WO2013191404A1 - Compound, organic electronic element using same, and electronic device thereof - Google Patents

Abstract

The present invention relates to a novel compound, an organic element using the same, and an electronic device thereof. According to the present invention, light-emitting efficiency, color purity, and lifespan of an element can be improved, and a driving voltage can be reduced.

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 in which electrical energy is converted 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 electrical 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.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions.

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 device has not been made sufficiently, and therefore, the development of new materials is still 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 (1).

Formula 1

In another aspect, the present invention provides an organic electronic device using the compound represented by Formula 1 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 term "halo" or "halogen" as used herein includes 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 The organic material layer according to the present invention can be formed by various methods, and the scope of the present invention is not limited by the method of forming the same.

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,

(1) Ar_One And Ar₂Are each independently hydrogen, deuterium, tritium, halogen, amino, nitrile, nitro, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C_One~ C₂₀Alkylamine groups, C₆~ C₆₀Arylamine group, C_One~ C₂₀Alkylthiophene groups, C₆~ C₂₀Arylthiophene group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₃~ C₂₀Cycloalkyl group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₈~ C₂₀Aryl alkenyl group, silane group, boron group, germanium group and C₂~ C₆₀C 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, C_One~ C₂₀Alkylamine groups, C₆~ C₆₀Arylamine group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₆₀Substituted or unsubstituted C substituted or unsubstituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group and containing at least one heteroatom of O, N, S, P and Si₂~ C₆₀Heterocyclic group of; 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 of C, substituted with deuterium₆~ C₆₀Aryl group and C₂~ C₆₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₃₀Aryloxy group; C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₆₀C 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, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₇~ C₂₀Arylalkyl group and C₈~ C₂₀A silane group substituted with a substituent selected from the group consisting of arylalkenyl groups;

(2) R_OneTo R₁₂ Each independently of one another is hydrogen; heavy hydrogen; Tritium; Hydrogen, deuterium, tritium, halogen, C_One~ C₆₀Alkyl group, C_One~ C₆₀Alkoxy group, C_One~ C₆₀Alkylamine groups, C₅~ C₆₀Arylamine group, C_One~ C₆₀Alkylthiophene groups, C₆~ C₆₀Aryl thiophene group, C₂~ C₆₀Alkenyl, C₂~ C₆₀Alkynyl, C₃~ C₆₀Cycloalkyl group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₈~ C₆₀Aryl alkenyl group, substituted or unsubstituted silane group, substituted or unsubstituted boron group, substituted or unsubstituted germanium group and substituted or unsubstituted C₂~ C₆₀Unsubstituted or substituted with a substituent selected from the group consisting of C₆~ C₆₀Aryl group; C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₆₀C 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; Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₆₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group₂~ C₄₀Alkenyl group; 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 of C, substituted with deuterium₆~ C₆₀Aryl group and C₂~ C₆₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups_One~ C₃₀An alkoxy group; Hydrogen, deuterium, tritium, halogen group, nitrile group, nitro group, C_One~ C₆₀Alkyl group, C_One~ C₆₀Alkoxy group, C_One~ C₆₀Alkylamine groups, C₆~ C₆₀Arylamine group, C_One~ C₆₀Alkylthio group, C₂~ C₆₀Alkenyl, C₂~ C₆₀Alkynyl, C₃~ C₆₀Cycloalkyl group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, substituted or unsubstituted silane group, substituted or unsubstituted boron group, substituted or unsubstituted germanium group and substituted or unsubstituted C₂~ C₆₀C substituted or unsubstituted with a substituent selected from the group consisting of heterocyclic groups and containing at least one heteroatom of O, N, S, P and Si₂~ C₆₀Heterocyclic group of; C₆~ C₆₀Aromatic ring of C₃~ C₆₀Condensed ring groups of aliphatic rings of; C_One~ C₆₀Alkyl group, C₂~ C₆₀Alkenyl, C₆~ C₆₀Aryl group, C₈~ C₆₀Aryl alkenyl group And C₂~ C₆₀Unsubstituted or substituted with a substituent selected from the group consisting of Amine group; Nitro group; Nitrile group; Amide group; And silane groups; Is selected from the group consisting of

(3) R ₆ and R ₇ , R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₁ and R ₁₂ may each combine with neighboring groups to form a saturated or unsaturated ring.

Specifically, the compound represented by Chemical Formula 1 may be one of the following Chemical Formulas (2) to (6).

More specifically, the compound represented by Formula 1 may be one of the following compounds P1-1 to P6-46.

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

Compounds (final products) according to the present invention is prepared by reacting with Sub C and one of Sub 1 to Sub 5, as shown in Scheme 1.

<Scheme 1>

Example 1

Sub C Synthesis

Sub C can be prepared by the following scheme.

Sub C Synthesis Example (1)

<Scheme 2>

In a round flask, mix C-1-1 (1 equivalent), C-1-2 (1 equivalent) and toluene with Pd ₂ (dba) ₃ (0.05 equivalent), (t-Bu) ₃ P (0.1 Equivalents), NaO t -Bu (3 equivalents), respectively, were added thereto, and the mixture was stirred under reflux at 100 ° C. for 8 hours, extracted with MC and water, and then the organic layer was dried over MgSO ₄ and concentrated to give an organic substance. And recrystallization to give the product.

Sub C Synthesis Example (2)

<Scheme 3>

Intermediate and final compound C-2 in Scheme 3 was prepared by the following method.

(1) Synthesis of Intermediate C-2-3

C-2-1 (1 equivalent), C-2-2 (1 equivalent), PdCl ₂ (PPh ₃ ) ₂ (0.03 equivalent), CuI (0.03 equivalent), and K ₂ CO ₃ (3 equivalent) in a round flask. After mixing the amount corresponding to DMF, and refluxed at 100 ℃ for 4 hours, and extracted with MC and water, the organic layer was dried over MgSO ₄ and concentrated to silicagel column and recrystallized to obtain a product.

(2) Synthesis of Intermediate C-2-4

In a round flask, C-2-3 (1 equivalent) and KOt-Bu (2 equivalent) and NMP (N-Methylpyrrolidone) are mixed and stirred at room temperature for 5 hours. After extracting with MC and water, the organic layer was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

(3) Synthesis of Final Compound C-2

C-2-4 (1 equiv), C-2-5 (1 equiv) in a round flask and Pd ₂ (dba) ₃ (0.05 equiv), (t-Bu) ₃ P (0.1 equiv) after mixing in toluene ), NaO t -Bu (3 equivalents), respectively, were added, stirred and refluxed at 100 ° C. for 8 hours, extracted with MC and water, and then the organic layer was dried over MgSO ₄ and concentrated to give an organic substance produced by silicagel column and Recrystallization gives the product.

Sub C Synthesis Example (3)

<Scheme 4>

Intermediate and final compound C-3 in Scheme 4 can be prepared by the following synthesis method.

(1) Synthesis of Intermediate C-3-3

C-3-1 (1 equivalent), C-3-2 (1 equivalent), Pd (OAc) ₂ (0.05 equivalent), D ^t BPF (0.1 equivalent), K ₂ CO ₃ (2.5 equivalent) ) Was mixed with N-Methylpyrrolidone (NMP), stirred under reflux at 120 ° C. for 12 hours, extracted with MC and water, and the organic layer was dried over MgSO ₄ and concentrated to silicagel column and recrystallized product. Get

(2) Synthesis of Final Compound C-3

Equivalent amounts of C-3-3 (1 equivalent) and C-3-4 (1 equivalent) to the round flask and Pd ₂ (dba) ₃ (0.05 equivalent), (t-Bu) ₃ P (0.1 equivalent) after mixing in toluene ), NaO t -Bu (3 equiv) were added respectively and stirred at reflux for 8 hours at 100 ° C. After extracting with MC and water, the organic layer was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

Sub C Synthesis Example (4)

Scheme 5

Intermediate and final compound C-4 in Scheme 5 were synthesized by the following method.

(1) Synthesis of Intermediate C-4-3

After mixing C-4-1 (1 equivalent) in THF in a round flask, the mixture is stirred while cooling to -40 ° C. C-4-2 (3 equiv.) The corresponding amount is slowly added dropwise and stirred at -40 ° C for 3 hours. After completion of the reaction, the mixture was raised to room temperature, and the organic layer extracted with MC and water was dried over MgSO ₄ , concentrated, and the resultant organic substance was obtained by silicagel column and recrystallization.

(2) Synthesis of Final Compound C-4

In a round flask, mix C-4-3 (1 equivalent), C-4-4 (1 equivalent) and toluene with Pd ₂ (dba) ₃ (0.05 equivalent), (t-Bu) ₃ P (0.1 equiv.), was added to an amount corresponding to NaO t -Bu (3 equiv), respectively, and refluxed at 100 ℃ stirring for 8 hours. The organic layer extracted with MC and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

Examples of Sub C compounds synthesized using the synthesis examples are as follows, but are not limited thereto, and their FD-MS are shown in Table 1 below.

Table 1

Example 2

S1, one of the reactants in Scheme 1, was prepared by the following method.

S 1 synthesis

Compound S 1 can be synthesized by the reaction route of Scheme 6 below.

<Scheme 6>

In Scheme 6, intermediate S-1-2 and final compound S1 were synthesized by the following method.

(1) Synthesis of Intermediate S-1-2

S-1-1 (1 equivalent), an aryl halide compound (1 equivalent) in a round flask and Pd ₂ (dba) ₃ (0.05 equivalent), (t-Bu) ₃ P (0.1 equivalent) after mixing in toluene, Each of the amounts corresponding to NaO t -Bu (3 equiv) was added and stirred at reflux at 100 ° C. for 8 hours. The organic layer extracted with MC and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

(2) synthesis of S 1

In a round flask, S-1-2 (1 equiv), bis (pinacolato) diboron (1.3 equiv) were mixed with DMF, followed by addition of PdCl ₂ (DPPF) (0.03 equiv) and AcOK (3 equiv), respectively. After stirring under reflux for 3 hours at 80 ° C., the organic layer extracted with MC and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

Example 3

S2, one of the reactants in Scheme 1, was prepared by the following method.

S 2 synthesis

Compound S 2 can be synthesized by the reaction route of Scheme 7 below.

Scheme 7

(1) Synthesis of Intermediate S-2-1

To the round flask, add boron acid compound (1 equivalent), nitro compound (1 equivalent) and THF, and mix with THF, then add Pd (PPh ₃ ) ₄ (0.05 equivalent) and aqueous NaOH solution, and reflux at 70 ° C for 12 hours. After extraction with MC and water, the organic layer was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

(2) Synthesis of Intermediate S-2-2

After mixing S-2-1 (1 equivalent), TPP (3 equivalents) and dichlorobenzene in a round flask, the mixture was stirred under reflux at 130 ° C for 24 hours, depressurized to remove dichlorobenzene, and extracted with MC and water. The resulting organics were dried over MgSO ₄ and concentrated to silicagel column and recrystallized to obtain the product.

(3) Synthesis of Intermediate S-2-3

S-2-2 (1 equiv), iodo compound (1 equiv) in a round flask and Pd ₂ (dba) ₃ (0.05 equiv), (t-Bu) ₃ P (0.1 equiv), after mixing with toluene Each of the amounts corresponding to NaO t -Bu (3 equiv) was added and stirred at reflux at 100 ° C. for 8 hours. The organic layer extracted with MC and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

(4) Synthesis of Final Compound S 2

In a round flask, S-2-3 (1 equiv) and bis (pinacolato) diborn (1.3 equiv) were mixed with DMF, followed by addition of PdCl ₂ (DPPF) (0.03 equiv) and AcOK (3 equiv), respectively. After stirring and refluxing at 3 ° C. for 3 hours, the organic layer extracted with MC and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

Example 4

S3, one of the reactants in Scheme 1, was prepared by the following method.

S 3 synthesis

Compound S 3 may be synthesized by the reaction pathway of Scheme 8 below.

Scheme 8

In the scheme 8 S3 intermediate and final compound was synthesized by the following method.

(1) Synthesis of Intermediate S-3-1

To the round flask, add boron acid compound (1 equivalent), nitro compound (1 equivalent) and THF, and mix with THF, then add Pd (PPh ₃ ) ₄ (0.05 equivalent) and aqueous NaOH solution, and reflux at 70 ° C for 12 hours. After the extraction, the mixture was extracted with MC and water, and the organic layer was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

(2) Synthesis of Intermediate S-3-2

After mixing S-3-1 (1 equivalent), TPP (3 equivalents) and dichlorobenzene in a round flask, the mixture was stirred under reflux at 140 ° C. to 160 ° C. for 24 hours, and distilled under reduced pressure to remove dichlorobenzene, followed by extraction with MC and water. The organic layer was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

(3) Synthesis of Intermediate S-3-3

In a round flask, add S-3-2 (1 equivalent), Iodo compound (1 equivalent) to toluene, and mix Pd ₂ (dba) ₃ (0.05 equivalent), (t-Bu) ₃ P (0.1 equivalent), Each of the amounts corresponding to NaO t -Bu (3 equiv) was added and stirred at reflux at 100 ° C. for 8 hours. The organic layer extracted with MC and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

(4) Synthesis of Final Compound S 3

In a round flask, S-3-3 (1 equiv), bis (pinacolato) diboron (1.3 equiv) were mixed with DMF, followed by addition of PdCl ₂ (DPPF) (0.03 equiv) and AcOK (3 equiv), respectively. After stirring and refluxing at 3 ° C. for 3 hours, the organic layer extracted with MC and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

Example 5

S4, one of the reactants in Scheme 1, was prepared by the following method.

S 4 synthesis

Compound S 4 may be synthesized by the reaction pathway of Scheme 9 below.

Scheme 9

In Scheme 9, intermediate and final compound S4 were prepared by the following method.

(1) Synthesis of Intermediate S-4-1

To the round flask, add boron acid compound (1 equivalent), nitro compound (1 equivalent) and THF, and mix with THF, then add Pd (PPh ₃ ) ₄ (0.05 equivalent) and aqueous NaOH solution, and reflux at 70 ° C for 12 hours. After the extraction, the mixture was extracted with MC and water, and the organic layer was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

(2) Synthesis of Intermediate S-4-2

After mixing S-4-1 (1 equivalent), TPP (3 equivalent) and dichlorobenzene in a round flask, the mixture was stirred under reflux at 130 ° C for 24 hours, distilled under reduced pressure to remove dichlorobenzene, and the organic layer extracted with MC and water was extracted with MgSO. _The resulting organics were dried and concentrated to ₄ silica gel column and recrystallized to obtain the product.

(3) Synthesis of Intermediate S-4-3

In a round flask, mix S-4-2 (1 equivalent), Iodo compound (1 equivalent) into toluene, and add Pd ₂ (dba) ₃ (0.05 equivalent), (t-Bu) ₃ P (0.1 equivalent), Each of the amounts corresponding to NaO t -Bu (3 equiv) was added and stirred at reflux at 100 ° C. for 8 hours. The organic layer extracted with MC and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

(4) Synthesis of Final Compound S 4

In a round flask, S-3-3 (1 equiv), bis (pinacolato) diboron (1.3 equiv) were mixed with DMF, followed by addition of PdCl ₂ (DPPF) (0.03 equiv) and AcOK (3 equiv), respectively. After stirring and refluxing at 3 ° C. for 3 hours, the organic layer extracted with MC and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

Example 6

S5, one of the reactants in Scheme 1, was prepared by the following method.

S 5 synthesis

Compound S 5 may be synthesized by the reaction pathway of Scheme 10 below.

Scheme 10

In Scheme 10, intermediate and final compound S5 were prepared by the following method.

(1) Synthesis of Intermediate S-5-1

Nitro compound (1 equiv), Triphenylphosphine (2.5 equiv) and o-Dichlorobenzene were added and then refluxed at 180 ° C. After the reaction was completed, the mixture was cooled to room temperature, and the organic layer extracted with methylene chloride and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

(2) Synthesis of Intermediate S-5-2

S-5-1 (1 equiv), Iodo compound (1 equiv) in a round flask and Pd ₂ (dba) ₃ (0.05 equiv), (t-Bu) ₃ P (0.1 equiv), NaO after mixing with toluene After adding the amounts corresponding to t- Bu (3 equiv) respectively and stirring and refluxing at 100 degreeC for 8 hours. The organic layer extracted with MC and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

(3) Synthesis of Intermediate S-5-3

After mixing S-5-2 (1 equivalent), NBS (1 equivalent) and MC in a round flask and stirring at reflux at room temperature for 24 hours, dichlorobenzene was removed under reduced pressure, and the organic layer extracted with MC and water was extracted with MgSO. _The resulting organics were dried and concentrated to ₄ silica gel column and recrystallized to obtain the product.

(4) Synthesis of Final Compound S 5

In a round flask, S-5-3 (1 equiv), bis (pinacolato) diboron (1.3 equiv) were mixed with DMF, followed by addition of PdCl ₂ (DPPF) (0.03 equiv) and AcOK (3 equiv), respectively. After stirring and refluxing at 3 ° C. for 3 hours, the organic layer extracted with MC and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization.

On the other hand, the compounds synthesized using the synthesis method of S 1 to S 5 are as follows, which is illustrative but not limited thereto. In the formula, B (pin) is

to be.

FD-MS of the compounds ST 1-1 to ST 5-13 is shown in Table 2 below.

TABLE 2

Example 7

The method for synthesizing the final compound by Scheme 1 is as follows.

Synthesis Examples of Final Compounds P1 to P6

In a round flask, Pd (PPh ₃ ) ₄ (0.05 equiv) and aqueous NaOH solution were added to the mixture corresponding to S1 to S5 compound (1 equiv), Sub C compound (1 equiv) and THF, followed by 12 hours at 70 ° C. After stirring and refluxing, the organic layer extracted with MC and water was dried over MgSO ₄ and concentrated to give a product by silicagel column and recrystallization. FD-MS of the obtained final compounds P1-1 to P6-46 is as Table 3 below.

TABLE 3

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, Miyaura boration reaction and Buchwald-Hartwig cross coupling reaction, etc. in addition to the substituents specified in the specific synthesis example Even when other substituents (substituents such as Ar _1, Ar ₂ , R ₁ to R _12, etc.) defined in the above are combined, the reactions described above do not affect progress. For example, the S-2-1 generation step in Scheme 7 and the S-3-1 generation step in Scheme 8 are based on the Suzuki cross-coupilng reaction, the C-1 generation step in Scheme 2, and the C-2 generation step in Scheme 3 , C3 generation step in Scheme 4, C4 generation step in Scheme 5, S-1-2 generation step in Scheme 6, S-2-3 generation step in Scheme 7, S-3-3 generation step in Scheme 8, Scheme 9 In the S-4-3 generation step, S-5-2 generation step in Scheme 10, etc. are all based on the Buchwald-Hartwig cross coupling reaction, S 1 generation step in Scheme 6, S 2 generation step in Scheme 7, Scheme 8 The S 3 generation step, the S 4 generation step in Scheme 9, and the S 5 generation step in Scheme 10 are all based on the Miyaura boration reaction. Therefore, it will be appreciated by those skilled in the art that the reaction will proceed with the same mechanism with respect to the compound to which other substituents are attached in addition to the substituents exemplified.

Manufacturing Evaluation of Organic Electrical Device

Example 8

First, by vacuum depositing 2-TNATA on the ITO layer (anode) formed on the organic substrate to form a hole injection layer with a thickness of 60nm, the hole transport layer by vacuum depositing the compound according to the present invention to a thickness of 20nm on the hole injection layer Formed. Next, CBP [4,4'-N, N'-dicarbazole-biphenyl] as the light emitting layer host material and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] as the dopant material were 9: The light emitting layer was deposited by doping to a thickness of 30nm with a weight ratio of 1. Subsequently, (1,1'-bisphenyl) -4-oleato) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer. After forming tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) to a thickness of 40 nm as a transport layer, LiF, an alkali metal halide, is deposited to a thickness of 0.2 nm as an electron injection layer, followed by Al An organic light emitting diode was manufactured by using Al as a cathode by evaporating at a thickness of 150 nm.

Comparative Example 1

An organic light emitting display device was manufactured in the same manner as in [Example 8], except that Comparative Compound 1 was used instead of the compound of the present invention when forming the hole transport layer.

<Comparative Compound 1>

Comparative Example 2

An organic light emitting display device was manufactured in the same manner as in [Example 8], except that Comparative Compound 2 was used instead of the compound of the present invention when forming the hole transport layer.

Comparative Compound 2

Comparative Example 3

An organic light emitting display device was manufactured in the same manner as in [Example 8], except that Comparative Compound 3 was used instead of the compound of the present invention when forming the hole transport layer.

Comparative Compound 3

[Example 8] (Example (1) to Example 272) and [Comparative Example 1] to [Comparative Example 3] (Comparative Example (1) to Comparative Example (3) of the present invention prepared as described above The electroluminescent (EL) characteristics were measured with a PR-650 photoresearch company by applying a forward bias DC voltage to the organic electroluminescent device of The instrument was measured for T90 life. Prepared according to [Example 8] (Examples (1) to (272)) and [Comparative Example 1] to [Comparative Example 3] (Comparative Example (1) to Comparative Example (3)) of the present invention. The driving voltage, current density, luminance, luminous efficiency, and lifetime of the organic light emitting diodes were measured, as shown in Table 4 below.

Table 4

From the results of Table 4, the organic electroluminescent device manufactured according to [Example 8] of the present invention using the compound of the present invention as a hole transport layer, rather than the organic electroluminescent device manufactured by [Comparative Example 1] to [Comparative Example 3] It can be seen that the driving voltage is low, and the luminous efficiency and lifespan are remarkably improved.

Example 9

First, a copper phthalocyanine (hereinafter abbreviated as CuPc) is vacuum deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 40 nm, and then the compound P3 of the present invention on the hole injection layer. -27 was vacuum deposited to a thickness of 20 nm to form a hole transport layer. Next, the compound of the present invention was vacuum deposited to a thickness of 20 nm on the hole transport layer to form a light emitting auxiliary layer. Subsequently, CBP [4,4'-N, N'-dicarbazole-biphenyl] is used as a phosphorescent host material on the light emitting auxiliary layer, and tris (2-phenylpyridine) iridium (hereinafter referred to as Ir (ppy) ₃ ) is used as a phosphorescent dopant material. The light emitting layer was doped to a thickness of 30 nm with a weight ratio of 95: 5. Vacuum deposition of (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) as a hole blocking layer on the emission layer to a thickness of 10 nm After forming tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) to a thickness of 40 nm with an electron transport layer, LiF, an alkali metal halide, is deposited to a thickness of 0.2 nm as an electron injection layer, Subsequently, Al was deposited to a thickness of 150 nm to prepare an organic EL device by using Al as a cathode. In this case, the reason why the compound P3-27 of the present invention is used as the hole transport layer material is because, as shown in Table 4, the driving voltage of the organic electric element to which the compound P3-27 is applied is low, the luminous efficiency is high, and the lifetime is also high. to be.

[Comparative Example 4]

An organic light emitting display device was manufactured in the same manner as in [Example 9], except that the light emitting auxiliary layer was omitted. That is, an organic light emitting display device was manufactured in the same manner as in [Example 9], except that the light emitting auxiliary layer was not formed.

[Comparative Example 5]

An organic light emitting display device was manufactured in the same manner as in [Example 9], except that the Comparative Compound 3 was used to form the emission auxiliary layer instead of the compound of the present invention.

[Example 9] (Examples 273 to 544), [Comparative Example 4] (Comparative Example (4)), and [Comparative Example 5] (Comparative Example (5) of the present invention prepared as described above. The electroluminescence (EL) characteristics of the organic electroluminescent elements of)) were applied to the PR-650 photoresearch company by applying a forward bias DC voltage. The T95 life was measured with a life measuring instrument. Manufactured according to [Example 9] (Examples 273 to 544), [Comparative Example 4] (Comparative Example (4)), and [Comparative Example 5] (Comparative Example (5)) of the present invention. The driving voltage, current density, luminance, light emission efficiency, and lifetime of the organic light emitting diodes were measured as shown in Table 5 below.

Table 5

As can be seen from the results of Table 5, when the compound according to the present invention is used as a light emitting auxiliary layer, [Comparative Example 4] and Comparative Compound 3, in which no light emitting auxiliary layer was used, were applied to form a light emitting auxiliary layer. Compared with Example 5, not only can the driving voltage of the organic electric element be lowered, but also the efficiency and lifespan can be remarkably improved.

Because of the excellent properties as described above, 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 lighting element, etc. May also be used.

On the other hand, 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, but those skilled in the art to which the present invention pertains may make various modifications 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 following 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 under No. 119 (a) (35 USC § 119 (a)) of the Patent Application No. 10-2012-0067270 filed to Korea on June 22, 2012. 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 Chemical Formula 1,

   (1) Ar_One And Ar₂Are each independently hydrogen, deuterium, tritium, halogen, amino, nitrile, nitro, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C_One~ C₂₀Alkylamine groups, C₆~ C₆₀Arylamine group, C_One~ C₂₀Alkylthiophene groups, C₆~ C₂₀Arylthiophene group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₃~ C₂₀Cycloalkyl group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₈~ C₂₀Aryl alkenyl group, silane group, boron group, germanium group and C₂~ C₆₀C 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, C_One~ C₂₀Alkylamine groups, C₆~ C₆₀Arylamine group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₆₀Substituted or unsubstituted C substituted or unsubstituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group and containing at least one heteroatom of O, N, S, P and Si₂~ C₆₀Heterocyclic group of; 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 of C, substituted with deuterium₆~ C₆₀Aryl group and C₂~ C₆₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₃₀Aryloxy group; C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₆₀C 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,C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₇~ C₂₀Arylalkyl group and C₈~ C₂₀A silane group substituted with a substituent selected from the group consisting of arylalkenyl groups;

   (2) R_OneTo R₁₂ Each independently of one another is hydrogen; heavy hydrogen; Tritium; Hydrogen, deuterium, tritium, halogen, C_One~ C₆₀Alkyl group, C_One~ C₆₀Alkoxy group, C_One~ C₆₀Alkylamine groups, C₅~ C₆₀Arylamine group, C_One~ C₆₀Alkylthiophene groups, C₆~ C₆₀Aryl thiophene group, C₂~ C₆₀Alkenyl, C₂~ C₆₀Alkynyl, C₃~ C₆₀Cycloalkyl group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₈~ C₆₀Aryl alkenyl group, substituted or unsubstituted silane group, substituted or unsubstituted boron group, substituted or unsubstituted germanium group and substituted or unsubstituted C₂~ C₆₀Unsubstituted or substituted with a substituent selected from the group consisting of C₆~ C₆₀Aryl group; C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₆₀C 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; Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₆₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group₂~ C₄₀Alkenyl group; 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 of C, substituted with deuterium₆~ C₆₀Aryl group and C₂~ C₆₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups_One~ C₃₀An alkoxy group; Hydrogen, deuterium, tritium, halogen group, nitrile group, nitro group, C_One~ C₆₀Alkyl group, C_One~ C₆₀Alkoxy group, C_One~ C₆₀Alkylamine groups, C₆~ C₆₀Arylamine group, C_One~ C₆₀Alkylthio group, C₂~ C₆₀Alkenyl, C₂~ C₆₀Alkynyl, C₃~ C₆₀Cycloalkyl group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₆₀Aryl group, substituted or unsubstituted silane group, substituted or unsubstituted boron group, substituted or unsubstituted germanium group and substituted or unsubstituted C₂~ C₆₀C substituted or unsubstituted with a substituent selected from the group consisting of heterocyclic groups and containing at least one heteroatom of O, N, S, P and Si₂~ C₆₀Heterocyclic group of; C₆~ C₆₀Aromatic ring of C₃~ C₆₀Condensed ring groups of aliphatic rings of; C_One~ C₆₀Alkyl group, C₂~ C₆₀Alkenyl, C₆~ C₆₀Aryl group, C₈~ C₆₀Aryl alkenyl group And C₂~ C₆₀Unsubstituted or substituted with a substituent selected from the group consisting of Amine group; Nitro group; Nitrile group; Amide group; And silane groups; Is selected from the group consisting of

   (3) R ₆ and R ₇ , R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₁ and R ₁₂ may each combine with neighboring groups to form a saturated or unsaturated ring.
2. The method of claim 1,

   Compounds, characterized in that one of the formula (2) to (6).

   
3. The method of claim 1,

   Compound which is one of the following compounds.

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
4. An organic electric device comprising a first electrode sequentially stacked, at least one organic material layer containing the compound of any one of claims 1 to 3, and a second electrode.
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 electroluminescent device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochrome or white illumination.

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