KR20170088601A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention relates to a compound for an organic electronic element, the organic electronic element using the compound, and an electronic device of the organic electronic element. The present invention provides a compound represented by chemical formula (1), a composition for a hole transport layer or an auxiliary light emitting layer including the compound, and an organic electronic element containing the compound. The element not only can achieve high light-emitting efficiency, low driving voltage and high heat resistance, but also can greatly improve color purity and lifetime by using the compound according to the present invention.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for organic electroluminescent devices, an organic electroluminescent device using the same, and an electronic device using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent (EL)

TECHNICAL FIELD The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device therefor.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer is often formed of a multilayer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

The most problematic aspects of organic electroluminescent devices are their lifetime and efficiency. As the display becomes larger, such efficiency and lifetime problems must be solved.

The efficiency, lifetime, and driving voltage are related to each other. As the efficiency increases, the driving voltage drops and the driving voltage drops. As a result, crystallization of the organic material due to Joule heating, which occurs during driving, And the lifetime tends to increase.

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

In order to solve the problem of light emission in the hole transporting layer in recent organic electroluminescent devices, it is necessary to have a light emitting auxiliary layer between the hole transporting layer and the light emitting layer, It is time to develop the layer.

Generally, 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, the material used for the hole transport layer has a low HOMO value and therefore has a low T 1 value. As a result, the exciton generated in the light emitting layer is transferred to the hole transport layer, resulting in a charge unbalance in the light emitting layer. And emits light at the interface of the hole transporting layer.

When light is emitted from the interface of the hole transporting layer, the color purity and efficiency of the organic electronic device are lowered and the lifetime is shortened. Therefore, it is urgently required to develop a light emitting auxiliary layer having a high T 1 value and a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light emitting layer.

On the other hand, while delaying penetration and diffusion of the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, to the organic layer, stable characteristics such as Joule heating, It is necessary to develop a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has a property of lowering the uniformity of the surface of the thin film when the device is driven, which has been reported to have a great influence on the lifetime of the device. In addition, OLED devices are mainly formed by a deposition method, and it is necessary to develop a material that can withstand a long period of time, that is, a material having high heat resistance characteristics.

That is, in order to sufficiently exhibit the excellent characteristics of the organic electronic device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, an electron injecting material, However, the development of a stable and efficient organic material layer for an organic electric device has not been sufficiently developed yet. Therefore, the development of new materials is continuously required, and in particular, the development of a material for a hole transporting layer or a light emitting auxiliary layer is urgently required.

KR 1020130076842 A

In order to solve the problems of the background art described above, an embodiment of the present invention has revealed a compound having a novel structure, and when the compound is applied to an organic electric device, the luminous efficiency, stability and lifetime of the device are greatly improved It can be done.

Accordingly, it is an object of the present invention to provide a novel compound, an organic electric device using the same, and an electronic device.

The present invention provides an organic electroluminescent device comprising a compound represented by the following formula (1), a composition for a hole transporting layer or a luminescent auxiliary layer containing the same, and the compound.

(1)

By using the compound according to the present invention, it is possible to achieve a high luminous efficiency, a low driving voltage, and a high heat resistance of the device, and can greatly improve the color purity and lifetime of the device.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an illustration of an organic electroluminescent device according to the present invention. FIG.

Hereinafter, embodiments of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

As used in this specification and the appended claims, unless stated otherwise, the following terms have the following meanings:

The term " halo "or" halogen ", as used herein, unless otherwise indicated, is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I).

As used herein, the term "alkyl" or "alkyl group " refers to a straight or branched Quot; means a radical of a saturated aliphatic group, including an alkyl group, a cycloalkyl-substituted alkyl group.

The term "haloalkyl group" or "halogenalkyl group" as used in the present invention means an alkyl group substituted with halogen unless otherwise stated.

The term "heteroalkyl group" as used herein means that at least one of the carbon atoms constituting the alkyl group is replaced by a heteroatom.

The term "alkenyl group "," alkenyl group ", or "alkynyl group ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms and include straight chain or branched chain groups , But is not limited thereto.

The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.

The term "alkoxyl group "," alkoxy group ", or "alkyloxy group" used in the present invention means an alkyl group to which an oxygen radical is attached and, unless otherwise stated, has a carbon number of 1 to 60, It is not.

The term "alkenoyl group "," alkenoyl group ", "alkenyloxy group ", or" alkenyloxy group "as used in the present invention means an alkenyl group to which an oxygen radical is attached, , But is not limited thereto.

As used herein, the term "aryloxyl group" or "aryloxy group" refers to an aryl group attached to an oxygen radical and, unless otherwise stated, has a carbon number of 6 to 60, but is not limited thereto.

The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirobifluorene group.

The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, the arylalkyl group is an alkyl group substituted with an aryl group, the arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described in the present specification.

Also, if prefixes are named consecutively, it means that the substituents are listed in the order listed first. For example, the arylalkoxy group means an alkoxy group substituted with an aryl group, the alkoxycarbonyl group means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, an alkenyl group substituted with an arylcarbonyl group means Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed in combination.

The term "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings and includes a heteroaliphatic ring and hetero Aromatic rings. Adjacent functional groups may be combined and formed.

As used herein, the term "heteroatom " refers to N, O, S, P or Si unless otherwise stated.

The "heterocyclic group" may also include a ring containing SO ₂ in place of the carbon forming the ring. For example, the "heterocyclic group" includes the following compounds.

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

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.

Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

Unless otherwise specified, the term "carbonyl" as used herein refers to -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, A cycloalkyl group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise indicated, the term "ether" used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group of 1-20 carbon atoms, An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C for use in the present invention ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C of ₂₀ alkynyl, 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 ~ C ₂₀ aryl alkenyl group, a silane group, a boron Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group.

Unless otherwise expressly stated, the formula used in the present invention is applied in the same manner as the definition of the substituent by the definition of the index of the following formula.

When a is an integer of 0, substituent R ¹ is absent. When a is an integer of 1, one substituent R ¹ is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3 each coupled as follows: and wherein R ¹ may be the same or different from each other, a is the case of 4 to 6 integer, and bonded to the carbon of the benzene ring in a similar way, while the display of the hydrogen bonded to the carbon to form a benzene ring Is omitted.

Hereinafter, a compound according to one aspect of the present invention and an organic electronic device including the same will be described.

According to a specific example of the present invention, there is provided a compound represented by the following formula (1).

            (1)

{In the above formula (1)

1) Ar ¹ is A C ₆ to C ₆₀ aryl group,

2) R ¹ to R ⁴ independently of one another are i) deuterium; Tritium; halogen; Cyano; A nitro group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; -L ' -N (R ' _a ) (R ' _b ); A C ₁ -C ₃₀ alkoxyl group; And a C ₆ -C ₃₀ aryloxy group, or ii) adjacent R ^{1 s} and R ^{2 s} may be bonded to each other to form a ring,

R ³ and R ⁴ are not bonded to each other to form a ring,

(Wherein L 'is a single bond; C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₃ ~ C a fused ring of an aromatic ring of an aliphatic ring and a C ₆ ~ C ₆₀ groups of _60; and a C ₂ ~ C _And R _a and R _b are independently selected from the group consisting of a C ₆ to C ₆₀ aryl group, a fluorenyl group, a C ₃ to C ₆₀ aliphatic ring and a C ₆ to C ₆₀ alicyclic ring, groups of the fused ring of an aromatic ring, and selected from the group consisting of a,); and O, N, S, Si, and heterocyclic of C ₂ ~ C ₆₀ group containing at least one hetero atom of the P

3) R ⁵ to R ⁶ are independently selected from: i) a C ₆ -C ₆₀ aryl group; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And aryloxy groups of C ₆ -C ₃₀ , or ii) R ⁵ and R ⁶ may be bonded to each other to form a spiro compound together with C to which they are bonded,

4) A rings and B rings are C ₆ to C ₂₀ aryl groups; Except when A ring and B ring are simultaneously C ₆ aryl groups,

5) L ¹ and L ² independently of one another are a single bond; C ₆ -C ₆₀ arylene groups; A fluorenylene group; And a C ₂ -C ₆₀ heteroarylene group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C3-C60 and an aromatic ring of C6-C60,

6) a is any integer from 0 to 17; b is an integer of 0 to 18; c is an integer of 0 to 4; d is an integer of 0 to 3;

A halogen group, a silyl group, a siloxane group, a boron group, a germanium group, a cyano group, a nitro group, a -L _{'-N (R a) (R} b); C 1 ~ Import alkylthio of C _20; C ₁ ~ alkoxy group of C _20; C ₁ ~ alkyl group of C _20; C ₂ ~ C ₂₀ alkenyl group a; ₂ C ~ alkynyl of C _20; an aryl group of C ₆ - C ₂₀ substituted with heavy hydrogen;; C ₆ ~ C ₂₀ aryl group, a fluorenyl group; C ₂ - heterocyclic group of C _20; C of ₃ ~ C ₂₀ cycloalkyl An alkyl group, an arylalkyl group having ₇ to ₂₀ carbon atoms, and an arylalkenyl group having ₈ to ₂₀ carbon atoms, and these substituents may be further bonded to each other to form a ring, wherein The term " ring " means an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof Refers to a luer binary fused ring, a saturated or unsaturated ring.)}

The present invention also includes a compound represented by any one of the following formulas (2-1) to (2-3).

(In the above formulas (2-1) to (2-3)

R ¹ to R ⁶ , L ¹ , L ² , Ar ¹ , ad, A, and B are the same as defined in Formula 1, and A and B are not simultaneously C ₆ aryl.

The present invention also includes a compound represented by any one of the following formulas (3-1) to (3-3).

(In the above formulas 3-1 to 3-3,

R ¹ to R ⁶ , L ¹ , L ² , Ar ¹ , ad, A, and B are as defined in Formula 1.)

In the present invention, the A ring and the B ring of the formula (1) are each independently any one of the following formulas (1a) to (1d).

The present invention provides the compounds represented by the above formula (1) including the following compounds.

1, an organic electroluminescent device 100 according to the present invention includes a first electrode 120, a second electrode 180 and a first electrode 120 formed on a substrate 110, (180), an organic material layer containing a compound represented by the general formula (1). In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, the remaining layers except the light emitting layer 150 may not be formed. An electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like, and the electron transport layer 160 may serve as a hole blocking layer.

Further, although not shown, the organic electroluminescent device according to the present invention may further include a protective layer formed on at least one surface of the first electrode and the second electrode opposite to the organic layer.

On the other hand, since the band gap, the electrical characteristics, the interface characteristics, and the like can be changed depending on which substituent is bonded at any position even in the same core, the selection of the core and the combination of the sub- Especially when energy level and T1 value between each organic material layer, and the intrinsic characteristics (mobility, interfacial characteristics, etc.) of the material are optimized, long life and high efficiency can be achieved at the same time.

The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a physical vapor deposition (PVD) method. For example, a positive hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron transport layer 160 are formed on a substrate by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, Forming an organic material layer including the electron injection layer 170, and then depositing a material usable as a cathode thereon.

Accordingly, the present invention provides a plasma display panel comprising: a first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer contains a compound included in the formula (1).

The organic electroluminescent device may further include a light efficiency improvement layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the one side of the second electrode opposite to the organic material layer And an organic electroluminescent device.

In the present invention, the organic material layer may be formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process and a roll-to-roll process, And an organic electroluminescent device.

As another specific example, the present invention provides an organic electroluminescent device characterized in that the organic material layer is mixed with the same or different compound of the compound represented by the formula (1).

The present invention also provides an organic electronic device containing a hole injecting layer, a hole transporting layer, a light emitting layer or a light emitting auxiliary layer containing one or more compounds represented by the above formula (1).

More specifically, the present invention provides an organic electroluminescent device comprising the compound represented by the formula (1) in the hole transporting layer or the light-emission facilitating layer in the organic layer.

The present invention also relates to a display device including the above organic electroluminescent device; And a control unit for driving the display device.

In another aspect, the present invention provides an electronic device characterized in that the organic electric device is at least one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device. At this time, the electronic device may be a current or a 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 synthesis examples of the compound represented by the formula (1) and the production example of the organic electroluminescent device of the present invention will be described in detail with reference to examples, but the present invention is not limited thereto .

[ Synthetic example ]

The final products of the present invention are prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below.

<Reaction Scheme 1>

X ¹ = Br, Cl, I

Synthetic example of Sub 1

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

<Reaction Scheme 2>

When R ⁵ and R ⁶ form a spiro

X ² = Cl, Br, I

R ⁷ and R ⁸ are the same as defined for R ³ to R ⁴ (R ⁷ and R ⁸ denote secondary substituents of R ⁵ and R ⁶ , respectively)

e, f = 0 to 4;

<Reaction Scheme 4> When R ⁵ and R ⁶ form a spiro

<Reaction Scheme 5> When L ¹ is not a single bond

Sub 1-I-1 Synthetic Example

1) Synthesis of Sub 1-I-1

After dissolving 2-bromo-4-chloro-1,1'-biphenyl (30 g, 112.13 mmol) and 9H-fluoren-9-one (20.21 g, 112.13 mmol) in THF (1065 ml) Deg.] C, n-BuLi (47.09 ml, 117.74 mmol) was slowly added dropwise, and the reaction was stirred at room temperature for 4 hours. After the reaction was completed, the reaction was quenched by adding H ₂ O. The water was removed, and the organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 35.16 g of product. (Yield: 85%).

2) Synthesis of Sub 1-II-1

HCl and acetic acid (209 ml) were added to Sub 1-I-1 (35 g, 94.89 mmol), and the mixture was stirred at 80 ° C for 1 hour. After the reaction was completed, the organic solvent was concentrated by vacuum filtration, and the resulting organic material was purified by silicagel column and recrystallized to obtain 30.63 g of the product. (Yield: 92%)

Sub 1-I-2 Synthetic Example

1) Synthesis of Sub 1-I-2

(20.21g, 112.13mmol), THF (1065ml), n-BuLi (47.09g, 117.74mmol) were added to a solution of 2-bromo-5-chloro-1,1'- ) Was obtained by using the synthesis method of Sub 1-I-1 described above to obtain 36.40 g of a product. (Yield: 88%).

2) Synthesis of Sub 1-II-2

Sub-1-I-2 (35 g, 94.89 mmol), HCl, and acetic acid (209 ml) were obtained using the Sub 1-II-1 synthesis method. (Yield: 89%).

Sub 1-5 Synthetic Example

1) Sub 1-III-1 synthesis

Sub 1-II-3 (30g , 109.82mmol) was dissolved in the DMF (692ml) in a round bottom flask, Bis (pinacolato) diboron (30.68g , 120.80mmol), Pd (dppf) Cl 2 (2.41 g, 3.29 mmol), KOAc (32.33 g, 329.47 mmol) was added and stirred at 90 &lt; 0 &gt; C. When the reaction was complete, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 23.70 g of the product. (Yield: 85%).

2) Sub 1-5 synthesis

(1.24 g, 1.08 mmol) and K ₂ CO ₃ (1 g) were added to a solution of 1-bromo-4-iodobenzene (20.32 g, 71.82 mmol) (14.89 g, 107.73 mmol), THF (316 ml) and water (158 ml) were added, and the mixture was stirred at 70 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ , wiped with water, and a small amount of water was removed with anhydrous MgSO _4. After filtration under reduced pressure, the organic solvent was concentrated and the resulting product was recrystallized using CH ₂ Cl ₂ and hexane 19.57 g of the product was obtained. (Yield: 78%).

Sub 1-21 Synthetic Example

1) Sub 1-III-2 synthesis

Sub 1-I-4 (30g , 85.02mmol), DMF (536ml), Bis (pinacolato) diboron (23.75g, 93.52mmol), Pd (dppf) Cl 2 (1.87 g, 2.55 mmol), KOAc (25.03 g, 255.06 mmol) was obtained by the synthesis of Sub 1-III-1. (Yield: 88%).

2) Sub 1-21 synthesis

(0.39 g, 0.34 mmol), 2-bromo-7-iododibenzo [b, d] thiophene (8.75 g, 22.50 mmol), tetrakis (triphenylphophine) palladium (0) K ₂ CO ₃ (4.67 g, 33.75 mmol), THF (99 ml) and water (49 ml) were subjected to the Sub 1-5 synthesis method to obtain 9.91 g of the product. (Yield: 76%).

Sub 1-34 Synthetic Example

1) Sub 1-III-3 synthesis

Sub 1-I-5 (30g , 85.51mmol) of was dissolved in DMF (539ml) in a round bottom flask, Bis (pinacolato) diboron (23.88g , 94.06mmol), Pd (dppf) Cl 2 (1.88 g, 2.57 mmol), KOAc (25.17 g, 256.52 mmol) was obtained by using the above synthesis method of Sub 1-III-1. (Yield: 74%).

2) Sub 1-34 synthesis

3-bromo-3'-iodo-1,1'-biphenyl (21.91 g, 61.03 mmol), tetrakis (triphenylphophine) palladium (0) (1.06 g, 0.92 mmol ), K ₂ CO ₃ (12.65 g, 91.55 mmol), THF (269 ml) and water (134 ml) were subjected to the synthesis method of Sub 1-5 to obtain 22.39 g of the product. (Yield: 67%).

On the other hand, the compound belonging to Sub 1 may be, but not limited to, the following compounds, and Table 1 shows the FD-MS value of the compound belonging to Sub 1.

Example of Sub 1

compound FD-MS compound FD-MS Sub 1-5 _{m / z = 348.05 (C 21} H 17 Br = 349.27) Sub 1-21 _{m / z = 578.07 (C 37} H 23 BrS = 579.56) Sub 1-24 _{m / z = 350.09 (C 25} H 15 Cl = 350.85) Sub 1-25 _{m / z = 350.09 (C 25} H 15 Cl = 350.85) Sub 1-34 _{m / z = 546.10 (C 37} H 23 Br = 547.50)

[Reference: Synthesis of M 1]

M 1 according to the present invention can be synthesized by the reaction path of the following Reaction Scheme 6 and Reaction Scheme 7, but is not limited thereto.

<Reaction Scheme 6>

<Reaction Scheme 7>

Synthesis example of Sub 2-I

<Reaction Scheme 9>

X ² , X ³ = Br, Cl

Sub 2-3 Composite Example

1) M 2-1 Synthesis

Methyl 2- (4-bromophenyl) -1-naphthoate (24.41 g, 71.54 mmol) obtained in the above synthesis was dissolved in THF (358 ml) in a round bottom flask and methylmagnesium bromide 1.0 M in THF (286.17 ml, 286.171 mmol) After the dropwise addition, the mixture was stirred at room temperature. After the reaction was completed, the reaction mixture was extracted with diethyl ether and water. The organic layer was dried over MgSO ₄ and concentrated to obtain an intermediate product. The intermediate product was dissolved in acetic acid solution (286 ml), and HCl (6 ml) was added thereto, followed by refluxing. After the completion of the reaction, water was added and stirred. The resulting solid was filtered under reduced pressure and washed with water and methanol to obtain 17.57 g (yield: 76% over two steps) of the product as a white powder.

2) Sub 2-3 synthesis

(10.47 g, 61.88 mmol), Pd ₂ (dba) ₃ (1.70 g, 1.86 mmol), P (t-Bu) ₃ (1.00 g, 4.95 mmol), NaOt-Bu (17.84 g, 185.63 mmol) and toluene (650 mL). After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 22.66 g of the product. (Yield: 89%).

Sub 2-11 Synthetic Example

1) M 2-2 synthesis

Intermediate products were obtained by using methylmagnesium bromide 1.0M in THF (504.2 ml, 504.22 mmol) and THF (630 ml) to methyl 1- (4-bromophenyl) -2-naphthoate (43.01 g, 126.06 mmol) , acetic acid solution (500 ml) and HCl (10 ml) were added to obtain 34.23 g (yield: 84% over two steps) of the product by the above M 2-1 synthesis.

2) Sub 2-11

To a round bottom flask was added M 2-2 (20 g, 61.88 mmol), 6-phenylnaphthalen-2-amine (13.57 g, 61.88 mmol), Pd ₂ (dba) ₃ (1.70 g, 1.86 mmol) ₃ (1.00 g, 4.95 mmol), NaOt-Bu (17.84 g, 185.63 mmol) and toluene (650 mL) were used to obtain 23.42 g of the product. (Yield: 82%)

Sub 2-16 Synthetic Example

1) M 2-3 Synthesis

The intermediate product was obtained by using methylmagnesium bromide 1.0 M in THF (460 ml, 460.05 mmol) and THF (575 ml) to methyl 10- (3-bromophenyl) phenanthrene-9- carboxylate (45 g, 115.01 mmol) , acetic acid solution (460 ml) and HCl (9 ml) were added to obtain 31.34 g (yield: 73% over two steps) of the product by the above M 2-1 synthesis.

2) Sub 2-16

To a round bottom flask M 2-3 (20g, 53.58mmol), [1,1 ': 3', 1 '' - terphenyl] -5'-amine (13.14g, 53.58mmol), Pd 2 (dba) 3 ( 1.47g, 1.61mmol), P (t -Bu) 3 (0.87g, 4.29mmol), NaOt-Bu (15.45g, 160.73mmol), toluene (563mL) to the Sub 2-3 using the synthesis product 22.47 g. (Yield: 78%).

Sub 2-22 Synthetic Example

1) M 2-4 Synthesis

The intermediate product was obtained by using methylmagnesium bromide 1.0M in THF (499.6 ml, 499.65 mmol) and THF (625 ml) to methyl 2- (4-bromonaphthalen-1-yl) benzoate (42.62 g, 124.91 mmol) After acetic acid solution (500 ml) and HCl (10 ml) were added, 33.51 g (yield: 83% over two steps) of the product was obtained by the above M 2-1 synthesis.

2) Sub 2-22 synthesis

To a round bottom flask M 2-4 (20g, 61.88mmol), aniline (5.76g, 61.88mmol), Pd 2 (dba) 3 (1.70g, 1.86mmol), P (t-Bu) 3 (1.00g, 4.95 mmol), NaOt-Bu (17.84 g, 185.63 mmol) and toluene (650 mL) were used to obtain 18.68 g of the product. (Yield: 90%).

Sub 2-24 Synthetic Example

1) M 2-5 Synthesis

The intermediate product was obtained by using methylmagnesium bromide 1.0M in THF (527.5ml, 527.55mmol) and THF (659ml) to methyl 2- (1-bromonaphthalen-2-yl) benzoate (45g, 131.89mmol) , acetic acid solution (528 ml) and HCl (11 ml) were added to obtain 29.41 g of the product (yield: 69% over two steps) by the above M 2-1 synthesis method.

2) Sub 2-24

(20 g, 61.88 mmol), [1,1'-biphenyl] -4-amine (10.47 g, 61.88 mmol), Pd ₂ (dba) ₃ (1.70 g, 1.86 mmol), P (t-Bu) ₃ (1.00 g, 4.95 mmol), NaOt-Bu (17.84 g, 185.63 mmol) and toluene (650 mL) were used to obtain 18.33 g of the product. (Yield: 72%).

Sub 2-34 Synthetic Example

1) M 2-6 Synthesis

Intermediate products were obtained by using methylmagnesium bromide 1.0M in THF (527.5 ml, 527.55 mmol) and THF (659 ml) in methyl 3- (4-bromophenyl) -2-naphthoate (45 g, 131.89 mmol) Acetic acid solution (528 ml) and HCl (11 ml) were added to obtain 34.10 g (yield: 80% over two steps) of the product by the above M 2-1 synthesis.

2) M 3-1 synthesis

M 2-6 (34.10g, 105.50mmol) was dissolved in the DMF (664ml) in a round bottom flask, Bis (pinacolato) diboron (29.47g , 116.05mmol), Pd (dppf) Cl 2 (2.32 g, 3.16 mmol), KOAc (31.06 g, 316.49 mmol) was added and stirred at 90 &lt; 0 &gt; C. When the reaction was complete, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 30.86 g of the product. (Yield: 79%).

3) Sub 2-I-1 synthesis

(22.92 g, 81.02 mmol), tetrakis (triphenylphophine) palladium (0) (1.40 g, 1.22 mmol) and K ₂ CO ₃ (30 g, 81.02 mmol), 1-bromo- (16.80 g, 121.52 mmol), THF (356 ml) and water (178 ml) were added, and the mixture was stirred at 70 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ , wiped with water, and a small amount of water was removed with anhydrous MgSO _4. After filtration under reduced pressure, the organic solvent was concentrated and the resulting product was recrystallized using CH ₂ Cl ₂ and hexane 23.94 g of the product was obtained. (Yield: 74%).

4) Sub 2-34

To a round bottom flask was added Sub 2-I-1 (10 g, 25.04 mmol), naphthalen-2-amine (3.59 g, 25.04 mmol), Pd ₂ (dba) ₃ (0.69 g, 0.75 mmol) ₃ (0.41 g, 2 mmol), NaOt-Bu (7.22 g, 75.13 mmol) and toluene (263 mL) were obtained 8.90 g of the product using the Sub 2-3 synthesis method. (Yield: 77%)

Sub 2-38 Synthetic Example

1) M 2-7 Synthesis

Methylmagnesium bromide 1.0M in THF (460.1 ml, 460.05 mmol) and THF (575 ml) were added to methyl 4-bromo- [1,2'-binaphthalene] -1'-carboxylate (45 g, 115.01 mmol) After obtaining an intermediate product, acetic acid solution (460 ml) and HCl (9 ml) were added to obtain 32.63 g (yield: 76% over two steps) of the product by the above M 2-1 synthesis.

2) M 3-2 synthesis

M 2-7 (32.63 g, 87.41 mmol), DMF (551 ml), Bis (pinacolato) diboron (24.42 g, 96.15 mmol), Pd (dppf) Cl ₂ (1.92 g, 2.62 mmol), KOAc (25.74 g, 262.24 mmol), 29.03 g of the product was obtained using the above M 3-1 synthesis method. (Yield: 79%).

3) Sub 2-I-2 synthesis

(29.6 g, 52.57 mmol), tetrakis (triphenylphophine) palladium (0) (0.91 g, 0.79 mmol) and K ₂ (dibenzylideneacetone) CO ₃ (10.90 g, 78.85 mmol), THF (231 ml) and water (115 ml) were added, and the mixture was stirred at 70 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ , wiped with water, and a small amount of water was removed with anhydrous MgSO _4. After filtration under reduced pressure, the organic solvent was concentrated and the resulting product was recrystallized using CH ₂ Cl ₂ and hexane 20.13 g of the product was obtained. (Yield: 71%).

4) Sub 2-38

To a round bottom flask Sub 2-I-2 (15g , 27.81mmol), aniline (2.59g, 27.81mmol), Pd 2 (dba) 3 (0.76g, 0.83mmol), P (t-Bu) 3 (0.45g , 2.22 mmol), NaOt-Bu (8.02 g, 83.42 mmol) and toluene (292 mL) were subjected to the Sub 2-3 synthesis method to obtain 12.89 g of the product. (Yield: 84%)

Sub 2-39 Synthetic Example

1) M 2-7 Synthesis

Methylmagnesium bromide 1.0M in THF (407.9 ml, 407.87 mmol) and THF (510 ml) were added to methyl 10- (6-bromonaphthalen-2-yl) phenanthrene-9- carboxylate (45 g, 101.97 mmol) After the product was obtained, acetic acid solution (408 ml) and HCl (8 ml) were added to obtain 26.33 g of the product (yield: 61% over two steps) by the above M 2-1 synthesis method.

2) Sub 2-39

To a round bottom flask M 2-8 (15g, 35.43mmol), naphthalen-1-amine (5.07g, 35.43mmol), Pd 2 (dba) 3 (0.97g, 1.06mmol), P (t-Bu) 3 ( NaOt-Bu (10.21 g, 106.30 mmol) and toluene (372 mL) were subjected to the Sub 2-3 synthesis method to obtain 14.45 g of the product. (Yield: 84%)

On the other hand, the compound belonging to Sub 2 may be, but not limited to, the following compound, and Table 2 shows the FD-MS value of the compound belonging to Sub 2

Example of Sub 2

compound FD-MS compound FD-MS Sub 2-3 m / z = 411.20 (C ₃₁ H ₂₅ N = 411.55) Sub 2-11 _{m / z = 461.21 (C 35} H 27 N = 461.61) Sub 2-16 m / z = 537.25 (C ₄₁ H ₃₁ N = 537.71) Sub 2-22 _{m / z = 335.17 (C 25} H 21 N = 335.45) Sub 2-24 m / z = 411.20 (C ₃₁ H ₂₅ N = 411.55) Sub 2-34 _{m / z = 461.21 (C 35} H 27 N = 461.61) Sub 2-38 m / z = 551.22 (C ₄₁ H ₂₉ NO = 551.69) Sub 2-39 _{m / z = 485.21 (C 37} H 27 N = 485.63)

Final Product Synthesis

After the Sub 1 (1 eq.) In a round bottom flask was dissolved in Toluene, Sub 2 (1 _{eq), Pd 2 (dba) 3} (0.03 eq.), P (t-bu) 3 (0.08 eq.), NaO t -Bu (3 eq.) And stirred at 80 &lt; 0 &gt; C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column and recrystallization to obtain final product.

1-1 Synthetic Example

To a round bottom flask Sub 1-1 (4g, 14.64mmol), Sub 2-1 (4.91g, 14.64mmol), Pd 2 (dba) 3 (0.40g, 0.44mmol), P (t-Bu) 3 (0.24 g, 1.17 mmol), NaOt-Bu (4.22 g, 43.93 mmol), and toluene (154 mL). After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 6.8 g of the product. (Yield: 88%).

1-12 Synthetic Examples

Sub 1-3 (3.5g, 12.81mmol), Sub 2-16 (6.89g, 12.81mmol), Pd 2 (dba) 3 (0.35g, 0.38mmol), P (t-Bu) 3 (0.21g, 1.03 mmol), NaOt-Bu (3.69 g, 38.44 mmol) and toluene (135 mL) were used to obtain 6.83 g of the product. (Yield: 73%)

1-15 Synthetic Examples

Sub 1-4 (4 g, 14.64 mmol), Sub 2-10 (6.03 g, 14.64 mmol), Pd ₂ (dba) ₃ (0.40 g, 0.44 mmol), P (t-Bu) ₃ (0.24 g, 1.17 mmol ), NaOt-Bu (4.22 g, 43.93 mmol) and toluene (154 mL) were used to obtain 6.72 g of the product. (Yield: 76%).

1-30 Synthetic Example

Sub 1-1 (3.5g, 12.81mmol), Sub 2-38 (7.07g, 12.81mmol), Pd 2 (dba) 3 (0.35g, 0.38mmol), P (t-Bu) 3 (0.21g, 1.03 mmol), NaOt-Bu (3.69 g, 38.44 mmol) and toluene (135 mL) were used to obtain 6.48 g of the product. (Yield: 68%).

1-32 Synthetic Examples

Sub-7 (5 g, 14.32 mmol), Sub 2-1 (4.8 g, 14.32 mmol), Pd ₂ (dba) ₃ (0.39 g, 0.43 mmol), P (t- Bu) ₃ (0.23 g, 1.15 mmol ), NaOt-Bu (4.13 g, 42.95 mmol) and toluene (150 mL) were used to obtain 6.22 g of the product. (Yield: 72%).

2-6 Synthetic Examples

Sub 1-13 (5g, 12.58mmol), Sub 2-8 (5.81g, 12.58mmol), Pd 2 (dba) 3 (0.35g, 0.38mmol), P (t-Bu) 3 (0.2g, 1.01mmol ), NaOt-Bu (3.63 g, 37.75 mmol) and toluene (132 mL) were used to obtain 6.56 g of the product. (Yield: 67%).

2-27 Synthetic Examples

Sub 1-21 (6g, 10.35mmol), Sub 2-10 (4.26g, 10.35mmol), Pd 2 (dba) 3 (0.28g, 0.31mmol), P (t-Bu) 3 (0.17g, 0.83mmol ), NaOt-Bu (2.98 g, 31.06 mmol) and toluene (109 mL) were used to obtain 6.60 g of the product. (Yield: 70%).

3-18 Synthetic Examples

Sub 1-26 (4.5g, 12.83mmol), Sub 2-40 (5.28g, 12.83mmol), Pd 2 (dba) 3 (0.35g, 0.38mmol), P (t-Bu) 3 (0.21g, 1.03 mmol), NaOt-Bu (3.70 g, 38.48 mmol) and toluene (135 mL) were used to obtain 6.80 g of the product. (Yield: 73%)

3-25 Synthetic Examples

Sub 1-28 (5.5g, 11.67mmol), Sub 2-1 (3.91g, 11.67mmol), Pd 2 (dba) 3 (0.32g, 0.35mmol), P (t-Bu) 3 (0.19g, 0.93 mmol), NaOt-Bu (3.36 g, 35 mmol) and toluene (123 mL) were used to obtain 6.61 g of the product. (Yield: 78%).

3-26 Synthetic Examples

Sub 1-24 (4.5g, 12.83mmol), Sub 2-34 (5.92g, 12.83mmol), Pd 2 (dba) 3 (0.35g, 0.38mmol), P (t-Bu) 3 (0.21g, 1.03 mmol), NaOt-Bu (3.7 g, 38.48 mmol) and toluene (135 mL) were used to obtain 6.57 g of the product. (Yield: 66%).

3-28 Synthetic Examples

P (t-Bu) ₃ (0.19 g, 0.93 mmol), Sub 2-21 (4.5 g, 11.67 mmol), Pd ₂ (dba) ₃ (0.32 g, 0.35 mmol) mmol), NaOt-Bu (3.36 g, 35 mmol) and toluene (123 mL) were used to obtain 6.61 g of the product. (Yield: 73%)

Meanwhile, FD-MS values of the compound of the present invention prepared according to the above Synthesis Example are shown in Table 3 below.

compound FD-MS compound FD-MS 1-1 m / z = 527.26 (C ₄₀ H ₃₃ N = 527.71) 1-3 m / z = 603.29 (C ₄₆ H ₃₇ N = 603.81) 1-4 m / z = 677.31 (C ₅₂ H ₃₉ N = 677.89) 1-5 m / z = 653.31 (C ₅₀ H ₃₉ N = 653.87) 1-9 m / z = 603.29 (C ₄₆ H ₃₇ N = 603.81) 1-10 m / z = 577.28 (C ₄₄ H ₃₅ N = 577.77) 1-12 m / z = 729.34 (C ₅₆ H ₄₃ N = 729.97) 1-13 m / z = 603.29 (C ₄₆ H ₃₇ N = 603.81) 1-14 m / z = 577.28 (C ₄₄ H ₃₅ N = 577.77) 1-15 m / z = 603.29 (C ₄₆ H ₃₇ N = 603.81) 1-16 m / z = 653.31 (C ₅₀ H ₃₉ N = 653.87) 1-21 m / z = 603.29 (C ₄₆ H ₃₇ N = 603.81) 1-22 m / z = 653.31 (C ₅₀ H ₃₉ N = 653.87) 1-23 m / z = 755.36 (C ₅₈ H ₄₅ N = 756.01) 1-26 m / z = 729.34 (C ₅₆ H ₄₃ N = 729.97) 1-27 m / z = 805.37 (C ₆₂ H ₄₇ N = 806.07) 1-29 m / z = 758.31 (C ₅₈ H ₄₃ NS = 756.05) 1-30 m / z = 743.32 (C ₅₆ H ₄₁ NO = 743.95) 1-32 m / z = 603.29 (C ₄₆ H ₃₇ N = 603.81) 2-1 _{m / z = 651.29 (C 50} H 37 N = 651.85) 2-3 m / z = 727.32 (C ₅₆ H ₄₁ N = 727.95) 2-6 m / z = 777.34 (C ₆₀ H ₄₃ N = 778.01) 2-8 m / z = 827.36 (C ₆₄ H ₄₅ N = 828.07) 2-9 m / z = 727.32 (C ₅₆ H ₄₁ N = 727.95) 2-11 m / z = 777.34 (C ₆₀ H ₄₃ N = 778.01) 2-12 m / z = 853.37 (C ₆₆ H ₄₇ N = 854.11) 2-13 m / z = 727.32 (C ₅₆ H ₄₁ N = 727.95) 2-14 m / z = 701.31 (C ₅₄ H ₃₉ N = 701.91) 2-15 m / z = 727.32 (C ₅₆ H ₄₁ N = 727.95) 2-16 m / z = 777.34 (C ₆₀ H ₄₃ N = 778.01) 2-17 m / z = 727.32 (C ₅₆ H ₄₁ N = 727.95) 2-18 m / z = 727.32 (C ₅₆ H ₄₁ N = 727.95) 2-21 m / z = 727.32 (C ₅₆ H ₄₁ N = 727.95) 2-22 m / z = 777.34 (C ₆₀ H ₄₃ N = 778.01) 2-23 m / z = 879.39 (C ₆₈ H ₄₉ N = 880.15) 2-25 m / z = 777.34 (C ₆₀ H ₄₃ N = 778.01) 2-26 m / z = 853.37 (C ₆₆ H ₄₇ N = 854.11) 2-27 m / z = 900.34 (C ₆₈ H ₄₇ NS = 910.19) 2-28 m / z = 727.32 (C ₅₆ H ₄₁ N = 727.95) 3-2 m / z = 699.29 (C ₅₄ H ₃₇ N = 699.90) 3-3 m / z = 725.31 (C ₅₆ H ₃₉ N = 725.94) 3-5 m / z = 725.31 (C ₅₆ H ₃₉ N = 725.94) 3-6 m / z = 775.32 (C ₆₀ H ₄₁ N = 776.00) 3-8 m / z = 825.34 (C ₆₄ H ₄₃ N = 826.06) 3-9 m / z = 725.31 (C ₅₆ H ₃₉ N = 725.94) 3-10 m / z = 699.29 (C ₅₄ H ₃₇ N = 699.90) 3-11 m / z = 725.31 (C ₅₆ H ₃₉ N = 725.94) 3-12 m / z = 775.32 (C ₆₀ H ₃₁ N = 776.00) 3-13 m / z = 725.31 (C ₅₆ H ₃₉ N = 725.94) 3-14 m / z = 725.31 (C ₅₆ H ₃₉ N = 725.94) 3-17 m / z = 725.31 (C ₅₆ H ₃₉ N = 725.94) 3-18 m / z = 725.31 (C ₅₆ H ₃₉ N = 725.94) 3-19 m / z = 725.31 (C ₅₆ H ₃₉ N = 725.94) 3-20 m / z = 775.32 (C ₆₀ H ₃₁ N = 776.00) 3-21 m / z = 725.31 (C ₅₆ H ₃₉ N = 725.94) 3-25 m / z = 725.31 (C ₅₆ H ₃₉ N = 725.94) 3-26 m / z = 775.32 (C ₆₀ H ₃₁ N = 776.00) 3-27 m / z = 877.37 (C ₆₈ H ₄₇ N = 878.13) 3-28 m / z = 775.32 (C ₆₀ H ₃₁ N = 776.00) 3-29 m / z = 775.32 (C ₆₀ H ₃₁ N = 776.00) 3-30 m / z = 851.36 (C ₆₆ H ₄₅ N = 852.09) 3-31 m / z = 927.39 (C ₇₂ H ₄₉ N = 928.19) 3-32 m / z = 877.37 (C ₆₈ H ₄₇ N = 878.13) 3-33 m / z = 907.33 (C ₆₈ H ₄₅ NS = 908.18) 3-34 m / z = 865.33 (C ₆₆ H ₄₃ NO = 866.08) 3-35 m / z = 725.31 (C ₅₆ H ₃₉ N = 725.94)

Evaluation of manufacturing of organic electric device

[ Example  One] Green organic electroluminescent device  ( Hole transport layer )

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a hole transport layer material. First, 4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as" 2-TNATA ") was deposited on the ITO layer (anode) To form a hole injection layer. Then, the compound 1-3 of the present invention was vacuum deposited on the hole injection layer to a thickness of 60 nm to form a hole transport layer. Subsequently, tris (2-phenylpyridine) -iridium (hereinafter referred to as "Ir (ppy) 2") was used as a host material on the hole transport layer, and 4,4'-N, N'-dicarbazole- ) ₃ &quot;) was used as a dopant material and doped in a ratio of 90:10 by weight to form a light emitting layer by vacuum evaporation to a thickness of 30 nm. Subsequently, aluminum (1,1'-biphenyl) -4-oleato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as "BAlq") was vacuum deposited on the light emitting layer to a thickness of 10 nm (8-quinolinol) aluminum (hereinafter abbreviated as &quot; Alq ₃ &quot;) was vacuum deposited on the hole blocking layer to a thickness of 40 nm to form an electron transporting layer. Thereafter, LiF as an alkali metal halide was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

[ Example  2] to [ Example  36] Green organic electroluminescent device  ( Hole transport layer )

Organic electroluminescent devices were fabricated in the same manner as in Example 1, except that the compounds 1-4 to 3-35 of the present invention described in the following Table 4 were used instead of the compound 1-3 of the present invention as the hole transport layer materials.

[ Comparative Example  1] to [ Comparative Example  2]

An organic electroluminescent device was fabricated in the same manner as in Example 1 except that the following Comparative Compounds 1 to 2 described in Table 4 were used in place of Compound 1-3 of the present invention as the hole transport layer material.

compound Driving voltage electric current
(mA / cm ² ) Luminance
(cd / m ² ) efficiency
(cd / A) T
(95) CIE x y Comparative Example (1) Comparative compound 1 5.8 19.4 5000 23.2 72.8 0.31 0.60 Comparative Example (2) Comparative compound 2 6.2 17.9 5000 27.9 92.7 0.33 0.61 Example (1) Compound 1-3 5.6 15.6 5000 32 119.1 0.31 0.60 Example (2) Compound 1-4 5.6 15.5 5000 32.2 118.8 0.32 0.61 Example (3) Compound 1-9 5.7 16.1 5000 31 118.8 0.32 0.60 Example (4) Compound 1-12 5.6 16.6 5000 30.1 117.2 0.32 0.61 Example (5) Compound 1-13 5.6 13.4 5000 37.4 123.5 0.32 0.61 Example (6) Compound 1-14 5.6 13.3 5000 37.5 122.8 0.33 0.60 Example (7) Compound 1-15 5.6 13.3 5000 37.6 121.5 0.32 0.61 Example (8) Compound 1-16 5.7 13.3 5000 37.7 122.4 0.32 0.61 Example (9) Compound 1-21 5.7 14.7 5000 34 120.9 0.31 0.60 Example (10) Compound 1-22 5.6 14.8 5000 33.8 121.2 0.31 0.60 Example (11) Compound 1-23 5.7 15.4 5000 32.5 119.6 0.33 0.61 Example (12) Compound 1-26 5.7 15.7 5000 31.8 118.8 0.32 0.60 Example (13) Compound 2-1 5.5 13.0 5000 38.6 126.3 0.32 0.61 Example (14) Compound 2-3 5.5 13.4 5000 37.4 121.6 0.33 0.61 Example (15) Compound 2-8 5.5 14.9 5000 33.6 121.3 0.32 0.61 Example (16) Compound 2-9 5.5 14.5 5000 34.6 121.2 0.32 0.60 Example (17) Compounds 2-12 5.5 15.0 5000 33.3 121.2 0.32 0.61 Example (18) Compound 2-14 5.5 12.3 5000 40.6 130.9 0.33 0.60 Example (19) Compound 2-15 5.5 12.3 5000 40.7 129.2 0.32 0.60 Example (20) Compound 2-17 5.5 15.6 5000 32 121.0 0.33 0.61 Example (21) Compound 2-21 5.6 13.9 5000 36 123.0 0.32 0.61 Example (22) Compound 2-23 5.5 14.1 5000 35.5 122.8 0.31 0.60 Example (23) Compound 3-2 5.4 11.3 5000 44.1 138.5 0.31 0.60 Example (24) Compound 3-5 5.4 11.3 5000 44.2 131.1 0.32 0.60 Example (25) Compound 3-8 5.4 11.3 5000 44.1 134.1 0.32 0.60 Example (26) Compound 3-9 5.3 11.8 5000 42.2 134.4 0.31 0.61 Example (27) Compound 3-11 5.4 11.7 5000 42.8 133.6 0.32 0.61 Example (28) Compounds 3-12 5.4 11.8 5000 42.3 130.9 0.31 0.61 Example (29) Compound 3-13 5.4 11.5 5000 43.4 134.0 0.32 0.61 Example (30) Compound 3-14 5.4 11.4 5000 43.8 131.1 0.32 0.61 Example (31) Compound 3-19 5.3 10.6 5000 47.2 135.8 0.33 0.60 Example (32) Compound 3-20 5.4 10.5 5000 47.4 137.9 0.32 0.61 Example (33) Compound 3-21 5.3 12.0 5000 41.8 131.9 0.31 0.60 Example (34) Compound 3-28 5.3 12.0 5000 41.7 134.7 0.32 0.61 Example (35) Compound 3-29 5.4 12.0 5000 41.8 130.8 0.33 0.61 Example (36) Compound 3-35 5.3 11.8 5000 42.3 132.8 0.33 0.61

As can be seen from the results of Table 4, it was confirmed that driving voltage and lifetime were significantly improved when the material for an organic electroluminescent device of the present invention was used as a hole transporting layer.

In other words, Comparative Example 2 using Comparative Compound 2 in which fluorene was substituted for tertiary amine as a hole transport layer showed better device results in terms of driving voltage, efficiency, and lifetime than Comparative Example 1 using NPB as a hole transport layer, Examples 1 to 36 using the compound of the present invention in which fluorene substituted with fused fluorene in the tertiary amine was used rather than in Example 2, but the driving voltage and lifetime were remarkably improved even though the efficiency was slightly increased.

This can be achieved by fusing the fluorene containing Sp3 carbon, thereby increasing the planarity and thereby introducing a substituent which increases the planarity of the molecule when the fused fluorene is substituted (Examples 1 to 36) π Stacking), the packing density is increased and the holes are easily transported. As a result, the charge balance in the light emitting layer is improved and the efficiency is considered to be increased. In addition, since the packing density is increased, It is considered that the lifetime is increased because the driving voltage and the Joule heat generated when the device is driven are reduced and the thermal stability is increased.

These results suggest that the physical properties of the fused fluorene compound and the result of the device are significantly different.

Further, in the case of the hole transporting layer, the correlation with the light emitting layer (host) must be grasped. Even if similar cores are used, it is very difficult for the ordinary artisan to deduce the characteristics of the compound of the present invention in the hole transporting layer used.

[ Example  37] Blue organic electroluminescent device  ( The light- )

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. 2-TNATA was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to a thickness of 60 nm to form a hole injection layer. Then, NPB was vacuum deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer Respectively. Subsequently, Compound 1-1 of the present invention was vacuum deposited on the hole transport layer to a thickness of 20 nm to form a light emitting auxiliary layer, and 9,10-Di (2-naphthyl) anthracene (Hereinafter abbreviated as &quot; ADN &quot;) was used as a host material and BD-052X (manufactured by Idemitsu Kosan) was used as a dopant in a ratio of 93: 7 by weight to form a light emitting layer by vacuum deposition to a thickness of 30 nm. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF as an alkali metal halide was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

[ Example  38] to [ Example  87] Blue organic electroluminescent device  ( The light- )

An organic electroluminescent device was fabricated in the same manner as in Example 37 except that the compound of the present invention described in Table 5 was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example  3]

An organic electroluminescent device was fabricated in the same manner as in Example 37 except that the luminescent auxiliary layer material was not used.

[ Comparative Example 4 ]

An organic electroluminescent device was fabricated in the same manner as in Example 37, except that the compound for comparison 2 was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material

The electroluminescence (EL) characteristics of the organic electroluminescent devices prepared in Examples 37 to 87 and Comparative Examples 3 to 4 of the present invention were measured by applying a forward bias DC voltage to PR-650 of a photoresearch company And the T95 lifetime was measured by a life measuring apparatus manufactured by Mac Science Inc. at a reference luminance of 500 cd / m ^2. The measurement results are shown in Table 5 below.

The light-
compound Driving
Voltage electric current
(mA / cm ² ) Luminance
(cd / m ² ) efficiency
(cd / A) T
(95) CIE x y Comparative Example (3) - 5.7 13.5 500 3.7 63.6 0.14 0.11 Comparative Example (4) Comparative compound 2 6.7 9.8 500 5.1 119.2 0.14 0.11 Example (37) Compound 1-1 6.3 7.2 500 6.9 130.8 0.14 0.11 Example (38) Compound 1-5 6.3 7.2 500 6.9 131.2 0.14 0.11 Example (39) Compound 1-9 6.4 7.4 500 6.7 130.4 0.14 0.12 Example (40) Compound 1-10 6.4 7.5 500 6.7 129.4 0.14 0.11 Example (41) Compound 1-12 6.5 7.6 500 6.6 127.4 0.14 0.11 Example (42) Compound 1-13 6.4 7.3 500 6.8 131.4 0.14 0.12 Example (43) Compound 1-14 6.4 7.3 500 6.8 131.1 0.14 0.12 Example (44) Compound 1-15 6.3 7.3 500 6.9 131.7 0.14 0.11 Example (45) Compound 1-16 6.4 7.3 500 6.8 131.7 0.14 0.12 Example (46) Compound 1-21 6.5 7.5 500 6.7 129.4 0.14 0.12 Example (47) Compound 1-22 6.5 7.5 500 6.7 129.1 0.14 0.11 Example (48) Compound 1-23 6.5 7.7 500 6.5 129.4 0.14 0.11 Example (49) Compound 1-26 6.5 7.6 500 6.6 128.8 0.14 0.12 Example (50) Compound 1-27 6.5 7.6 500 6.6 129.2 0.14 0.11 Example (51) Compound 1-29 6.5 7.6 500 6.6 127.8 0.14 0.11 Example (52) Compound 2-1 6.3 6.9 500 7.3 135.4 0.14 0.12 Example (53) Compound 2-3 6.4 6.8 500 7.3 131.3 0.14 0.12 Example (54) Compound 2-6 6.5 7.0 500 7.2 134.3 0.14 0.11 Example (55) Compound 2-9 6.3 7.2 500 6.9 135.3 0.14 0.11 Example (56) Compound 2-11 6.4 7.4 500 6.8 134.8 0.14 0.11 Example (57) Compound 2-13 6.4 6.8 500 7.4 130.7 0.14 0.12 Example (58) Compound 2-14 6.4 6.8 500 7.3 130.8 0.14 0.11 Example (59) Compound 2-15 6.3 6.8 500 7.3 131.5 0.14 0.12 Example (60) Compound 2-16 6.4 6.8 500 7.4 130.6 0.14 0.11 Example (61) Compound 2-18 6.5 7.2 500 6.9 128.6 0.14 0.12 Example (62) Compound 2-21 6.4 7.0 500 7.2 135.5 0.14 0.12 Example (63) Compound 2-22 6.4 7.0 500 7.2 134.7 0.14 0.12 Example (64) Compound 2-23 6.3 7.1 500 7.1 135.2 0.14 0.11 Example (65) Compound 2-25 6.4 7.1 500 7.0 135.6 0.14 0.12 Example (66) Compound 2-26 6.3 7.1 500 7.1 135.3 0.14 0.11 Example (67) Compound 2-28 6.4 7.3 500 6.9 130.5 0.14 0.11 Example (68) Compound 3-3 6.2 6.4 500 7.8 140.3 0.14 0.12 Example (69) Compound 3-6 6.3 6.7 500 7.4 134.2 0.14 0.11 Example (70) Compound 3-8 6.1 6.4 500 7.8 139.5 0.14 0.11 Example (71) Compound 3-9 6.2 6.7 500 7.4 133.9 0.14 0.12 Example (72) Compound 3-10 6.3 6.8 500 7.3 133.4 0.14 0.12 Example (73) Compound 3-11 6.2 6.7 500 7.4 133.4 0.14 0.12 Example (74) Compounds 3-12 6.2 6.7 500 7.5 134.5 0.14 0.12 Example (75) Compound 3-17 6.1 6.5 500 7.7 141.1 0.14 0.12 Example (76) Compound 3-18 6.2 6.5 500 7.7 139.9 0.14 0.11 Example (77) Compound 3-19 6.2 6.5 500 7.7 140.3 0.14 0.11 Example (78) Compound 3-20 6.2 6.4 500 7.8 140.8 0.14 0.12 Example (79) Compound 3-25 6.2 6.8 500 7.4 133.6 0.14 0.12 Example (80) Compound 3-26 6.2 6.8 500 7.4 133.1 0.14 0.11 Example (81) Compound 3-27 6.3 6.8 500 7.3 132.7 0.14 0.12 Example (82) Compound 3-28 6.3 6.8 500 7.4 133.4 0.14 0.11 Example (83) Compound 3-30 6.3 6.7 500 7.5 132.1 0.14 0.11 Example (84) Compound 3-31 6.2 6.7 500 7.5 132.1 0.14 0.12 Example (85) Compound 3-32 6.3 6.7 500 7.5 131.7 0.14 0.11 Example (86) Compound 3-33 6.3 6.9 500 7.3 130.6 0.14 0.12 Example (87) Compound 3-34 6.2 6.9 500 7.3 130.3 0.14 0.11

As can be seen from the results of Table 5, the organic electroluminescent device using the compound of the present invention as the material of the light emitting auxiliary layer has improved luminous efficiency and significantly improved lifetime compared to the organic electroluminescent devices of Comparative Examples 3 to 4 .

It can be seen from the results that the device using Comparative Compound 3 and the compound of the present invention as a light emitting auxiliary layer has improved luminescence efficiency and lifetime compared with the device not having a luminescent auxiliary layer, And the life span of the product.

It has been found that a fluorene having a fused form in which an aromatic ring is additionally added to a tertiary amine (introduction of a substituent for increasing the planarity of a molecule) acts as a main factor for improving the performance of the device in the hole transport layer as well as the light- And the packing density of the present invention used as the light emitting auxiliary layer material is increased to facilitate the movement of the holes. As a result, the charge balance in the light emitting layer is improved and the efficiency is considered to be increased. As the movement of the hole is facilitated, it is confirmed that the charge balance is maintained in the light emitting layer, thereby improving the driving voltage and lifetime.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of equivalents should be construed as falling within the scope of the present invention.

100: organic electric element 110: substrate
120: First electrode (anode) 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 (cathode)

Claims (12)

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

{In the above formula (1)
1) Ar ¹ is A C ₆ to C ₆₀ aryl group,
2) R ¹ to R ⁴ independently of one another are i) deuterium; Tritium; halogen; Cyano; A nitro group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; -L ' -N (R ' _a ) (R ' _b ); A C ₁ -C ₃₀ alkoxyl group; And a C ₆ -C ₃₀ aryloxy group, or ii) adjacent R ^{1 s} and R ^{2 s} may be bonded to each other to form a ring,
R ³ and R ⁴ are not bonded to each other to form a ring,
(Wherein L 'is a single bond; C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₃ ~ C a fused ring of an aromatic ring of an aliphatic ring and a C ₆ ~ C ₆₀ groups of _60; and a C ₂ ~ C _And R _a and R _b are independently selected from the group consisting of a C ₆ to C ₆₀ aryl group, a fluorenyl group, a C ₃ to C ₆₀ aliphatic ring and a C ₆ to C ₆₀ alicyclic ring, groups of the fused ring of an aromatic ring, and selected from the group consisting of a,); and O, N, S, Si, and heterocyclic of C ₂ ~ C ₆₀ group containing at least one hetero atom of the P
3) R ⁵ to R ⁶ are independently selected from: i) a C ₆ -C ₆₀ aryl group; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And aryloxy groups of C ₆ -C ₃₀ , or ii) R ⁵ and R ⁶ may be bonded to each other to form a spiro compound together with C to which they are bonded,
4) A rings and B rings are C ₆ to C ₂₀ aryl groups; Except when A ring and B ring are simultaneously C ₆ aryl groups,
5) L ¹ and L ² independently of one another are a single bond; C ₆ -C ₆₀ arylene groups; A fluorenylene group; And a C ₂ -C ₆₀ heteroarylene group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C3-C60 and an aromatic ring of C6-C60,
6) a is any integer from 0 to 17; b is an integer of 0 to 18; c is an integer of 0 to 4; d is an integer of 0 to 3;
A halogen group, a silyl group, a siloxane group, a boron group, a germanium group, a cyano group, a nitro group, a -L _{'-N (R a) (R} b); C 1 ~ Import alkylthio of C _20; C ₁ ~ alkoxy group of C _20; C ₁ ~ alkyl group of C _20; C ₂ ~ C ₂₀ alkenyl group a; ₂ C ~ alkynyl of C _20; an aryl group of C ₆ - C ₂₀ substituted with heavy hydrogen;; C ₆ ~ C ₂₀ aryl group, a fluorenyl group; C ₂ - heterocyclic group of C _20; C of ₃ ~ C ₂₀ cycloalkyl An alkyl group, an arylalkyl group having ₇ to ₂₀ carbon atoms, and an arylalkenyl group having ₈ to ₂₀ carbon atoms, and these substituents may be further bonded to each other to form a ring, wherein The term &quot; ring &quot; means an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof Refers to a luer binary fused ring, a saturated or unsaturated ring.)}
The method according to claim 1,
Wherein the formula (1) is represented by any one of the following formulas (2-1) to (2-3) &Lt; / RTI &gt;

(In the above formulas (2-1) to (2-3)
R ¹ to R ⁶ , L ¹ , L ² , Ar ¹ , ad, A and B are the same as defined in claim 1, and A and B are not simultaneously C ₆ aryl.
The method according to claim 1,
Wherein the formula (1) is represented by any one of the following formulas (3-1) to (3-3).

(In the above formulas 3-1 to 3-3,
R ¹ to R ⁶ , L ¹ , L ² , Ar ¹ , ad, A and B are as defined in claim 1.
The method according to claim 1,
Wherein the A ring and the B ring in the above formula (1) are each independently any one of the following formulas (1a) to (1d).

The compound according to claim 1, wherein the compound represented by the formula (1) is any of the compounds represented by the following formulas.

A first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode,
The organic electroluminescent device according to any one of claims 1 to 5, wherein the organic layer comprises the compound of any one of claims 1 to 5.
The method according to claim 6,
Wherein the organic material layer is selected from the group consisting of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, and a light emitting layer, and the organic material layer contains one or more of the compounds.
The organic electroluminescent device according to claim 7, wherein the organic material layer is a hole transporting layer or a light-emitting auxiliary layer.
The method according to claim 6,
Further comprising a light-efficiency-improvement layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the one side of the second electrode opposite to the organic material layer.
The method according to claim 6,
Wherein the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process.
A display device including the organic electroluminescent device of claim 6; And a control unit for driving the display device.
12. The method of claim 11,
Wherein the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.

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