KR20170084917A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides a novel compound capable of improving luminous efficiency, stability and lifetime of a device, an organic electric device using the same, and an electronic device thereof.

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.

The present invention relates to a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer material and an organic electric device including the same, which have low driving voltage characteristics. Flat panel display devices are playing a very important role in supporting a high image information society centered on the Internet, which is experiencing rapid growth in recent years. In particular, an organic electroluminescent device (organic EL device) capable of being driven by a low voltage in a self-emission type is superior to a liquid crystal display (LCD), which is a mainstream of a flat panel display device, and has excellent viewing angle and contrast ratio, Lightweight and thin, and advantageous in terms of power consumption. In addition, the response speed is fast and the color reproduction range is wide, and attention has been paid as a next generation display device. In general, an organic EL element is formed on a glass substrate in the order of an anode made of a transparent electrode, an organic thin film including a light emitting region, and a metal electrode in this order. The organic thin film may include a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron injection layer (ETL) in addition to an emission layer (EML) EIL), and may further include an electron blocking layer (EBL), a hole blocking layer (HBL), and a light emitting auxiliary layer in light emission characteristics of the light emitting layer. When an electric field is applied to the organic EL device having such a structure, holes are injected from the anode and electrons are injected from the cathode. The injected holes and electrons are recombined in the light emitting layer through the hole transporting layer and the electron transporting layer, . The luminescent exciton thus formed emits light while transitioning to ground states. At this time, a luminescent dye (guest) is doped in the luminescent layer (host) to increase the efficiency and stability of the luminescent state. In order to utilize such an organic electric device in various display media, the lifetime of the device is important, and various studies are currently under way to increase the lifetime of the organic electric device. Particularly, in order to improve the lifetime characteristics of organic electronic devices, various studies have been conducted on organic materials to be inserted into a buffer layer such as a hole transporting layer or a light emitting auxiliary layer. For this purpose, a high hole transporting property from an anode to an organic layer There is a demand for a hole injection layer and a hole transport layer material having high uniformity and low crystallinity when forming a thin film after deposition.

It is possible to delay penetration and diffusion of the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the lifetime of the organic electronic device, and to stabilize the joule heating caused by driving the device, It is necessary to develop a hole injection layer and a hole transport layer material. It is also reported that the low glass transition temperature of the hole transporting layer material significantly affects the lifetime of the device depending on the characteristics of the uniformity of the thin film surface collapsing during device operation. In addition, the deposition method is the mainstream in the formation of OLED devices, and a material that can withstand such a long time, that is, a material having high heat resistance characteristics, is required. Particularly, the major overcoming problem of the organic light emitting device is that it is urgent to overcome the problem of power consumption and lifetime as the size of a mobile phone or a tablet PC becomes larger.

However, it is difficult to simultaneously overcome the driving voltage and the lifetime as the hole transporting layer material. Most of the materials with high hole mobility have mostly planar structures rich in electrons. For example, naphthyl, fluorene and phenanthrene. However, when a compound having the above structure is introduced into a hole transporting material as a substituent, the hole mobility increases up to a certain number and the lifetime is also affected. However, in order to reach the low voltage driving target required in the present industry, The driving voltage can be lowered while the driving voltage can be lowered, but the lifetime characteristic is markedly deteriorated. The reason for this is that, in the case of the molecule in which the electron-rich planar structures are excessively introduced, when the constant current is continuously supplied in the device life evaluation, holes are trapped and stabilized between the plate-like structures, As the driving voltage rises to apply the current, the lifetime of the device is rapidly deteriorated. This is expressed by the following equation.

J = Space Charge limited current

ε = Permittibility

μ = Mobility Coefficient

θ = Charge Trap Coefficient (Free Carrier / total Carrier)

V = Voltage

d = Thickness

When the number of free carriers decreases due to a trap phenomenon, the value of? Decreases. Therefore, in a current driven organic electroluminescent device requiring a constant current, the driving voltage rises, The results can be retrieved. Therefore, as described above, introduction of a certain number or more of the plate-like structure rich in electrons capable of increasing the hole mobility has an unfavorable effect on the lifetime, and thus there is little possibility of lowering the driving voltage by using it.

Therefore, in order to solve the above-mentioned problems of the prior art and to achieve the object of the present invention, the present invention proposes a method having a long lifetime by using a method of substituting an appropriate ratio of deuterium .

KR 1020130076842 A

The object of the present invention is to replace a fluorene-substituted amine compound with deuterium to complete a low-voltage driving and a high-life device in order to realize a low-voltage driving and a high-definition device which are required characteristics of an organic electric device.

The present invention provides a compound represented by the following formula (1) and an organic electric device comprising the same.

(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.

Compared with the unsubstituted compound, deuterium substituted compounds showed much thermodynamic behavior. Among these thermal properties, when the iridium compound was substituted with deuterium, the characteristics varied depending on the difference in carbon, hydrogen, carbon, and deuterium bond lengths. Compared to the compound in which the deuterium compound was not substituted with deuterium, It is possible to obtain a higher luminous efficiency due to the weakening of the intermolecular Van der Waals force generated in accordance with the present invention.

In addition, when substituted by deuterium, the energy of the zero point energy, that is, the bottom state is lowered. As the bond length of deuterium-carbon is shorter than the bond length of hydrogen-carbon, the molecular hardcore volume And thus the electric polarizability can be reduced. It was determined that this would be very effective in realizing the necessary amorphous state in order to increase OLED lifetime and driving characteristics in general.

However, a method of lowering the driving voltage by replacing with deuterium, that is, increasing the hole transporting mobility of the hole transporting material, has not been studied at present. In this study, various kinds of compounds are used Therefore, many experiments were carried out. In addition, when a film is formed of a compound substituted with deuterium, a film is formed in an amorphous glass state which can greatly affect the hole mobility of the thin film, and the amorphous glass state is isotropic and homogeneous ) Characteristics, it is confirmed that the charge flow, that is, the hole mobility, can be increased by reducing the grain boundary.

To explain the present invention in more detail, there is a disadvantage that the lifetime of amine compounds substituted with fluorene decreases. However, the prior art has not proved the effect of improvement on such a part, and the prior art which improves the life characteristic by substituting deuterium at a specific position has not been reported yet.

As a result of the research and development of the inventors, the present invention provides an amine compound containing a deuterated substituted fluorene compound while maintaining excellent characteristics of the organic material layers of the organic electric device as described above.

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; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₃₀ carbon atoms; An alkynyl group of C ₂ to C ₃₀ ; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₆₀ ; And R &_lt; _b >), wherein L 'is a single bond, an arylene group having ₆ to ₆₀ carbon atoms, a fluorenylene group having ₃ to ₆₀ carbon atoms, A fused ring group of an aliphatic ring of C ₆ to C ₆₀ aromatic rings, and a heterocyclic group of C ₂ to C ₆₀ ; and R _a and R _b are each independently selected from the group consisting of C ₆ to C ₆₀ aryl group; fluorene 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 O, N, S, Si and C containing at least one hetero atom of the P A heterocyclic group having ₂ to ₆₀ carbon atoms;

2) R ¹ and R ² are independently selected from: i) independently of one another hydrogen; heavy hydrogen; A C ₁ -C ₅₀ alkyl group; A C ₂ -C ₃₀ alkenyl group; A C ₂ -C ₃₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And an aryloxy group of C ₆ -C ₆₀ ; A C ₁ -C ₃₀ silyl group; An aryl group of C ₆ -C ₆₀ ; 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 fluorenyl group; And -L'-N (R _a ) (R _b ), or ii) R ¹ and R ² are bonded to each other to form a spiro compound together with the carbon or Si to which they are bonded And,

3) R ⁴ to R ⁸ are independently selected from: i) independently of each other hydrogen; heavy hydrogen; A C ₁ -C ₅₀ alkyl group; A C ₂ -C ₃₀ alkenyl group; A C ₂ -C ₃₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And an aryloxy group of C ₆ -C ₆₀ ; A C ₁ -C ₃₀ silyl group; An aryl group of C ₆ -C ₆₀ ; 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 fluorenyl group; And -L'-N (R _a) selected from the group consisting of (R _b), or, or ⅱ) of adjacent R ⁴ together, R ⁵ each other, R ⁶ together, R ⁷ to each other, at least one R ⁸ combine with each other to each other A ring can be formed,

4) At least one of R ¹ to R ⁸ must be substituted with deuterium,

5) L ¹ and L ² are single bonds; 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 a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring,

6) a and d are integers of 0 to 3, and b, c, e and f represent an integer of 0 to 4;

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

Wherein R ¹ to R ⁸ , a to f, L ¹ to L ² , and Ar ¹ are the same as defined in Formula 1, and D is deuterium.

In the present invention, the formula (1) includes the compounds represented by any one of the following formulas (3-1) to (3-4) and (4-1-4-4).

(Wherein R ¹ to R ⁸ , a to f, L ¹ to L ² and Ar ¹ are the same as defined in the above formula (1) in the formulas (3-1) to (3-4)

In the present invention, the compound of formula (1) includes the following compounds and provides such 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 a hole transport layer or a light emitting auxiliary layer composition comprising the compound represented by the above formula (1), and provides the organic electric device including the hole transport layer or the light emitting auxiliary 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.

&Lt; Reaction Formula 2 > When L is not a single bond

X ² = Cl, Br, I

Synthetic example of Sub 1-I

Sub 1-I of Reaction Scheme 1 can be synthesized by the reaction path of Reaction Scheme 3 and Reaction Scheme 4, but is not limited thereto.

&Lt; Reaction formula 3 > X ² = Cl, Br, I

<Reaction Scheme 4>

Sub 1-I-1 Synthetic Example

1) Synthesis of Sub 1-I-I-1

2-bromo-4-chloro- 1,1'-biphenyl-2 ', 3', 4 ', 5', 6'-d 5 (9.9g, 36.32mmol) and M 1-1 (6.84g, 36.32mmol ) Was dissolved in THF (363 ml), the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.44 g, 64.06 mmol) was slowly added dropwise and the reaction mixture 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 11.93 g of product. (Yield: 86%)

2) Synthesis of Sub 1-I-1

HCl and acetic acid (61 ml) were added to Sub 1-I-I-1 (11.7 g, 30.63 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 subjected to silicagel column and recrystallization to obtain 10.23 g of the product. (Yield: 92%)

Sub 1-I-2 Synthetic Example

1) Synthesis of Sub 1-I-I-2

2-bromo-5-chloro-1,1'-biphenyl-2 ', 3', 4 ', 5', 6'-d ₅ (10.5 g, 38.52 mmol), M 1-1 (7.25 g, 38.52 mmol ), THF (385 ml) and the synthesis method of Sub 1-II-1, to obtain 12.21 g of the product. (Yield: 83%)

2) Synthesis of Sub 1-I-2

Sub-1-I-2 (12 g, 31.42 mmol), HCl, and acetic acid (63 ml) were obtained using the Sub 1-I-1 synthesis method. (Yield: 88%).

Sub 1-11 Synthetic Example

1) Sub 1-II-1 synthesis

Sub 1-I-1 (9.50g , 26.18mmol) of was dissolved in DMF (165ml) in a round bottom flask, Bis (pinacolato) diboron (7.31g , 28.79mmol), Pd (dppf) Cl 2 (0.57 g, 0.79 mmol), KOAc (7.71 g, 28.79 mmol) was added and stirred at 90 [deg.] 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 9.16 g of product. (Yield: 77%)

2) Sub 1-11 synthesis

Iodo-1,1'-biphenyl (9g, 25.07mmol) and tetrakis (triphenylphophine) palladium (0) (0.87g, 0.75mmol) were added to a mixture of Sub 1-II-1 (11.39g, 25.07mmol), 3-bromo- ) And K ₂ CO ₃ (10.39 g, 75.21 mmol) were added, THF (162 ml) and water (81 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 10.10 g of the product was obtained. (Yield: 72%).

Sub 1-13 Synthetic Example

1) Sub 1-13 synthesis

Sub-II-1 (10.02 g, 22.05 mmol), 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (8.80 g, 22.05 mmol), tetrakis (triphenylphophine) palladium , 0.66mmol), K ₂ CO ₃ (9.14 g, 66.15 mmol), THF (97 ml) and water (49 ml) were obtained using the Sub 1-11 synthesis method described above. (Yield: 76%).

Sub 1-21 Synthetic Example

1) Sub 1-II-2 synthesis

Sub 1-I-3 (11g , 31.35mmol), DMF (198ml), Bis (pinacolato) diboron (8.76g, 34.49mmol), Pd (dppf) Cl 2 (0.69 g, 0.94 mmol), KOAc (9.23 g, 94.06 mmol) was subjected to the synthesis of Sub 1-II-1 to obtain 12.07 g of the product. (Yield: 87%).

2) Sub 1-20 synthesis

Sub 1-II-2 (11.73g , 26.51mmol), 1-bromo-3-iodobenzene (7.50g, 26.51mmol), tetrakis (triphenylphophine) palladium (0) (0.92g, 0.8mmol), K 2 CO 3 (10.99 g, 79.53 mmol), THF (117 ml) and water (58 ml) were obtained by using the above Sub 1-11 synthesis method. (Yield: 80%).

Sub 1-26 Synthetic Example

Sub-II-2 (g, mmol), 3-bromo-7-iododibenzo [b, d] thiophene (9.30 g, 23.90 mmol), tetrakis (triphenylphophine) palladium (0) (0.83 g, 0.72 mmol) ₂ CO ₃ (9.91 g, 71.71 mmol), THF (105 ml) and water (53 ml) were used to obtain 10.08 g of the product. (Yield: 73%)

Sub 1-28 Synthetic Example

1) Synthesis of Sub 1-I-I-3

M-1-1 (9.90 g, 52.58 mmol), THF (526 ml) and the synthesis method of Sub 1-II-1 were used to synthesize 2- (2-bromo-4-chlorophenyl) naphthalene (16.7 g, 52.58 mmol) 17.96 g of the product was obtained. (Yield: 80%).

2) Synthesis of Sub 1-28

Subsequently, 10.06 g of the product was obtained by using Sub 1-I-I-3 (17.8 g, 41.69 mmol), HCl and Acetic acid (83 ml) (Yield: 59%)

Sub 1-32 Synthetic Example

1) Synthesis of Sub 1-I-I-4

9- (2-bromo-4-chlorophenyl) phenanthrene-1,2,3,4,5,6,7,8,10-d ₉ (14.9 g, 39.55 mmol), M 1-1 (7.45 g, 39.55 mmol), THF (396 ml), and the synthesis method of Sub 1-II-1 was used to obtain 13.81 g of the product. (Yield: 72%).

2) Synthesis of Sub 1-32

Sub-1-I-I-4 (13.6 g, 28.04 mmol), HCl and Acetic acid (56 ml) were obtained using the Sub 1-I-1 synthesis method. (Yield: 77%)

[Reference: Synthesis of M 1]

M 1 according to the present invention can be synthesized by the reaction path of the following Reaction Scheme 5 and Reaction Scheme 6, but is not limited thereto.

<Reaction Scheme 5>

<Reaction Scheme 6>

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

compound FD-MS compound FD-MS Sub 1-1 _{m / z = 358.14 (C 25} H 7 D 8 Cl = 358.89) Sub 1-3 m / z = 362.16 (C ₂₅ H ₃ D ₁₂ Cl = 362.92) Sub 1-4 m / z = 362.16 (C ₂₅ H ₃ D ₁₂ Cl = 362.92) Sub 1-6 m / z = 482.14 (C ₃₁ H ₇ D ₁₂ Br = 483.47) Sub 1-11 m / z = 558.17 (C ₃₇ H ₁₁ D ₁₂ Br = 559.57) Sub 1-13 m / z = 598.20 (C ₄₀ H ₁₅ D ₁₂ Br = 599.63) Sub 1-14 m / z = 598.20 (C ₄₀ H ₁₅ D ₁₂ Br = 599.63) Sub 1-16 _{m / z = 350.09 (C 25} H 15 Cl = 350.85) Sub 1-18 _{m / z = 350.09 (C 25} H 15 Cl = 350.85) Sub 1-20 m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40) Sub 1-21 m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40) Sub 1-26 m / z = 576.05 (C ₃₇ H ₂₁ BrS = 577.54) Sub 1-28 m / z = 408.15 (C ₂₉ H ₉ D ₈ Cl = 408.95) Sub 1-31 m / z = 458.17 (C ₃₃ H ₁₁ D ₈ Cl = 459.01) Sub 1-32 m / z = 466.22 (C ₃₃ H ₃ D ₁₆ Cl = 467.06)

Synthetic example of Sub 2

Sub 2 of Reaction Scheme 1 can be synthesized by the route of Reaction Scheme 7 and Reaction Scheme 8 below, but is not limited thereto.

<Reaction Scheme 7>

Hal = Br, I, Cl < RTI ID = 0.0 >

Synthesis example of Sub 2-I

(R ⁷ ) _e -> (R ⁵ ) _c and (R ⁸ ) _f -> (R ⁶ ) _f in the reaction scheme 5 and the reaction scheme 6,

(When R ¹ and R ² are cyclized, see Schemes 3 to 4)

Hal ² = Br, Cl

Synthesis of Sub 2-9

(10.00 g, 36.61 mmol), Pd ₂ (dba) ₃ (1.01 g, 1.10 mmol) in a round bottom flask was added dropwise to a stirred solution of [1,1'-biphenyl] -4-amine (6.20 g, 36.61 mmol), Sub 2-1 ), P (t-Bu) ₃ (0.59 g, 2.93 mmol), NaOt-Bu (10.55 g, 109.82 mmol) and toluene (384 ml). 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 organic material was purified by silicagel column and recrystallized to obtain 10.85 g (yield: 82%) of the product.

Synthesis of Sub 2-16

1) Sub 2-II-1 Synthesis

P (t-Bu) ₃ (0.41 g, 2.01 mmol), Pd ₂ (dba) ₃ (0.69 g, 0.76 mmol), Sub 2-1-2 (10.00 g, 25.17 mmol) ), NaOt-Bu (7.26 g, 75.51 mmol) and toluene (264 ml) were obtained 6.80 g (Yield: 81%) of the product using the synthesis method of Sub 2-9.

2) Sub 2-16 synthesis

Pd ₂ (dba) ₃ (0.55 g, 0.61 mmol), P (t, ₂ , ₃ ) (Yield: 87%) was obtained by using the synthesis method of Sub 2-9 as described in the above Synthesis Example ₁ (0.33 g, 1.61 mmol), NaOt-Bu (5.82 g, 60.52 mmol) and toluene .

Synthesis of Sub 2-17

P (t-Bu) ₃ (1.13 g, 2.06 mmol), Pd ₂ (dba) ₃ (1.91 g, 2.09 mmol), Sub 2-1-1 (9.50 g, 34.78 mmol) ), NaOt-Bu (13.37 g, 139.11 mmol) and toluene (365 ml) were obtained by the synthesis method of Sub 2-9.

Synthesis of Sub 2-24

1) Sub 2-II-2 synthesis

P (t-Bu) ₃ (0.74g, 3.66mmol), Pd ₂ (dba) ₃ (1.26g, 1.37mmol), Sub 2-1-1 (12.50g, 45.76mmol) ), NaOt-Bu (13.19 g, 137.28 mmol), and toluene (480 ml) were obtained 7.09 g (yield: 74%) of the product using the synthesis method of Sub 2-9.

2) Sub 2-24 synthesis

Sub 2-II-2 (6.92g , 33.06mmol), 3-bromodibenzo [b, d] thiophene (8.70g, 33.06mmol), Pd 2 (dba) 3 (0.91g, 0.99mmol), P (t-Bu to obtain _{78%):) 3 (0.54g} , 2.64mmol), NaOt-Bu (9.53g, 99.18mmol), toluene (347ml) to 10.10g (yield product using the synthesis method of the Sub 2-9.

Synthesis of Sub 2-32

P (t-Bu) ₃ (0.48 g, 29.49 mmol), Pd ₂ (dba) ₃ (0.81 g, 0.88 mmol), Sub 2-1-3 g, 2.36 mmol), NaOt-Bu (8.50 g, 88.47 mmol) and toluene (310 ml) were subjected to the synthesis method of Sub 2-9 to obtain 10.07 g (yield: 83%) of the product.

Synthesis of Sub 2-46

1) Sub 1-I-I-5 synthesis

2-bromo-4-chloro- 1,1'-biphenyl-2 ', 3', 4 ', 5', 6'-d 5 (9g, 33.64mmol) and M 1-1 (6.33g, 33.64mmol) Was dissolved in THF (336 ml), the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.26 g, 35.32 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 purified by silicagel column and recrystallized to obtain 10.40 g of the product. (Yield: 82%)

2) Synthesis of Sub 2-I-4

HCl and acetic acid (53 ml) were added to Sub 1-I-I-5 (10 g, 26.53 mmol) and the mixture was stirred at 80 ° C for 1 hour. After the reaction was completed, the organic solvent was concentrated by filtration under reduced pressure, and the resulting organic material was subjected to silicagel column and recrystallization to obtain 8.09 g of the product. (Yield: 85%).

3) Sub 2-46 synthesis

Pd ₂ (dba) ₃ (0.53 g, 19.23 mmol), Sub 2-1-4 (6.90 g, 19.23 mmol), 4- (9,9- diphenyl-9H- 9), P (t-Bu) ₃ (0.31 g, 1.54 mmol), NaOt-Bu (5.54 g, 57.68 mmol) and toluene (202 ml) Yield: 72%).

Synthesis of Sub 2-49

1) M 2-I-5 synthesis

M -2 (11.00 g, 50.30 mmol) obtained in the above synthesis was dissolved in ethylene glycol (201 mL), and then hydrazine monohydrate (75.55 g, 1509.12 mmol), KOH (7.06 g, 125.76 mmol), followed by stirring at 185 ° C. When the reaction was completed, the temperature was lowered to 0 &lt; 0 &gt; C, water was added, and the precipitated solid was filtered and washed with a small amount of water. The residue was redissolved in CH ₂ Cl ₂ , dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 9.78 g of the product. (Yield: 95%).

2) Synthesis of M 2-1

(9.50 g, 46.41 mmol), KOt-Bu (15.62 g, 139.23 mmol) and DMSO (302 ml) were added to the round bottom flask and stirred at 0 ° C for 5 minutes. Iodomethane (19.76 g, 139.23 mmol) was added. 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 purified by silicagel column and recrystallized to obtain 9.72 g of the product. (Yield: 90%).

3) Sub 2-II-3 synthesis

ammonia (0.70g, 41.25mmol), M 2-1 (9.60g, 41.25mmol), Pd 2 (dba) 3 (1.13g, 1.24mmol), P (t-Bu) 3 (0.67g, 3.30mmol), NaOt-Bu (11.89 g, 123.74 mmol) and toluene (433 ml) were used to obtain 6.25 g of the product (yield: 71%).

4) Sub 2-49 Synthesis

Sub 2-II-3 (6.21g , 29.10mmol), 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (11.30g, 29.10mmol), Pd 2 (dba) 3 ( ₉ (0.47 g, 2.33 mmol), NaOt-Bu (8.39 g, 87.31 mmol) and toluene (306 ml) 10.00 g (yield: 66%) was obtained.

Synthesis of Sub 2-53

1) M 2-I-6 synthesis

M -3 (11.00 g, 50.30 mmol) obtained in the above synthesis was dissolved in ethylene glycol (201 mL), and then hydrazine monohydrate (75.55 g, 1509.12 mmol), KOH (7.06 g, 125.76 mmol), followed by stirring at 185 ° C. When the reaction was completed, the temperature was lowered to 0 ° C, water was added, and the solid precipitate was filtered and washed with a small amount of water. The residue was redissolved in CH ₂ Cl ₂ , dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 9.58 g of product. (Yield: 93%).

2) M 2-2 synthesis

(9.70 g, 86.47 mmol), DMSO (187 ml) and iodobenzene (17.64 g, 86.47 mmol) were used for the synthesis of M 2-I-6 (5.90 g, 28.82 mmol) 9.05 g of the product was obtained. (Yield: 88%).

3) Sub 2-53 synthesis

9-phenyl-9H-carbazol- 3-amine (6.51g, 25.22mmol), M 2-2 (9.00g, 25.22mmol), Pd 2 (dba) 3 (0.69g, 0.76mmol), P (t-Bu _{) 3 (0.41g, 2.02mmol),} NaOt-Bu (7.27g, 75.65mmol), toluene (10.07g ( yield 265ml) and the product using the method for the synthesis of the Sub 2-9: yield 69%).

Synthesis of Sub 2-57

Sub 2-II-4 (8.92g , 36.10mmol), 2-bromodibenzo [b, d] furan (7.70g, 36.10mmol), Pd 2 (dba) 3 (0.99g, 1.08mmol), P (t-Bu to obtain _{73%):) 3 (0.58g} , 2.89mmol), NaOt-Bu (10.41g, 108.29mmol), toluene (379ml) the synthesis 10.00g (yield product using the Sub 2-9.

Synthesis of Sub 2-61

P (t-Bu), Pd ₂ (dba) ₃ (0.77 g, 0.84 mmol), M 2-1 (6.50 g, 27.93 mmol), 4- (naphthalen- ₃ (0.45 g, 2.23 mmol), NaOt-Bu (8.05 g, 83.78 mmol) and toluene (293 ml) were used to obtain 10.02 g (yield: 73%) of the product.

Synthesis of Sub 2-65

1) M 2-I-7 synthesis

M-1-4 (13.30 g, 60.82 mmol), Ethylene glycol (243 mL), Hydrazine monohydrate (91.34 g, 1824.67 mmol) (8.53 g, 152.06 mmol) was obtained by using the above synthesis method of M 2-I-6. (Yield: 90%).

2) M 2-3 Synthesis

(18.09 g, 161.22 mmol), DMSO (349 ml), iodomethane (22.88 g, 161.22 mmol) were reacted with the product 11.13 g. (Yield: 89%).

3) Synthesis of M3-1

M 2-3 (10.80g, 46.40mmol) of was dissolved in DMF (292ml) in a round bottom flask, Bis (pinacolato) diboron (12.96g , 51.04mmol), Pd (dppf) Cl 2 (1.02 g, 1.39 mmol), KOAc (13.66 g, 139.21 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 12.04 g of the product. (Yield: 80%).

4) Sub 2-II-5 synthesis

(0.64 g, 0.55 mmol) and tetrakis (triphenylphophine) palladium (0) (0.64 g, 0.55 mmol) and 3-bromo-7-iododibenzo [b, d] thiophene (36.76 g, 36.76 mmol) ₂ CO ₃ (7.62 g, 55.13 mmol), THF (162 ml) and water (81 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 12.16 g of the product was obtained. (Yield: 72%).

5) Sub 2-65 Synthesis

aniline (2.43g, 26.12mmol), Sub 2-II-5 (12.00g, 26.12mmol), Pd 2 (dba) 3 (0.72g, 0.78mmol), P (t-Bu) 3 (0.42g, 2.09mmol ), NaOt-Bu (7.53 g, 78.36 mmol) and toluene (274 ml) were obtained by the synthesis method of Sub 2-9.

Examples of Sub 2 include, but are not limited to, the following.

<FD-MS of Sub 2>

compound FD-MS compound FD-MS Sub 2-5 m / z = 361.18 (C ₂₇ H ₂₃ N = 361.49) Sub 2-8 _{m / z = 286.15 (C 20} H 18 N 2 = 286.38) Sub 2-9 m / z = 361.18 (C ₂₇ H ₂₃ N = 361.49) Sub 2-16 m / z = 574.24 (C ₄₃ H ₃₀ N ₂ = 574.73) Sub 2-17 _{m / z = 401.21 (C 30} H 27 N = 401.55) Sub 2-24 m / z = 391.14 (C ₂₇ H ₂₁ NS = 391.53) Sub 2-31 _{m / z = 455.22 (C 33} H 21 D 4 NO = 455.59) Sub 2-32 m / z = 411.20 (C ₃₁ H ₂₅ N = 411.55) Sub 2-33 m / z = 415.22 (C ₃₁ H ₂₁ D ₄ N = 415.57) Sub 2-40 m / z = 415.22 (C ₃₁ H ₂₁ D ₄ N = 415.57) Sub 2-41 m / z = 405.24 (C ₃₀ H ₂₃ D ₄ N = 405.58) Sub 2-46 m / z = 731.34 (C ₅₆ H ₂₉ D ₈ N = 731.97) Sub 2-49 m / z = 520.26 (C ₃₆ H ₂₄ D ₄ N ₄ = 520.67) Sub 2-53 m / z = 578.27 (C ₄₃ H ₂₆ D ₄ N ₂ = 578.75) Sub 2-57 m / z = 379.19 (C ₂₇ H ₁₇ D ₄ NO = 379.50) Sub 2-60 m / z = 493.27 (C ₃₇ H ₂₃ D ₆ N = 493.68) Sub 2-61 _{m / z = 491.26 (C 37} H 25 D 4 N = 491.67) Sub 2-65 _{m / z = 471.20 (C 33} H 21 D 4 NS = 471.65) Sub 2-74 _{m / z = 339.19 (C 25} H 17 D 4 N = 339.47) Sub 2-78 m / z = 367.22 (C ₂₇ H ₁₇ D ₆ N = 367.52)

Example of synthesis of Final Products

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) was added and stirred at 100 &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.

Synthetic examples 1-4

The Sub 1-3 (4.00 g, 11.02 mmol) obtained in the above synthesis was dissolved in toluene (116 ml) in a round bottom flask and Sub 2-17 (4.43 g, 11.02 mmol), Pd ₂ (dba) ₃ (0.30 g, P ( t- Bu) ₃ (0.18 g, 0.88 mmol) and NaO t- Bu (3.18 g, 33.07 mmol) were added and stirred at 100 ° 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 purified by silicagel column and recrystallized to obtain 6.66 g (yield: 83%) of the product.

Synthesis Example of 1-13

Obtained in the above Synthesis Sub 1-6 (4.80g, 9.93mmol), toluene (104ml), Sub 2-5 (3.59g, 9.93mmol), Pd 2 (dba) 3 (0.27g, 0.30mmol), P (t -Bu) ₃ (0.16g, 0.79mmol) and NaO t- Bu (2.86g, 29.78mmol) were obtained 6.60g (yield: 87%) of the product using the above Sub 1-4 synthesis method.

Synthesis Example of 1-18

Obtained in the above Synthesis Sub 1-11 (5.30g, 9.47mmol), toluene (99ml), Sub 2-24 (3.71g, 9.47mmol), Pd 2 (dba) 3 (0.26g, 0.28mmol), P (t -Bu) ₃ (0.15 g, 0.76 mmol) and NaO t- Bu (2.73 g, 28.41 mmol) were obtained 6.68 g (Yield: 81%) of the product using the above synthesis method of Sub 1-4.

Synthetic Example 1-24

Obtained in the above Synthesis Sub 1-3 (3.50g, 9.64mmol), toluene (101ml), Sub 2-16 (5.54g, 9.64mmol), Pd 2 (dba) 3 (0.26g, 0.29mmol), P (t -Bu) ₃ (0.16 g, 0.77 mmol) and NaO t- Bu (2.78 g, 28.93 mmol) were obtained.

Synthetic Example of 1-45

Obtained in the above Synthesis Sub 1-28 (4.40g, 10.76mmol), toluene (113ml), Sub 2-5 (3.89g, 10.76mmol), Pd 2 (dba) 3 (0.30g, 0.32mmol), P (t -Bu) ₃ (0.17 g, 0.86 mmol) and NaO t- Bu (3.10 g, 32.28 mmol) were subjected to the synthesis of Sub 1-4 to obtain 6.71 g (yield: 85%) of the product.

Synthetic example of 1-48

Obtained in the above Synthesis Sub 1-31 (6.50g, 14.16mmol), toluene (149ml), Sub 2-8 (4.06g, 14.16mmol), Pd 2 (dba) 3 (0.39g, 0.42mmol), P (t -Bu) ₃ (0.23 g, 1.13 mmol) and NaO t- Bu (4.08 g, 42.48 mmol) were subjected to the synthesis method of Sub 1-4 to obtain 6.43 g (yield: 64%) of the product.

Synthetic examples of 2-15

Sub 1-21 (5.5g, 11.67mmol) obtained in the synthesis, toluene (123ml), Sub 2-40 (4.85g, 11.67mmol), Pd 2 (dba) 3 (0.32g, 0.35mmol), P (t -Bu) ₃ (0.19 g, 0.93 mmol) and NaO t- Bu (3.36 g, 35.00 mmol) were subjected to the synthesis method of Sub 1-4 to obtain 6.40 g (yield: 68%) of the product.

Synthetic examples of 2-20

Obtained in the above Synthesis Sub 1-26 (5.20g, 9.00mmol), toluene (95ml), Sub 2-60 (4.44g, 9.00mmol), Pd 2 (dba) 3 (0.25g, 0.27mmol), P (t -Bu) ₃ (0.15g, 0.72mmol) and NaO t- Bu (2.60g, 27.01mmol) were obtained in a yield of 6.51g (yield: 73%).

Synthetic example of 2-23

Obtained in the above Synthesis Sub 1-16 (3.30g, 9.41mmol), toluene (99ml), Sub 2-53 (5.44g, 9.41mmol), Pd 2 (dba) 3 (0.26g, 0.28mmol), P (t -Bu) ₃ (0.15 g, 0.75 mmol) and NaO t- Bu (2.71 g, 28.22 mmol) were subjected to the synthesis method of Sub 1-4 to obtain 6.72 g (yield: 80%) of the product.

Synthetic example of 2-24

Obtained in the above Synthesis Sub 1-16 (3.30g, 9.41mmol), toluene (99ml), Sub 2-46 (6.88g, 9.41mmol), Pd 2 (dba) 3 (0.26g, 0.28mmol), P (t -Bu) ₃ (0.15g, 0.75mmol) and NaO t- Bu (2.71g, 28.22mmol) were obtained 6.69g (Yield: 68%) of the product using the above synthesis method of Sub 1-4.

Synthetic examples of 2-31

Obtained in the above Synthesis Sub 1-18 (5.00g, 14.25mmol), toluene (150ml), Sub 2-74 (4.84g, 14.25mmol), Pd 2 (dba) 3 (0.39g, 0.43mmol), P (t -Bu) ₃ (0.23 g, 1.14 mmol) and NaO t- Bu (4.11 g, 42.75 mmol) were subjected to the synthesis of Sub 1-4 to obtain 6.71 g (yield: 72%) of the product.

Synthetic Example of 3-4

Obtained in the above Synthesis Sub 1-3 (3.90g, 10.75mmol), toluene (113ml), Sub 2-41 (4.36g, 10.75mmol), Pd 2 (dba) 3 (0.30g, 0.32mmol), P (t -Bu) ₃ (0.17g, 0.86mmol) and NaO t- Bu (3.10g, 32.24mmol) were obtained in a yield of 6.53g (yield: 83%).

Synthetic examples of 3-15

Obtained in the above Synthesis Sub 1-4 (3.90g, 10.75mmol), toluene (113ml), Sub 2-31 (4.90g, 10.75mmol), Pd 2 (dba) 3 (0.30g, 0.32mmol), P (t -Bu) ₃ (0.17g, 0.86mmol) and NaO t- Bu (3.10g, 32.24mmol) were obtained in a yield of 6.56g (yield: 78%).

Synthetic examples of 3-24

Sub 1-14 (6g, 10.01mmol) obtained in the synthesis, toluene (105ml), Sub 2-33 (4.16g, 10.01mmol), Pd 2 (dba) 3 (0.27g, 0.30mmol), P (t - Bu) ₃ (0.16g, 0.80mmol) and NaO t- Bu (2.88g, 30.02mmol) were obtained 6.92g (yield: 74%) of the product using the above Sub 1-4 synthesis method.

Synthetic examples of 4-3

Sub 1-16 (4g, 11.40mmol) obtained in the synthesis, toluene (120ml), Sub 2-78 (4.19g, 11.40mmol), Pd 2 (dba) 3 (0.31g, 0.34mmol), P (t - Bu) ₃ (0.18 g, 0.91 mmol) and NaO t- Bu (3.29 g, 34.20 mmol) were obtained by using the above Sub 1-4 synthesis method.

<Final Products FD-MS>

compound FD-MS compound FD-MS 1-1 m / z = 611.34 (C ₄₆ H ₂₁ D ₁₂ N = 611.85) 1-3 m / z = 687.37 (C ₅₂ H ₂₅ D ₁₂ N = 687.95) 1-4 m / z = 727.40 (C ₅₅ H ₂₉ D ₁₂ N = 728.01) 1-5 m / z = 851.43 (C ₆₅ H ₃₃ D ₁₂ N = 852.16) 1-6 m / z = 849.41 (C ₆₅ H ₃₁ D ₁₂ N = 850.14) 1-7 m / z = 717.32 (C ₅₂ H ₂₃ D ₁₂ NS = 717.99) 1-13 m / z = 763.40 (C ₅₈ H ₂₉ D ₁₂ N = 764.05) 1-14 m / z = 813.41 (C ₆₂ H ₃₁ D ₁₂ N = 814.11) 1-15 m / z = 813.41 (C ₆₂ H ₃₁ D ₁₂ N = 814.11) 1-17 m / z = 928.46 (C ₇₀ H ₃₆ D ₁₂ N ₂ = 929.24) 1-18 m / z = 869.39 (C ₆₄ H ₃₁ D ₁₂ NS = 870.19) 1-20 m / z = 919.40 (C ₆₈ H ₃₃ D ₁₂ NS = 920.25) 1-21 m / z = 929.48 (C ₇₁ H ₃₉ D ₁₂ N = 930.27) 1-23 m / z = 1049.48 (C ₈₁ H ₃₉ D ₁₂ N = 1050.38) 1-24 m / z = 900.43 (C ₆₈ H ₃₂ D ₁₂ N ₂ = 901.19) 1-25 m / z = 661.35 (C ₅₀ H ₂₃ D ₁₂ N = 661.91) 1-30 m / z = 849.41 (C ₆₅ H ₃₁ D ₁₂ N = 850.14) 1-35 m / z = 845.38 (C ₆₂ H ₂₇ D ₁₄ NS = 846.16) 1-38 m / z = 657.33 (C ₅₀ H ₂₇ D ₈ N = 657.89) 1-41 m / z = 733.36 (C ₅₆ H ₃₁ D ₈ N = 733.98) 1-42 m / z = 713.30 (C ₅₂ H ₂₇ D ₈ NS = 713.97) 1-45 m / z = 733.36 (C ₅₆ H ₃₁ D ₈ N = 733.98) 1-46 m / z = 747.34 (C ₅₆ H ₂₉ D ₈ NO = 747.97) 1-48 m / z = 708.34 (C ₅₃ H ₂₈ D ₈ N ₂ = 708.93) 2-1 m / z = 603.29 (C ₄₆ H ₂₉ D ₄ N = 603.80) 2-2 m / z = 653.30 (C ₅₀ H ₃₁ D ₄ N = 653.86) 2-3 m / z = 679.32 (C ₅₂ H ₃₃ D ₄ N = 679.90) 2-4 m / z = 719.35 (C ₅₅ H ₃₇ D ₄ N = 719.96) 2-5 m / z = 843.38 (C ₆₅ H ₄₁ D ₄ N = 844.11) 2-7 m / z = 709.27 (C ₅₂ H ₃₁ D ₄ NS = 709.94) 2-9 m / z = 768.34 (C ₅₈ H ₃₆ D ₄ N ₂ = 769.00) 2-10 m / z = 844.38 (C ₆₄ H ₄₀ D ₄ N ₂ = 845.09) 2-13 _{m / z = 755.35 (C 25} H 37 D 4 N = 756.00) 2-14 m / z = 805.36 (C ₆₂ H ₃₉ D ₄ N = 806.06) 2-15 m / z = 805.36 (C ₆₂ H ₃₉ D ₄ N = 806.06) 2-16 m / z = 871.41 (C ₆₇ H ₄₅ D ₄ N = 872.16) 2-17 m / z = 920.41 (C ₇₁ H ₄₄ D ₄ N ₂ = 921.19) 2-18 m / z = 861.34 (C ₆₄ H ₃₉ D ₄ NS = 862.14) 2-20 m / z = 989.40 (C ₇₄ H ₄₃ D ₆ NS = 990.31) 2-22 m / z = 785.31 (C ₅₈ H ₃₅ D ₄ NS = 786.04) 2-23 m / z = 892.38 (C ₆₈ H ₄₀ D ₄ N ₂ = 893.14) 2-24 m / z = 1045.45 (C ₈₁ H ₄₃ D ₈ N = 1046.35) 2-26 m / z = 891.38 (C ₆₉ H ₄₁ D ₄ N = 892.15) 2-29 m / z = 861.34 (C ₆₄ H ₃₉ D ₄ NS = 862.14) 2-30 m / z = 831.38 (C ₆₄ H ₄₁ D ₄ N = 832.10) 2-31 m / z = 653.30 (C ₅₀ H ₃₁ D ₄ N = 653.86) 3-1 m / z = 615.36 (C ₄₆ H ₁₇ D ₁₆ N = 615.87) 3-4 m / z = 731.42 (C ₅₅ H ₂₅ D ₁₆ N = 732.04) 3-5 m / z = 855.46 (C ₆₅ H ₂₉ D ₁₆ N = 856.18) 3-6 m / z = 853.44 (C ₆₅ H ₂₇ D ₁₆ N = 854.16) 3-8 m / z = 705.37 (C ₅₂ H ₁₉ D ₁₆ NO = 705.96) 3-9 m / z = 780.42 (C ₅₈ H ₂₄ D ₁₆ N ₂ = 781.07) 3-10 m / z = 856.45 (C ₆₄ H ₂₈ D ₁₆ N ₂ = 857.17) 3-13 m / z = 665.38 (C ₅₀ H ₁₉ D ₁₆ N = 665.93) 3-14 m / z = 903.46 (C ₆₉ H ₂₉ D ₁₆ N = 904.22) 3-15 m / z = 781.40 (C ₅₈ H ₂₃ D ₁₆ NO = 782.05) 3-16 m / z = 691.39 (C ₅₂ H ₂₁ D ₁₆ N = 691.97) 3-17 m / z = 767.42 (C ₅₈ H ₂₅ D ₁₆ N = 768.07) 3-18 m / z = 817.44 (C ₆₂ H ₂₇ D ₁₆ N = 818.13) 3-19 m / z = 817.44 (C ₆₂ H ₂₇ D ₁₆ N = 818.13) 3-21 m / z = 817.44 (C ₆₂ H ₂₇ D ₁₆ N = 818.13) 3-22 m / z = 893.47 (C ₆₈ H ₃₁ D ₁₆ N = 894.23) 3-23 m / z = 1001.47 (C ₇₄ H ₃₁ D ₁₈ NS = 1002.38) 3-24 m / z = 933.50 (C ₇₁ H ₃₅ D ₁₆ N = 934.29) 4-3 m / z = 681.33 (C ₅₂ H ₃₁ D ₆ N = 681.91) 4-4 m / z = 721.36 (C ₅₅ H ₃₅ D ₆ N = 721.98)

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, a 2-TNATA film was vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm. Then, the compound 1-1 of the present invention was deposited on the hole injection layer to a thickness of 60 nm Vacuum vapor deposition was performed to form a hole transport layer. 4,4'-N, N'-dicarbazole-biphenyl (hereinafter abbreviated as "CBP") was used as a host on the hole transport layer and doped with Ir (ppy) ₃ as a dopant in a 90:10 weight ratio A light emitting layer was deposited to a thickness of 30 nm. Subsequently, BAlq was vacuum deposited as a hole blocking layer to a thickness of 10 nm, and Alq ₃ was formed to a thickness of 40 nm as an electron transporting layer. Then, LiF, an alkali metal halide serving as an electron injecting layer, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm as an anode to produce an organic electroluminescent device.

[ Example  2] to [ Example  46] Green organic electroluminescent device

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the compound of the present invention described in Table 4 was used instead of the compound 1-1 according to Example 1 of the present invention as the hole transport layer material.

[ Comparative Example  1] to [ Comparative Example  3]

The organic electroluminescence device was manufactured in the same manner as in Example 1 except that one of the comparative compounds 1 to 3 described in the following Table 4 was used instead of the compound 1-1 according to Example 1 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 6 21.6 5000 23.2 57.4 0.33 0.62 Comparative Example (2) Comparative compound 2 5.9 19.0 5000 26.3 67.6 0.32 0.62 Comparative Example (3) Comparative compound 3 5.8 18.2 5000 27.5 79.2 0.32 0.62 Example (1) Compound 1-1 5.7 10.5 5000 45.8 139.5 0.33 0.62 Example (2) Compound 1-3 5.5 10.4 5000 46.3 136.5 0.32 0.62 Example (3) Compound 1-4 5.7 11.8 5000 42.5 130.4 0.33 0.61 Example (4) Compound 1-5 5.7 11.5 5000 43.4 122.2 0.33 0.61 Example (5) Compound 1-6 5.7 11.7 5000 42.8 126.1 0.33 0.62 Example (6) Compound 1-7 5.6 11.0 5000 45.4 141.3 0.33 0.62 Example (7) Compound 1-13 5.7 12.4 5000 40.2 127.6 0.33 0.62 Example (8) Compound 1-14 5.7 12.3 5000 40.5 123.7 0.32 0.62 Example (9) Compound 1-15 5.6 12.6 5000 39.6 127 0.33 0.62 Example (10) Compound 1-17 5.6 12.6 5000 39.8 126.7 0.32 0.62 Example (11) Compound 1-20 5.5 12.5 5000 40 130.9 0.32 0.62 Example (12) Compound 1-21 5.5 12.8 5000 39.2 123.6 0.32 0.62 Example (13) Compound 1-24 5.7 13.3 5000 37.7 118.7 0.33 0.62 Example (14) Compound 1-25 5.6 11.3 5000 44.2 130.9 0.33 0.61 Example (15) Compound 1-30 5.7 12.5 5000 40.1 128.4 0.33 0.62 Example (16) Compound 1-38 5.6 12.7 5000 39.4 128.3 0.32 0.62 Example (17) Compound 1-45 5.7 10.6 5000 47.3 140.6 0.32 0.61 Example (18) Compound 1-46 5.7 11.1 5000 45.2 138.2 0.33 0.62 Example (19) Compound 2-1 5.6 12.9 5000 38.8 115.6 0.33 0.61 Example (20) Compound 2-3 5.7 13.3 5000 37.7 118.7 0.33 0.62 Example (21) Compound 2-4 5.6 15.2 5000 33 115.8 0.33 0.62 Example (22) Compound 2-10 5.5 14.6 5000 34.3 118.0 0.33 0.61 Example (23) Compound 2-13 5.7 13.4 5000 37.2 114.8 0.33 0.62 Example (24) Compound 2-14 5.7 14.5 5000 34.6 110.9 0.32 0.62 Example (25) Compound 2-15 5.6 15.2 5000 32.9 109.0 0.33 0.62 Example (26) Compound 2-16 5.7 15.2 5000 32.8 106.2 0.33 0.62 Example (27) Compound 2-17 5.6 15.2 5000 33 106.4 0.32 0.62 Example (28) Compound 2-18 5.5 16.7 5000 30 103.2 0.33 0.61 Example (29) Compound 2-24 5.7 13.2 5000 37.8 121.6 0.33 0.61 Example (30) Compound 2-29 5.7 15.4 5000 32.5 111.0 0.33 0.61 Example (31) Compound 2-31 5.7 14.2 5000 35.2 112.8 0.32 0.62 Example (32) Compound 3-1 5.5 9.4 5000 53.2 143.3 0.33 0.62 Example (33) Compound 3-4 5.7 10.8 5000 44.4 137 0.33 0.62 Example (34) Compound 3-5 5.7 11.0 5000 44.6 132.2 0.33 0.62 Example (35) Compound 3-6 5.7 11.0 5000 44.5 133.7 0.32 0.61 Example (36) Compound 3-8 5.7 10.5 5000 45.8 136.4 0.32 0.62 Example (37) Compound 3-9 5.6 10.1 5000 47.7 141.1 0.32 0.62 Example (38) Compound 3-10 5.6 10.5 5000 47.8 141.6 0.32 0.61 Example (39) Compound 3-13 5.5 10.8 5000 42.5 136.3 0.33 0.62 Example (40) Compound 3-14 5.7 11.6 5000 43.2 139.3 0.33 0.62 Example (41) Compound 3-17 5.6 11.1 5000 45.1 142.5 0.32 0.61 Example (42) Compound 3-18 5.7 11.3 5000 44.3 136.3 0.32 0.62 Example (43) Compound 3-21 5.7 10.8 5000 46.3 143.1 0.32 0.62 Example (44) Compound 3-24 5.6 12.2 5000 41.1 136.8 0.32 0.61 Example (45) Compound 4-3 5.6 11.9 5000 42 120.3 0.33 0.61 Example (46) Compound 4-4 5.7 12.6 5000 39.8 110.5 0.33 0.61

(1) When D (deuterium) is substituted for R ³ to R ⁸

As can be seen from the results of Table 4, it was confirmed that the organic electroluminescence device using the organic electroluminescent device material of the present invention as the hole transport layer exhibits a relatively high efficiency and a long lifetime.

In other words, Comparative Compound 2, which has a structure similar to that of the present invention, is superior to Comparative Compound 1 which is NPB in terms of driving voltage, efficiency, and lifetime, and has a general aryl group structure substituted with deuterium The comparative compound 3 exhibited a device result in which the efficiency and the lifetime were slightly increased.

Especially, when deuterium was substituted with fluorene and spirofluorene (Examples 1 to 46), it was confirmed that the efficiency and life span were maximized in the case where deuterium was substituted for the general aryl (Comparative Example 3).

The molecules are subjected to heat damage by the movement of electrons when the device is driven. In particular, structures containing fluorene and spirobifluorene are most likely to cause defects in Sp3 carbon, the most unstable site. Therefore, replacing the hydrogen of fluorene and spirobifluorene with deuterium increases the packing density, which shortens the intermolecular distance when fabricating the device. In addition, it decreases the degree of electrical polarization, and thus it is considered that the defects concentrated on Sp3 carbon are lowered and at the same time, the hole mobility and heat damage are reduced.

This suggests that the physical properties of the compound and the result of the device are significantly different as the compound of the present invention is substituted with deuterium.

The substitution of deuterium with deuterium suggests that the properties of the compound and the result of the device may be significantly different depending on the kind of the substituent substituted with deuterium.

(2) Comparison of substitution of D (deuterium) for R ¹ to R ²

When deuterium is substituted at the position of R ¹ to R ^2, the sites having Sp 3 carbon can be stabilized (Examples 45 and 46). In particular, when substituted with deuterium, the energy of the zero point energy, that is, the bottom state, is lowered. As the bond length of deuterium-carbon is shorter than the bond length of hydrogen-carbon, the molecular hardcore volume And thus, the electrical polarizability can be reduced. These characteristics can produce the effect of lowering the crystallinity of the thin film, that is, an amorphous state. The amorphous state reduces the grain boundaries through isotropic and homogeneous characteristics, That is, the hole mobility. Therefore, it is considered that the substitution of deuterium plays a very effective role in realizing the necessary amorphous state in order to improve OLED lifetime and driving characteristics.

This suggests that the substitution of deuterium results in a significant change in the physical properties and device results of the compound.

[ Example  47] 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 1-3 of the present invention was vacuum-deposited on the hole transport layer to a thickness of 20 nm to form a light-emission assisting 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  48] to [ Example  75] Blue organic electroluminescent device  ( The light- )

An organic electroluminescent device was fabricated in the same manner as in Example 47 except that the compound of the present invention described in Table 5 was used instead of the compound 1-3 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example  4]

An organic electroluminescent device was fabricated in the same manner as in Example 47 except that the luminescent auxiliary layer material was not used.

[ Comparative Example 5 ] To [ Comparative Example  6]

An organic electroluminescent device was fabricated in the same manner as in Example 47 except that one of the above-described Comparative Compounds 2 to 3 was used instead of the Compound 1-3 of the present invention as the luminescent auxiliary layer material

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 47 to 78 and Comparative Examples 4 to 6 of the present invention 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.

compound Driving voltage electric current
(mA / cm ² ) Luminance
(cd / m ² ) efficiency
(cd / A) T (95) CIE X Y Comparative Example (4) - 5.7 13.5 500 3.7 62.5 0.14 0.11 Comparative Example (5) Comparative compound 2 6.4 11.9 500 4.2 70.6 0.13 0.12 Comparative Example (6) Comparative compound 3 6.3 9.8 500 5.1 79.8 0.13 0.12 Example (47) Compound 1-3 6.1 7.2 500 6.9 112.3 0.13 0.11 Example (48) Compound 1-6 6.1 7.7 500 6.5 107.2 0.13 0.12 Example (49) Compound 1-13 6.1 8.0 500 6.2 101.1 0.14 0.11 Example (50) Compound 1-17 6.1 8.7 500 5.7 98.1 0.14 0.11 Example (51) Compound 1-23 6.2 7.7 500 6.5 103.3 0.14 0.11 Example (52) Compound 1-35 5.9 7.8 500 6.4 106.4 0.14 0.11 Example (53) Compound 1-41 6.0 7.5 500 6.7 104.4 0.14 0.12 Example (54) Compound 1-42 6.1 7.8 500 6.4 104.1 0.13 0.12 Example (55) Compound 1-45 5.9 7.0 500 7.1 113.8 0.13 0.12 Example (56) Compound 2-2 5.9 7.1 500 7.1 105.2 0.13 0.12 Example (57) Compound 2-5 6.0 7.2 500 7.0 102.5 0.13 0.12 Example (58) Compound 2-7 6.2 7.2 500 6.9 103.6 0.14 0.11 Example (59) Compound 2-9 6.0 7.3 500 6.8 97.7 0.13 0.11 Example (60) Compound 2-16 5.9 8.2 500 6.1 91.7 0.14 0.11 Example (61) Compound 2-22 6.0 7.7 500 6.5 97.5 0.13 0.12 Example (62) Compound 2-26 6.2 8.0 500 6.2 99.7 0.14 0.11 Example (63) Compound 2-30 6.0 7.8 500 6.4 95.0 0.14 0.11 Example (64) Compound 3-1 6.0 6.5 500 7.7 122.0 0.14 0.11 Example (65) Compound 3-8 6.0 6.3 500 8.0 121.1 0.14 0.12 Example (66) Compound 3-9 6.1 6.7 500 7.5 111.7 0.14 0.12 Example (67) Compound 3-13 5.9 7.3 500 6.9 110.5 0.13 0.12 Example (68) Compound 3-14 5.9 6.9 500 7.2 117.6 0.13 0.11 Example (69) Compound 3-15 6.2 6.9 500 7.3 119.0 0.13 0.12 Example (70) Compound 3-16 6.0 7.2 500 7.0 108.9 0.14 0.11 Example (71) Compound 3-17 5.9 6.9 500 7.3 117.1 0.13 0.11 Example (72) Compound 3-18 6.0 6.9 500 7.2 117.3 0.13 0.12 Example (73) Compound 3-19 6.0 7.1 500 7.0 117.5 0.14 0.11 Example (74) Compound 3-21 6.0 6.5 500 7.7 124.8 0.14 0.12 Example (75) Compound 3-22 6.0 6.6 500 7.6 118.2 0.13 0.12 Example (76) Compound 3-23 6.1 6.6 500 7.6 119.0 0.14 0.12 Example (77) Compound 3-24 6.0 6.9 500 7.2 112.2 0.13 0.12 Example (78) Compound 4-3 6.0 7.5 500 6.7 116.4 0.13 0.12

 As can be seen from the results of Table 5, it was confirmed that the use of the material for an organic electroluminescence device of the present invention as a light-emitting auxiliary layer remarkably improves the luminous efficiency and life span.

In other words, it was confirmed that the efficiency and lifetime were increased when the light-emitting auxiliary layer was used as the light-emitting auxiliary layer (Comparative Example 4). In Comparative Example 5 in which deuterium was not substituted and the general aryl group was substituted with deuterium The devices using the inventive compounds of the present invention in which deuterium was substituted with fluorene and spirofluorene rather than the compound of Comparative Example 6 (Examples 47 to 78) could further lower the driving voltage of the device, and the luminous efficiency and lifetime It was able to improve remarkably. This can be explained as having a high T1 energy level when the compound of the present invention is used alone as a light-emitting auxiliary layer, and improving the low voltage, high luminous efficiency and device lifetime of an organic electroluminescent device due to a deep HOMO energy level.

This is indicated by the substitution of deuterium for fluorene and spirofluorene as described in the results of Table 4, suggesting that the properties of the compound may vary significantly depending on the position at which deuterium is substituted even though it has a similar structure .

In addition, in the evaluation results of the above-described device fabrication, the device characteristics of applying the compound of the present invention to only one layer of the hole transporting layer and the light emitting auxiliary layer have been described. However, the compound of the present invention can be used by applying both the hole transporting layer and the light emitting supporting layer.

While the present invention has been described with reference to exemplary embodiments, 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 the same should be construed as being included in 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 (11)

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; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₃₀ carbon atoms; An alkynyl group of C ₂ to C ₃₀ ; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₆₀ ; And R &_lt; _b &gt;), wherein L 'is a single bond, an arylene group having ₆ to ₆₀ carbon atoms, a fluorenylene group having ₃ to ₆₀ carbon atoms, A fused ring group of an aliphatic ring of C ₆ to C ₆₀ aromatic rings, and a heterocyclic group of C ₂ to C ₆₀ ; and R _a and R _b are each independently selected from the group consisting of C ₆ to C ₆₀ aryl group; fluorene 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 O, N, S, Si and C containing at least one hetero atom of the P A heterocyclic group having ₂ to ₆₀ carbon atoms;
2) R ¹ and R ² are independently selected from: i) independently of one another hydrogen; heavy hydrogen; A C ₁ -C ₅₀ alkyl group; A C ₂ -C ₃₀ alkenyl group; A C ₂ -C ₃₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And an aryloxy group of C ₆ -C ₆₀ ; A C ₁ -C ₃₀ silyl group; An aryl group of C ₆ -C ₆₀ ; 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 fluorenyl group; And -L'-N (R _a ) (R _b ), or ii) R ¹ and R ² are bonded to each other to form a spiro compound together with the carbon or Si to which they are bonded And,
3) R ⁴ to R ⁸ are independently selected from: i) independently of each other hydrogen; heavy hydrogen; A C ₁ -C ₅₀ alkyl group; A C ₂ -C ₃₀ alkenyl group; A C ₂ -C ₃₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And an aryloxy group of C ₆ -C ₆₀ ; A C ₁ -C ₃₀ silyl group; An aryl group of C ₆ -C ₆₀ ; 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 fluorenyl group; And -L'-N (R _a) selected from the group consisting of (R _b), or, or ⅱ) of adjacent R ⁴ together, R ⁵ each other, R ⁶ together, R ⁷ to each other, at least one R ⁸ combine with each other to each other A ring can be formed,
4) At least one of R ¹ to R ⁸ must be substituted with deuterium,
5) L ¹ and L ² are single bonds; 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 a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring,
6) a and d are integers of 0 to 3, and b, c, e and f represent an integer of 0 to 4;
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.)}
2. The compound according to claim 1, wherein the formula (1) is represented by any one of the following formulas (2-1) to (2-3).

Wherein R ¹ to R ⁸ , a to f, L ¹ to L ² and Ar ¹ are the same as defined in claim 1, and D is deuterium.
The compound according to claim 1, wherein the formula (1) is represented by any one of the following formulas (3-1) to (3-4) and (4-1) to (4-4).

(Wherein R ¹ to R ⁸ , a to f, L ¹ to L ² , and Ar ¹ in the above Formulas 3-1 to 3-4 and 4-1 to 4-4 are the same as defined in Formula 1 of claim 1 .)
The compound of claim 1, wherein the compound represented by the formula (1) is represented by any one of the following formulas 1-1 to 1-48, 2-1 to 2-32, 3-1 to 3-28, and 4-1 to 4-4 A compound represented by any one of &lt; RTI ID = 0.0 &gt;

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 comprises the compound according to claim 1. 6. The method of claim 5,
Wherein the organic material layer is a hole transporting layer or a light emitting auxiliary layer. 6. The method of claim 5,
And a light efficiency improving 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. 6. The method of claim 5,
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. 6. The method of claim 5,
Wherein the organic compound layer is a mixture of the same or different compounds. A display device comprising the organic electroluminescent device of claim 5; And a control unit for driving the display device 11. The method of claim 10,
Wherein the organic electronic 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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