WO2014010910A1 - Compound, organic electronic element using same, and electronic device thereof - Google Patents

Abstract

The present invention relates to a novel compound, to an organic electronic element using same, and to an electronic device thereof. According to the present invention, the luminous efficiency, color purity, and lifespan of the element can be improved, and the voltage required for driving the element can be lowered.

Description

Compounds, Organic Electrical Devices And Electronic Devices Using The Same

The present invention relates to a compound, an organic electric element comprising the same, and an electronic device thereof.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

The material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.

On the other hand, it delays the diffusion of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, and stable characteristics, that is, high glass transition even for Joule heating generated when driving the device. There is a need for development of a hole injection layer material having a temperature. In addition, the low glass transition temperature of the hole transport layer material has been reported to have a significant effect on the device life, depending on the characteristics of the uniformity of the surface of the thin film when driving the device. In addition, the deposition method is the mainstream in the formation of the OLED device, a situation that requires a material that can withstand a long time, that is, a material having a strong heat resistance characteristics.

In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.

An object of the present invention is to provide a compound capable of improving high luminous efficiency, low driving voltage, high heat resistance, color purity, and lifetime of an element, an organic electric element using the same, and an electronic device thereof.

In one aspect, the present invention provides a compound represented by the following formula.

In another aspect, the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device thereof.

By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and life of the device can be greatly improved.

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

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

On the other hand, the terms "halo" or "halogen" as used herein include fluorine, chlorine, bromine, and iodine unless otherwise stated.

As used herein, the term "alkyl" or "alkyl group" has a carbon number of 1 to 60 unless otherwise specified, but is not limited thereto.

As used herein, the term "alkenyl" or "alkynyl" has a double bond or a triple bond having 2 to 60 carbon atoms, respectively, unless otherwise specified, but is not limited thereto.

The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.

The term "alkoxy group" used in the present invention has a carbon number of 1 to 60 unless otherwise stated, it is not limited thereto.

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto.

In the present invention, an aryl group or an arylene group means a monocyclic or polycyclic aromatic, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirofluorene group.

As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 3 to 60 carbon atoms, each of which includes one or more heteroatoms, unless otherwise specified. In addition, it includes not only single ring but also multiple rings, and adjacent groups may be formed by combining.

As used herein, the terms "heterocycloalkyl", "heterocyclic group" includes one or more heteroatoms, unless otherwise indicated, having from 2 to 60 carbon atoms, including single rings as well as multicycles. Adjacent groups may be formed in combination. In addition, "heterocyclic group" may mean an alicyclic and / or aromatic including a heteroatom.

As used herein, the term “heteroatom” refers to N, O, S, P, and Si unless otherwise indicated.

Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise stated, the term "saturated or unsaturated ring" as used herein means a saturated or unsaturated aliphatic ring or an aromatic ring or heterocyclic ring having 6 to 60 carbon atoms.

Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.

Also, unless stated otherwise, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy groups, C ₁ to C ₂₀ alkylamine groups, C ₁ to C ₂₀ alkylthiophene groups, C ₆ to C ₂₀ arylthiophene groups, C ₂ to C ₂₀ alkenyl groups, C ₂ to C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron Group, germanium group, and C ₅ ~ C _{20 It} is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.

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

Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110. An organic material layer containing a compound represented by the formula (1) between) is provided. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed. The hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.

In addition, although not shown, the organic electronic device according to the present invention may further include a protective layer formed on one surface of the first electrode and the second electrode opposite to the organic material layer.

The compound according to the present invention applied to the organic material layer is a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, the electron injection layer 170, the host of the light emitting layer 150 or the material of the dopant or capping layer Can be used as

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and the electron transport layer are formed thereon. After forming the organic material layer including the 160 and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.

In addition, the organic material layer using a variety of polymer materials is less by a solution process or solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing or thermal transfer method, rather than deposition It can be prepared in a number of layers. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.

In addition, the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochromatic or white illumination device.

Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the compound which concerns on one aspect of this invention is demonstrated.

The compound according to one aspect of the present invention is represented by the following formula (1).

Formula 1

In Chemical Formula 1,AIs Two adjacent rings (R_One, R₂Represents a benzene ring condensed by sharing a pentagon ring and D) with one side, respectively, and may be represented by the following Chemical Formula 1a.

<Formula 1a>

In Formula 1, B represents a benzene ring condensed by sharing one side with two adjacent rings (D and E), respectively, and may be represented by Formula 1a.

In Formula 1, D is a pentagonal ring condensed by sharing one side with two adjacent rings (A and B), respectively, and may be represented by Formula 1b. At this time, the side connecting the * and * of Formula 1b condensed by sharing with any one of the A ring and the B ring, and condensed by sharing the side connecting the ** and ** with the other.

<Formula 1b>

In Formula 1, E is a pentagonal ring condensed by sharing two sides with two adjacent rings (B and a benzene ring substituted with R ₇ to R ₁₀ ), respectively, which may include Y, and may be represented by the following Formula 1c: have. At this time, the side connecting the * and * in Formula 1c condensed by sharing with any one of the ring B and the benzene ring substituted with R ₇ to R ₁₀ , by sharing the side connecting ** and ** with the other To condense.

<Formula 1c>

In Chemical Formula 1, Chemical Formula 1a, Chemical Formula 1b, Chemical Formula 1c,

(1) X and Y are each independently NR ', SiR'R ", CR'R" or S.

(2) R ′, R ″ may be each independently represented by one of the following chemical formulas, and in the following chemical formulas, Z ₁ to Z ₂₃ may be each independently C or N.

(3) Ar ₁ is hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkyl Thiophene group, C ₆ -C ₂₀ arylamine group, C ₆ -C ₂₀ arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cyclo alkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted with a heavy hydrogen aryl, C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron group, a heteroaryl of germanium group, a C ₂ ~ C ₂₀ C ₆ ~ C ₆₀ aryl group unsubstituted or substituted with a substituent selected from the group consisting of a cyclic group; Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of acetylene groups, and having at least one heteroatom of O, N, S, Si, P; Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₁ ~ C ₅₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₈ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group An alkyl group; And hydrogen, deuterium, tritium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ a cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₂ ~ C substituted with a substituent selected from the ₆₀ group yirwojin group heterocyclic or unsubstituted C for ₆ ~ C ₆₀ aryl group Amine group; Is selected from the group consisting of

(4) R_One, R₂Are each independently hydrogen, deuterium, tritium, halogen, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group_One~ C₅₀Alkyl groups; or Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C_One~ C₂₀Alkylamine groups, C_One~ C₂₀Alkylthiophene groups, C₆~ C₂₀Arylamine group, C₆~ C₂₀Arylthiophene group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₃~ C₂₀Cycloalkyl group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₈~ C₂₀Aryl alkenyl group, silane group, boron group, germanium group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀Aryl group; Which may bind to each other to form spiro compounds.

(5) R ₃ to R ₁₁ are each independently hydrogen; heavy hydrogen; Tritium; Halogen group;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₁ ~ C ₅₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group An alkyl group; Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of acetylene groups, and having at least one heteroatom of O, N, S, Si, P; Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ aryl amine group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ of the aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, a C ₂ ~ C ₂₀ heterocyclic group selected from the group consisting of C ₆ ~ C ₆₀ aryl group unsubstituted or substituted with a substituent; And hydrogen, deuterium, tritium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ a cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₂ ~ C substituted with a substituent selected from the ₆₀ group yirwojin group heterocyclic or unsubstituted C for ₆ ~ C ₆₀ aryl Amine group; Is selected from the group consisting of

(6) n is an integer of 1 or 2, and m is an integer of 0-5.

Specifically, the compound represented by Chemical Formula 1 may be one of the following Chemical Formulas 2 to 8.

Formula 2

Formula 3

Formula 4

Formula 5

Formula 6

Formula 7

Formula 8

In the above formula,

A, B, R ′, R ″, R ₁ to R ₁₁ , n, m are the same as A, B, R ′, R ″, R ₁ to R ₁₁ , n, m defined in Chemical Formula 1.

More specifically, the compound represented by Formula 1 may be one of the following compounds 1-1 to 7-20.

Hereinafter, the synthesis examples of the compound represented by the formula (1) according to the present invention and the production examples of the organic electric device will be described in detail by way of examples, but the present invention is not limited to the following examples.

Synthesis Example

Synthesis of the compound was carried out in the following manner.

Example 1

Product 1 Synthesis Example

<Scheme 1>

(1) Synthesis of Sub 1-2

Put the Sub 1-1 compound, Nitric acid and carbon tetrachloride in the round bottom flask and proceed the reaction at 50 ℃. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain a product.

Examples of Sub 1-1 are as follows, but are not limited thereto, and their FD-MS are shown in Table 1 below.

Table 1

(2) Synthesis of Sub 1-4

Sub 1-2, Sub 1-3, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ obtained were dissolved in toluene and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ and filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated using column chromatography to obtain the desired product.

(3) Synthesis of Sub 1

The obtained Sub 1-4 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and then the concentrated product was separated using column chromatography to obtain the desired product.

Examples of Sub 1 are as follows, but are not limited thereto, and their FD-MS are shown in Table 2 below.

TABLE 2

(4) Synthesis of Product 1

Sub 1 (1 equiv), Sub 6 (1.1 equiv), Pd ₂ (dba) ₃ (0.05 mol%), PPh ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL) / 1 mmol) and then proceed with the reaction at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain product Product 1.

Examples of Sub 6 are as follows, but are not limited thereto, and FD-MS of Sub 6-5 to Sub 6-14 is shown in Table 3 below.

TABLE 3

(5) Example of compound synthesis

end. 1-71 Synthesis Example

<Scheme 2>

15- (2,4-diphenylpyrimidin-5-yl) -13,13-dimethyl-13,15-dihydro-7H-indeno [1,2-b] indolo [2,3-g] carbazole ( 12.1 g, 20 mmol), bromobenzene (3.8 g, 24 mmol), Pd ₂ (dba) ₃ (0.06-0.1 mmol), PPh ₃ (0.2 equiv), NaO t -Bu (6 equiv), toluene (10.5 mL / 1 mmol ) Is added and the reaction proceeds at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 8.6g (yield: 63%) of the final product.

I. 1-73 Synthesis Example

<Scheme 3>

13,13-dimethyl-15- (4-phenylquinazolin-2-yl) -13,15-dihydro-7H-indeno [1,2-b] indolo [2,3-g] carbazole (11.5 g in a round bottom flask) , 20 mmol), bromobenzene (3.8 g, 24 mmol), Pd ₂ (dba) ₃ (0.06-0.1 mmol), PPh ₃ (0.2 equiv), NaO t -Bu (6 equiv), toluene (10.5 mL / 1 mmol) After the addition, the reaction proceeds at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 8.5g (yield: 65%) of the final product.

All. 1-75 Synthesis Example

<Scheme 4>

Deuterated polycyclic ring compound (12.3g, 20mmol), 4-bromo-1,1'-biphenyl (5.6g, 24mmol), Pd ₂ (dba) ₃ (0.06 ~ 0.1mmol), PPh ₃ (0.2 equiv), NaO t -Bu (6 equiv) and toluene (10.5 mL / 1 mmol) were added and the reaction was carried out at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 8.9 g (yield: 58%) of the final product.

la. 2-31 Synthesis Example

Scheme 5

13,13-dimethyl-7,13-dihydrobenzo [4,5] thieno [2,3-g] indeno [1,2-b] carbazole (7.8 g, 20 mmol) and 2-substituted deuterium in a round bottom flask bromo-4,6-diphenylpyrimidine (7.7g, 24mmol), Pd ₂ (dba) ₃ (0.06 ~ 0.1 mmol), PPh ₃ (0.2 equiv), NaO t -Bu (6 equiv), toluene (10.5 mL / 1 mmol ) Is added and the reaction proceeds at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain 6.9 g (yield: 55%) of the final product.

hemp. 3-6 Synthesis Example

<Scheme 6>

13,13,15,15-tetramethyl-14,15-dihydro-13H-diindeno [2,1-a: 1 ', 2'-i] carbazole (8.0 g, 20 mmol), 2-bromo- in a round bottom flask 4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol), Pd ₂ (dba) ₃ (0.06 ~ 0.1 mmol), PPh ₃ (0.2 equiv), NaO t -Bu (6 equiv), toluene (10.5 mL / 1 mmol) was added and the reaction proceeds at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallization to obtain 7.6 g (yield: 60%) of the final product.

bar. 3-26 Synthesis Example

Scheme 7

12,12,15,15-tetramethyl-12,15-dihydro-6H-diindeno [1,2-b: 2 ', 1'-h] carbazole (8.0 g, 20 mmol), 2-bromo- in a round bottom flask 4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol), Pd ₂ (dba) ₃ (0.06 ~ 0.1 mmol), PPh ₃ (0.2 equiv), NaO t -Bu (6 equiv), toluene (10.5 mL / 1 mmol) was added and the reaction proceeds at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 7.4 g (yield: 59%) of the final product.

four. 3-27 Synthesis Example

Scheme 8

12,12,15,15-tetramethyl-12,15-dihydro-6H-diindeno [1,2-b: 2 ', 1'-h] carbazole (8.0 g, 20 mmol), 4-bromo- in a round bottom flask 2-phenylquinazoline (6.8 g, 24 mmol), Pd ₂ (dba) ₃ (0.06 ~ 0.1 mmol), PPh ₃ (0.2 equiv), NaO t -Bu (6 equiv), toluene (10.5 mL / 1 mmol) The reaction proceeds at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.4 g (yield: 61%) of the final product.

Ah. 3-40 Synthesis Example

Scheme 9

12,12,15,15-tetramethyl-12,15-dihydro-6H-diindeno [1,2-b: 2 ', 1'-h] carbazole (8.0 g, 20 mmol), 5-bromo- in a round bottom flask 2,4-diphenylpyrimidine (7.5 g, 24 mmol), Pd ₂ (dba) ₃ (0.06-0.1 mmol), PPh ₃ (0.2 equiv), NaO t -Bu (6 equiv), toluene (10.5 mL / 1 mmol) After the addition, the reaction proceeds at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.8g (yield: 62%) of the final product.

Example 2

Product 2 Synthesis Example

Scheme 10

(1) Synthesis of Sub 2-2

To a 1000 mL two-necked round bottom flask, add Sub 2-1 (1 equivalent), 2-boronobenzoic acid substituted with R ₃ to R ₆ , Pd (PPh ₃ ) ₄ , K ₂ CO ₃ , and add Tetrahydrofuran and water. After the addition, the mixture was charged with nitrogen and stirred at 80 ° C. for 12 hours. After the reaction is completed, the reaction solution is cooled to room temperature, extracted with dichloromethane, and the organic solvent layer is removed using MgSO _4, and dried under reduced pressure to remove the solvent. The obtained reaction product was recrystallized with ethanol to obtain Sub 2-2.

(2) Synthesis of Sub 2-3

Add Sub 2-2, chlorobenzene and PPA to a 500 mL 2-necked round bottom flask and stir at room temperature for 12 hours. 100 ml of water was added to the reaction mixture, followed by stirring for 10 minutes. The organic layer and the water layer were separated. After extraction with normal hexane, the water of the organic solvent layer is removed using MgSO ₄ and dried under reduced pressure to remove the solvent. The crude product thus obtained was separated and purified through silica gel column chromatography using normal hexane to obtain Sub 2-3.

(3) Synthesis of Sub 2-4

In a 250 mL 2-necked round bottom flask, add Sub 2-3 and dissolve in THF as a solvent. The reaction temperature was lowered to -78 ° C and n-BuLi at a concentration of 2.5 M was added thereto, followed by further stirring at room temperature for 1 hour. The reaction mixture was lowered back to -78 ° C, and R ₁ and R ₂ substituted with iodo were added thereto, followed by further stirring at room temperature for 3 hours. After the reaction was completed, 20 mL of water was added thereto, followed by extraction with diethyl ether. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to remove the solvent to obtain a crude product. The resulting mixture was purified by silica gel column chromatography using ethyl acetate and normal hexane to give Sub 2-4.

(4) Synthesis of Sub 2-5

Put the Sub 2-4 compound, Nitric acid and carbon tetrachloride in the round bottom flask and proceed the reaction at 50 ℃. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain a product.

(5) Synthesis of Sub 2-7

Sub 2-5, Sub 2-6, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ obtained were dissolved in toluene and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ and filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated using column chromatography to obtain the desired product.

(6) Synthesis of Sub 2

The obtained Sub 2-7 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and then the concentrated product was separated using column chromatography to obtain the desired product.

Examples of Sub 2 are as follows, but are not limited thereto, and their FD-MS are shown in Table 4 below.

Table 4

(7) Synthesis of Product 2

Sub 2 (1 equiv), Sub 6 (1.1 equiv), Pd ₂ (dba) ₃ (0.05 mol%), PPh ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL) / 1 mmol) and then proceed with the reaction at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain product Product 2.

(8) Example of compound synthesis

end. 4-31 Synthesis Example

Scheme 11

13,13-dimethyl-13,15-dihydrofluoreno [2 ', 3': 4,5] thieno [3,2-a] carbazole (7.8 g, 20 mmol) and 2-bromo- substituted with deuterium in a round bottom flask 4,6-diphenylpyrimidine (7.7g, 24mmol), Pd ₂ (dba) ₃ (0.06 ~ 0.1 mmol), PPh ₃ (0.2 equiv), NaO t -Bu (6 equiv), toluene (10.5 mL / 1 mmol) After the addition, the reaction proceeds at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallization to obtain 7.6 g (yield: 60%) of the final product.

Example 3

Product 3 Synthesis Example

Scheme 12

(1) Synthesis of Sub 3-1

Into a 1000 mL two-necked round bottom flask, add Sub 2-4 (1 equivalent), 2-boronobenzoic acid substituted with R ₇ to R ₁₀ , Pd (PPh ₃ ) ₄ , K ₂ CO ₃ , and add Tetrahydrofuran and water. After the addition, the mixture was charged with nitrogen and stirred at 80 ° C. for 12 hours. After the reaction is completed, the reaction solution is cooled to room temperature, extracted with dichloromethane, and the organic solvent layer is removed using MgSO _4, and dried under reduced pressure to remove the solvent. The obtained reaction product was recrystallized with ethanol to obtain Sub 3-1.

(2) Synthesis of Sub 3-2

Put Sub 3-1, chlorobenzene and PPA into a 500 mL 2-necked round bottom flask and stir at room temperature for 12 hours. 100 ml of water was added to the reaction mixture, followed by stirring for 10 minutes. The organic layer and the water layer were separated. After extraction with normal hexane, the water of the organic solvent layer is removed using MgSO ₄ and dried under reduced pressure to remove the solvent. The crude product thus obtained was separated and purified through silica gel column chromatography using normal hexane to obtain Sub 3-2.

Examples of Sub 3-2 are as follows, but are not limited thereto, and their FD-MS are shown in Table 5 below.

Table 5

(3) Synthesis of Product 3

Add Sub 3-2 to a 250 mL 2-necked round bottom flask and add THF as a solvent to dissolve it. The reaction temperature was lowered to -78 ° C and n-BuLi at a concentration of 2.5 M was added thereto, followed by further stirring at room temperature for 1 hour. The reaction mixture was lowered to -78 ° C again, and R 'and R ″ substituted with iodo were added thereto, followed by further stirring at room temperature for 3 hours. After the reaction was completed, 20 mL of water was added thereto, followed by extraction with diethyl ether. The resulting extract was dried over MgSO ₄ , dried under reduced pressure to remove the solvent to obtain a crude product, and purified by silica gel column chromatography using ethyl acetate and normal hexane to obtain Product 3.

(4) Example of compound synthesis

end. 5-13 Synthesis Example

Scheme 13

15,15-dimethyl-N, N-diphenyl-8,15-dihydrodifluoreno [1,2-b: 2 ', 3'-d] thiophen-10-amine (11.1 g, 20 mmol in a 250 mL two-neck round bottom flask ) And add THF as a solvent to dissolve it. The reaction temperature was lowered to -78 ° C and n-BuLi at a concentration of 2.5 M was added thereto, followed by further stirring at room temperature for 1 hour. Lower the reaction mixture to -78 ℃ again, add iodomethane (5.7g, 40mmol) to it and again stirred for 3 hours at room temperature. After the reaction was completed, 20 mL of water was added thereto, followed by extraction with diethyl ether. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to remove the solvent to obtain a crude product. The resulting product was purified by silica gel column chromatography using ethyl acetate and normal hexane to obtain 10.0 g (yield: 86%) of the final product.

Example 4

Product 4 Synthesis Example

Scheme 14

(1) Synthesis of Sub 4-1

Into a 1000 mL two-necked round bottom flask, add Sub 1-1 (1 equivalent), Br-substituted 2-boronobenzoic acid, Pd (PPh ₃ ) ₄ , K ₂ CO ₃ , add Tedrahydrofuran, water, and nitrogen. After stirring for 12 hours at 80 ℃. After the reaction is completed, the reaction solution is cooled to room temperature, extracted with dichloromethane, and the organic solvent layer is removed using MgSO _4, and dried under reduced pressure to remove the solvent. The obtained reaction product was recrystallized with ethanol to obtain Sub 4-1.

(2) Synthesis of Sub 4-2

Put Sub 4-1, chlorobenzene and PPA into a 500 mL 2-necked round bottom flask and stir at room temperature for 12 hours. 100 ml of water was added to the reaction mixture, followed by stirring for 10 minutes. The organic layer and the water layer were separated. After extraction with normal hexane, the water of the organic solvent layer is removed using MgSO ₄ and dried under reduced pressure to remove the solvent. The crude product thus obtained was separated and purified through silica gel column chromatography using normal hexane to obtain Sub 4-2.

(3) Synthesis of Sub 4-3

Add Sub 4-2 to a 250 mL 2-necked round bottom flask and add THF as a solvent to dissolve it. The reaction temperature was lowered to -78 ° C and n-BuLi at a concentration of 2.5 M was added thereto, followed by further stirring at room temperature for 1 hour. The reaction mixture was lowered back to -78 ° C, and R 'and R "substituted with iodo were added thereto, followed by further stirring at room temperature for 3 hours. After the reaction was completed, 20 mL of water was added thereto, followed by extraction with diethyl ether. The obtained extract was dried over MgSO ₄ , dried under reduced pressure to remove the solvent to obtain a crude product, and purified by silica gel column chromatography using ethyl acetate and normal hexane to obtain Sub 4-3.

(4) Synthesis of Sub 4-4

Put the Sub 4-3 compound, Nitric acid and carbon tetrachloride in the round bottom flask and proceed with the reaction at 50 ℃. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain a product.

(5) Synthesis of Sub 4-5

Sub 4-4, Sub 2-6, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ obtained were dissolved in toluene and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ and filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated using column chromatography to obtain the desired product.

(6) Synthesis of Sub 4

Sub 4-5 and triphenylphosphine obtained were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain the desired product.

Examples of Sub 4 are as follows, but are not limited thereto, and their FD-MS are shown in Table 6 below.

Table 6

(7) Synthesis of Product 4

Sub 4 (1 equiv), Sub 6 (1.1 equiv), Pd ₂ (dba) ₃ (0.05 mol%), PPh ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL) / 1 mmol) and then proceed with the reaction at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain product Product 4.

(8) Example of compound synthesis

end. 6-15 Synthesis Example

Scheme 15

5,5,6,6-tetramethyl-3-phenyl-6,8-dihydro-5H-benzo [6,7] -as-indaceno [2,3-b] carbazole (9.5g, 20mmol) in a round bottom flask , bromobenzene (3.8g, 24mmol), Pd ₂ (dba) ₃ (0.06 ~ 0.1 mmol), PPh ₃ (0.2 equiv), NaO t -Bu (6 equiv), toluene (10.5 mL / 1 mmol) The reaction proceeds at 占 폚. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain 7.0g (yield: 63%) of the final product.

Example 5

Product 5 Synthesis Example

Scheme 16

(1) Sub 5-1 synthesis method

Subki-3 and tetrakis (triphenylphophine) palladium (0) and potassium carbonate were added to (2- (methylthio) phenyl) boronic acid substituted with R ₇ to R ₁₀ and THF (tetrahydrofuran) and water (3: Add 1) and stir at 70 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ , washed with water, a small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was recrystallized with CH ₂ Cl ₂ and hexane solvent. The desired Sub 5-1 was obtained.

(2) Sub 5-2 synthesis method

Sub 5-1 is dissolved in acetic acid, and hydrogen peroxide dissolved in acetic acid is dropped dropwise and stirred at room temperature for 6 hours. Upon completion of the reaction, acetic acid was removed using a decompression device and separated using column chromatography to obtain the desired Sub 5-2.

Examples of Sub 5-2 are as follows, but are not limited thereto, and their FD-MSs are shown in Table 7 below.

TABLE 7

(3) Product 5 synthesis

The obtained Sub 5-2 and trifluoromethanesulfonic acid were added thereto, stirred at room temperature for 24 hours, and slowly added water and pyridine (8: 1) to reflux for 30 minutes. Lower the temperature, extract with CH ₂ Cl ₂ and wipe with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the resulting product was concentrated by separating an organic solvent. The desired product 5 was obtained by column chromatography.

(4) Example of compound synthesis

end. 7-20 Synthesis Example

Scheme 17

11,11-dimethyl-3- (3- (methylsulfinyl)-[1,1'-biphenyl] -4-yl) -12,12-diphenyl-11,12-dihydroindeno [2,1-a] fluorine (13g , 20mmol) and trifluoromethanesulfonic acid were added and stirred at room temperature for 24 hours. Then, water and pyridine (8: 1) were slowly added and refluxed for 30 minutes. Lower the temperature, extract with CH ₂ Cl ₂ and wipe with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give 11.0 g (yield: 89%) of the desired final product.

FD-MS of the exemplary compounds of Compounds 1-1 to 7-20 are shown in Table 8 below.

Table 8

On the other hand, in the above described an exemplary synthesis example of the present invention represented by the formula (1), these are all based on the Suzuki cross-coupling reaction and Buchwald-Hartwig cross coupling reaction, etc., in addition to the substituents specified in the specific synthesis example other Even if the substituent is bonded, it does not affect the progress of the reaction. For example, "Sub 1-2 + Sub 1-3 → Sub 1-4" in Scheme 1, "Sub 2-1 → Sub 2-2" in Scheme 10, "Sub 2-5 + Sub 2-6 → Sub 2 -7 "," Sub 2-4 → Sub 3-1 "in Scheme 12," Sub 1-1 → Sub 4-1 "in Scheme 14," Sub 4-4 → Sub 4-5 ", in Scheme 16 Rebounds such as Sub 4-3 → Sub 5-1 "are all based on the Suzuki cross-coupling reaction, and" Sub 1 + Sub 6 → Product 1 "in Scheme 1, Scheme 2 to Scheme 9, and" Sub 2 in Scheme 10 ". + Sub 6 → Product 2 ", Scheme 11, Scheme 14," Sub 4 + Sub 6 → Product 4 ", Scheme 15, etc. are all based on the Buchwald-Hartwig cross coupling reaction, substituents not specifically specified in these The reactions will proceed even if is combined.

Manufacture of Organic Electrical Device

An organic electroluminescent device was manufactured according to a conventional method using a compound obtained through synthesis as a light emitting host material or a light emitting auxiliary layer material of the light emitting layer.

Experimental Example I Examples (1) to (367)

A copper phthalocyanine (hereinafter abbreviated as CuPc) film was first vacuum deposited on the ITO layer (anode) formed on the glass substrate to form a thickness of 10 nm. Subsequently, 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 30 nm as a hole transport compound on the film by a hole transport layer. Formed. After forming the hole transport layer, the compounds of the present invention (compounds 1-1 to 1-90, 2-1 to 2-60, 3-1 to 3-60, 4-1 to 4-60, 5-1 to 5) -20, 6-1 to 6-60 and 7-1 to 7-20) are deposited as a phosphorescent host material to form a light emitting layer, and then tris (2-phenylpyridine) iridium as a phosphorescent Ir metal complex dopant. (Hereinafter abbreviated as Ir (ppy) ₃ ) was added. At this time, the concentration of Ir (ppy) ₃ in the light emitting layer was added at 5% by weight to form a light emitting layer by vacuum deposition at a thickness of 30 nm. As a hole blocking layer, (1,1′-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm and electron injection was performed. Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited into the layer to a thickness of 40 nm. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device by using the Al / LiF as a cathode.

Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as Experimental Example I, except that Comparative Compound 1 (CBP) was used instead of the compound of the present invention as a light emitting host material.

Comparative Compound 1: CBP

Comparative Example 2

An organic electroluminescent device was manufactured in the same manner as Experimental Example I, except that Comparative Compound 2 was used instead of the compound of the present invention as a light emitting host material.

<Comparative Compound 2>

Comparative Example 3

An organic electroluminescent device was manufactured in the same manner as Experimental Example I, except that Comparative Compound 3 was used instead of the compound of the present invention as a light emitting host material.

Comparative Compound 3

Photoresearch by applying a forward bias DC voltage to the organic electroluminescent elements of [Experimental Example I] Examples (1) to (367), Comparative Example 1, Comparative Example 2 and Comparative Example 3 prepared as described above The electroluminescence (EL) characteristics were measured with PR-650, and the T90 life was measured using the life-time measurement equipment manufactured by McScience Inc. at 300 cd / m2 reference luminance. [Experimental Example I] Driving voltage, current density, luminance, luminous efficiency of organic electroluminescent devices manufactured according to Examples (1) to (367), Comparative Example 1, Comparative Example 2 and Comparative Example 3 of the present invention. The results of measuring the lifetime and the color purity were as shown in Table 9 below.

Table 9

As can be seen from the results of Table 9, the organic electroluminescent device using the organic electroluminescent device material of the present invention is used as a light emitting layer material and the driving voltage is higher than that of Comparative Example 1 (CPB), Comparative Example 2 and Comparative Example 3. It is low, the luminous efficiency is not only improved, but also the color purity and life are remarkably improved. In other words, it can be seen that the compounds of the present invention significantly improve efficiency and lifespan than Comparative Compounds 1, 2, and 3 having CBP, carbazole, or five-membered heterocycle as a core. Due to such excellent device characteristics, the compound according to the present invention is not only an organic electroluminescent device (OLED) but also a display device, an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochromatic or white illumination device, and the like. May also be used. In addition, even if the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a hole injection layer, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, the same effect can be obtained.

Experimental Example II Examples (368) to (377)

On the ITO layer (anode) formed on the glass substrate, a copper phthalocyanine (hereinafter abbreviated as CuPc) film was first vacuum deposited as a hole injection layer to form a 40 nm thick. Subsequently, 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 20 nm as a hole transport compound on the membrane to form a hole transport layer. Formed. Subsequently, the compounds of the present invention as luminescent auxiliary layer materials (compounds 1-71, 1-73, 1-75, 2-31, 3-6, 3-27, 4-31, 5-13, 6-15 and 7). One of -20) was vacuum deposited to a thickness of 20 nm to form a light emission auxiliary layer. After forming the light emission auxiliary layer, CBP [4,4'-N, N'-dicarbazole-biphenyl] as a host and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] as a host. The light emitting layer having a thickness of 30 nm was deposited on the light emitting auxiliary layer by doping at 95: 5 weight. As a hole blocking layer, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm, and the electron transport layer Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed into a 40 nm thick film. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device.

<Comparative Example 4>

An organic electroluminescent device was manufactured in the same manner as in Experimental Example II, but the emission auxiliary layer was omitted. That is, the organic electroluminescent device was manufactured by the same method as Experimental Example II except that the light emitting auxiliary layer was not formed.

Comparative Example 5

An organic electroluminescent device was manufactured in the same manner as in Experimental Example II, except that Comparative Compound 3 was used to form a light-emitting auxiliary layer instead of the compound of the present invention.

[Experimental Example II] to the organic electroluminescent elements of Example (368) to Example (377), Comparative Example 4 and Comparative Example 5 prepared as described above by applying a forward bias DC voltage PR- Photoresearch (PR) The electroluminescence (EL) characteristics were measured at 650, and the T90 life was measured using a life-time measurement device manufactured by McScience Inc. at a luminance of 300 cd / m2. [Experimental Example II] The driving voltage, current density, luminance, luminous efficiency, lifetime and color purity of the organic electroluminescent device manufactured according to Example (368) to Example (377), Comparative Example 4 and Comparative Example 5 of the present invention. The measurement results are shown in Table 10 below.

Table 10

As can be seen from the results of Table 10, the organic electroluminescent device using the organic electroluminescent device material of the present invention is used as a light emitting auxiliary layer material, Comparative Example 4, Comparative Compound 3, the light emitting auxiliary layer is not used, Compared with Comparative Example 5 used as the layer material, the driving voltage was lower, the luminous efficiency was improved, and the color purity and life were significantly improved. This is because, when the compound of the present invention is used alone as a light emitting auxiliary layer, it has a high T1 energy level and improves the low voltage, high luminous efficiency and device life of the organic electroluminescent device due to the deep HOMO energy level. Due to such excellent device characteristics, the compound according to the present invention is not only an organic electroluminescent device (OLED) but also a display device, an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochrome or white lighting device May also be used. In addition, even if the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a hole injection layer, a light emitting layer, an electron injection layer, an electron transport layer, the same effect can be obtained.

The present invention has been described above by way of example, and those skilled in the art will appreciate that various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be interpreted by the claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application claims priority to US Patent Application No. 10-2012-0076770, filed with Korea on July 13, 2012, pursuant to section 35 of the United States Patent Act 119 (a) (35 USC § 119 (a)). All content is incorporated by reference in this patent application. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.

Claims (8)

1. A compound represented by the following formula (1).

   <Formula 1>

   

   (In the above formula,

   A and B are each

   

   Condensing by sharing one side with two adjacent rings,

   D is

   

   And condensate by sharing the side connecting * and * with any one of A ring and B ring, condensing by sharing the side connecting ** and ** with the other,

   E is

   

   Condensing the side linking * and * with any one of the ring B and the benzene ring substituted with R ₇ to R ₁₀ , and the side linking ** and ** with the other)

   In Chemical Formula 1,

   (One)X, YAre each independently NR ', SiR'R ", CR'R" or S. here,R ′, R ″Each independently

   

   ,

   

   or

   

   , Where Z_One To Z₂₃Are independently of each other C or N, and Ar_OneSilver hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C_One~ C₂₀Alkylamine groups, C_One~ C₂₀Alkylthiophene groups, C₆~ C₂₀Arylamine group, C₆~ C₂₀Arylthiophene group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₃~ C₂₀Cycloalkyl group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₈~ C₂₀Aryl alkenyl group, silane group, boron group, germanium group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀Aryl group; Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Arylamine group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C which is unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group, and has at least one heteroatom of O, N, S, Si, or P₂~ C₆₀Heterocyclic group of; Hydrogen, deuterium, tritium, halogen, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₈~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group_One~ C₅₀Alkyl groups; And Hydrogen, deuterium, tritium, halogen group, amino group, nitrile group, nitro group, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₃~ C₃₀Cycloalkyl group, C₂~ C₃₀Heterocycloalkyl group, C₆~ C₆₀Aryl group, C₂~ C₆₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀Arylamine group; Is selected from the group consisting ofmIs an integer of 0 to 5.

   (2) R_One, R₂Are each independently hydrogen, deuterium, tritium, halogen, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group_One~ C₅₀Alkyl groups; or Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C_One~ C₂₀Alkylamine groups, C_One~ C₂₀Alkylthiophene groups, C₆~ C₂₀Arylamine group, C₆~ C₂₀Arylthiophene group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₃~ C₂₀Cycloalkyl group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₈~ C₂₀Aryl alkenyl group, silane group, boron group, germanium group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀Aryl group; Which may bind to each other to form spiro compounds.

   (3) R ₃ to R ₁₁ are each independently hydrogen; heavy hydrogen; Tritium; Halogen group;

   Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₁ ~ C ₅₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group An alkyl group; Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of acetylene groups, and having at least one heteroatom of O, N, S, Si, P; Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ aryl amine group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ of the aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, a C ₂ ~ C ₂₀ heterocyclic group selected from the group consisting of C ₆ ~ C ₆₀ aryl group unsubstituted or substituted with a substituent; And hydrogen, deuterium, tritium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ a cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₂ ~ C substituted with a substituent selected from the ₆₀ group consisting of a heterocyclic or unsubstituted C for ₆ ~ C ₆₀ aryl Amine groups; Is selected from the group consisting of

   (4) n is an integer of 1 or 2.
2. The method of claim 1,

   A compound according to one of the following formulas (2) to (8).

   
3. The method of claim 1,

   Compound which is one of the following compounds.

   

   

   

   

   

   

   

   

   

   
4. An organic electric device comprising a first electrode, one or more organic material layers containing a compound of any one of claims 1 to 3, and a second electrode sequentially stacked.
5. The method of claim 4, wherein

   An organic electric device, characterized in that to form the compound to the organic material layer by a solution process.
6. The method of claim 4, wherein

   The organic material layer comprises at least one of a hole transport layer, a light emitting auxiliary layer, a light emitting layer, a hole injection layer, an electron injection layer and an electron transport layer.
7. Claim 4 display device comprising the organic electroluminescent element; And

   A controller for driving the display device; Electronic device comprising a.
8. The method of claim 7, wherein

   The organic electronic device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochrome or white lighting device.

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