WO2014129764A1 - Compound for organic electronic element, organic electronic element using same, and electronic device thereof - Google Patents

Abstract

The present invention provides a novel compound which improves the light emitting efficiency, stability and life of an element, an organic electronic element using the same, and an electronic device thereof.

Description

Compound for organic electric element, organic electric element using same and electronic device thereof

The present invention relates to a compound for an organic electric device, an organic electric device using 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. In this case, the organic material layer is often formed of a multi-layered 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.

Materials used as the organic material layer in the organic electric device 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.

The biggest problem for organic electroluminescent devices is life and efficiency. As the display becomes larger, such efficiency and life problems must be solved.

Efficiency, lifespan, and driving voltage are related to each other, and as efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic materials due to Joule heating generated during driving decreases. It shows a tendency to increase lifespan.

However, simply improving the organic material layer does not maximize the efficiency. This is because a long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

In addition, in order to solve the light emission problem in the hole transport layer in the recent organic electroluminescent device, a light emitting auxiliary layer must exist between the hole transport layer and the light emitting layer, and different light emission assist according to each light emitting layer (R, G, B) It is time to develop the floor.

In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.

However, in the case of the material used in the hole transport layer, since it has to have a low HOMO value, most have a low T1 value, which causes the excitons generated in the light emitting layer to pass to the hole transport layer, resulting in charge unbalance in the light emitting layer. This causes light emission at the hole transport layer interface.

When emitting light at the hole transport layer interface, the color purity and efficiency of the organic electric element is reduced and the life is shortened. Therefore, the development of a light emitting auxiliary layer having a high T1 value and a HOMO level between the hole transport layer HOMO energy level and the light emitting layer HOMO energy level is urgently required.

On the other hand, while delaying the penetration of metal oxides into the organic layer from the anode electrode (ITO), which is one of the causes of the shortening of the life of the organic electric device, stable properties, that is, high glass transition even for Joule heating generated when the device is driven. There is a need for development of a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has a characteristic of decreasing the uniformity of the surface of the thin film when the device is driven, which has been reported to have a great effect on the device life. In addition, the OLED device is mainly formed by a deposition method, which requires development of a material that can withstand a long time during deposition, that is, a material having strong heat resistance.

That is, in order to fully exhibit the excellent characteristics of the organic electric device, the materials 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, a light emitting auxiliary layer material, etc. Supported by the material should be preceded, but development of a stable and efficient organic material layer for an organic electric device has not been made yet. Therefore, the development of new materials continues to be required, and in particular, the development of material combinations of the light emitting auxiliary layer and the hole transport layer is urgently 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 an aromatic of a single ring or multiple rings, 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, a spirobifluorene 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 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. And not only a single ring, but also multiple rings, and adjacent groups may be formed by bonding.

As used herein, the terms "heterocycloalkyl", "heterocyclic group" include one or more heteroatoms, unless otherwise indicated, have a carbon number from 2 to 60, include not only a single ring but also multiple rings; 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 "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof. Saturated or unsaturated rings.

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 ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ arylalkenyl group, a silane group, a boron of C ₂₀ of Group, germanium group, and C ₂ ~ 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 electric 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 Preferably, the compound of the present invention may be used as at least one of the host material, the hole transport layer material and the light emitting auxiliary layer material of the light emitting layer.

On the other hand, even in the same core, the band gap, electrical characteristics, interface characteristics, etc. may vary depending on which substituents are bonded at which positions, so the selection of the cores and the combination of sub-substituents bound thereto are very good. In particular, long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

As described above, in order to solve the light emission problem in the hole transport layer in the organic electroluminescent device, it is preferable that a light emitting auxiliary layer be formed between the hole transport layer and the light emitting layer, and the light emitting layer R, G, and B may be formed according to each other. It is time to develop another light emitting auxiliary layer. Meanwhile, in the case of the light emitting auxiliary layer, it is difficult to infer the characteristics of the organic material layer used even if a similar core is used, since the correlation between the hole transport layer and the light emitting layer (host) must be understood.

Therefore, in the present invention, by using the compound represented by the formula (1) as a hole transport layer material and the light emitting auxiliary layer material, the energy level (level) and T1 value between each organic material layer, the intrinsic properties (mobility, interfacial properties, etc.) between the organic layer By optimizing it can improve the life and efficiency of the organic electric device at the same time.

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 conductive metal oxide or an alloy thereof on the substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and the electron transport layer (on the substrate) 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 may be formed by using a variety of polymer materials, but not by a deposition process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. 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, an organic solar cell, an organic photoconductor, an organic transistor, a monochromatic or white illumination device.

Another embodiment of the present invention may include an electronic device including a display device including the organic electric element of the present invention described above, and 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.

Compound according to an aspect of the present invention is represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

Ar ₁ and Ar ₂ are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl groups; C ₁ ~ C ₅₀ Alkyl group; And C ₆ ~ C ₃₀ An aryloxy group; may be selected from the group consisting of.

m and n are each an integer of 1-4. In this case, when n is 2 or more, a plurality of R ₁ may be the same as or different from each other, and when m is 2 or more, a plurality of R ₂ may be the same or different from each other.

R ₁ and R ₂ are, independently from each other, hydrogen; heavy hydrogen; Tritium; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl groups; C ₂ -C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; -LN (Ar ₄ ) (Ar ₅ ); C ₁ -C ₃₀ alkoxyl group; And C ₆ ~ C ₃₀ An aryloxy group; may be selected from the group consisting of.

R ₁ and R ₂ may combine with each other to form at least one ring. In this case, the group that does not form a ring may be as defined above.

 At this time, since it is important that the adjacent groups are bonded to each other to form a ring, the scope of the present invention is not limited by the substituents and which reactions form the ring. At this time, the ring is a known reaction (Heck reaction or Chem. Eur. J. 2009, 15, 742, Molecules. 2008, 13, 3236-3245, J. Am. Chem. Soc. 2008, 130, 472-480, Tetrahedron Letters. 1997, 38, 4761-4764 and the like).

In addition, the ring formed by adjoining adjacent groups to each other may be a single ring or a heterocyclic ring containing at least one heterocyclic ring or multiple rings, as well as a fused form of an aromatic ring and an aliphatic ring, or an aromatic formed The nuclear carbon number of the ring may be 6 to 60.

In addition, adjacent groups may combine with each other to form a hetero ring such as thiophene, furan, pyridine, indole, quinoline, etc., wherein the carbon number may be 2 to 60. In the case of multiple rings, the ring may be fused to each other, a plurality of rings may not be fused to each other, or a ring in which the fused and non-fused forms are mixed.

For example, compounds 1-152 to 1-204 of the present invention are examples of the case where R ₁ and / or R ₂ form a ring.

L in -LN (Ar ₄ ) (Ar ₅ ) is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And divalent aliphatic hydrocarbon group; may be selected from the group consisting of. At this time, the arylene group, fluorenylene group, heterocyclic group and aliphatic hydrocarbon group are each nitro group, cyano group, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ It may be substituted with one or more substituents selected from the group consisting of a heterocyclic group, a C ₁ ~ C ₂₀ alkoxyl group and an amino group.

And, Ar ₄ And Ar _{5 It} is a C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P independently of each other; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ ~ C ₅₀ Alkyl group; And fluorenyl group; may be selected from the group consisting of.

Meanwhile, R ₁ , R ₂ , Ar ₁ , Ar ₂ , Ar _4, and Ar ₅ may be further substituted with other substituents.

When R ₁ , R ₂ , Ar ₁ , Ar ₂ , Ar _4, and Ar ₅ are aryl groups, this is deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C ₁ ~ C ₂₀ alkyl Cthio, C ₁ ~ C ₂₀ Alkoxyl, C ₁ ~ C ₂₀ Alkyl, C ₂ ~ C ₂₀ Alkenyl, C ₂ ~ C ₂₀ Alkynyl, C ₆ ~ C ₂₀ Aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ It may be substituted with one or more substituents selected from the group consisting of an arylalkyl group and an arylalkenyl group of C ₈ to C ₂₀ .

When R ₁ , R ₂ , Ar ₄ and Ar ₅ are heterocyclic groups, it is deuterium, halogen, silane group, cyano group, nitro group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C of ₂ ~ C ₂₀ alkenyl group _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₂ ~ C heterocyclic group of _20, cycloalkyl of C ₃ ~ C ₂₀ Alkyl group, C ₇ ~ C ₂₀ It may be substituted with one or more substituents selected from the group consisting of an arylalkyl group and an arylalkenyl group of C ₈ to C ₂₀ .

When R ₁ , R ₂ , Ar ₁ , Ar ₂ , Ar _4, and Ar ₅ are fluorenyl groups, this is deuterium, halogen, silane group, cyano group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, from the group consisting of a cycloalkyl group of C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ of It may be substituted with one or more substituents selected.

When R ₁ , R ₂ , Ar ₁ , Ar ₂ , Ar _4, and Ar ₅ are alkyl groups, this is halogen, silane group, boron group, cyano group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a heterocyclic group of _{C 2 ~ C 20, C 7} ~ C ₂₀ of It may be substituted with one or more substituents selected from the group consisting of an arylalkyl group and an arylalkenyl group of C ₈ to C ₂₀ .

When R ₁ , R ₂ , Ar ₄ and Ar ₅ are alkenyl groups, it is deuterium, halogen, silane group, cyano group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C _20, an alkenyl group (alkenyl), a heterocyclic group of C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ substituted by deuterium, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ to C ₂₀ It may be substituted with one or more substituents selected from the group consisting of an arylalkyl group and an arylalkenyl group of C ₈ to C ₂₀ .

When the R ₁ and R ₂ is an alkoxy group, which is heavy hydrogen, a halogen, a silane group, a C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, It may be substituted with one or more substituents selected from the group consisting of C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ cycloalkyl group.

When R ₁ , R ₂ , Ar _1, and Ar ₂ are aryloxy groups, they are deuterium, silane groups, cyano groups, C ₁ ~ C ₂₀ alkyl groups, C ₆ ~ C ₂₀ aryl groups, C ₆ substituted with deuterium It may be substituted with one or more substituents selected from the group consisting of an aryl group of ~ C ₂₀ , a heterocyclic group of C ₂ ~ C ₂₀ and a cycloalkyl group of C ₃ ~ C ₂₀ .

Here, in the case of the aryl group, the carbon number may be 6 to 60, preferably 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms,

When the heterocyclic group has 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms, more preferably a hetero ring having 2 to 20 carbon atoms,

In the case of the arylene group, the carbon number may be 6 to 60, preferably 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms,

In the case of the alkyl group, the carbon number is 1 to 50, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 10 carbon atoms.

Ar ₁ and Ar ₂ may be any one of the following groups independently of each other.

On the other hand, the compound represented by Formula 1 may be represented by one of the following formula.

In Formulas 2 to 13, Ar ₁ and Ar ₂ may be defined the same as defined in Formula 1, R ₃ and R ₄ may be defined the same as the definition of R ₁ and R ₂ in Formula 1. .

O in Formula 2 to Formula 5, Formula 9, and Formula 10 are integers of 1 to 4, p in Formulas 2 to 4 and 6 to 8 is an integer of 1 to 6, q in Formulas 6 to 8 Is an integer of 1 to 6.

More specifically, the formula represented by Formula 1 may be one of the following compounds.

Hereinafter, the synthesis examples of the compounds represented by the chemical formulas according to the present invention and the production examples of the organic electric device will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

Synthesis Example

Illustratively, the compound according to the present invention (Final Products) is prepared by reacting Sub 2 and Sub 3 as in Scheme 1, but is not limited thereto.

<Scheme 1>

I. Sub  1, synthesis

Sub 1 may be synthesized by the reaction route of Scheme 2, but is not limited thereto.

<Scheme 2>

Synthesis examples of specific compounds belonging to Sub 1 are as follows.

One. Sub  1-1 Synthesis

<Scheme 3>

(One) Sub  1-I-1 Synthesis

After starting material (2,4-dichlorophenyl) boronic acid (99.93 g, 523.7 mmol) was dissolved in toluene in a round bottom flask, 2-bromo-6-iodoaniline (234.03 g, 785.5 mmol), Pd (PPh ₃ ) ₄ (30.26 g, 26.2 mmol), K ₂ CO ₃ (217.14 g, 1571.1 mmol), water were added and stirred at 95 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 101.27 g (yield: 61%) of the product.

(2)  Sub  One- II -1 synthesis

Sub 1-I-1 (101.07 g, 319.5 mmol) obtained in the above synthesis was dissolved in MeOH in a round bottom flask, and the temperature of the reactant was lowered to 0 ° C., and conc. hydrochloric acid was slowly added dropwise for 15 minutes. Sodium nitrite (22.04 g, 319.5 mmol) solution was slowly added dropwise at 0 ° C. and stirred for 10 minutes, followed by potassium thiocyanate (99.34 g, 1022.3 mmol) and iron (III) chloride (36.27 g, 223.6 mmol) An aqueous solution was added and stirred at room temperature. After the reaction was completed, the mixture was neutralized with 2 M NaOH aqueous solution, extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 79.15 g (yield: 69%) of the product.

(3) Sub  One- III -1 synthesis

Sub 1-II-1 (79.15 g, 220.4 mmol) obtained in the above synthesis was dissolved in THF in a round bottom flask, and the temperature of the reactant was lowered to 0 ° C. and LiAlH ₄ (1 M in THF, 242.5 mL, 242.5 mmol) was slowly added dropwise and stirred at 0 ° C. After the reaction was completed, water was carefully added to remove the remaining LiAlH ₄ and extracted with 2M HCl aqueous solution, EtOAc and water, and then the organic layer was dried over MgSO ₄ and concentrated to give 64.06 g (yield: 87%) of the product.

(4)  Sub  1-1 Synthesis

Sub 1-1 (64.06, 191.8 mmol) obtained in the above synthesis was dissolved in a round bottom flask with acetonitrile, and then Cs ₂ CO ₃ (93.72 g, 287.6 mmol) was added and stirred at 130 ° C. by microwave irradiation. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a product 47.37 g (yield: 83%).

2. Sub  1-4 Synthesis Example

<Scheme 4>

(One) Sub  1-I-4 Synthesis

In the starting material (2,4-dichlorophenyl) boronic acid (113.7 g, 595.8 mmol), 5-bromo-2-iodoaniline (266.27 g, 893.8 mmol), Pd (PPh ₃ ) ₄ (34.43 g, 29.8 mmol), K ₂ CO ₃ (247.06 g, 1787.5 mmol), Toluene, water was obtained using the Sub 1-I-1 synthesis above to give 111.45 g (yield: 59%) of product.

(2) Sub  One- II -4 synthetic

To Sub 1-I-4 (111.45 g, 351.6 mmol) obtained in the above synthesis. Hydrochloric acid, sodium nitrite (24.26 g, 351.6 mmol) aqueous solution, potassium thiocyanate (109.33 g, 1125 mmol), iron (III) chloride (39.92 g, 246.1 mmol) aqueous solution, MeOH using the Sub 1-II-1 synthesis method This gave 88.37 g (yield: 70%) of product.

(3) Sub  One- III -4 synthetic

Li AlH _{4 in} Sub 1-II-4 (88.37 g, 246.1 mmol) obtained in the above synthesis (1 M in THF, 270.7 mL, 270.7 mmol) and THF were obtained using the Sub 1-III-1 synthesis method above to give 69.88 g (yield: 85%) of product.

(4) Sub  1-4 Synthesis

Sub 1-III-4 (69.88 g, 209.2 mmol) obtained in the above synthesis was obtained with 52.29 g (Yield: 84%) of Cs ₂ CO ₃ (102.23 g, 313.8 mmol) and acetonitrile using the Sub 1-1 synthesis method. Got.

3. Sub  1-5 Synthesis Example

Scheme 5

Subs 1-III-5 (65.82 g, 197 mmol) in Cs ₂ CO ₃ (96.29 g, 295.5 mmol) and acetonitrile gave the product 48.67 g (yield: 83%) using the Sub 1-1 synthesis method.

4. Sub  1-7 Synthesis Example

<Scheme 6>

Subs 1-III-7 (68.37 g, 204.7 mmol) in Cs ₂ CO ₃ (100.03 g, 307 mmol) and acetonitrile gave 49.34 g (yield: 81%) of the product using the Sub 1-1 synthesis method.

Examples of Sub 1 are as follows, but are not limited thereto.

II. Sub  2, synthesis

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 7, but is not limited thereto.

Scheme 7

Synthesis examples of specific compounds belonging to Sub 2 are as follows.

One. Sub  2-4 Synthesis Example

Scheme 8

Sub 2-II-4 (8.01 g, 47.9 mmol) was dissolved in nitrobenzene in a round bottom flask, then Sub 1-4 (18.53 g, 62.3 mmol) and Na ₂ SO ₄ (6.8 g, 47.9 mmol), K ₂ CO ₃ (6.62 g, 47.9 mmol), Cu (0.91 g, 14.4 mmol) was added and stirred at 200 ° C. After the reaction was completed, nitrobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 11.95 g (yield: 65%) of the product.

2. Sub  2-8 Synthesis Example

Scheme 9

Sub 2-II-8 (7.53 g, 45 mmol) in Sub 1-7 (17.42 g, 58.5 mmol), Na ₂ SO ₄ (6.4 g, 45 mmol), K ₂ CO ₃ (6.22 g, 45 mmol), Cu (0.86 g, 13.5 mmol) and nitrobenzene were obtained using the Sub 2-4 synthesis method to give 11.06 g (yield: 64%) of the product.

3. Sub  2-13 Synthesis Example

Scheme 10

Sub 2-II-13 (9.27 g, 38.1 mmol) in Sub 1-1 (14.74 g, 49.5 mmol), Na ₂ SO ₄ (5.41 g, 38.1 mmol), K ₂ CO ₃ (5.27 g, 38.1 mmol), Cu (0.73 g, 11.4 mmol) and nitrobenzene were obtained using the Sub 2-4 synthesis method to obtain 10.87 g (yield: 62%) of the product.

4. Sub  2-21 Synthesis Example

Scheme 11

(One) Sub  2-I-21 Synthesis

After starting material [1,1'-biphenyl] -4-ylboronic acid (13.56 g, 68.5 mmol) was dissolved in THF in a round bottom flask, 1-bromo-2-nitrobenzene (15.22 g, 75.3 mmol), Pd ( PPh ₃ ) ₄ (3.96 g, 3.4 mmol), K ₂ CO ₃ (28.39 g, 205.4 mmol), water were added and stirred at 80 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 16.21 g (yield: 86%) of the product.

(2) Sub  2- II -21 synthetic

Sub 2-I-21 (16.21 g, 58.9 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene in a round bottom flask, triphenylphosphine (38.61 g, 147.2 mmol) was added and stirred at 200 ° C. After the reaction was completed, o -dichlorobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was silicagel column and recrystallized to give the product 10.31 g (yield: 72%).

(3) 2-21 synthesis

To Sub 2-II-21 (10.31 g, 42.4 mmol) obtained in the synthesis above Sub 1-5 (16.39 g, 55.1 mmol), Na ₂ SO ₄ (6.02 g, 42.4 mmol), K ₂ CO ₃ (5.86 g, 42.4 mmol), Cu (0.81 g, 12.7 mmol) and nitrobenzene were obtained using the Sub 2-4 synthesis method to obtain 12.86 g (yield: 66%) of the product.

5. Sub  2-25 Synthesis Example

Scheme 12

Sub 2-II-25 (15.36 g, 48.1 mmol) in Sub 1-1 (18.61 g, 62.5 mmol), Na ₂ SO ₄ (6.83 g, 48.1 mmol), K ₂ CO ₃ (6.65 g, 48.1 mmol), Cu (0.92 g, 14.4 mmol) and nitrobenzene were obtained using the Sub 2-4 synthesis method to give 15.21 g (yield: 59%) of the product.

6. Sub  2-39 Synthesis Example

Scheme 13

(One) Sub  2-I-39 Synthesis

Naphthalen-1-ylboronic acid (13.61 g, 79.1 mmol), starting material, 1-bromo-2-nitrobenzene (17.58 g, 87 mmol), Pd (PPh ₃ ) ₄ (4.57 g, 4 mmol), K ₂ CO ₃ (32.81 g, 237.4 mmol), THF, and water were obtained using the Sub 2-I-21 synthesis method to obtain 17.55 g (yield: 89%) of the product.

(2) Sub  2- II -39 synthetic

Sub 2-I-39 (17.55 g, 70.4 mmol) obtained in the above synthesis of triphenylphosphine (46.17 g, 176 mmol) and o -dichlorobenzene using the above-described Sub 2-II-21 synthesis method, 11.32 g (yield: 74%) )

(3) Sub  2-39 Synthesis Example

To Sub 2-II-39 (11.32 g, 52.1 mmol) obtained in the above synthesis, Sub 1-7 (20.16 g, 67.7 mmol), Na ₂ SO ₄ (7.4 g, 52.1 mmol), K ₂ CO ₃ (7.2 g, 52.1 mmol), Cu (0.99 g, 15.6 mmol) and nitrobenzene were obtained using the Sub 2-4 synthesis method to give 14.02 g (yield: 62%) of the product.

7. Sub  2-42 Synthesis Example

Scheme 14

Sub 2-II-42 (12.59 g, 47.1 mmol) in Sub 1-4 (18.22 g, 61.2 mmol), Na ₂ SO ₄ (6.69 g, 47.1 mmol), K ₂ CO ₃ (6.51 g, 47.1 mmol), Cu (0.9 g, 14.1 mmol) and nitrobenzene were obtained using the Sub 2-4 synthesis method to obtain 13.91 g (yield: 61%) of the product.

8. Sub  2-53 Synthesis Example

Scheme 15

Sub 2-II-53 (12.32 g, 46.1 mmol) in Sub 1-5 (17.83 g, 59.9 mmol), Na ₂ SO ₄ (6.55 g, 46.1 mmol), K ₂ CO ₃ (6.37 g, 46.1 mmol), Cu (0.88 g, 13.8 mmol) and nitrobenzene were obtained using the Sub 2-4 synthesis method to obtain 12.94 g (yield: 58%) of the product.

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

TABLE 1

III. Sub  3, synthesis

Sub 3 of Scheme 1 may be synthesized by the reaction route of Scheme 16 below.

Scheme 16

Synthesis examples of specific compounds belonging to Sub 3 are as follows.

One. Sub  3-17 Synthesis Example

Scheme 17

After starting material 4-bromo-1,1'-biphenyl (53.86 g, 231.1 mmol) was dissolved in toluene in a round bottom flask, [1,1'-biphenyl] -4-amine (78.2 g, 462.1 mmol), Pd ₂ (dba) ₃ (6.35 g, 6.9 mmol), 50% P ( t- Bu) ₃ (9ml, 18.5 mmol), NaO t- Bu (66.62 g, 693.2 mmol) was added and stirred at 40 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 58.67 g (yield: 79%).

2. Sub  3-21 Synthesis Example

Scheme 18

Aniline (33.9 g, 364 mmol), Pd ₂ (dba) ₃ (5 g, 5.5 mmol), 50% in starting material 2-bromo-9,9-dimethyl-9 H -fluorene (49.72 g, 182 mmol) P ( t -Bu) ₃ (7.1 ml, 14.6 mmol), NaO t -Bu (52.48 g, 546 mmol) and toluene were obtained using the above Sub 3-17 synthesis to give 38.96 g (yield: 75%) of the product.

3. Sub  3-23 Synthesis Example

Scheme 19

[1,1'-biphenyl] -4-amine (58.8 g, 347.5 mmol), Pd ₂ (dba) in 2-bromo-9,9-dimethyl-9 H -fluorene (47.46 g, 173.7 mmol) as starting material ₃ (4.77 g, 5.2 mmol), 50% P ( t -Bu) ₃ (6.8ml, 13.9 mmol), NaO t -Bu (50.09 g, 521.2 mmol), toluene were obtained using the Sub 3-17 synthesis 45.85 g (yield: 73%) were obtained.

4. Sub  3-26 Synthesis Example

Scheme 20

[1,1'-biphenyl] -4-amine (45.64 g, 269.7 mmol), Pd ₂ (dba), as starting material 2-bromo-9,9-diphenyl-9 H -fluorene (53.58 g, 134.9 mmol) ₃ (3.7 g, 4 mmol), 50% P ( t -Bu) ₃ (5.3 ml, 10.8 mmol), NaO t -Bu (38.88 g, 404.6 mmol), toluene were obtained using the Sub 3-17 synthesis 49.77 g (yield 76%) were obtained.

5. Sub  3-27 Synthesis Example

Scheme 21

To the starting material 2-bromo-9,9'-spirobi [fluorene] (55.56 g, 140.6 mmol) aniline (26.18 g, 281.1 mmol), Pd ₂ (dba) ₃ (3.86 g, 4.2 mmol), 50% P ( t -Bu) ₃ (5.5 ml, 11.2 mmol), NaO t -Bu (40.53 g, 421.7 mmol) and toluene were obtained using the Sub 3-17 synthesis to obtain 39.52 g (yield: 69%) of the product.

Meanwhile, examples of Sub 3 are as follows, but are not limited thereto, and their FD-MSs are shown in Table 2 below.

TABLE 2

IV. Final product Products  synthesis

Sub 1 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 2 (1.2 equiv), Pd ₂ (dba) ₃ (0.03 equiv), P (t-Bu) ₃ (0.08 equiv), NaO t -Bu (3 equiv) was added and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain final products.

One. Product  1-52 Synthesis Example

Scheme 22

Sub 3-17 (7.49 g, 23.3 mmol) obtained in the above synthesis was dissolved in toluene in a round bottom flask, and then Sub 2-4 (10.74 g, 28 mmol), Pd ₂ (dba) ₃ (0.64 g, 0.7 mmol) , 50% P ( t -Bu) ₃ (0.9 ml, 1.9 mmol), NaO t -Bu (6.72 g, 69.9 mmol) was added and stirred at 100 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 11.85 g (yield: 76%).

2. Product  1-80 Synthesis Example

Scheme 23

To Sub 3-26 (8.13 g, 16.7 mmol) obtained in the above synthesis, Sub 2-8 (7.71 g, 20.1 mmol), Pd ₂ (dba) ₃ (0.46 g, 0.5 mmol), 50% P ( t -Bu) ₃ (0.7 ml, 1.3 mmol), NaO t -Bu (4.83 g, 50.2 mmol) and toluene were obtained using the Product 1-52 synthesis method to obtain 10.32 g (yield: 74%) of the product.

3. Product  1-129 Synthesis Example

Scheme 24

To Sub 3-26 (8.02 g, 16.5 mmol) obtained in the above synthesis, Sub 2-13 (9.12 g, 19.8 mmol), Pd ₂ (dba) ₃ (0.45 g, 0.5 mmol), 50% P ( t -Bu) ₃ (0.6 ml, 1.3 mmol), NaO t -Bu (4.76 g, 49.5 mmol) and toluene were obtained using the Product 1-52 synthesis method to obtain 10.66 g (yield: 71%) of the product.

4. Product  1-139 Synthesis Example

Scheme 25

Sub 3-23 (7.19 g, 19.9 mmol) obtained in the above synthesis in Sub 2-21 (10.98 g, 23.9 mmol), Pd ₂ (dba) ₃ (0.55 g, 0.6 mmol), 50% P ( t -Bu) ₃ (0.8 ml, 1.6 mmol), NaO t -Bu (5.74 g, 59.7 mmol) and toluene were obtained using the Product 1-52 synthesis method to give 11.71 g (yield: 75%) of the product.

5. Product  1-145 Synthesis Example

Scheme 26

To Sub 3-17 (7.25 g, 22.6 mmol) obtained in the above synthesis Sub 2-25 (14.51 g, 27.1 mmol), Pd ₂ (dba) ₃ (0.62 g, 0.7 mmol), 50% P ( t -Bu) ₃ (0.9 ml, 1.8 mmol), NaO t -Bu (6.5 g, 67.7 mmol) and toluene were obtained using the Product 1-52 synthesis method to obtain 12.96 g (yield: 70%) of the product.

6. Product  1-180 Synthesis Example

Scheme 27

Sub 3-17 (7.37 g, 22.9 mmol) obtained in the above synthesis in Sub 2-39 (11.94 g, 27.5 mmol), Pd ₂ (dba) ₃ (0.63 g, 0.7 mmol), 50% P ( t -Bu) ₃ (0.9 ml, 1.8 mmol), NaO t -Bu (6.61 g, 68.8 mmol) and toluene were obtained using the Product 1-52 synthesis method to obtain 12.03 g (yield: 73%) of the product.

7. Product  1-199 Synthesis Example

Scheme 28

To Sub 3-21 (6.71 g, 23.5 mmol) obtained in the above synthesis, Sub 2-42 (13.66 g, 28.2 mmol), Pd ₂ (dba) ₃ (0.65 g, 0.7 mmol), 50% P ( t -Bu) ₃ (0.9 ml, 1.9 mmol), NaO t -Bu (6.78 g, 70.5 mmol) and toluene were obtained using the Product 1-52 synthesis method to yield 11.72 g (yield: 68%) of the product.

8. Product  1-200 Synthesis Example

Scheme 29

Sub 3-27 (8.39 g, 20.6 mmol) obtained in the above synthesis to Sub 2-53 (11.96 g, 24.7 mmol), Pd ₂ (dba) ₃ (0.57 g, 0.6 mmol), 50% P ( t -Bu) ₃ (0.8 ml, 1.6 mmol), NaO t -Bu (5.94 g, 61.8 mmol) and toluene were obtained using 11.09 g (yield: 63%) of the product using the Product 1-52 synthesis method.

On the other hand, FD-MS values of the compounds 1-1 to 1-204 of the present invention prepared according to the synthesis examples as described above are shown in Table 3.

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 Suzuki cross-coupling reaction, Diazotization-Thiocyanation reaction ( Org . Biomol . Chem . 2011, 9 , 6066), Reduction reaction, MW (Microwave) -assisted cyclization reaction ( Org . Biomol . Chem . 2011, 9 , 6066), PPh ₃ -mediated reductive cyclization reaction ( J. Org . Chem . 2005, 70 , 5014.), Ullmann reaction and Buchwald-Hartwig cross It will be readily understood by those skilled in the art that the reaction proceeds even if other substituents (substituents such as R ₁ , R ₂ , Ar ₁ , Ar _2, etc.) defined in Chemical Formula 1 are combined, in addition to the substituents specified in the specific synthesis examples, based on the coupling reaction. will be.

For example, the reaction with starting material-> Sub 1-I in Scheme 2 and the reaction with starting material-> Sub 2-I in Scheme 7 are all based on the Suzuki cross-coupling reaction, and the Sub 1-I in Scheme 2 -> Sub 1-II reaction is based on Diazotization-Thiocyanation reaction, Sub 1-II-> Sub 1-III reaction in Scheme 2 is based on Reduction reaction, and Sub 1-III-> Sub 1 reaction in Scheme 2 It is based on the MW (Microwave) -assisted cyclization reaction. Sub-I-> Sub 2-II reaction in Scheme 7 is then based on PPh ₃ -mediated reductive cyclization reaction, and Sub 2-II-> Sub 2 reaction in Scheme 7 is based on Ullmann reaction, starting from Scheme 16 Substance-> Sub 3, Product Synthesis Schemes (Scheme 22-29) are based on the Buchwald-Hartwig cross coupling reaction, which will proceed even if the substituents are not specified.

Manufacturing Evaluation of Organic Electrical Device

[ Example  1] Green organic light emitting device Hole transport layer )

First, 4,4 ', 4''-Tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as 2-TNATA) is vacuum-deposited on an ITO layer (anode) formed on an organic substrate to form a hole having a thickness of 60 nm. After the injection layer was formed, Compound 1-1 of the present invention was vacuum deposited to a thickness of 20 nm on the hole injection layer to form a hole transport layer. Next, 4,4'-N, N'-dicarbazole-biphenyl (abbreviated as CBP) as a host material on the hole transport layer and tris (2-phenylpyridine) -iridium (hereinafter referred to as Ir (ppy) ₃ ) as a dopant material. The light emitting layer was deposited to a thickness of 30 nm with a weight ratio of 95: 5. Subsequently, (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 on the light emitting layer to hold A layer was formed, and an electron transport layer was formed to a thickness of 40 nm on tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) on the holding layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[Example 2] to [Example 204] Green organic electroluminescent device (hole transport layer)

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that one of Compounds 1-2 to 1-204 of the present invention shown in Table 4 was used instead of Compound 1-1 of the present invention as a hole transport layer material. Prepared.

Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 was used instead of Compound 1-1 of the present invention as a hole transport layer material.

<Comparative Compound 1>

Comparative Example 2

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 2 was used instead of Compound 1-1 of the present invention as a hole transport layer material.

Comparative Compound 2

Comparative Example 3

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 3 was used instead of Compound 1-1 of the present invention as a hole transport layer material.

Comparative Compound 3

[Comparative Example 4]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 4 was used instead of Compound 1-1 of the present invention as a hole transport layer material.

Comparative Compound 4

[Comparative Example 5]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 5 was used instead of Compound 1-1 of the present invention as a hole transport layer material.

Comparative Compound 5

Comparative Example 6

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 6 was used instead of Compound 1-1 of the present invention as a hole transport layer material.

Comparative Compound 6

Comparative Example 7

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 7 was used instead of Compound 1-1 of the present invention as a hole transport layer material.

Comparative Compound 7

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared by Examples 1 to 204 and Comparative Examples 1 to 7 of the present invention The T90 lifetime was measured using a lifespan measuring instrument manufactured by McScience Inc. at a luminance of 300 cd / m ^2. The measurement results are shown in Table 4 below.

TABLE 4

As can be seen from the results of Table 4, Comparative Examples 1 to 7 using Example 1 to Example 204 and Comparative Compound 1 to Comparative Compound 7 using the compound according to the present invention as the hole transport layer material were used as the hole transport layer material. In comparison, in the case of the embodiment of the present invention using the compound of the present invention as the hole transport layer material, the driving voltage is relatively low, the luminous efficiency is improved, and the life is significantly improved as compared with Comparative Examples 1 to 7.

Among the above results, Comparative Examples 2 to 7 in which the compound of the present invention and the linking group were different showed a tendency to show higher driving voltage, lower efficiency, and lower lifetime than the compound of the present invention.

This is because the compound of the present invention wherein the linking group is dibenzothiophene has a relatively shorter conjugation length than Comparative Examples 2 to 7 in which one more phenyl group is connected to the dibenzothiophene. It has a band gap and a high T1 value, which makes it easier to block electrons from the light emitting layer. In addition, the packing density of the compound of the present invention is better than Comparative Examples 2 to 7 has a fast hole mobility (hole mobility) is lowered the driving voltage, the thermal damage is reduced due to the low driving voltage Efficiency and lifetime are improved.

When combining the above-mentioned characteristics (wide band gap, high T1 value, high thermal stability), the band gap, electrical characteristics, and interfacial characteristics can be greatly changed depending on the type of linking group between carbazole and diarylamine. It can be seen that this can be a major factor in improving device performance.

In addition, in the case of the hole transport layer, it is necessary to grasp the interrelationship with the light emitting layer (host), and even if a similar core is used, it will be very difficult for a person skilled in the art to infer the characteristics indicated in the hole transport layer in which the compound according to the present invention is used. .

Example 205 Green organic electroluminescent element (light emitting auxiliary layer)

After vacuum depositing 2-TNATA on the ITO layer (anode) formed on the glass substrate to form a hole injection layer having a thickness of 60 nm, the compound 1-52 of the present invention was vacuum deposited on the hole injection layer to a thickness of 20 nm to form a hole transport layer. Formed. Next, Compound 1-49 of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emission auxiliary layer. Next, a light emitting layer was deposited on the light emitting auxiliary layer by doping CBP as a host material and Ir (ppy) ₃ as a dopant material in a 95: 5 weight ratio. Subsequently, BAlq was vacuum-deposited on the light emitting layer to a thickness of 10 nm to form a holdoff layer, and an electron transport layer was formed on the holdoff layer to form 40 nm thick of Alq ₃ . Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[Example 206] to [Example 299] Green organic electroluminescent device (light emitting auxiliary layer)

Compound 1-50 to 1-51, 1-53 to 1-84, 1-121 to 1-144, 1-153 to 1-49 of the present invention shown in Table 5 instead of Compound 1-49 of the present invention An organic electroluminescent device was manufactured in the same manner as in Example 205, except that one of 1-188 was used.

Comparative Example 8

An organic electroluminescent device was manufactured in the same manner as in Example 205, except that the light emitting auxiliary layer was not formed.

Comparative Example 9

An organic electroluminescent device was manufactured in the same manner as in Example 205, except that Comparative Compound 2 was used instead of Compound 1-49 of the present invention as a light emitting auxiliary layer material.

Comparative Example 10

An organic electroluminescent device was manufactured in the same manner as in Example 205, except that Comparative Compound 3 was used instead of Compound 1-49 of the present invention as a light-emitting auxiliary layer material.

Comparative Example 11

An organic electroluminescent device was manufactured in the same manner as in Example 205, except that Comparative Compound 4 was used instead of Compound 1-49 of the present invention as a light-emitting auxiliary layer material.

Comparative Example 12

An organic electroluminescent device was manufactured in the same manner as in Example 205, except that Comparative Compound 5 was used instead of Compound 1-49 of the present invention.

Comparative Example 13

An organic electroluminescent device was manufactured in the same manner as in Example 205, except that Comparative Compound 6 was used instead of Compound 1-49 of the present invention as a light-emitting auxiliary layer material.

Comparative Example 14

An organic electroluminescent device was manufactured in the same manner as in Example 205, except that Comparative Compound 7 was used instead of Compound 1-49 of the present invention as a light-emitting auxiliary layer material.

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples 205 to 299 and Comparative Examples 8 to 14 of the present invention The T90 lifetime was measured using a life-time measuring instrument manufactured by McScience Inc. at 300 cd / m ² reference luminance. The measurement results are shown in Table 5 below.

TABLE 5

Similarly to Table 4, even when using a compound of Comparative Compound 2 to Comparative Compound 7 in which the phenyl is further connected to the diarylamine in the dibenzothiophene as the light emitting auxiliary layer material, only the dibenzothiophene is connected. It was confirmed that the present invention exhibits lower efficiency and lower lifetime than the compound of the present invention.

This is because the compound according to the present invention using only dibenzothiophene as a linker between carbazole and diarylamine has higher T1 value and deep HOMO energy level in the light emitting auxiliary layer as well as the hole transport layer than Comparative Compounds 2 to 7. This is because holes and electrons achieve charge balance and emit light inside the light emitting layer instead of the hole transport layer interface, thereby maximizing higher efficiency and lifespan.

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 following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

[Description of the code]

100: organic electric element 110: substrate

120: first electrode 130: hole injection layer

140: hole transport layer 141: buffer layer

150: light emitting layer 151: light emitting auxiliary layer

160: electron transport layer 170: electron injection layer

180: second electrode

CROSS-REFERENCE TO RELATED APPLICATION

This patent application claims priority under Patent Application No. 10-2013-0017440, filed in Korea on February 19, 2013, under section 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 (10)

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

   <Formula 1>

   

   [In Formula 1,

   Ar ₁ and Ar ₂ are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl groups; C ₁ ~ C ₅₀ Alkyl group; And C ₆ ~ C ₃₀ An aryloxy group; It is selected from the group consisting of,

   m and n are each an integer of 1 to 4,

   R ₁ and R ₂ are, independently from each other, i) hydrogen; heavy hydrogen; Tritium; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl groups; C ₂ -C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; -LN (Ar ₄ ) (Ar ₅ ); C ₁ -C ₃₀ alkoxyl group; And an aryloxy group of C ₆ to C ₃₀ ; or ii) adjacent groups combine with each other to form at least one ring (where the group that does not form a ring is defined in i) equivalence),

   L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And divalent aliphatic hydrocarbon group; selected from the group consisting of,

   Ar ₄ and Ar ₅ are each independently a heterocyclic group of C ₂ ~ C ₆₀ including at least one hetero atom of O, N, S, Si and P; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ ~ C ₅₀ Alkyl group; And fluorenyl group; selected from the group consisting of,

   Herein, the aryl group, heterocyclic group, fluorenyl group, alkyl group, alkenyl group, alkoxyl group, and aryloxy group are each deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C ₁ ~ for C ₂₀ come alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 2 ~ C} 20 of the alkynyl group (alkynyl), C of the of ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ aryl group substituted with a heavy hydrogen, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ of the It may be substituted with one or more substituents selected from the group consisting of an arylalkyl group and an arylalkenyl group of C ₈ ~ C ₂₀ ,

   Each of the arylene group, fluorenylene group, heterocyclic group and aliphatic hydrocarbon group may be a nitro group, a cyano group, a halogen group, an alkyl group of C ₁ to C ₂₀ , an aryl group of C ₆ to C ₂₀ , and a C ₂ to C _{20 group} . Heterocyclic group, C ₁ ~ C ₂₀ It may be substituted with one or more substituents selected from the group consisting of an alkoxyl group and an amino group]
2. The method of claim 1,

   Ar ₁ and Ar ₂ are independently of each other, characterized in that any one of the following groups.

   
3. The method of claim 1,

   Compound represented by one of the following formula.

   

   

   [In Formulas 2 to 13, Ar ₁ and Ar ₂ are defined the same as defined in claim ₁ , R ₃ and R ₄ are defined the same as the definition of R ₁ and R ₂ in claim ₁ ,

   O in Formula 2 to Formula 5, Formula 9, and Formula 10 are integers of 1 to 4, p in Formulas 2 to 4 and 6 to 8 is an integer of 1 to 6, q in Formulas 6 to 8 Is an integer of 1 to 6]
4. The method of claim 1,

   Compound represented by one of the following formula.

   

   

   

   

   

   

   

   

   
5. In an organic electric device comprising a first electrode, a second electrode, and an organic material layer positioned between the first electrode and the second electrode,

   The organic material layer comprises an organic electroluminescent device comprising the compound of claim 1.
6. The method of claim 5,

   And forming the compound into the organic material layer by a soluble process.
7. The method of claim 5,

   And the organic material layer is at least one of a light emitting layer, a hole injection layer, a hole transporting layer, a light emitting auxiliary layer, an electron injection layer, and an electron transporting layer.
8. The method of claim 7, wherein

   The organic electric device, characterized in that the compound is contained in the hole transport layer or the light emitting auxiliary layer.
9. A display device comprising the organic electroluminescent device of claim 5; And

   And a controller for driving the display device.
10. The method of claim 9,

    The organic electronic device is at least one of an organic electroluminescent device, an organic solar cell, an organic photosensitive member, an organic transistor, and a device for monochrome or white illumination.

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