KR102595744B1 - Organic electronic element comprising mixture mixed with different compounds as host material and an electronic device thereof - Google Patents

Abstract

The present invention provides an organic electric device and its electronic device using a mixture of two or more compounds represented by Formula 1 and a compound represented by Formula 2 as a host material for a phosphorescent light-emitting layer, and this mixture is used as a phosphorescent host material. By using it, the driving voltage of the organic electric device can be lowered and the luminous efficiency and lifespan can be improved.

Description

Organic electric device comprising a mixture of heterogeneous compounds as a host and its electronic device {ORGANIC ELECTRONIC ELEMENT COMPRISING MIXTURE MIXED WITH DIFFERENT COMPOUNDS AS HOST MATERIAL AND AN ELECTRONIC DEVICE THEREOF}

The present invention relates to organic electric devices and their electronic devices, and more specifically, to organic electric devices and their electronic devices with improved driving voltage, luminous efficiency, lifespan, etc. by using a mixture of heterogeneous compounds as a host material.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic electric devices that utilize the organic light emission phenomenon usually have a structure including an anode, a cathode, and an organic material layer between them. Here, the organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of the organic electric device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as organic layers in organic electric devices can be classified into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their function. In addition, the light-emitting materials can be classified into high-molecular and low-molecular types depending on their molecular weight, and can be classified into fluorescent materials derived from the singlet excited state of electrons and phosphorescent materials derived from the triplet excited state of electrons depending on the luminescence mechanism. You can. In addition, light-emitting materials can be divided into blue, green, and red light-emitting materials depending on the color of the light, and yellow and orange light-emitting materials necessary to realize better natural colors.

On the other hand, when only one substance is used as a light-emitting material, the maximum emission wavelength moves to a longer wavelength due to intermolecular interactions, and problems arise such as a decrease in color purity or a decrease in the efficiency of the device due to the emission attenuation effect, thereby increasing color purity and energy transfer. In order to increase luminous efficiency through , a host/dopant system can be used as a luminescent material. The principle is that when a small amount of a dopant with a smaller energy band gap than the host forming the light-emitting layer is mixed into the light-emitting layer, excitons generated in the light-emitting layer are transported to the dopant, producing highly efficient light. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of the desired wavelength can be obtained depending on the type of dopant used.

Currently, the portable display market is increasing in size toward large-area displays, which requires greater power consumption than that required for existing portable displays. Therefore, power consumption has become a very important factor for portable displays that have a limited power source such as batteries, and issues of efficiency and lifespan must also be resolved.

Efficiency, lifespan, and driving voltage are related to each other. As efficiency increases, the driving voltage relatively decreases. As the driving voltage decreases, crystallization of organic substances due to Joule heating generated during driving decreases, resulting in less crystallization of organic substances. Life expectancy tends to increase. However, efficiency cannot be maximized simply by improving the organic layer. This is because long lifespan and high efficiency can be achieved at the same time when the energy level and T ₁ value between each organic layer and the intrinsic properties of the material (mobility, interface properties, etc.) are optimally combined. .

Therefore, there is a need to develop a host material that has high thermal stability and can efficiently achieve charge balance within the light-emitting layer, and in particular, the development of a phosphorescent host material is needed.

Therefore, the present invention uses a mixture containing three or more different compounds as a host material for a phosphorescent organic electric device, thereby facilitating control of the HOMO level and LUMO level of the phosphorescent host material to maintain charge balance in the light-emitting layer. ) The purpose is to provide an organic electric device and its electronic device that can significantly improve driving voltage, efficiency, and lifespan.

In one aspect, the present invention provides an organic electric device using a mixture of two compounds represented by the following formula (1) and a compound represented by the formula (2) as a phosphorescent host material of the light-emitting layer.

<Formula 1> <Formula 2>

In another aspect, the present invention provides an electronic device including the organic electric device.

According to the present invention, by using a mixture of three or more different compounds as a phosphorescent host material to improve hole/electron control between the constituent layers of an organic electric device, the driving voltage of the device can be lowered, and the luminous efficiency and lifespan can be improved. can be improved.

1 is an exemplary diagram of an organic electroluminescent device according to the present invention.

The terms “aryl group” and “arylene group” used in the present invention each have 6 to 60 carbon atoms unless otherwise specified, and are not limited thereto. In the present invention, an aryl group or arylene group includes a single ring type, a ring aggregate, a fused multiple ring system, a spiro compound, etc.

The term "heterocyclic group" used in the present invention includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group" but also non-aromatic rings, and unless otherwise specified, each carbon number containing one or more heteroatoms. It refers to a ring numbered from 2 to 60, but is not limited thereto. As used herein, the term "heteroatom" refers to N, O, S, P, or Si, unless otherwise specified, and the heterocyclic group refers to a single ring containing heteroatoms, a ring aggregate, a fused multiple ring system, or a ring group. refers to compounds, etc.

The term "heterocyclic group" used in the present invention refers to a ring containing heteroatoms such as N, O, S, P or Si instead of carbon forming the ring, and "heteroaryl group" or "heteroarylene group". It includes not only aromatic rings such as but also non-aromatic rings, and may also include compounds containing heteroatoms such as SO ₂ , P=O, etc., such as the compounds below, instead of carbon forming a ring.

As used in the present invention, the term "fluorenyl group" or "fluorenylene group" refers to a monovalent or divalent functional group in which R, R' and R" are all hydrogen in the following structure, respectively, unless otherwise specified. Substituted fluorenyl group" or "substituted fluorenylene group" means that at least one of the substituents R, R', and R" is a substituent other than hydrogen, and R and R' are bonded to each other and the carbon to which they are bonded This includes cases where they form a spiro compound together.

The term "spiro compound" used in the present invention has a 'spiro union', and the spiro union refers to a connection made by two rings sharing only one atom. At this time, the atom shared between the two rings is called a 'spiro atom', and depending on the number of spiro atoms in one compound, they are 'monospiro-', 'dispiro-', and 'trispiro-' respectively. 'It is called a compound.

In this specification, the 'group name' corresponding to the aryl group, arylene group, heterocyclic group, etc., as examples of each symbol and its substituent, may be written as the 'name of the group reflecting the valence', but is written as the 'parent compound name'. You may. For example, in the case of 'phenanthrene', a type of aryl group, the name of the group may be written by distinguishing the valence, such as the monovalent 'group' is 'phenanthryl' and the divalent group is 'phenanthrylene', but the valence and Regardless, it can also be written as the parent compound name, ‘phenanthrene’. Similarly, in the case of pyrimidine, it can be written as 'pyrimidine' regardless of the valence, or it can be written as the 'name of the group' of the valence, such as pyrimidineyl group in the case of monovalent group, pyrimidineylene in the case of divalent group, etc. there is.

In addition, unless explicitly stated otherwise, the chemical formula used in the present invention is applied identically to the substituent definition according to the exponent definition of the following chemical formula.

Here, when a is an integer of 0, the substituent R ¹ is absent, and when a is an integer of 1, one substituent R ¹ is bonded to any one of the carbons forming the benzene ring, and when a is an integer of 2 or 3, Each is combined as follows, and at this time, R ¹ may be the same or different from each other. When a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner. Meanwhile, the indication of hydrogen bonded to the carbon forming the benzene ring can be omitted.

Hereinafter, the layered structure of an organic electric device containing the compound of the present invention will be described with reference to FIG. 1.

In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted. Additionally, when a component, such as a layer, membrane, region, plate, etc., is said to be "on" or "on" another component, it means not only that it is "directly above" the other component, but also that there is another component in between. It should be understood that it can also include cases. Conversely, when an element is said to be "right on top" of another part, it should be understood to mean that there is no other part in between.

1 is an exemplary diagram of an organic electric device according to an embodiment of the present invention.

Referring to Figure 1, the organic electric device 100 according to an embodiment of the present invention includes a first electrode 120, a second electrode 180, and a first electrode 120 formed on a substrate 110. It includes an organic material layer containing a compound according to the present invention between the second electrodes 180. At this time, the first electrode 120 may be an anode and the second electrode 180 may be a cathode. In the case of the inverted type, the first electrode may be the cathode and the second electrode may be the anode.

The organic material layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, an electron injection layer 170, etc., sequentially stacked on the first electrode 120. . At this time, at least one of these layers may be omitted, or a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, etc. may be further included, and an electron transport layer 160, etc. It may also act as a hole blocking layer.

In addition, although not shown, the organic electric device according to an embodiment of the present invention may further include a protective layer or a light efficiency improvement layer. This light efficiency improvement layer may be formed on a side of both sides of the first electrode that is not in contact with the organic material layer, or on both sides of the second electrode that is not in contact with the organic material layer.

On the other hand, when using one type of single compound as the host material of the light-emitting layer and when using a mixture of heterogeneous compounds, the band gap, electrical properties, and interface properties may vary, so the organic electric device In order to improve electrical properties such as lifespan and efficiency, it is very important to determine what compounds each component of the mixture will consist of.

In the present invention, a mixture of two or more compounds represented by Formula 1 and a compound represented by Formula 2, that is, a mixture containing at least three types of compounds, is used as a host material for the light-emitting layer, thereby maintaining the energy level and T ₁ between each organic layer. We sought to simultaneously improve the lifespan and efficiency of organic electric devices by optimizing the values and intrinsic properties of materials (mobility, interface properties, etc.).

An organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. It can be manufactured using a deposition method such as PVD or CVD. For example, an anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injection layer 130 is formed thereon. , It can be manufactured by forming an organic material layer including the hole transport layer 140, the light emitting layer 150, the electron transport layer 160, and the electron injection layer 170, and then depositing a material that can be used as the cathode 180 thereon. there is. In addition, an auxiliary light emitting layer 151 may be formed between the hole transport layer 140 and the light emitting layer 150, and an auxiliary electron transport layer may be further formed between the light emitting layer 150 and the electron transport layer 160.

In addition, the organic material layer uses a variety of polymer materials, such as a solution process or solvent process rather than a deposition method, such as spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, and doctor bleed process. It can be manufactured with fewer layers by methods such as a printing process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the formation method.

The organic electric device according to an embodiment of the present invention may be a front-emitting type, a rear-emitting type, or a double-sided emitting type depending on the material used.

Additionally, the organic electric device according to an embodiment of the present invention may be selected from the group consisting of organic electroluminescent devices, organic solar cells, organic photoreceptors, organic transistors, monochromatic lighting devices, and quantum dot display devices.

Another embodiment of the present invention may include a display device including the organic electric device of the present invention described above, and an electronic device including a control unit that controls the display device. At this time, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game consoles, various TVs, and various computers.

Hereinafter, an organic electric device according to one aspect of the present invention will be described.

The organic electric device according to one aspect of the present invention includes a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode. At this time, the organic layer includes a phosphorescent light-emitting layer, and the host of the phosphorescent light-emitting layer includes a first compound represented by Formula 1 below, a second compound represented by Formula 2 below, and a third compound represented by Formula 1 below. And the first compound and the third compound are different from each other.

<Formula 1> <Formula 2>

Hereinafter, the symbols used in each chemical formula will be explained.

First, each symbol in Chemical Formula 1 will be explained.

Ring A and Ring B are each independently an aromatic ring of C ₆ to C ₂₀ or a heterocycle of C ₂ to C ₂₀ .

When ring A and ring B are aromatic rings, they are preferably aromatic rings of C ₆ to C ₁₄ , and may be, for example, benzene, naphthalene, phenanthrene, etc.

The A ring may be substituted with one or more R ² and the B ring may be substituted with one or more R ³ , and R ² and R ³ are independently hydrogen; heavy hydrogen; halogen; Cyano group; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₃₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N(R _a )(R _b ); and a plurality of R ² and R ³ may be the same or different from each other.

When R ² and R ³ are an aryl group, preferably an aryl group of C ₆ to C ₃₀ , more preferably an aryl group of C ₆ to C ₁₈ , such as phenyl, naphthyl, biphenyl, terphenyl, etc. .

When R ² and R ³ are alkenyl groups, they are preferably alkenyl groups of C ₂ to C ₂₀ , more preferably alkenyl groups of C ₂ to C ₂₀ , such as ethene and propene.

X ^{1 and} is an integer greater than or equal to 1. When l or m is 0, X ¹ or X ² is absent, meaning that immediately adjacent carbon atoms are not bonded through X ^{1 or} Since m is an integer greater than 1, cases where X ¹ and X ² are simultaneously a single bond are excluded.

When both X ^{1 and} It may be the same or different.

Ar ¹ and Ar are C ₆ to C ₆₀ aryl groups; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; and -L'-N(R _a )(R _b );

When Ar ¹ and Ar are an aryl group, preferably an aryl group of C ₆ to C ₃₀ , more preferably an aryl group of C ₆ to C ₁₈ , such as phenyl, naphthyl, biphenyl, terphenyl, phenanthrene, It may be triphenylene, etc.

When Ar ¹ and Ar are heterocyclic groups, preferably C ₂ to C ₃₀ heterocyclic groups, more preferably C ₂ to C ₁₆ heterocyclic groups, such as pyridine, pyrimidine, triazine, quinoline, quina. It may be zoline, quinoxaline, benzothienopyrimidine, benzofuropyrimidine, naphthofuropyrimidine, benzoquinazoline, dibenzothiophene, benzimidazole, dibenzoquinazoline, etc.

When Ar ¹ and Ar are fluorenyl groups, they may be 9,9-dimethylfluorene, 9,9-diphenylfluorene, etc.

L ¹ and L are single bonds; C ₆ ~ C ₆₀ arylene group; fluorenylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; and a fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ .

When L ¹ and L are arylene groups, they are preferably C ₆ to C ₃₀ arylene groups, more preferably C ₆ to C ₁₈ arylene groups, such as phenyl, naphthyl, biphenyl, terphenyl, etc. .

When L ¹ and L are heterocyclic groups, preferably C ₂ to C ₃₀ heterocyclic groups, more preferably C ₂ to C ₁₆ heterocyclic groups, such as pyridine, pyrimidine, triazine, quinoline, quina. It may be zoline, quinoxaline, benzimidazole, benzothienopyrimidine, naphthofuropyrimidine, benzoquinazoline, dibenzoquinazoline, dibenzothiophene, benzofuropyrimidine, etc.

R' and R" are hydrogen; deuterium; halogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₂ ~ C ₆₀ containing at least one heteroatom among O, N, S, Si, and P. Heterocyclic group; C ₃ ~ C ₆₀ aliphatic ring; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N(R _a )(R _b ); in the group consisting of is selected, and R' and R" may be combined with each other to form a ring. When R' and R" are bonded to each other to form a ring, a spiro compound can be formed together with C to which they are bonded.

When R' and R" are aryl groups, they may be preferably C ₆ to C ₃₀ aryl groups, more preferably C ₆ to C ₁₂ aryl groups, such as phenyl, biphenyl, naphthyl, etc.

When R' and R" are alkyl groups, they may be preferably C ₁ -C ₁₀ alkyl groups, more preferably C ₁ -C ₄ alkyl groups, such as methyl, t-butyl, etc.

R ¹ is hydrogen; heavy hydrogen; halogen; Cyano group; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₃₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N(R _a )(R _b ); and adjacent groups may be bonded to each other to form a ring.

The ring formed by bonding adjacent R ¹ to each other is an aromatic ring group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; Or it may be a fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ . For example, when neighboring R ¹ bonds with each other, aromatic rings such as benzene, naphthalene, phenanthrene, etc. may be formed.

a is an integer of 0 to 2, and when a is an integer of 2 or more, each R ¹ may be the same or different from each other.

When R ¹ is a heterocyclic group, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₂₂ heterocyclic group, such as carbazole, phenyl-carbazole, naphthyl-carbazole. It may be, etc.

The L' is independently a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; and a fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ .

R _a and R _b are each independently an aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; and a fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ .

The rings formed by combining the above R ¹ , R ² , R ³ , Ar ¹ , Ar, L ¹ , L', L, R _a , R _b , R', R", and adjacent groups are each selected from deuterium; halogen; Silane group substituted or unsubstituted with C ₁ -C ₂₀ alkyl group or C ₆ -C ₂₀ aryl group; siloxane group; boron group; germanium group; cyano group; nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkynyl group; C ₆ -C ₂₀ Aryl group; Aryl group of C ₆ -C ₂₀ substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocycle containing at least one heteroatom selected from the group consisting of O, N, S, Si and P Group; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; -L'-N(R _a )(R _b ); and combinations thereof It may be further substituted with one or more substituents selected from the group consisting of.

In Formula 2, each symbol can be defined as follows.

Ring C and Ring D are each independently an aromatic ring of C ₆ to C ₂₀ or a heterocycle of C ₂ to C ₂₀ .

When the C ring and the D ring are aromatic rings, they are preferably aromatic rings of C ₆ to C ₁₄ , and may be, for example, benzene, naphthalene, anthracene, phenanthrene, etc.

The C ring and the D ring may be independently substituted with one or more substituents R, where the substituent R is hydrogen; heavy hydrogen; halogen; Cyano group; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₃₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N(R _a )(R _b ); and a plurality of R may be the same or different from each other. Here, L', R _a and R _b may be defined the same as those defined in Formula 1.

When R is an aryl group, it may be preferably a C ₆ to C ₃₀ aryl group, more preferably a C ₆ to C ₁₄ aryl group, such as phenyl, naphthyl, biphenyl, phenanthrene, etc.

When R is a heterocyclic group, it is preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₉ heterocyclic group, such as quinoline, quinazoline, quinoxaline, etc.

When R is an alkyl group, it is preferably an alkyl group of C ₁ to C ₁₀ , more preferably an alkyl group of C ₁ to C ₄ , such as methyl, t-butyl, etc.

X ³ is O or S.

Ar ² to Ar ⁵ may be defined the same as Ar ¹ defined in Formula 1, and each of them may be the same or different from each other. That is, Ar ² to Ar ⁵ are independently an aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; and -L'-N(R _a )(R _b );

When Ar ² to Ar ⁵ are an aryl group, preferably an aryl group of C ₆ to C ₃₀ , more preferably an aryl group of C ₆ to C ₁₈ , such as phenyl, biphenyl, naphthyl, terphenyl, phenanthrene. , triphenylene, etc.

When Ar ² to Ar ⁵ are heterocyclic groups, preferably C ₂ to C ₃₀ heterocyclic groups, more preferably C ₂ to C ₁₈ heterocyclic groups, such as pyridine, carbazole, phenylcarbazole, benzo. It may be thiophene, dibenzothiophene, dibenzofuran, benzonaphthothiophene, benzonaphthofuran, etc.

When Ar ² to Ar ⁵ are a fluorenyl group, they may be 9,9-dimethylfluorene, 9,9-diphenylfluorene, 9,9'-spirofluorene, etc.

Additionally, Ar ² and Ar ³ or Ar ⁴ and Ar ⁵ may combine with each other to form a ring, and in this case, the ring formed may be a C ₂ to C ₃₀ heterocycle containing at least one N.

L ² and L ³ may be defined the same as L ¹ defined in Formula 1, and each of them may be the same or different from each other.

When L ² and L ³ are arylene groups, they may be preferably C ₆ to C ₃₀ arylene groups, more preferably C ₆ to C ₁₂ arylene groups, such as phenyl, biphenyl, naphthyl, etc.

When L ² and L ³ are heterocyclic groups, preferably C ₂ to C ₃₀ heterocyclic groups, more preferably C ₂ to C ₈ heterocyclic groups, such as pyridine, thiophene, pyrimidine, quinazoline. It may be, etc.

The rings formed by combining R, Ar ² to Ar ⁵ , L ² , L ³ , L', R _a , R _b and adjacent groups each contain deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group; siloxane group; boron group; Germanium group; Cyano group; nitro group; C ₁ -C ₂₀ alkylthio group; C ₁ -C ₂₀ alkoxy group; C ₆ -C ₂₀ aryloxy group; C ₁ -C ₂₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₂ -C ₂₀ alkyne group; C ₆ -C ₂₀ aryl group; C ₆ -C ₂₀ aryl group substituted with deuterium; fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; C ₃ -C ₂₀ aliphatic ring group; C ₇ -C ₂₀ arylalkyl group; C ₈ -C ₂₀ arylalkenyl group; -L'-N(R _a )(R _b ); and may be further substituted with one or more substituents selected from the group consisting of combinations thereof.

Preferably, in Formulas 1 and 2, ring A, ring B, ring C, and ring D may be independently selected from the group consisting of the following formulas (a-1) to (a-7).

<Formula a-1> <Formula a-2> <Formula a-3> <Formula a-4>

<Formula a-5> <Formula a-6> <Formula a-7>

In the above chemical formula, each symbol can be defined as follows, and * indicates the binding site.

Z ¹ to Z ⁴⁸ are each independently C, C(R ^c ), or N. When Z ¹ to Z ⁴⁸ are C, the substituent R ¹ or R ² may be bonded to C or bonded to L ² or L ³ .

R ^c is hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₂₀ aryloxy group; and -L ^a -N(R ^a )(R ^b );

The L ^a is a single bond independently of each other; C ₆ ~ C ₂₀ arylene group; fluorenylene group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof, wherein R ^a and R ^b are each independently an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof.

Preferably, in Formulas 1 and 2, L ¹ to L ³ may be independently selected from the group consisting of the following Formulas b-1 to b-13.

<Formula b-1> <Formula b-2> <Formula b-3> <Formula b-4> <Formula b-5> <Formula b-6>

<Formula b-7> <Formula b-8> <Formula b-9> <Formula b-10>

<Formula b-11> <Formula b-12> <Formula b-13>

In the above chemical formula, each symbol can be defined as follows.

R ⁴ to R ⁶ are independently hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₂₀ aryloxy group; and -L ^a -N(R ^a )(R ^b ); and adjacent groups may be bonded to each other to form a ring.

Y is independently from each other N-(L ^a -Ar ^a ), O, S or C(R ^d )(R ^e ), Z ⁴⁹ to Z ⁵¹ are independently from each other C, C(R ^c ) or N, At least one of Z ⁴⁹ to Z ⁵¹ is N.

f, h, i and j are each an integer from 0 to 4, g is an integer from 0 to 6, k and l' are each an integer from 0 to 3, m' is an integer from 0 to 2, and n is It is an integer from 0 to 3, and when each of them is an integer of 2 or more, each R ⁴ , each R ⁵ , and each R ⁶ are the same or different from each other,

R ^c , R ^d and R ^e are independently hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₂₀ aryloxy group; and -L ^a -N(R ^a )(R ^b ); and R ^d and R ^e may be combined with each other to form a ring. When R ^d and R ^e combine with each other to form a ring, a spiro compound is formed.

Ar ^a is an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof.

The L ^a is a single bond independently of each other; C ₆ ~ C ₂₀ arylene group; fluorenylene group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,

R ^a and R ^b are each independently an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof.

Preferably, Formula 1 may be represented by the following Formula 1-A or 1-B.

<Formula 1-A> <Formula 1-B>

In the above formula, ring A, ring B, R ¹ , L ¹ , Ar ¹ , X ¹ , X ² and a are as defined in Formula 1.

Preferably, Formula 1 may be represented by one of the following Formulas 1-1 to 1-44.

<Formula 1-1> <Formula 1-2> <Formula 1-3> <Formula 1-4>

<Formula 1-5> <Formula 1-6> <Formula 1-7> <Formula 1-8>

<Formula 1-9> <Formula 1-10> <Formula 1-11> <Formula 1-12>

<Formula 1-13> <Formula 1-14> <Formula 1-15> <Formula 1-16>

<Formula 1-17> <Formula 1-18> <Formula 1-19> <Formula 1-20>

<Formula 1-21> <Formula 1-22> <Formula 1-23> <Formula 1-24>

<Formula 1-25> <Formula 1-26> <Formula 1-27> <Formula 1-28>

<Formula 1-29> <Formula 1-30> <Formula 1-31> <Formula 1-32>

<Formula 1-33> <Formula 1-34> <Formula 1-35> <Formula 1-36>

<Formula 1-37> <Formula 1-38> <Formula 1-39> <Formula 1-40>

<Formula 1-41> <Formula 1-42> <Formula 1-43> <Formula 1-44>

In the above chemical formula, each symbol can be defined as follows.

R ¹¹ are independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₂₀ aryloxy group; and -L ^a -N(R ^a )(R ^b ); and adjacent groups may be bonded to each other to form a ring.

b, c and a' are each integers from 0 to 4, b' and c' are each integers from 0 to 6, b" and c" are each integers from 0 to 8, and each of these is an integer of 2 or more. , each R ¹ , each R ² , each R ³ , and each R ¹¹ are the same as or different from each other.

The L ^a is a single bond independently of each other; C ₆ ~ C ₂₀ arylene group; fluorenylene group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,

R ^a and R ^b are each independently an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof.

X ¹ , X ² , Ar ¹ , L ¹ , R ¹ , R ² , R ³ and a are as defined in Formula 1.

Preferably, Formula 1 may be represented by one of the following Formulas 1-C to 1-J.

<Formula 1-C> <Formula 1-D> <Formula 1-E> <Formula 1-F>

<Formula 1-G> <Formula 1-H> <Formula 1-I> <Formula 1-J>

In the above formula, ring A, ring B, R ¹ , R', R", L ¹ , L, Ar ¹ , Ar and a are as defined in Formula 1.

Preferably, Formula 2 may be represented by one of the following Formulas 2-A to 2-C.

<Formula 2-A> <Formula 2-B>

<Formula 2-C>

In the above chemical formula, each symbol can be defined as follows.

The E ring and the F ring are independently a C ₆ to C ₂₀ aromatic ring or a C ₂ to C ₂₀ heterocycle.

When the E ring and the F ring are aromatic rings, they are preferably C ₆ to C ₁₀ aromatic rings, and may be, for example, benzene, naphthalene, etc.

W is N-(L ^a -Ar ^a ), O, S or C(R ^d )(R ^e ).

L ⁵ to L ⁷ are independently a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; and a fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ .

Ar ^a is an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,

R ^d and R ^e are independently hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L ^a -N(R ^a )(R ^b ); and R ^d and R ^e may be combined with each other to form a ring. When R ^d and R ^e combine with each other to form a ring, a spiro compound is formed.

The L ^a is a single bond independently of each other; C ₆ ~ C ₂₀ arylene group; fluorenylene group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof.

R ^a and R ^b are each independently an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof.

C ring, D ring, X ³ , L ² , L ³ , Ar ³ to Ar ⁵ are as defined in Formula 2.

Also, preferably, Formula 2 may be represented by the following Formula 2-D.

<Formula 2-D>

In the above chemical formula, each symbol can be defined as follows.

Z ¹ to Z ⁴ , and Z ^5' to Z ^8' are independently C, C (R ^c ) or N, and Z ^1' to Z ^4' are independently C (R ^c ) or N, W is N-(L ^a -Ar ^a ), O, S or C(R ^d )(R ^e ).

R ^c , R ^d and R ^e are hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₂₀ aryloxy group; and -L ^a -N(R ^a )(R ^b ); and R ^d and R ^e may be combined with each other to form a ring. When R ^d and R ^e combine with each other to form a ring, a spiro compound is formed.

Wherein L ^a is a single bond; C ₆ ~ C ₂₀ arylene group; fluorenylene group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof.

R ^a and R ^b are each independently an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof.

Ar ³ to Ar ⁵ and X ³ are as defined in Formula 2.

Preferably, Formula 2 may be represented by one of the following Formulas 2-E to 2-G.

<Formula 2-E> <Formula 2-F>

<Formula 2-G>

In the above chemical formula, each symbol can be defined as follows.

Z ¹ to Z ⁴ , and Z ^1' to Z ^4' are independently C (R ^c ) or N, Z ^5' to Z ^8' are independently C, C (R ^c ) or N, W is N-(L ^a -Ar ^a ), O, S or C(R ^d )(R ^e ).

R ^c , R ^d and R ^e are hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₂₀ aryloxy group; and -L ^a -N(R ^a )(R ^b ); and R ^d and R ^e may be combined with each other to form a ring. When R ^d and R ^e combine with each other to form a ring, a spiro compound is formed.

Ar ^a is an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof.

The L ^a is a single bond independently of each other; C ₆ ~ C ₂₀ arylene group; fluorenylene group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof.

R ^a and R ^b are each independently an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof.

Ar ³ to Ar ⁵ and X ³ are as defined in Formula 2 above.

Specifically, the compound represented by Formula 1 may be one of the following compounds, but is not limited thereto.

Specifically, the compound represented by Formula 2 may be one of the following compounds, but is not limited thereto.

Preferably, the host contains 40 to 80% by weight of the first compound represented by Formula 1, 10 to 30% by weight of the second compound represented by Formula 2, and 10 to 40% by weight of the third compound represented by Formula 1. It comes true.

Hereinafter, examples of the synthesis of compounds represented by Formula 1 and Formula 2 and manufacturing examples of organic electric devices according to the present invention will be described in detail through examples, but the present invention is not limited to the examples below.

Synthesis example

[ Synthesis example One]

The compound represented by Formula 1 according to the present invention can be prepared by reacting Sub 1 and Sub 2 as shown in Scheme 1 below.

<Scheme 1>

I. Sub 1 Synthesis example

Sub 1 of Scheme 1 can be synthesized through the reaction route of Scheme 2 below, but is not limited thereto.

<Scheme 2>

1. Sub 1-1 Synthesis example

(1) Sub 1-1a synthesis

2-bromo-9-phenyl-9H-carbazole (50g, 155.18mol), bis(pinacolato)diboron (32.17g, 126.70mmol), KOAc (45.69g, 465.54mmol), PdCl ₂ (dppf) (3.41g, 4.66 mmol) was dissolved in DMF (1L) solvent and refluxed at 120°C for 12 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and washed with water. The organic layer was dried with MgSO ₄ and concentrated. Afterwards, the concentrate was recrystallized using CH ₂ Cl ₂ and methanol solvent to obtain the product (47.03 g, 81%).

(2) Sub 1-1b synthesis

Sub 1-1a (46.94g, 127.12mmol), 1-bromo-2-nitrobenzene (25.68g, 127.12mmol), K ₂ CO ₃ (52.70g, 381.36mmol), Pd(PPh ₃ ) ₄ (4.41g, 3.81 mmol) was placed in a round bottom flask, dissolved in THF (600 mL) and water (300 mL), and then refluxed at 80°C for 12 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and washed with water. The organic layer was dried over MgSO ₄ , concentrated, and separated using a silica gel column to obtain the product (31.97 g, 69%).

(3) Sub 1-1 synthesis

Sub 1-1b (31.97g, 87.73mmol) and triphenylphosphine (57.53g, 219.33mmol) were dissolved in o -dichlorobenzene (500mL) and refluxed at 200°C for 24 hours. When the reaction was completed, the solvent was removed using reduced pressure distillation, and the concentrated product was separated on a silica gel column and recrystallized to obtain the desired product (20.42 g, 70%).

2. Sub 1-8 Synthesis example

(1) Sub 1-8a synthesis

2-bromodibenzo[b,d]thiophene (50g, 190mmol), bis(pinacolato)diboron (53.07g, 209 mmol), KOAc (55.94g, 570 mmol), PdCl ₂ (dppf) (4.17 g, 5.7mmol) The product (46.87g, 81%) was obtained in the same manner as the synthesis of Sub 1-1a.

(2) Sub 1-8b synthesis

Sub 1-8a (46.87g, 151.09mmol), 1-bromo-2-nitrobenzene (30.52g, 151.09mmol), K ₂ CO ₃ (62.64g, 453.27mmol), Pd(PPh ₃ ) ₄ (5.24g, 4.53 mmol) ), THF (540 mL), and water (270 mL) were used to obtain the product (32.68 g, 71%) in the same manner as the synthesis of Sub 1-1b.

(3) Sub 1-8 synthesis

Sub 1-8b (32.68g, 107.02mmol) and triphenylphosphine (70.18g, 267.55mmol) were synthesized using o -dichlorobenzene (466 mL) in the same manner as the synthesis method of Sub 1-1 to obtain the product (19.83g, 68 %) was obtained.

3. Sub 1-16 Synthesis example

(1) Sub 1-16a synthesis

5-bromobenzo[b]naphtha[1,2-d]thiophene (50g, 159.64mmol), bis(pinacolato)diboron (44.59g, 175.60mmol), KOAc (47g, 478.91mmol), PdCl ₂ (dppf) (3.50 g, 4.79 mmol), and the product (46.01 g, 80%) was obtained by proceeding in the same manner as the synthesis of Sub 1-1a using DMF (1L) as a solvent.

(2) Sub 1-16b synthesis

Sub 1-16a (45.94g, 156.17mmol), 1-bromo-2-nitrobenzene (38.90g, 156.17mmol), K ₂ CO ₃ (64.75g, 468.51mmol), Pd(PPh ₃ ) ₄ (5.41g, 4.69 mmol), THF (680 mL), and water (340 mL) were used to obtain the product (38.85 g, 70%) in the same manner as the synthesis of Sub 1-1b.

(3) Sub 1-16 synthesis

Proceed in the same manner as the synthesis of Sub 1-1 using Sub 1-16b (38.85g, 109.31mmol), triphenylphosphine (71.68g, 273.28mmol), and o -dichlorobenzene (547mL) to obtain the product (25.81g, 73% ) was obtained.

4. Sub 1-17 Synthesis example

(1) Sub 1-17a synthesis

5-bromobenzo[b]naphtho[2,1-d]thiophene (55g, 175.60mmol), bis(pinacolato)diboron (49.05g, 193.16mmol), KOAc (51.7g, 526.80mmol), PdCl ₂ (dppf) ( The product (49.35g, 78%) was obtained by using 3.86g, 5.27mmol) and DMF (1.11L) in the same manner as the synthesis method of Sub 1-1a.

(2) Sub 1-17b synthesis

Sub 1-17a (49.22g, 136.63mmol), 1-bromo-2-nitrobenzene (27.60g, 136.63mmol), K ₂ CO ₃ (56.65g, 409.88mmol), Pd(PPh ₃ ) ₄ (4.74g, 4.1 mmol), THF (601 mL), and water (301 mL) were used to obtain the product (26.16 g, 67%) in the same manner as the synthesis method of Sub 1-1b.

(3) Sub 1-17 synthesis

Proceed in the same manner as the synthesis method of Sub 1-1 above using Sub 1-17b (26.16g, 73.61mmol), triphenylphosphine (48.26g, 184.01mmol), and o -dichlorobenzene (368mL) to obtain the product (15.95g, 67 %) was obtained.

5. Sub 1-22 Synthesis example

(1) Sub 1-22a synthesis

9-bromo-11-phenyl-11H-benzo[a]carbazole (55g, 147.74mmol), bis(pinacolato)diboron (41.27g, 162.52mmol), KOAc (43.5g, 443.23mmol), PdCl ₂ (dppf) ( The product (51.42g, 83%) was obtained by using 3.24g, 4.43mmol) in the same manner as the synthesis method of Sub 1-1a.

(2) Sub 1-22b synthesis

Sub 1-22a (51.42g, 122.62mmol), 1-bromo-2-nitrobenzene (24.77g, 122.62mmol), K ₂ CO ₃ (50.84g, 367.87mmol), Pd(PPh ₃ ) ₄ (4.25g, 3.68 mmol) ), THF (540 mL), and water (270 mL) were used to obtain the product (38.63 g, 76%) in the same manner as the synthesis method of Sub 1-1b.

(3) Sub 1-22 synthesis

The product (14.97g, 42%) was obtained.

6. Sub 1-28 Synthesis example

(1) Sub 1-28a synthesis

11-bromophenanthro[9,10-b]benzofuran (60g, 172.81mmol), bis(pinacolato)diboron (48.27g, 190.09mmol), KOAc (50.88g, 518.42mmol), PdCl ₂ (dppf) (3.79g, 5.18 The product (52.46g, 77%) was obtained in the same manner as the synthesis method of Sub 1-1a (mmol).

(2) Sub 1-28b synthesis

Sub 1-28a (52.46g, 133.05mmol), 1-bromo-2-nitrobenzene (26.88g, 133.05mmol), K ₂ CO ₃ (55.17g, 399.16mmol), Pd(PPh ₃ ) ₄ (4.61g, 3.99 mmol), THF (574 mL), and water (287 mL) were used to obtain the product (40.93 g, 79%) in the same manner as the synthesis method for Sub 1-1b.

(3) Sub 1-28 synthesis

Sub 1-28b (40.93g, 105.11mmol), triphenylphosphine (68.92g, 262.77mmol), and o -dichlorobenzene (526mL) were synthesized in the same manner as in Sub 1-1, producing Sub 1-28 (15.03g). , 40%) was obtained.

7. Sub 1-41 Synthesis example

(1) Sub 1-41a synthesis

2-bromo-11,11-dimethyl-11H-benzo[b]fluorene (60g, 185.63mmol), bis(pinacolato)diboron (51.85g, 204.19mmol), KOAc (54.65g, 556.88mmol), PdCl ₂ (dppf ) (4.08g, 5.57mmol) was used in the same manner as the synthesis method of Sub 1-1a to obtain the product (50.87g, 74%).

(2) Sub 1-41b synthesis

Sub 1-41a (50.87g, 137.38mmol), 2-bromo-1-nitronaphthalene (34.63g, 137.38mmol), K ₂ CO ₃ (56.96g, 412.13mmol), Pd(PPh ₃ ) ₄ (4.76g, 4.12 mmol), THF (568 mL), and water (284 mL) were used to obtain the product (45.09 g, 79%) in the same manner as the synthesis method of Sub 1-1b.

(3) Sub 1-41 synthesis

Sub 1-41b (45.09g, 108.52mmol) and triphenylphosphine (71.16g, 271.31mmol) were synthesized in the same manner as for Sub 1-1 using o -dichlorobenzene (543mL) to obtain the product (15.81g, 38 %) was obtained.

8. Sub 1-50 Synthesis example

(1) Sub 1-50a synthesis

9-bromo-7-phenyl-7H-benzo[c]carbazole (60g, 161.17mmol), bis(pinacolato)diboron (45.02g, 177.29mmol), KOAc (47.45g, 483.52mmol), PdCl ₂ (dppf) ( The product (52.04g, 77%) was obtained by using 3.54g, 4.84mmol) in the same manner as the synthesis method of Sub 1-1a.

(2) Sub 1-50b synthesis

Sub 1-50a (52.04g, 124.10mmol), 2-bromo-3-nitronaphthalene (31.28g, 124.10mmol), K ₂ CO ₃ (51.46g, 372.31mmol), Pd(PPh ₃ ) ₄ (4.30g, 3.72 mmol), THF (546 mL), and water (273 mL) were used to obtain the product (45.54 g, 79%) in the same manner as the synthesis method of Sub 1-1b.

(3) Sub 1-50 synthesis

Proceed in the same manner as the synthesis method of Sub 1-1 above using Sub 1-50b (45.54g, 98.04mmol), triphenylphosphine (64.29g, 245.09mmol), and o -dichlorobenzene (490mL) to obtain the product (16.96g, 40 %) was obtained.

9. Sub 1-56 Synthesis example

(1) Sub 1-56a synthesis

2-bromonaphtho[2,3-b]benzofuran (60g, 201.92mmol), bis(pinacolato)diboron (56.40g, 222.11mmol), KOAc (59.45g, 605.75 mmol), PdCl ₂ (dppf) (4.43g, 6.06 The product (55.60 g, 80%) was obtained in the same manner as the synthesis method of Sub 1-1a (mmol).

(2) Sub 1-56b synthesis

Sub 1-56a (55.60g, 161.52mmol), 1-bromo-2-nitronaphthalene (40.72g, 161.52mmol), K ₂ CO ₃ (66.97g, 484.57mmol), Pd(PPh ₃ ) ₄ (5.60g, 4.85 mmol), THF (711 mL), and water (355 mL) were used to obtain the product (45.55 g, 74%) in the same manner as the synthesis method of Sub 1-1b.

(3) Sub 1-56 synthesis

Sub 1-56b (45.55g, 116.97mmol), triphenylphosphine (76.7g, 292.43mmol), and o -dichlorobenzene (585 mL) were used to produce the product (15.89g, 38%) was obtained.

10. Sub 1-76 Synthesis example

(1) Sub 1-76a synthesis

5-bromodinaphtho[1,2-b:2',1'-d]furan (60g, 172.81mmol), bis(pinacolato)diboron (48.27g, 190.09mmol), KOAc (50.88g, 518.42mmol), PdCl ₂ (dppf) (3.79g, 5.18mmol) was used in the same manner as the synthesis method of Sub 1-1a to obtain the product (52.46g, 77%).

(2) Sub 1-76b synthesis

Sub 1-76a (52.46g, 133.05mmol), 1-bromo-2-nitronaphthalene (33.54g, 133.05mmol), K ₂ CO ₃ (55.17g, 399.16mmol), Pd(PPh ₃ ) ₄ (4.61g, 3.99 mmol), THF (585 mL), and water (293 mL) were used to obtain the product (40.93 g, 70%) in the same manner as the synthesis method of Sub 1-1b.

(3) Sub 1-76 synthesis

Proceed in the same manner as the synthesis method of Sub 1-1 above using Sub 1-76b (40.93g, 93.13mmol), triphenylphosphine (61.07g, 232.84mmol), and o -dichlorobenzene (466mL) to obtain the product (23.15g, 61 %) was obtained.

11. Sub 1-82 Synthesis example

(1) Sub 1-82a synthesis

11-bromo-13,13-dimethyl-13H-indeno[1,2-l]phenanthrene (60g, 219.64mmol), bis(pinacolato) diboron (61.35g, 241.61mmol), KOAc (64.67g, 658.93mmol), PdCl ₂ (dppf) (4.82g, 6.59mmol) was used in the same manner as the synthesis method of Sub 1-1a to obtain (52.05g, 74%).

(2) Sub 1-82b synthesis

Sub 1-82a (52.05g, 162.53mmol), 1-bromo-2-nitrobenzene (49.11g, 162.53mmol), K ₂ CO ₃ (67.39g, 487.60mmol), Pd(PPh ₃ ) ₄ (5.63g, 4.88 mmol), THF (715ml), and water (358ml) were used to obtain the product (47.95, 71%) in the same manner as the synthesis method of Sub 1-1b.

(3) Sub 1-82 synthesis

Proceed in the same manner as the synthesis method of Sub 1-1 above using Sub 1-82b (47.95g, 115.41mmol), triphenylphosphine (75.67g, 288.51mmol), and o -dichlorobenzene (577mL) to produce the product (18.59g, 42 %) was obtained.

12. Sub 1-93 Synthesis example

(1) Sub 1-93a synthesis

3-bromo-9,9-dimethyl-9H-fluorene (60g, 219.64mmol), bis(pinacolato)diboron (61.35g, 241.61mmol), KOAc (64.67g, 658.93mmol), PdCl ₂ (dppf) (4.82g , 6.59 mmol) was used to obtain (52.05 g, 74%) in the same manner as the synthesis method of Sub 1-1a.

(2) Sub 1-93b synthesis

Sub 1-93a (52.05g, 162.53mmol), 9-bromo-10-nitrophenanthrene (49.11g, 162.53mmol), K ₂ CO ₃ (67.39g, 487.60mmol), Pd(PPh ₃ ) ₄ (5.63g, 4.88 mmol), THF (715ml), and water (358ml) were used to obtain the product (47.95, 71%) in the same manner as the synthesis method of Sub 1-1b.

(3) Sub 1-93 synthesis

Proceed in the same manner as the synthesis method of Sub 1-1 above using Sub 1-93b (47.95g, 115.41mmol), triphenylphosphine (75.67g, 288.51mmol), and o -dichlorobenzene (577mL) to obtain the product (18.59g, 42 %) was obtained.

13. Sub 1-94 Synthesis example

(1) Sub 1-94b synthesis

Sub 1-94a (40g, 111.02mmol), 3-bromo-4-nitro-1,1'-biphenyl (30.88g, 111.02mmol), K ₂ CO ₃ (46.03g, 333.07mmol), Pd(PPh ₃ ) The product (34.97, 73%) was obtained in the same manner as the synthesis method of Sub 1-1b using ₄ (3.85g, 3.33mmol), THF (489ml), and water (244ml).

(2) Sub 1-94 synthesis

Proceed in the same manner as the synthesis method of Sub 1-1 above using Sub 1-94b (34.97g, 81.04mmol), triphenylphosphine (53.14g, 202.60mmol), and o -dichlorobenzene (405mL) to obtain the product (21.69g, 67 %) was obtained.

14. Sub 1-97 Synthesis example

(1) Sub 1-97b synthesis

Sub 1-97a (40g, 111.02mmol), 3-(4-bromo-3-nitrophenyl)-9-phenyl-9H-carbazole (49.22g, 111.02mmol), K ₂ CO ₃ (46.03g, 333.07mmol), The product (42.40, 64%) was obtained in the same manner as the synthesis method of Sub 1-1b using Pd(PPh ₃ ) ₄ (3.85g, 3.33mmol), THF (489ml), and water (244ml).

(2) Sub 1-97 synthesis

Proceed in the same manner as the synthesis method of Sub 1-1 above using Sub 1-97b (42.40g, 71.06mmol), triphenylphosphine (46.59g, 177.64mmol), and o -dichlorobenzene (355mL) to obtain the product (24.48g, 61 %) was obtained.

15. Sub 1-103 Synthesis example

(1) Sub 1-103b synthesis

Sub 1-103a (57.17g, 158.69mmol), 2-bromo-1-nitronaphthalene (40g, 158.69mmol), K ₂ CO ₃ (65.80g, 476.06mmol), Pd(PPh ₃ ) ₄ (5.50g, 4.76mmol) ), THF (698ml), and water (349ml) were used to obtain the product (47.61, 74%) in the same manner as the synthesis method of Sub 1-1b.

(2) Sub 1-103 synthesis

Proceed in the same manner as the synthesis method of Sub 1-1 above using Sub 1-103b (47.61g, 117.42mmol), triphenylphosphine (76.99g, 293.55mmol), and o -dichlorobenzene (587mL) to obtain the product (28.07g, 64 %) was obtained.

Compounds belonging to Sub 1 are the same as, but are not limited to, the following compounds, and Table 1 shows the FD-MS (Field Desorption-Mass Spectrometry) values of the following compounds.

[Table 1]

Ⅱ. Sub 2's Synthesis example

Sub 2 of Scheme 1 can be synthesized through the reaction route of Scheme 3 below, but is not limited thereto.

<Scheme 3> (Hal ¹ is I, Br or Cl, and Hal ² is Br or Cl)

1. Sub 2-35 Synthesis example

(1) Sub 2-35a synthesis

1-amino-2-naphthoic acid (CAS Registry Number: 4919-43-1) (75.11 g, 401.25 mmol) was added to urea (CAS Registry Number: 57-13-6) (168.69 g, 2808.75 mmol) in a round bottom flask. and stirred at 160°C. After confirming the reaction by TLC, the mixture was cooled to 100°C, water (200ml) was added, and stirred for 1 hour. When the reaction was completed, the resulting solid was filtered under reduced pressure, washed with water, and dried to obtain 63.86 g of product (yield: 75%).

(2) Sub 2-35b synthesis

After dissolving Sub 2-35a (63.86 g, 300.94 mmol) in POCl ₃ (200ml) at room temperature, N , N -Diisopropylethylamine (97.23 g, 752.36 mmol) was slowly added dropwise and stirred at 90°C. When the reaction was completed, the product was concentrated, then ice water (500ml) was added and stirred at room temperature for 1 hour. The resulting solid was filtered under reduced pressure and dried to obtain 67.47 g of product (yield: 90%).

(3) Sub 2-35 synthesis

Sub 2-35b (67.47 g, 270.86 mmol) was placed in a round bottom flask, dissolved in THF (950ml), and then 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (CAS Registry Number : 24388-23-6) (60.80 g, 297.94 mmol), Pd(PPh ₃ ) ₄ (12.52 g, 10.83 mmol), K ₂ CO ₃ (112.30 g, 812.57 mmol), and water (475ml) were added and stirred at 90°C. When the reaction was completed, the extract was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated. Afterwards, the concentrate was separated using a silica gel column and recrystallized to obtain 44.89 g of product (yield: 57%).

2. Sub 2-40 Synthesis example

Sub 2-40b (19g, 76.28mmol), 2-(dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS Registry Number: 947770-80-1) (22.44g, 76.28mmol), Pd(PPh ₃ ) ₄ (1.32g, 1.14mmol), K ₂ CO ₃ (15.81g, 114.42mmol), THF (336ml), and water (168ml) were added, and then proceeded in the same manner as the synthesis method of Sub 2-35 to obtain 15.69 g of product. (yield: 54%) was obtained.

3. Sub 2-43 Synthesis example

4,4,5,5-tetramethyl-2- in 2,4-dichlorobenzo[4,5]thieno[3,2- d ]pyrimidine (CAS Registry Number: 160199-05-3) (32.01 g, 125.47 mmol) (naphthalen-1-yl)-1,3,2-dioxaborolane (CAS Registry Number: 68716-52-9) (35.07 g, 138.02 mmol), Pd(PPh ₃ ) ₄ (5.80 g, 5.02 mmol), K ₂ CO ₃ (52.02 g, 376.41 mmol), THF (440ml), and water (220ml) were added and the procedure was carried out in the same manner as the Sub 2-35 synthesis method to obtain 19.58 g of product (yield: 45%) was obtained.

Compounds belonging to Sub 2 may be, but are not limited to, the following compounds, and Table 2 shows the FD-MS values of the following compounds.

[Table 2]

Ⅲ. Compound of Formula 1 Synthesis example

1. 1-1 Synthesis example

Sub 1-1 (10g, 30.08mmol) was placed in a round bottom flask, dissolved in toluene (302 mL), and Sub 2-1 (5.19g, 33.09mmol), Pd ₂ (dba) ₃ (0.83g, 0.90mmol) ), P( t -Bu) ₃ (0.61g, 3.01mmol), NaO t -Bu (8.67g, 90.24mmol) were added and stirred at 100°C. When the reaction was completed, the extract was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated. Afterwards, the concentrate was separated using a silica gel column and recrystallized to obtain 8.14 g of product (yield: 66%).

2. 1-9 Synthesis example

Sub 1-6 (15g, 45.12mmol), Toluene (500 mL), Sub 2-9 (13.56g, 49.63 mmol), Pd ₂ (dba) ₃ (1.24g, 1.35mmol), P( t -Bu) ₃ (0.91g, 4.51mmol) and NaO t -Bu (13.01g, 135.36mmol) were used in the same manner as the above 1-1 synthesis method to obtain 16.82g of product (yield: 71%).

3. 1-21 Synthesis example

Sub 1-22 (11g, 28.76mmol), Toluene (300 mL), Sub 2-1 (4.52g, 28.76mmol), Pd ₂ (dba) ₃ (0.79g, 0.86mmol), P( t -Bu) ₃ (0.35g, 1.73mmol) and NaO t -Bu (8.29g, 86.28mmol) were used to obtain 9.50g of product (yield: 72%) in the same manner as the 1-1 synthesis method.

4. 1-26 Synthesis example

Sub 1-16 (15.3g, 47.3 mmol), Toluene (500 mL), Sub 2-28 (14.8g, 52.0 mmol), Pd ₂ (dba) ₃ (1.3g, 1.42mmol), P( t -Bu) ₃ (0.57g, 2.84mmol) and NaO t -Bu (13.64g, 141.93mmol) were used in the same manner as the above 1-1 synthesis to obtain 18.97g of product (yield: 72%).

5. 1-27 Synthesis example

Sub 1-16 (10g, 30.92mmol), Toluene (325mL), Sub 2-42 (10.0g, 34.01mmol), Pd ₂ (dba) ₃ (0.85g, 0.93mmol), P( t -Bu) ₃ ( 0.38g, 1.86mmol) and NaO t -Bu (8.91g, 92.76mmol) were used to obtain 12.81g of product (yield: 71%) in the same manner as in synthesis method 1-1.

6. 1-28 Synthesis example

Sub 1-16 (10g, 30.92mmol), Toluene (325 mL), Sub 2-35 (9.89g, 34.01mmol), Pd ₂ (dba) ₃ (0.85g, 0.93mmol), P( t -Bu) ₃ (0.38g, 1.86mmol) and NaO t -Bu (8.91g, 92.76mmol) were used in the same manner as the above 1-1 synthesis method to obtain 13.04g of product (yield: 73%).

7. 1-31 Synthesis example

Sub 1-28 (10g, 27.98mmol), Toluene (294mL), Sub 2-6 (9.52g, 30.78mmol), Pd ₂ (dba) ₃ (0.77g, 0.84mmol), P( t -Bu) ₃ ( 0.34g, 1.68mmol) and NaO t -Bu (8.07g, 83.94mmol) were used to obtain 12.45g of product (yield: 76%) in the same manner as in synthesis method 1-1.

8. 1-36 Synthesis example

Sub 1-32 (10g, 26.08mmol), Toluene (274mL), Sub 2-10 (9.24g, 28.68mmol), Pd ₂ (dba) ₃ (0.72g, 0.78mmol), P( t -Bu) ₃ ( 0.32g, 1.56mmol) and NaO t -Bu (7.52g, 78.23mmol) were used to obtain 11.08g of product (yield: 68%) in the same manner as in synthesis method 1-1.

9. 1-67 Synthesis example

Sub 1-56 (10g, 27.98mmol), Toluene (294mL), Sub 2-47 (8.64g, 30.78mmol), Pd ₂ (dba) ₃ (0.77g, 0.84mmol), P( t -Bu) ₃ ( 0.34g, 1.68mmol) and NaO t -Bu (8.07g, 83.94mmol) were used to obtain 11.45g of product (yield: 68%) in the same manner as in synthesis method 1-1.

10. 1-72 Synthesis example

Sub 1-61 (10g, 29.99mmol), Toluene (500 mL), Sub 2-24 (12.78g, 32.99mmol), Pd ₂ (dba) ₃ (0.82g, 0.90mmol), P( t -Bu) ₃ (0.36 g, 1.80mmol) and NaO t -Bu (8.65g, 89.97mmol) were used in the same manner as the above 1-1 synthesis method to obtain 13.82g of product (yield: 72%).

11. 1-90 Synthesis example

Sub 1-91 (10g, 26.78mmol), Toluene (281mL), Sub 2-36 (10.04g, 29.45mmol), Pd ₂ (dba) ₃ (0.74g, 0.80mmol), P( t -Bu) ₃ ( 0.33g, 1.61mmol) and NaO t -Bu (7.72g, 80.33mmol) were used to obtain 12.16g of product (yield: 67%) in the same manner as in synthesis method 1-1.

12. 1-112 Synthesis example

Sub 1-103 (10g, 26.78mmol), Toluene (281mL), Sub 2-55 (9.67g, 26.78mmol), Pd ₂ (dba) ₃ (0.37g, 0.40mmol), P( t -Bu) ₃ ( 0.16g, 0.80mmol) and NaO t -Bu (3.86g, 40.16mmol) were used to obtain 12.25g of product (yield: 70%) in the same manner as in synthesis method 1-1.

The FD-MS values of compounds 1-1 to 1-120 synthesized by the above synthesis method are shown in Table 3 below.

[Table 3]

[ Synthesis example 2]

The compound represented by Formula 2 according to the present invention is synthesized by reacting Sub 3 and Sub 4 as shown in Scheme 4 below, but is not limited thereto.

<Scheme 4> (Hal ² is Br or Cl)

I. Synthesis of Sub 3

Sub 3 of Scheme 4 is synthesized through the reaction route of Scheme 5 below, but is not limited thereto.

<Scheme 5>

1. Sub 3-1 Synthesis example

Diphenylamine (15.22 g, 89.94 mmol) was placed in a round bottom flask and dissolved in toluene (750ml), followed by Sub 3-1c (CAS Registry Number: 669773-34-6) (46.14 g, 134.91 mmol), Pd ₂ (dba). ₃ (2.47 g, 2.70 mmol), P( t -Bu) ₃ (1.82 g, 8.99 mmol), and NaO t -Bu (25.93 g, 269.81 mmol) were added and stirred at 80°C. When the reaction is completed, the extract is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Afterwards, the concentrate was separated using a silica gel column and recrystallized to obtain 23.61 g of product (yield: 61%).

2. Sub 3-3 Synthesis example

N-phenylnaphthalen-2-amine (13.94 g, 63.57 mmol), Sub 3-3e (CAS Registry Number: 201138-91-2) (31.08 g, 95.35 mmol), Pd ₂ (dba) ₃ (1.75 g, 1.91 mmol) ) P( t -Bu) ₃ (1.29 g, 6.36 mmol), NaO t -Bu (18.33 g, 190.71 mmol), and Toluene (530ml) were added and proceeded in the same manner as the Sub 3-1 synthesis method above to obtain 19.78 g of product. (yield: 67%) was obtained.

3. Sub 3-5 Synthesis example

(1) Synthesis of Sub 3-5a

(2-bromo-6-iodophenyl)(ethyl)sulfane (9.94 g, 28.98 mmol) was placed in a round bottom flask, dissolved in THF (100ml), (4-chlorophenyl)boronic acid (4.53 g, 28.98 mmol), and Pd. (PPh ₃ ) ₄ (1.00 g, 0.87 mmol), NaOH (2.32 g, 57.96 mmol), and water (50ml) were added and stirred at 80°C. When the reaction is completed, the extract is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Afterwards, the concentrate was separated using a silica gel column and recrystallized to obtain 8.55 g of product (yield: 90%).

(2) Synthesis of Sub 3-5b

After adding acetic acid (90ml) to Sub 3-5a (8.55 g, 26.09 mmol), 35% hydrogen peroxide (H ₂ O ₂ ) (2.66 g, 78.28 mmol) was added and stirred at room temperature. When the reaction was completed, it was neutralized with NaOH aqueous solution, extracted with EA, and washed with water. The organic layer was dried over MgSO ₄ and concentrated, and then separated using a silica gel column to obtain 8.70 g (97%) of the product.

(3) Synthesis of Sub 3-5c

Add sulfuric acid (H ₂ SO ₄ ) (50ml) to Sub 3-5b (8.70 g, 25.32 mmol) and stir at room temperature. When the reaction was completed, it was neutralized with NaOH aqueous solution, extracted with MC, and washed with water. The organic layer was dried over MgSO ₄ and concentrated, and then separated using a silica gel column to obtain 7.16 g (95%) of the product.

(4) Synthesis of Sub 3-5

Sub 3-5c (7.16 g, 24.06 mmol) was placed in a round bottom flask and dissolved in toluene (240ml), then N-phenylnaphthalen-1-amine (5.28 g, 24.06 mmol), Pd ₂ (dba) ₃ (0.66 g, 0.72 mmol), P( t -Bu) ₃ (0.49 g, 2.41 mmol), and NaO t -Bu (6.94 g, 72.18 mmol) were added and stirred at 80°C. When the reaction is completed, the extract is extracted with CH ₂ Cl ₂ and water, and the organic layer is dried over MgSO ₄ and concentrated. Afterwards, the concentrate was separated using a silica gel column and recrystallized to obtain 8.08 g of product (yield: 77%).

4. Sub 3-17 Synthesis example

(1) Synthesis of Sub 3-17a

(4-bromo-2-iodophenyl)(ethyl)sulfane (10.65 g, 31.05 mmol), (4-chloro-[1,1'-biphenyl] -2-yl)boronic acid (7.22 g, 31.05 mmol), Pd (PPh ₃ ) ₄ (1.08 g, 0.93 mmol), NaOH (2.48 g, 62.10 mmol), THF (100ml), and water (50ml) were added and proceeded in the same manner as the synthesis method of Sub 3-5a to obtain 9.90 g of product. (yield: 79%) was obtained.

(2) Synthesis of Sub 3-17b

Proceed in the same manner as the synthesis of Sub 3-5b using Sub 3-17a (9.90 g, 24.52 mmol), acetic acid (80ml), and 35% hydrogen peroxide (H ₂ O ₂ ) (2.50 g, 73.56 mmol). 9.78 g (95%) of product was obtained.

(3) Synthesis of Sub 3-17c

Sub 3-17b (9.78 g, 23.30 mmol) and sulfuric acid (H ₂ SO ₄ ) (50ml) were used in the same manner as the synthesis of Sub 3-5c to obtain 7.84 g (90%) of the product.

(4) Synthesis of Sub 3-17

Sub 3-17c (7.84 g, 20.98 mmol) N,9-diphenyl-9H-carbazol-3-amine (7.02 g, 20.98 mmol), Pd ₂ (dba) ₃ (0.58 g, 0.63 mmol) P( t- Add Bu) ₃ (0.42 g, 2.10 mmol), NaO t -Bu (6.05 g, 62.94 mmol), and Toluene (210ml) and proceed in the same manner as the synthesis method of Sub 3-5 above to obtain 10.79 g of product (yield: 82) %) was obtained.

5. Sub 3-82 Synthesis example

Diphenylamine (16.48 g, 97.38 mmol) Sub 3-82c (CAS Registry Number: 83834-10-0) (49.96 g, 146.07 mmol), Pd ₂ (dba) ₃ (2.68 g, 2.92 mmol) P( t -Bu ) ₃ (1.97 g, 9.74 mmol), NaO t -Bu (28.08 g, 292.15 mmol), and Toluene (810ml) were added and proceeded in the same manner as the synthesis method of Sub 3-1 above, resulting in 26.40 g of product (yield: 63%) ) was obtained.

6. Sub 3-102 Synthesis example

(1) Synthesis of Sub 3-102d

4-bromo-2-iodophenol (39.85 g, 133.32 mmol), (2-chlorophenyl)boronic acid (20.85 g, 133.32 mmol), Pd(PPh ₃ ) ₄ (4.62 g, 4.00 mmol), NaOH (10.67 g, 266.64 mmol), THF (440ml), and water (220ml) were added and the reaction was carried out in the same manner as the synthesis of Sub 3-5a to obtain 28.73 g of product (yield: 76%).

(2) Synthesis of Sub 3-102e

Sub 3-102d (28.73 g, 101.32 mmol), Pd(OAc) ₂ (2.27 g, 10.13 mmol), 3-nitropyridine (1.26 g, 10.13 mmol), BzOO t Bu (tert-butyl peroxybenzoate) (39.36 g, 202.65 mmol), C ₆ F ₆ (hexafluorobenzene) (150ml), and DMI (N,N'-dimethylimidazolidinone) (100ml) were added and refluxed at 90°C for 3 hours. When the reaction is completed, the temperature of the reactant is cooled to room temperature, extracted with EA, and washed with water. The organic layer was dried over MgSO ₄ and concentrated, then separated using a silica gel column to obtain 13.69 g (48%) of product.

(3) Synthesis of Sub 3-102

Sub 3-102e (13.69 g, 48.63 mmol), N-phenyldibenzo[b,d]thiophen-2-amine (13.39 g, 48.63 mmol), Pd ₂ (dba) ₃ (1.34 g, 1.46 mmol) P( t - Bu) ₃ (0.98 g, 4.86 mmol), NaO t -Bu (14.02 g, 145.89 mmol), and Toluene (490ml) were added and the procedure was carried out in the same manner as the synthesis method of Sub 3-5 above, resulting in 19.67 g of product (yield: 85). %) was obtained.

7. Sub 3-104 Synthesis example

Diphenylamine (9.15 g, 54.04 mmol) Sub 3-104c (CAS Registry Number: 31574-87-5) (27.73 g, 81.07 mmol), Pd ₂ (dba) ₃ (1.48 g, 1.62 mmol) P( t -Bu ) ₃ (1.09 g, 5.40 mmol), NaO t -Bu (15.58 g, 162.13 mmol), and Toluene (450ml) were added and proceeded in the same manner as the synthesis method of Sub 3-1 above, resulting in 15.12 g of product (yield: 65%) ) was obtained.

8. Sub 3-112 Synthesis example

(1) Synthesis of Sub 3-112a

(3-bromo-2-iodophenyl)(ethyl)sulfane (12.73 g, 37.11 mmol), (2-chlorophenyl)boronic acid (5.80 g, 37.11 mmol), Pd(PPh ₃ ) ₄ (1.29 g, 1.11 mmol), NaOH (2.97 g, 74.22 mmol), THF (120ml), and water (60ml) were added, and the reaction was carried out in the same manner as the synthesis of Sub 3-5a to obtain 9.48 g of product (yield: 78%).

(2) Synthesis of Sub 3-112b

Proceed in the same manner as the synthesis of Sub 3-5b above using Sub 3-112a (9.48 g, 28.93 mmol), acetic acid (95ml), and 35% hydrogen peroxide (H ₂ O ₂ ) (2.95 g, 86.80 mmol). 9.74 g (98%) of product was obtained.

(3) Synthesis of Sub 3-112c

Sub 3-112b (9.74 g, 28.34 mmol) and sulfuric acid (H ₂ SO ₄ ) (60ml) were used in the same manner as the synthesis of Sub 3-5c to obtain 7.76 g (92%) of the product.

(4) Synthesis of Sub 3-112

Sub 3-112c (7.76 g, 26.08 mmol) Diphenylamine (4.41 g, 26.08 mmol), Pd ₂ (dba) ₃ (0.72 g, 0.78 mmol) P( t -Bu) ₃ (0.53 g, 2.61 mmol), NaO t -Bu (7.52 g, 78.24 mmol) and Toluene (260ml) were added and the same procedure as the synthesis method of Sub 3-5 was performed to obtain 5.84 g of product (yield: 58%).

Compounds belonging to Sub 3 may be, but are not limited to, the following compounds, and Table 4 shows the FD-MS values of the following compounds.

[Table 4]

II. Synthesis of Sub 4

Sub 4 of Scheme 4 may be synthesized (disclosed in Korean Patent No. 10-1251451 (registration notice dated April 5, 2013) of the applicant) by the reaction route of Scheme 6 below, but is not limited thereto.

<Scheme 6>

Compounds belonging to Sub 4 may be, but are not limited to, the following compounds, and Table 5 shows the FD-MS values of the following compounds.

[Table 5]

III. Compound of Formula 2 Synthesis example

Inventive compounds 2-30, 2-32, 2-35, 2-37, 2-67, 2-80, 2-86, 2-94, 2-111. 2-119 and 2-133 are manufactured by the synthesis method disclosed in Korean Patent No. 10-1668448 (registration notice dated October 17, 2016) and Korean Patent No. 10-1789998 (registration notice dated October 19, 2017) of the present applicant. It has been done.

1. 2-1 Synthesis example

Sub 3-1 (5.97 g, 13.87 mmol) was placed in a round bottom flask and dissolved in toluene (140ml), followed by Sub 4-17 (3.74 g, 13.87 mmol) and Pd ₂ (dba) ₃ (0.38 g, 0.42 mmol). , P( t -Bu) ₃ (0.28 g, 1.39 mmol), NaO t -Bu (4.00 g, 41.61 mmol) were added and stirred at 100°C. When the reaction was completed, the extract was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated. Afterwards, the concentrate was separated using a silica gel column and recrystallized to obtain 6.09 g of product (yield: 71%).

2. 2-2 Synthesis example

Sub 3-1 (5.29 g, 12.29 mmol) Sub 4-37 (4.32 g, 12.29 mmol), Pd ₂ (dba) ₃ (0.34 g, 0.37 mmol) P( t -Bu) ₃ (0.25 g, 1.23 mmol) ), NaO t -Bu (3.54 g, 36.87 mmol), and Toluene (125ml) were added and proceeded in the same manner as the synthesis method in 2-1 above to obtain 6.81 g of product (yield: 79%).

3. 2-4 Synthesis example

Sub 3-3 (6.13 g, 13.20 mmol) Sub 4-41 (4.08 g, 13.20 mmol), Pd ₂ (dba) ₃ (0.36 g, 0.40 mmol) P( t -Bu) ₃ (0.27 g, 1.32 mmol) ), NaO t -Bu (3.81 g, 39.60 mmol), and Toluene (130ml) were added and proceeded in the same manner as the synthesis method in 2-1 above to obtain 7.32 g of product (yield: 80%).

4. 2-10 Synthesis example

Sub 3-5 (5.56 g, 12.75 mmol) Sub 4-43 (4.28 g, 12.75 mmol), Pd ₂ (dba) ₃ (0.35 g, 0.38 mmol) P( t -Bu) ₃ (0.26 g, 1.28 mmol) ), NaO t -Bu (3.68 g, 38.25 mmol), and Toluene (130ml) were added and proceeded in the same manner as the synthesis method in 2-1 above to obtain 8.06 g of product (yield: 86%).

5. 2-24 Synthesis example

Sub 3-17 (6.18 g, 9.85 mmol) Sub 4-1 (1.67 g, 9.85 mmol), Pd ₂ (dba) ₃ (0.27 g, 0.30 mmol) P( t -Bu) ₃ (0.20 g, 0.99 mmol) ), NaO t -Bu (2.84 g, 29.55 mmol), and Toluene (100ml) were added and proceeded in the same manner as the synthesis method in 2-1 above to obtain 5.62 g of product (yield: 75%).

6. 2-122 Synthesis example

Sub 3-82 (5.05 g, 11.73 mmol) Sub 4-49 (4.12 g, 11.73 mmol), Pd ₂ (dba) ₃ (0.32 g, 0.35 mmol) P( t -Bu) ₃ (0.24 g, 1.17 mmol) ), NaO t -Bu (3.38 g, 35.19 mmol), and Toluene (120ml) were added and proceeded in the same manner as the synthesis method in 2-1 above to obtain 7.65 g of product (yield: 93%).

7. 2-125 Synthesis example

Sub 3-82 (5.20 g, 12.08 mmol) Sub 4-40 (3.13 g, 12.08 mmol), Pd ₂ (dba) ₃ (0.33 g, 0.36 mmol) P( t -Bu) ₃ (0.24 g, 1.21 mmol) ), NaO t -Bu (3.48 g, 36.24 mmol), and Toluene (120ml) were added and proceeded in the same manner as the synthesis method in 2-1 above to obtain 6.69 g of product (yield: 91%).

8. 2-141 Synthesis example

Sub 3-102 (6.26 g, 13.15 mmol) Sub 4-1 (2.23 g, 13.15 mmol), Pd ₂ (dba) ₃ (0.36 g, 0.39 mmol) P( t -Bu) ₃ (0.27 g, 1.32 mmol) ), NaO t -Bu (3.79 g, 39.45 mmol), and Toluene (130ml) were added and proceeded in the same manner as the synthesis method in 2-1 above to obtain 6.57 g of product (yield: 82%).

9. 2-146 Synthesis example

Sub 3-104 (6.12 g, 14.22 mmol) Sub 4-83 (5.84 g, 14.22 mmol), Pd ₂ (dba) ₃ (0.39 g, 0.43 mmol) P( t -Bu) ₃ (0.29 g, 1.42 mmol) ), NaO t -Bu (4.10 g, 42.66 mmol), and Toluene (140ml) were added and proceeded in the same manner as the synthesis method in 2-1 above to obtain 8.00 g of product (yield: 74%).

10. 2-158 Synthesis example

Sub 3-112 (5.75 g, 14.90 mmol) Sub 4-29 (4.10 g, 14.90 mmol), Pd ₂ (dba) ₃ (0.41 g, 0.45 mmol) P( t -Bu) ₃ (0.30 g, 1.49 mmol) ), NaO t -Bu (4.30 g, 44.70 mmol), and Toluene (150ml) were added and proceeded in the same manner as the synthesis method in 2-1 above to obtain 6.24 g of product (yield: 67%).

The FD-MS values of compounds 2-1 to 2-175 prepared according to the above synthesis example are shown in Table 6 below.

[Table 6]

Manufacturing evaluation of organic electric devices

[ Example One] Red organic light emitting device (Mixed phosphohost)

A 60 nm thick hole injection layer was created by vacuum depositing a 4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as 2-TNATA) film on the ITO layer (anode) formed on the glass substrate. Next, N,N'-Bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (hereinafter abbreviated as NPB) was formed. A hole transport layer was formed by vacuum deposition to a thickness of 60 nm.

Next, a 30 nm thick light emitting layer was formed on top of the hole transport layer, where compound 1-17 (first host), compound 2-36 (second host), and compound 1-119 (third host) were mixed in a ratio of 5:3: A mixture mixed at a weight ratio of 2 is used as a host, and bis-(1-phenylisoquinolyl)iridium(Ⅲ) (hereinafter abbreviated as (piq) ₂ Ir(acac)) is used as a dopant, and the host and dopant are mixed at a ratio of 95: It was used at a weight ratio of 5.

Next, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinoline oleato)aluminum (hereinafter abbreviated as BAlq) was vacuum deposited on the emitting layer to a thickness of 10 nm. A hole blocking layer was formed, and Bis(10-hydroxybenzo[h]quinolinato)beryllium (hereinafter abbreviated as BeBq ₂ ) was deposited on it to a thickness of 50 nm to form an electron transport layer. Afterwards, LiF was deposited on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[ Example 2] to [ Example 18]

An organic electroluminescent device was manufactured in the same manner as Example 1, except that a mixture of compounds listed in Table 7 below was used as the host material of the light emitting layer.

[ Comparative example 1] and [ Comparative example 2]

An organic electroluminescent device was prepared in the same manner as in Example 1 except that Compound 1-101 was used alone as the host material of the light-emitting layer (Comparative Example 1) or Compound 2-36 was used alone (Comparative Example 2). was produced.

[ Comparative example 3]

An organic electroluminescent device was manufactured in the same manner as Example 1, except that a mixture of Compound 1-101 and Compound 2-36 was used as the host material of the light-emitting layer.

[ Comparative example 4] and [ Comparative example 5]

An organic electroluminescent device was manufactured in the same manner as Example 1, except that the following three comparative compounds were mixed and used as host materials for the light-emitting layer.

[ Comparative example 6]

An organic electroluminescent device was manufactured in the same manner as Example 1, except that a mixture of Compounds 1-17, ref 2, and ref 4 was used as a host material for the light emitting layer.

Forward bias direct current voltage was applied to the organic electroluminescent devices manufactured in Examples 1 to 18 and Comparative Examples 1 to 6 of the present invention, and electroluminescence (EL) characteristics were measured using PR-650 from Photoresearch. The T95 lifespan was measured using McScience's lifespan measurement equipment at a standard luminance of 2500 cd/m ² . The measurement results are shown in Table 7 below.

<ref 1> <ref 2> <ref 3>

<ref 4> <ref 5>

[Table 7]

From the results in Table 7, Example 1 of the present invention used a mixture of two different types of compounds (first and third compounds) represented by Formula 1 and the second compound represented by Formula 2 as a phosphorescent host. In the case of Examples 18 to 18, a device using a single material (Comparative Example 1, Comparative Example 2), a device using a mixture of only two compounds (Comparative Example 3), and a device using a mixture of three types of comparative compounds (Comparative Example 4, In Comparative Example 5), it can be seen that the driving voltage, efficiency, and lifespan are significantly improved compared to the device (Comparative Example 6) using a mixture of one of the compounds of the present invention and two comparative compounds (Comparative Example 6).

In detail, rather than Comparative Example 1 and Comparative Example 2, which used a single compound represented by Formula 1 or a single compound represented by Formula 2 as a host, a comparison using a mixture of two compounds represented by Formula 1 and Formula 2 as a host. In Example 3, the device characteristics were significantly improved.

In addition, it can be confirmed that Comparative Examples 4 to 6, which used a mixture of three materials as a host, showed higher efficiency than Comparative Example 3, which used a mixture of two materials.

And, rather than Comparative Examples 4 to 6, which were a mixture of three materials, a mixture of three types of materials, i.e., two types of materials represented by Formula 1 of the present invention and one type of material corresponding to Formula 2, was used as a host. It can be seen that the devices of Examples 1 to 18 exhibit overall improved device characteristics.

Based on the above experimental results, the inventors of the present invention produced a single substance represented by Formula 1, a single substance represented by Formula 2, two types of substances represented by Formula 1, and one type of substance represented by Formula 2. In the case of a mixed mixture, that is, a mixture of three types of compounds, it was determined that it had new properties other than the properties of the substance, and the PL lifetime of these compounds and mixtures was measured. As a result, it was confirmed that in the case of a mixture of three types of compounds, two types of compounds represented by Formula 1 and one type of compound represented by Formula 2, a new PL wavelength was formed, unlike when a single compound was used. It was confirmed that the decrease and extinction time of the newly formed PL wavelength of the mixture increased from about 60 times to about 360 times the decrease and extinction time of each substance represented by Formula 1 and Formula 2.

This means that when the compounds of the present invention are mixed and used, not only do electrons and holes move through the energy levels of each material, but also electrons and holes move or energy due to a new region (exciplex) with a new energy level formed by mixing. It is believed that this is because efficiency and lifespan increase through delivery. As a result, this can be said to be an important example in which the mixed thin film exhibits exciplex energy transfer and light emission processes when using the mixture of the present invention.

In addition, when combining compounds represented by a specific chemical formula as in the present invention, the reason for excellent device characteristics is that there are two types of polycyclic compounds represented by Formula 1, which have characteristics such as stability against electrons as well as holes, and high T1, and hole When mixing one type of compound represented by Formula 2 with strong properties, the electron blocking ability is improved due to the high T1 and high LUMO energy value, and more holes move quickly and easily to the light-emitting layer, resulting in the light-emitting layer of holes and electrons. This appears to be because the internal charge balance is increased, allowing light to be emitted from within the light emitting layer rather than at the hole transport layer interface, which also reduces deterioration at the HTL interface, maximizing the driving voltage, efficiency, and lifespan of the entire device. In conclusion, when a mixture of two types of heterogeneous compounds represented by Formula 1 and one compound represented by Formula 2, that is, a mixture containing three types of compounds, is used as a host material, an electrochemical synergistic effect occurs. The overall performance of the device has improved.

The above description is merely an illustrative description of the present invention, and those skilled in the art will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in this specification are for illustrative purposes rather than limiting the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be interpreted in accordance with the claims below, and all technologies within the equivalent scope should be interpreted as being included in the scope of rights of the present invention.

100: organic electric device 110: substrate
120: first electrode 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light-emitting layer 151: light-emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (14)

In an organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode,
The organic layer includes a phosphorescent light-emitting layer, and the host of the phosphorescent light-emitting layer includes a first compound represented by Formula 1 below, a second compound represented by Formula 2 below, and a third compound represented by Formula 1 below, Organic electric device, characterized in that the first compound and the third compound are different from each other:
<Formula 1><Formula2>

In the above formula,
X ¹ and X ² are independently a single bond, N-(L ^- Ar), O, S, or C(R')(R"), is an integer of 1, l+m is an integer of 1 or more,
Ring A, ring B, ring C, and ring D are each independently an aromatic ring of C ₆ to C ₂₀ or a heterocycle of C ₂ to C ₂₀ ,
Ar ¹ to Ar ⁵ are independently C ₆ to C ₆₀ aryl groups; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; and -L'-N(R _a )(R _b ); and Ar ² and Ar ³ or Ar ⁴ and Ar ⁵ may be bonded to each other to form a ring,
L ¹ to L ³ are independently a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; and a fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ;
R ¹ is hydrogen; heavy hydrogen; halogen; Cyano group; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₃₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N(R _a )(R _b ); and adjacent groups may bond to each other to form a ring,
a is an integer from 0 to 2, and when a is an integer of 2 or more, each R ¹ is the same as or different from each other,
The A ring may be substituted with one or more R ² , the B ring may be substituted with one or more R ³ , and the C and D rings may be substituted with one or more R, and R ² , R ³ and R are independently hydrogen; heavy hydrogen; halogen; Cyano group; Aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₃₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N(R _a )(R _b ); wherein each R ² , each R ³ , and each R may be the same or different from each other,
R' and R" are hydrogen; deuterium; halogen; C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₂ ~ C ₆₀ containing at least one heteroatom among O, N, S, Si, and P. Heterocyclic group; C ₃ ~ C ₆₀ aliphatic ring; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L'-N(R _a )(R _b ); in the group consisting of is selected, and R' and R" can be combined with each other to form a ring,
Ar is an aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₆₀ and an aromatic ring from C ₆ to C ₆₀ ; and -L'-N(R _a )(R _b );
L and L' are independently a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; and a fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ;
R _a and R _b are each independently an aryl group of C ₆ to C ₆₀ ; fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; and a fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ . According to clause 1,
The A ring, B ring, C ring, and D ring are each independently selected from the group consisting of the following formulas (a-1) to (a-7):
<Formula a-1><Formulaa-2><Formulaa-3><Formulaa-4>

<Formula a-5><Formulaa-6><Formulaa-7>

In the above formula,
Z ¹ to Z ⁴⁸ are independently C, C (R ^c ) or N,
R ^c is hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L ^a -N(R ^a )(R ^b );
The L ^a is a single bond independently of each other; C ₆ ~ C ₂₀ arylene group; fluorenylene group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,
R ^a and R ^b are each independently an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof. According to clause 1,
Wherein L ¹ to L ³ are independently selected from the group consisting of the following formulas b-1 to b-13:
<Formula b-1><Formulab-2><Formulab-3><Formulab-4><Formulab-5><Formulab-6>

<Formula b-7><Formulab-8><Formulab-9><Formulab-10>

<Formula b-11><Formulab-12><Formulab-13>

In the above formula,
R ⁴ to R ⁶ are independently hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L ^a -N(R ^a )(R ^b ); and adjacent groups may bond to each other to form a ring,
Y is, independently of each other, N-(L ^a -Ar ^a ), O, S, or C(R ^d )(R ^e ),
Z ⁴⁹ to Z ⁵¹ are independently C, C (R ^c ) or N, and at least one of Z ⁴⁹ to Z ⁵¹ is N,
f, h, i and j are each an integer from 0 to 4, g is an integer from 0 to 6, k and l' are each an integer from 0 to 3, m' is an integer from 0 to 2, and n is It is an integer from 0 to 3, and when each of them is an integer of 2 or more, each R ⁴ , each R ⁵ , and each R ⁶ are the same or different from each other,
R ^c , R ^d and R ^e are independently hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L ^a -N(R ^a )(R ^b ); where R ^d and R ^e may be combined with each other to form a ring,
Ar ^a is an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,
The L ^a is a single bond independently of each other; C ₆ ~ C ₂₀ arylene group; fluorenylene group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,
R ^a and R ^b are each independently an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof. According to clause 1,
The above Chemical Formula 1 is an organic electric device characterized in that it is represented by the following Chemical Formula 1-A or 1-B:
<Formula 1-A><Formula1-B>

In the above formula, ring A, ring B, R ¹ , L ¹ , Ar ¹ , X ¹ , X ² and a are as defined in claim 1. According to clause 1,
The above Chemical Formula 1 is an organic electric device characterized in that it is represented by one of the following Chemical Formulas 1-1 to 1-44:
<Formula 1-1><Formula1-2><Formula1-3><Formula1-4>

<Formula 1-5><Formula1-6><Formula1-7><Formula1-8>

<Formula 1-9><Formula1-10><Formula1-11><Formula1-12>

<Formula 1-13><Formula1-14><Formula1-15><Formula1-16>

<Formula 1-17><Formula1-18><Formula1-19><Formula1-20>

<Formula 1-21><Formula1-22><Formula1-23><Formula1-24>

<Formula 1-25><Formula1-26><Formula1-27><Formula1-28>

<Formula 1-29><Formula1-30><Formula1-31><Formula1-32>

<Formula 1-33><Formula1-34><Formula1-35><Formula1-36>

<Formula 1-37><Formula1-38><Formula1-39><Formula1-40>

<Formula 1-41><Formula1-42><Formula1-43><Formula1-44>

In the above formula,
R ¹¹ are independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₂₀ aryloxy group; and -L ^a -N(R ^a )(R ^b ); and adjacent groups may bond to each other to form a ring,
b, c and a' are each integers from 0 to 4, b' and c' are each integers from 0 to 6, b" and c" are each integers from 0 to 8, and each of these is an integer of 2 or more. , each R ¹ , each R ² , each R ³ , and each R ¹¹ are the same as or different from each other,
The L ^a is a single bond independently of each other; C ₆ ~ C ₂₀ arylene group; fluorenylene group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,
R ^a and R ^b are each independently an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and combinations thereof.
X ¹ , X ² , Ar ¹ , L ¹ , R ¹ , R ² , R ³ and a are as defined in clause 1. According to clause 1,
The formula 1 is an organic electric device characterized in that it is represented by one of the following formulas 1-C to 1-J:
<Formula 1-C><Formula1-D><Formula1-E><Formula1-F>

<Formula 1-G><Formula1-H><Formula1-I><Formula1-J>

In the above formula, ring A, ring B, R ¹ , L ¹ , Ar ¹ , L, Ar, R', R" and a are as defined in claim 1. According to clause 1,
The formula 2 is an organic electric device characterized in that it is represented by one of the following formulas 2-A to 2-C:
<Formula 2-A><Formula2-B>

<Formula 2-C>

In the above formula,
The E ring and F ring are independently C ₆ ~ C ₂₀ aromatic ring or C ₂ ~ C ₂₀ heterocycle,
W is N-(L ^a -Ar ^a ), O, S or C(R ^d )(R ^e ),
L ⁵ to L ⁷ are independently a single bond; C ₆ ~ C ₆₀ arylene group; fluorenylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom among O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring group; and a fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ;
Ar ^a is an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,
R ^d and R ^e are independently hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L ^a -N(R ^a )(R ^b ); where R ^d and R ^e may be combined with each other to form a ring,
The L ^a is a single bond independently of each other; C ₆ ~ C ₂₀ arylene group; fluorenylene group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,
R ^a and R ^b are each independently an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and may be selected from the group consisting of combinations thereof,
C ring, D ring, X ³ , L ² , L ³ , Ar ³ to Ar ⁵ are as defined in claim 1. According to clause 1,
The above Chemical Formula 2 is an organic electric device characterized in that it is represented by the following Chemical Formula 2-D:
<Formula 2-D>

In the above formula,
Z ¹ to Z ⁴ , and Z ^5' to Z ^8' are independently C, C (R ^c ) or N,
Z ^1' to Z ^4' are independently C(R ^c ) or N,
W is N-(L ^a -Ar ^a ), O, S or C(R ^d )(R ^e ),
R ^c , R ^d and R ^e are hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L ^a -N(R ^a )(R ^b ); where R ^d and R ^e may be combined with each other to form a ring,
Ar ^a is an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,
Wherein L ^a is a single bond; C ₆ ~ C ₂₀ arylene group; fluorenylene group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,
R ^a and R ^b are each independently an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and may be selected from the group consisting of combinations thereof,
Ar ³ to Ar ⁵ and X ³ are as defined in clause 1. According to clause 1,
The formula 2 is an organic electric device characterized in that it is represented by one of the following formulas 2-E to 2-G:
<Formula 2-E><Formula2-F>

<Formula 2-G>

In the above formula,
Z ¹ to Z ⁴ , and Z ^1' to Z ^4' are independently C(R ^c ) or N,
Z ^5' to Z ^8' are independently C, C(R ^c ) or N,
W is N-(L ^a -Ar ^a ), O, S or C(R ^d )(R ^e ),
R ^c , R ^d and R ^e are hydrogen; heavy hydrogen; halogen; Cyano group; nitro group; C ₆ ~ C ₂₀ aryl group; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; A fused ring group of an aliphatic ring from C ₃ to C ₂₀ and an aromatic ring from C ₆ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkyne group; C ₁ ~ C ₂₀ alkoxy group; C ₆ ~ C ₃₀ aryloxy group; and -L ^a -N(R ^a )(R ^b ); where R ^d and R ^e may be combined with each other to form a ring,
Ar ^a is an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,
The L ^a is a single bond independently of each other; C ₆ ~ C ₂₀ arylene group; fluorenylene group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,
R ^a and R ^b are each independently an aryl group of C ₆ to C ₂₀ ; fluorenyl group; A C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P; C ₃ ~ C ₂₀ aliphatic ring group; and is selected from the group consisting of combinations thereof,
Ar ³ to Ar ⁵ and X ³ are as defined in clause 1. According to clause 1,
The compound represented by Formula 1 is an organic electric device, characterized in that one of the following compounds:






. According to clause 1,
The compound represented by Formula 2 is an organic electric device, characterized in that one of the following compounds:







. According to clause 1,
An organic electric device, characterized in that the first compound is 40 to 80% by weight, the second compound is 10 to 30% by weight, and the third compound is 10 to 40% by weight. A display device including the organic electric element of claim 1; and
An electronic device comprising a control unit that drives the display device. According to clause 13,
The organic electric device is an electronic device characterized in that it is selected from the group consisting of organic electroluminescent devices, organic transistors, monochromatic lighting devices, and quantum dot display devices.