1, the same process as the above-mentioned Synthesis Example 31 was carried out to obtain D-6 (8.41 g, yield 51%) as the target compound.

[0448] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0449] Synthesis Example 37: Synthesis of D-7

[0450]

[0451] The same process as in Synthesis Example 31 was carried out except that Cz-D13 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain D-7 (5.47 g, yield 31%) as the target compound.

[0452] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0453] Synthesis Example 38: Synthesis of E-1

[0454]

[0455] Under nitrogen flow, BCz-D5 (10.0 g, 23.6 mmol), Cz-D1 (9.3 g, 28.3 mmol), Pd(OAc) 2 (1.36 g, 1.18 mmol), P(t-Bu) 3 (0.57 ml, 2.36 mmol), NaO(t-Bu) (4.55 g, 47.3 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain E-1 (11.43 g, yield 72%) as the target compound.

[0456] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0457] Synthesis Example 39: Synthesis of E-2

[0458]

[0459] The same process as in Synthesis Example 38 was carried out except that Cz-D5 (9.3 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound E-2 (10.00 g, yield 63%).

[0460] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0461] Synthesis Example 40: Synthesis of E-3

[0462]

[0463] The same process as in Synthesis Example 38 was carried out except that Cz-D9 (9.3 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound E-3 (8.73 g, yield 55%).

[0464] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0465] Synthesis Example 41: Synthesis of E-4

[0466]

[0467] The same process as in Synthesis Example 38 was carried out except that Cz-D13 (9.3 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound E-4 (9.21 g, yield 58%).

[0468] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0469] Synthesis Example 42: Synthesis of F-1

[0470]

[0471] Under nitrogen flow, BCz-D6 (10.0 g, 20.1 mmol), Cz-D1 (7.9 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain the target compound F-1 (13.79 g, yield 78%).

[0472] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0473] Synthesis Example 43: Synthesis of F-2

[0474]

[0475] The same process as in Synthesis Example 42 was carried out except that Cz-D5 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound F-2 (11.84 g, yield 67%).

[0476] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0477] Synthesis Example 44: Synthesis of F-3

[0478]

[0479] The same process as in Synthesis Example 42 was carried out except that Cz-D9 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound F-3 (11.31 g, yield 64%).

[0480] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0481] Synthesis Example 45: Synthesis of F-4

[0482]

[0483] The same process as in Synthesis Example 42 was carried out except that Cz-D13 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound F-4 (9.90 g, yield 56%).

[0484] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0485] Synthesis Example 46: Synthesis of G-1

[0486]

[0487] Under nitrogen flow, BCz-D7 (10.0 g, 20.1 mmol), Cz-D1 (7.9 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110°C for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then recrystallized and purified to obtain the target compound G-1 (12.90 g, yield 73%).

[0488] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0489] Synthesis Example 47: Synthesis of G-2

[0490]

[0491] Except for using Cz-D5 (7.9 g, 24.1 mmol) instead of Cz-D1, the same process as the above-mentioned Synthesis Example 46 was carried out to obtain G-2 (12.55 g, yield 71%) as the target compound.

[0492] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0493] Synthesis Example 48: Synthesis of G-3

[0494]

[0495] Except for using Cz-D9 (7.9 g, 24.1 mmol) instead of Cz-D1, the same process as the above-mentioned Synthesis Example 46 was carried out to obtain G-3 (13.08 g, yield 74%) as the target compound.

[0496] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0497] Synthesis Example 49: Synthesis of G-4

[0498]

[0499] The same process as in Synthesis Example 46 was carried out except that Cz-D13 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain G-4 (9.37 g, yield 53%) as the target compound.

[0500] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0501] Synthesis Example 50: Synthesis of H-1

[0502]

[0503] Under nitrogen flow, BCz-D8 (10.0 g, 20.1 mmol), Cz-D1 (7.9 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110°C for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain the target compound H-1 (13.42 g, yield 76%).

[0504] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0505] Synthesis Example 51: Synthesis of H-2

[0506]

[0507] The same process as in Synthesis Example 50 was carried out except that Cz-D5 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound H-2 (11.84 g, yield 67%).

[0508] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0509] Synthesis Example 52: Synthesis of H-3

[0510]

[0511] The same process as in Synthesis Example 50 was carried out except that Cz-D9 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound H-3 (13.26 g, yield 75%).

[0512] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0513] Synthesis Example 53: Synthesis of H-4

[0514]

[0515] The same process as in Synthesis Example 50 was carried out except that Cz-D13 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound H-4 (9.19 g, yield 52%).

[0516] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0517] Synthesis Example 54: Synthesis of I-1

[0518]

[0519] Under nitrogen flow, BCz-D9 (10.0 g, 23.6 mmol), Cz-D1 (9.3 g, 28.3 mmol), Pd(OAc) 2 (1.36 g, 1.18 mmol), P(t-Bu) 3(0.57 ml, 2.36 mmol), NaO(t-Bu) (4.55 g, 47.3 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain I-1 (11.27 g, yield 71%) as the target compound.

[0520] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0521] Synthesis Example 55: Synthesis of I-2

[0522]

[0523] The same process as in Synthesis Example 54 was carried out except that Cz-D5 (9.3 g, 23.6 mmol) was used instead of Cz-D1 to obtain I-2 (10.63 g, yield 67%) as the target compound.

[0524] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0525] Synthesis Example 56: Synthesis of I-3

[0526]

[0527] The same process as in Synthesis Example 54 was carried out except that Cz-D9 (9.3 g, 23.6 mmol) was used instead of Cz-D1 to obtain I-3 (8.25 g, yield 52%) as the target compound.

[0528] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0529] Synthesis Example 57: Synthesis of I-4

[0530]

[0531] The same process as in Synthesis Example 54 was carried out except that Cz-D13 (9.3 g, 23.6 mmol) was used instead of Cz-D1 to obtain I-4 (8.10 g, yield 51%) as the target compound.

[0532] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0533] Synthesis Example 58: Synthesis of J-1

[0534]

[0535] Under nitrogen flow, BCz-D10 (10.0 g, 20.1 mmol), Cz-D1 (7.9 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain the target compound J-1 (12.90 g, yield 73%).

[0536] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0537] Synthesis Example 59: Synthesis of J-2

[0538]

[0539] The same process as in Synthesis Example 58 was carried out except that Cz-D5 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound J-2 (11.49 g, yield 65%).

[0540] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0541] Synthesis Example 60: Synthesis of J-3

[0542]

[0543] The same process as in Synthesis Example 58 was carried out except that Cz-D9 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound J-3 (10.95 g, yield 62%).

[0544] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0545] Synthesis Example 61: Synthesis of J-4

[0546]

[0547] The same process as in Synthesis Example 58 was carried out except that Cz-D13 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound J-4 (10.25 g, yield 58%).

[0548] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0549] Synthesis Example 62: Synthesis of K-1

[0550]

[0551] Under nitrogen flow, BCz-D11 (10.0 g, 20.1 mmol), Cz-D1 (7.9 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110°C for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain the target compound K-1 (12.37 g, yield 70%).

[0552] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0553] Synthesis Example 63: Synthesis of K-2

[0554]

[0555] The same process as in Synthesis Example 62 was carried out except that Cz-D5 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound K-2 (13.61 g, yield 77%).

[0556] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0557] Synthesis Example 64: Synthesis of K-3

[0558]

[0559] The same process as in Synthesis Example 62 was carried out except that Cz-D9 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound K-3 (12.55 g, yield 71%).

[0560] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0561] Synthesis Example 65: Synthesis of K-4

[0562]

[0563] The same process as in Synthesis Example 62 was carried out except that Cz-D13 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound K-4 (10.61 g, yield 60%).

[0564] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0565] Synthesis Example 66: Synthesis of L-1

[0566]

[0567] Under nitrogen flow, BCz-D12 (10.0 g, 20.1 mmol), Cz-D1 (7.9 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then recrystallized and purified to obtain the target compound L-1 (13.42 g, yield 76%).

[0568] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0569] Synthesis Example 67: Synthesis of L-2

[0570]

[0571] Except for using Cz-D5 (7.9 g, 24.1 mmol) instead of Cz-D1, the same process as the above-mentioned Synthesis Example 66 was carried out to obtain L-2 (11.84 g, yield 67%) as the target compound.

[0572] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0573] Synthesis Example 68: Synthesis of L-3

[0574]

[0575] Except for using Cz-D9 (7.9 g, 24.1 mmol) instead of Cz-D1, the same process as the above-mentioned Synthesis Example 66 was carried out to obtain L-3 (13.26 g, yield 75%) as the target compound.

[0576] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0577] Synthesis Example 69: Synthesis of L-4

[0578]

[0579] The same process as in Synthesis Example 66 was carried out except that Cz-D13 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound L-4 (9.19 g, yield 52%).

[0580] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0581] Synthesis Example 70: Synthesis of M-1

[0582]

[0583] Under nitrogen flow, BCz-D13 (10.0 g, 23.6 mmol), Cz-D1 (9.3 g, 28.3 mmol), Pd(OAc) 2 (1.36 g, 1.18 mmol), P(t-Bu) 3 (0.57 ml, 2.36 mmol), NaO(t-Bu) (4.55 g, 47.3 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain M-1 (10.16 g, yield 64%) as the target compound.

[0584] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0585] Synthesis Example 71: Synthesis of M-2

[0586]

[0587] The same process as in Synthesis Example 70 was carried out except that Cz-D5 (9.3 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound M-2 (9.37 g, yield 59%).

[0588] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0589] Synthesis Example 72: Synthesis of M-3

[0590]

[0591] The same process as in Synthesis Example 70 was carried out except that Cz-D9 (9.3 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound M-3 (7.78 g, yield 49%).

[0592] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0593] Synthesis Example 73: Synthesis of M-4

[0594]

[0595] The same process as in Synthesis Example 70 was carried out except that Cz-D13 (9.3 g, 23.6 mmol) was used instead of Cz-D1 to obtain the target compound M-4 (6.82 g, yield 43%).

[0596] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0597] Synthesis Example 74: Synthesis of N-1

[0598]

[0599] Under nitrogen flow, BCz-D14 (10.0 g, 20.1 mmol), Cz-D1 (7.9 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain the target compound N-1 (11.49 g, yield 65%).

[0600] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0601] Synthesis Example 75: Synthesis of N-2

[0602]

[0603] The same process as in Synthesis Example 74 was carried out except that Cz-D5 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound N-2 (10.96 g, yield 62%).

[0604] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0605] Synthesis Example 76: Synthesis of N-3

[0606]

[0607] The same process as in Synthesis Example 74 was carried out except that Cz-D9 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound N-3 (9.55 g, yield 54%).

[0608] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0609] Synthesis Example 77: Synthesis of N-4

[0610]

[0611] The same process as in Synthesis Example 74 was carried out except that Cz-D13 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound N-4 (8.84 g, yield 50%).

[0612] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0613] Synthesis Example 78: Synthesis of O-1

[0614]

[0615] Under nitrogen flow, BCz-D15 (10.0 g, 20.1 mmol), Cz-D1 (7.9 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then recrystallized and purified to obtain the target compound O-1 (11.14 g, yield 63%).

[0616] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0617] Synthesis Example 79: Synthesis of O-2

[0618]

[0619] The same process as in Synthesis Example 78 was carried out except that Cz-D5 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound O-2 (11.49 g, yield 65%).

[0620] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0621] Synthesis Example 80: Synthesis of O-3

[0622]

[0623] The same process as in Synthesis Example 78 was carried out except that Cz-D9 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain O-3 (10.07 g, yield 57%) as the target compound.

[0624] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0625] Synthesis Example 81: Synthesis of O-4

[0626]

[0627] The same process as in Synthesis Example 78 was carried out except that Cz-D13 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain O-4 (8.49 g, yield 48%) as the target compound.

[0628] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0629] Synthesis Example 82: Synthesis of P-1

[0630]

[0631] Under nitrogen flow, BCz-D16 (10.0 g, 20.1 mmol), Cz-D1 (7.9 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3(0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110°C for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain the target compound P-1 (10.95 g, yield 62%).

[0632] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0633] Synthesis Example 83: Synthesis of P-2

[0634]

[0635] The same process as in Synthesis Example 82 was carried out except that Cz-D5 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound P-2 (11.31 g, yield 64%).

[0636] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0637] Synthesis Example 84: Synthesis of P-3

[0638]

[0639] The same process as in Synthesis Example 82 was carried out except that Cz-D9 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound P-3 (11.84 g, yield 67%).

[0640] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0641] Synthesis Example 85: Synthesis of P-4

[0642]

[0643] The same process as in Synthesis Example 82 was carried out except that Cz-D13 (7.9 g, 24.1 mmol) was used instead of Cz-D1 to obtain the target compound P-4 (9.55 g, yield 54%).

[0644] Mass (theoretical value: 747.02, measured value: 747 g / mol)

[0645] Synthesis Example 86: Synthesis of Q-1

[0646]

[0647] Under nitrogen flow, BCz-D17 (10.0 g, 23.6 mmol), Cz-D1 (9.3 g, 28.3 mmol), Pd(OAc) 2 (1.36 g, 1.18 mmol), P(t-Bu) 3 (0.57 ml, 2.36 mmol), NaO(t-Bu) (4.55 g, 47.3 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain Q-1 (6.67 g, yield 42%) as the target compound.

[0648] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0649] Synthesis Example 87: Synthesis of R-1

[0650]

[0651] Under nitrogen flow, BCz-D18 (10.0 g, 23.6 mmol), Cz-D1 (9.3 g, 28.3 mmol), Pd(OAc) 2 (1.36 g, 1.18 mmol), P(t-Bu) 3 (0.57 ml, 2.36 mmol), NaO(t-Bu) (4.55 g, 47.3 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain R-1 (11.27 g, yield 71%) as the target compound.

[0652] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0653] Synthesis Example 88: Synthesis of S-1

[0654]

[0655] Under nitrogen flow, BCz-D19 (10.0 g, 23.6 mmol), Cz-D1 (9.3 g, 28.3 mmol), Pd(OAc) 2 (1.36 g, 1.18 mmol), P(t-Bu) 3(0.57 ml, 2.36 mmol), NaO(t-Bu) (4.55 g, 47.3 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain S-1 (11.75 g, yield 74%) as the target compound.

[0656] Mass (theoretical value: 670.93, measured value: 670 g / mol)

[0657] Synthesis Example 89: Synthesis of T-1

[0658]

[0659] Under nitrogen flow, BCz-D3 (10.0 g, 20.1 mmol), 3-bromo-9-phenyl-9H-carbazole (7.8 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3 (0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain T-1 (10.8 g, yield 73%) as the target compound.

[0660] Mass (theoretical value: 739.98, measured value: 739 g / mol)

[0661] Synthesis Example 90: Synthesis of U-1

[0662]

[0663] Under nitrogen flow, BCz-D3 (10.0 g, 20.1 mmol), 9-([1,1'-biphenyl]-4-yl-2',3',4',5',6'-d5)-3-bromo-9H-carbazole (9.7 g, 24.1 mmol), Pd(OAc) 2 (1.15 g, 1.0 mmol), P(t-Bu) 3(0.49 ml, 2.0 mmol), NaO(t-Bu) (3.85 g, 40.1 mmol) and toluene (100 ml) were mixed and stirred at 110° C. for 5 hours. After the reaction was completed, toluene was concentrated, and the solid salt was filtered and then purified by recrystallization to obtain U-1 (10.7 g, yield 65%) as the target compound.

[0664] Mass (theoretical value: 821.11, measured value: 821 g / mol)

[0665] Reference example

[0666] The compounds HT, HA, PA, Ir(ppy) used in preparing the organic EL devices according to the following examples and evaluation examples are 3 ,EA,ET,(piq) 2 The structures of Ir(acac) and CBP are as follows.

[0667]

[0668] Example 1: Preparation of green organic EL device

[0669] The compound A-1 synthesized in Synthesis Example 1 was purified by sublimation to a high purity by a generally known method, and then a green organic EL device was prepared according to the following process.

[0670] First, use distilled water to ultrasonically clean the After washing with distilled water, ultrasonic cleaning with isopropyl alcohol, acetone, methanol and other solvents and drying, the substrate was transferred to a UV-ozone (OZONE) cleaning machine (Power sonic405, HWASHIN TECH), and then the substrate was cleaned with UV for 5 minutes and transferred to a vacuum evaporation machine.

[0671] On the ITO transparent electrode prepared as above, HT+2% / 60% Compound A-1 + 30% Solus E-type HOST + 10% Ir(ppy) 3 The layers are stacked sequentially to prepare an organic EL device.

[0672] Examples 2 to 88: Preparation of green organic EL devices

[0673] The green organic EL devices of Examples 2 to 90 are prepared in the same manner as in Example 1 above, except that compounds A-2 to U-1 synthesized in Synthesis Examples 2 to 90 are used instead of Compound A-1 used as the light-emitting main material when forming the light-emitting layer (refer to Tables 1 and 2 below).

[0674] Comparative Example 1: Preparation of green organic EL device

[0675] A green organic EL device of Comparative Example 1 was prepared in the same manner as in Example 1, except that Compound A-1-1 having the same structure and not substituted with deuterium was used instead of Compound A-1 as the luminescent host substance when forming the luminescent layer. The structure of Compound A-1-1 used is as follows.

[0676]

[0677] Comparative Example 2: Preparation of Green Organic EL Device

[0678] A green organic EL device of Comparative Example 2 was prepared in the same manner as in Example 2 except that Compound A-2-1 having the same structure and not substituted with deuterium was used instead of Compound A-2 as the luminescent host substance when forming the luminescent layer. The structure of Compound A-2-1 used is as follows.

[0679]

[0680] Comparative Example 3: Preparation of Green Organic EL Device

[0681] A green organic EL device of Comparative Example 3 was prepared in the same manner as in Example 3 except that Compound A-3-1 having the same structure and not substituted with deuterium was used instead of Compound A-3 as the luminescent host substance when forming the luminescent layer. The structure of Compound A-3-1 used is as follows.

[0682]

[0683] Comparative Example 4: Preparation of Green Organic EL Device

[0684] A green organic EL device of Comparative Example 4 was prepared in the same manner as in Example 4 except that Compound A-4-1 having the same structure and not substituted with deuterium was used instead of Compound A-4 as the luminescent host substance when forming the luminescent layer. The structure of Compound A-4-1 used is as follows.

[0685]

[0686] Evaluation Example 1

[0687] The green organic EL devices prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were measured at (10) mA / cm 2 The driving voltage, current efficiency, luminescence peak and life span at a current density of , are shown in the following Table 1.

[0688] Table 1

[0689]

[0690] As shown in Table 1 above, it can be confirmed that the green organic EL devices of Examples 1 to 4 using Compounds A-1 to A-4 of the present invention as light-emitting layer materials are significantly superior to the green organic EL devices of Comparative Examples 1 to 4 using Compounds A-1-1 to A-4-1 which are not deuterium-substituted and have the same structure in terms of device efficiency, driving voltage and life characteristics.

[0691] Evaluation Example 2

[0692] The green organic EL devices prepared in the following Examples 5 to 90 were measured at (10) mA / cm 2 The driving voltage, current efficiency, luminescence peak and life span at a current density of , are shown in the following Table 2.

[0693] Table 2

[0694]

[0695]

[0696]

[0697]

[0698] As shown in Table 2 above, it can be confirmed that the green organic EL devices of Examples 5 to 90 using Compounds A-1 to S-1 of the present invention as light-emitting layer materials are also excellent in device efficiency, driving voltage and life characteristics, just like the green organic EL devices of Examples 1 to 4 above.

[0699] Example 91: Preparation of red organic EL device

[0700] The compound A-1 synthesized in Synthesis Example 1 was sublimated and purified to high purity by a generally known method, and then a red organic electroluminescent device was prepared according to the following process.

[0701] First, use distilled water to ultrasonically clean the After washing with distilled water, ultrasonic cleaning with isopropyl alcohol, acetone, methanol and other solvents and drying, the substrate was transferred to a UV-ozone (OZONE) cleaning machine (Power sonic405, HWASHIN TECH), and then the substrate was cleaned with UV for 5 minutes and transferred to a vacuum evaporation machine.

[0702] On the ITO transparent electrode prepared as above, HT+2% Compound A-1 + 40% Solus E-type host (E-type HOST) + 10%

[0704] The layers are stacked sequentially to prepare an organic EL device.

[0705] Examples 92 to 106: Preparation of red organic EL devices

[0706] A red organic EL device was prepared in the same manner as in Example 89, except that compounds A-2 to A-16 synthesized in Synthesis Examples 2 to 16 were used instead of compound A-1 used as a light-emitting host substance when forming the light-emitting layer (refer to Table 3 below).

[0707] Comparative Example 5

[0708] The red organic electroluminescent device of Comparative Example 5 was prepared in the same manner as in Example 91, except that CBP was used instead of Compound A-1 used as a light-emitting host substance when forming the light-emitting layer.

[0709] Evaluation Example 3

[0710] The organic electroluminescent devices prepared in Examples 91 to 106 and Comparative Example 5 were measured at 10 mA / cm 2 The driving voltage and current efficiency at a current density of , and the results are shown in the following Table 3.

[0711] Table 3

[0712]

[0713]

[0714] As shown in Table 3 above, it can be confirmed that the red organic EL devices of Examples 91 to 106 using Compounds A-1 to A-16 of the present invention as light-emitting layer materials are superior to the red organic electroluminescent device of Comparative Example 5 using existing CBP in terms of device efficiency and driving voltage.

[0715] Examples 107-110: Preparation of Green Organic EL Devices

[0716] The compound A-1 synthesized in Synthesis Example 1 was purified by sublimation to a high purity by a generally known method, and then a green organic EL device was prepared according to the following process.

[0717] First, use distilled water to ultrasonically clean the After washing with distilled water, ultrasonic cleaning with isopropyl alcohol, acetone, methanol and other solvents and drying, the substrate was transferred to a UV-ozone (OZONE) cleaning machine (Power sonic405, HWASHIN TECH), and then the substrate was cleaned with UV for 5 minutes and transferred to a vacuum evaporation machine.

[0718] On the ITO transparent electrode prepared as above, HT+2% Compound A-1 + 30% Solus E-type host (E-type HOST) + 10% Ir (ppy) 3 to The layers are stacked sequentially to prepare an organic EL device.

[0719] In this case, the compounds ET-1, ET-2, ET-3 and ET-4 used as the electron transport layer material are dual electron transfer type materials, and their structures are as follows.

[0720]

[0721] Embodiments 111 to 114

[0722] Green organic EL devices were prepared in the same manner as in Examples 107 to 110 except that Compound A-2 synthesized in Synthesis Example 2 was used instead of Compound A-1 as the light-emitting host substance when forming the light-emitting layer (see Table 4 below).

[0723] Embodiments 115 to 118

[0724] Green organic EL devices were prepared in the same manner as in Examples 107 to 110 except that Compound A-3 synthesized in Synthesis Example 3 was used instead of Compound A-1 as the light-emitting host substance when forming the light-emitting layer (see Table 4 below).

[0725] Embodiments 119 to 122

[0726] Green organic EL devices were prepared in the same manner as in Examples 107 to 110 except that Compound A-4 synthesized in Synthesis Example 4 was used instead of Compound A-1 as the light-emitting host substance when forming the light-emitting layer (see Table 4 below).

[0727] Comparative Examples 6 to 9: Preparation of Green Organic EL Devices

[0728] A green organic EL device was prepared in the same manner as in Example 107, except that a single electron transport material ET having 1 EWG was used instead of ET-1 as the electron transport layer material, and A-1 to A-4 were used as the light-emitting host materials, respectively.

[0729]

[0730] Evaluation Example 4

[0731] The organic electroluminescent devices prepared in Examples 107 to 122 and Comparative Examples 6 to 9 were measured at 10 mA / cm 2 The driving voltage, current efficiency, emission wavelength and life (T97) at a current density of , and the results are shown in the following Table 4.

[0732] Table 4

[0733]

[0734]

[0735] As shown in Table 4 above, it can be confirmed that the green organic EL devices of Examples 107 to 122 using the light-emitting layer materials including deuterated compounds A-1 to A-4 and using dual electron-withdrawing group type (dual EWG type) electron transport layer materials are significantly improved in the driving voltage, current efficiency and life characteristics of the device compared to Comparative Examples 6 to Comparative Examples 9 using deuterated compounds and existing single EWG type electron transport layers. It can be seen that this is due to the combination of the excellent hole stability of the deuterated compound of the present invention used for the light-emitting layer and the high electron transport ability of the dual electron-withdrawing group type (dual EWG type) electron transport layer material, which achieves a significant synergy effect in the performance characteristics of the device. Therefore, it can be seen that in the present invention, the light-emitting layer including the compound represented by Chemical Formula 1 and the dual electron withdrawing group type (dual EWG type) electron transport layer including at least two EWG groups are used in combination, so that the performance of the organic electroluminescent device can be optimized by enhancing the hole stability of the light-emitting layer (EML) and maximizing the electron transport ability of the electron transport layer (ETL).

Claims

1. A compound represented by the following chemical formula 1, characterized in that: Chemical formula 1: In the above chemical formula 1, Ar1 and Ar2 are the same or different from each other and are independently selected from C1 to C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C6~C 40 aryl, heteroaryl having 5 to 40 nuclear atoms, C6 to C 40 Aryloxy, C1~C 40 Alkoxy, C6~C 40 Aromatic amine group, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 nuclear atoms, C1 to C 40 Alkyl silyl, C1~C 40 Alkyl boron, C6~C 40 Aryl boron, C6~C 40 Arylphosphine, C6~C 40 Aryl phosphine oxide and C6~C 40 In the group consisting of arylsilyl groups, a, d and f are each independently 1 to 3, b, c, e are each independently 1 to 4, but a+b+c+d+e+f≥15, The hydrogen on the benzene ring of the deuterium-unsubstituted carbazole can be selected from C1 to C 40 Alkyl, C6~C 40 substituted with a substituent selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms, The alkyl, alkenyl, alkynyl, aryl, heteroaryl, aryloxy, alkoxy, arylamino, cycloalkyl, heterocycloalkyl, alkylsilyl, alkylboryl, arylboryl, arylphosphino, arylphosphine oxide and arylsilyl groups of Ar1 to Ar2 are each independently selected from deuterium, halogen, cyano, nitro, C1 to C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 nuclear atoms, C6 to C 40 aryl, heteroaryl having 5 to 40 nuclear atoms, C1 to C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 40 Aryl silyl, C1~C 40 Alkyl boron, C6~C 40 Aryl boron, C6~C 40 Arylphosphine, C6~C 40 Aryl phosphine oxide and C6~C 40 The aromatic amine group may be substituted or unsubstituted with one or more substituents. When a plurality of such substituents are present, they may be the same as or different from each other.

2. The compound according to claim 1, characterized in that The compound represented by the above Chemical Formula 1 contains 21 or more deuteriums.

3. The compound according to claim 1, characterized in that Ar1 and Ar2 are the same or different from each other and are independently selected from C6 to C 40 The group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms, The aryl and heteroaryl groups of Ar1 to Ar2 are each independently selected from deuterium, halogen, cyano, C6 to C 40 The invention may be substituted or unsubstituted with one or more substituents selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms.

4. The compound according to claim 1, characterized in that Ar1 and Ar2 are each independently selected from the group consisting of the following substituents S1 to S9: In the above formula, * indicates the site of connection with Chemical Formula 1.

5. The compound according to claim 1, characterized in that The compound represented by the above Chemical Formula 1 is shown in any one of the following Chemical Formulas 2 to 17: Chemical formula 2: Chemical formula 3: Chemical formula 4: Chemical formula 5: Chemical formula 6: Chemical formula 7: Chemical formula 8: Chemical formula 9: Chemical formula 10: Chemical formula 11: Chemical formula 12: Chemical formula 13: Chemical formula 14: Chemical formula 15: Chemical formula 16: Chemical formula 17: In the above formula, Ar1, Ar2, a, b, c, d, e and f are respectively as defined in claim 1.

6. The compound according to claim 1, characterized in that The compound represented by the above Chemical Formula 1 is a host material of the light emitting layer.

7. The compound according to claim 1, characterized in that The compound represented by the above Chemical Formula 1 is selected from the group consisting of the following compounds A-1 to U-1:

8. An organic electroluminescent device, characterized in that: It includes an anode, a cathode and one or more organic layers between the anode and the cathode. At least one of the one or more organic layers contains the compound according to any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, characterized in that: The one or more organic layers include at least one 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, an electron transport layer and an electron transport auxiliary layer, The light emitting layer includes the compound represented by Chemical Formula 1 as a host.

10. The organic electroluminescent device according to claim 9, characterized in that: The light-emitting layer further includes at least one of a P-type host material, an N-type host material, a fluorescent dopant and a phosphorescent dopant.

11. The organic electroluminescent device according to claim 9, characterized in that: The electron transport layer includes a compound represented by the following Chemical Formula 18: Chemical formula 18: In the above chemical formula 18, L can be selected from C6~C 40 arylene and substituted or unsubstituted heteroarylene having 5 to 40 nuclear atoms, X1 to X 10 are each independently N or C(R1), When there are a plurality of C(R1), the plurality of R1 are the same or different from each other and are independently selected from C1 to C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C6~C 40 aryl, heteroaryl having 5 to 40 nuclear atoms, C6 to C 40 Aryloxy, C1~C 40 Alkoxy, C6~C 40 Aromatic amine group, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 nuclear atoms, C1 to C 40 Alkyl silyl, C1~C 40 Alkyl boron, C6~C 40 Aryl boron, C6~C 40 Arylphosphine, C6~C 40 Aryl phosphine oxide and C6~C 40 In the group consisting of arylsilyl groups, The arylene group and heteroarylene group of L and the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, arylamino group, cycloalkyl group, heterocycloalkyl group, alkylsilyl group, alkylboryl group, arylboryl group, arylphosphino group, arylphosphine oxide group and arylsilyl group of R1 can be independently selected from deuterium, halogen, cyano group, nitro group, C1-C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkynyl, C3~C 40 Cycloalkyl, heterocycloalkyl with 3 to 40 nuclear atoms, C6 to C 60 aryl, heteroaryl having 5 to 60 nuclear atoms, C1 to C 40 Alkoxy, C6~C 60 Aryloxy, C1~C 40 Alkyl silyl, C6~C 60 Aryl silyl, C1~C 40 Alkyl boron, C6~C 60 Aryl boron, C6~C 60 Arylphosphine, C6~C 60 Aryl phosphine oxide and C6~C 60 The substituents may be substituted with one or more substituents selected from the group consisting of an aromatic amine group and, in this case, when a plurality of the substituents are present, they may be the same as or different from each other.

12. The organic electroluminescent device according to claim 11, characterized in that: The above rings containing X1 to X5 and rings containing X6 to X 10 The rings are the same as or different from each other and are each independently selected from the group consisting of the following substituents A-1 to A-5: In the above formula, Z1 and Z2 are the same or different from each other and are independently selected from C6 to C 40 The group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms, R1 is independently selected from hydrogen, C1 to C 40 Alkyl, C6~C 40 The group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms, The aryl and heteroaryl groups of Z1 to Z2 and the alkyl, aryl and heteroaryl groups of R1 can be independently selected from deuterium, halogen, cyano, C6-C 40 The substituent may be substituted by one or more substituents selected from the group consisting of an aryl group and a heteroaryl group having 5 to 40 nuclear atoms. In this case, when a plurality of the substituents are present, they may be the same as or different from each other.

13. The organic electroluminescent device according to claim 12, characterized in that: The above Z1 and Z2 are each independently selected from the following structural formula: In the above formula, * indicates the site of connection with Chemical Formula 18.

14. The organic electroluminescent device according to claim 11, characterized in that: The above L is a linking group selected from the following structural formulas: In the above formula, * indicates the site of connection with Chemical Formula 18.

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