WO2017122988A1 - Compound for organic electric element, organic electric element using same, and electronic device thereof - Google Patents

Abstract

The present invention provides: a novel compound capable of improving the light-emitting efficiency, stability, and lifespan of an element; an organic electric element using same; and an electronic device thereof.

Description

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

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

The present invention relates to a hole injection layer, a hole transport layer, a light emitting auxiliary layer material having a low driving voltage characteristics and an organic electric element comprising the same. The flat panel display plays a very important role in supporting a highly visual information society, centered on the internet which is rapidly growing in recent years. In particular, organic electroluminescent devices (organic EL devices) capable of low voltage driving with self-luminous type have superior viewing angles and contrast ratios compared to liquid crystal displays (LCDs), which are mainstream flat panel displays, and require no backlight. Light weight and thinness are possible, and it has an advantage in terms of power consumption. In addition, the fast response speed and wide color reproduction range have attracted attention as a next generation display device. In general, an organic EL device is formed on a glass substrate in order of an anode made of a transparent electrode, an organic thin film including a light emitting region, and a metal electrode. In this case, 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 (electronjection layer) in addition to the emitting layer (EML). EIL), and may further include an electron blocking layer (EBL), a hole blocking layer (HBL), and an auxiliary light emitting layer due to 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, and the injected holes and electrons are recombined in the emission layer through the hole transport layer and the electron transport layer, respectively, to emit light excitons. To form. The light emitting excitation emits light as it transitions to ground states, in which a light emitting layer (guest) is doped into the light emitting layer (host) to increase the efficiency and stability of the light emitting state. In order to utilize the organic electronic device in various display media, the life of the device is important, and various studies are being conducted to increase the life of the organic electronic device. In particular, various studies have been conducted on organic materials inserted into a buffer layer such as a hole transporting layer or a light emitting auxiliary layer for excellent life characteristics of the organic electronic device. 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.

Delays penetration of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of the shortening of the life of the organic electric device, and stable properties for Joule heating generated when driving the device, that is, high glass transition temperature. There is a need for development of a hole injection layer and a hole transport layer material having a. In addition, the low glass transition temperature of the hole transport layer material has been reported to have a significant effect on the device life, depending on the characteristics of the uniformity of the surface of the thin film when driving the device. In addition, the deposition method is the mainstream in the formation of the OLED device, a situation that requires a material that can withstand a long time, that is, a material having a strong heat resistance characteristics. In particular, the major overcoming problem of the present organic light emitting device is the urgent need to overcome the problems of power consumption and lifespan as the panel size of mobile phones and tablet PCs is increased.

However, it is difficult to simultaneously overcome the driving voltage and the lifetime as the hole transport layer material. Most materials with high hole mobility have a planar structure rich in electrons. Examples are naphthyl, fluorene and phenanthrene. However, when the compound of the above structure is introduced into the hole transport material as a substituent, the hole mobility increases to a certain number and has a good effect on the lifetime, but the number of introduction into the molecule is required to reach the low voltage driving target required by the current industry. Increasingly, the driving voltage is lowered and the low voltage driving is possible, but the life characteristics are rapidly worsened. The reason for this is that in the case of a molecule in which electron-rich planar structures are excessively introduced, when a constant current is continuously supplied during device life evaluation, holes are trapped and stabilized between the plate structures, which lowers hole mobility and eventually causes As the driving voltage is increased to apply the current, the device life is drastically deteriorated. This is represented by the following formula.

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 is reduced due to the trap phenomenon, the value of θ decreases. Therefore, the driving voltage increases in the current-driven organic electroluminescent device which requires a constant current, which is very fatal for life. You can get results. Therefore, as described above, the introduction of a certain number of electron-rich plate structures capable of increasing hole mobility adversely affects the lifespan, so the possibility of using the same to lower the driving voltage is not great.

Therefore, in the present invention, in order to solve the above-mentioned problems of the prior art and to achieve the object of the present invention, by using a method of replacing deuterium in an appropriate ratio as a method for obtaining a high lifetime, a method having a high lifetime is proposed. .

Reference patent documents may include KR1020130076842 A.

An object of the present invention is to complete the low-voltage drive and high-life device by substituting deuterium in the amine compound substituted with fluorene in order to implement a low voltage drive and a high-life device required characteristics of the organic electrical device.

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

Formula (1)

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

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

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)

Compounds substituted with deuterium showed much thermodynamic behavior compared to unsubstituted compounds. Among these thermal properties, when the iridium compound is substituted with deuterium, the properties vary according to the difference in the bond lengths of carbon, hydrogen, carbon and deuterium, and the bond length of the deuterium compound is shorter than that of the compound not substituted with deuterium. It was confirmed that due to the weakening of the intermolecular van der Waals force generated by the can have a higher luminous efficiency.

In addition, when deuterium is substituted, the zero point energy, that is, the energy of the ground state is lowered, and as the bond length of deuterium-carbon is shorter than the bond length of hydrogen-carbon, the molecular hardcore volume is increased. It can be reduced, thereby reducing the electrical polarizability (Electropolar polarizability). In general, it was judged that it would be very effective to realize the necessary amorphous state in order to increase OLED lifetime and driving characteristics.

However, there have not been many studies on the method of lowering the driving voltage by increasing the deuterium, that is, increasing the mobility of the hole transport material, and in this study, various kinds of compounds are used to confirm such characteristics. Thus, many experiments were conducted. In addition, when the film is formed of a compound substituted with deuterium, the film is formed in an amorphous glass state that can greatly affect the hole mobility of the thin film, and the amorphous glass state is isotropic and homogeneous (Homogeneous). By reducing the grain boundary through the () characteristic, it was confirmed that the flow of charge, that is, the hole mobility, can be increased.

In more detail, the amine compound substituted with fluorene has a disadvantage in that the lifetime is reduced. However, the prior art has not proved the effect of the improvement on this part, and in particular, the prior art which has improved the life characteristics by deuterium substitution at a specific position has not been reported yet.

As a result of the research and development of these inventors, the present invention provides an amine compound including a fluorene-based compound substituted with deuterium so as to meet the requirements of the organic material while maintaining the excellent properties of the organic material layers of the aforementioned organic electric device.

Hereinafter, with reference to the embodiment of the present invention will be described in detail. In describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

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

As used in this specification and the appended claims, unless otherwise indicated, the meanings of the following terms are as follows:

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

As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, unless otherwise indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.

As used herein, the term "haloalkyl group" or "halogenalkyl group" means an alkyl group substituted with halogen unless otherwise specified.

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

As used herein, the terms "alkenyl group", "alkenyl group" or "alkynyl group" have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise stated, and include straight or branched chain groups. It is not limited to this.

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

As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" means an alkyl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 1 to 60, and is limited herein. It is not.

As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.

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

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirofluorene group.

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

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

As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.

As used herein, the term “heterocyclic group” includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.

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

"Heterocyclic groups" may also include rings comprising SO ₂ instead of carbon forming the ring. For example, a "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 the "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise stated, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof. Saturated or unsaturated rings.

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

Unless otherwise stated, the term "carbonyl" used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise specified, the term "ether" as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" as used herein refers to deuterium, halogen, amino, nitrile, nitro, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ arylthiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C 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 Group, germanium group, and C ₂ ~ C _{20 It} is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.

In addition, unless otherwise specified, the formulas used in the present invention apply in the same manner as the substituent definitions by the exponential definition of the following formula.

Herein, when a is an integer of 0, the substituent R ¹ is absent, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 Are each bonded as follows, where R ¹ may be the same or different from each other, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bonded to the carbon forming the benzene ring Is omitted.

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

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

            Formula (1)

{In the above formula (1),

1) Ar ¹ is C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; An alkenyl group of C ₂ to C ₃₀ ; Alkynyl groups of C ₂ to C ₃₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₆₀ aryloxy group; And -L'-N (R _a ) (R _b );

2) R ¹ and R ² are a) independently of each other hydrogen; heavy hydrogen; C ₁ -C ₅₀ alkyl group; C ₂ -C ₃₀ alkenyl group; C ₂ -C ₃₀ alkynyl group; An alkoxyl group of C ₁ -C ₃₀ ; And an aryloxy group of C ₆ -C ₆₀ ; C ₁ -C ₃₀ silyl group; C ₆ -C ₆₀ aryl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; And fluorenyl group; or b) R ¹ and R ² may be bonded to each other to form a spiro compound together with carbon or Si to which they are bonded.

3) R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are a) independently of each other, hydrogen; heavy hydrogen; C ₁ -C ₅₀ alkyl group; C ₂ -C ₃₀ alkenyl group; C ₂ -C ₃₀ alkynyl group; An alkoxyl group of C ₁ -C ₃₀ ; And an aryloxy group of C ₆ -C ₆₀ ; C ₁ -C ₃₀ silyl group; C ₆ -C ₆₀ aryl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl group; And -L'-N (R _a ) (R _b ), or b) adjacent R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ combine with each other and at least one Can form a ring,

4) ^{where, R 1, R 2, R} 3, R 4, R 5, R 6, R 7 and R ⁸ must be of more than one is to be replaced by deuterium,

5) L ¹ and L ² are each independently a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene groups; And a C ₂ -C ₆₀ heteroarylene group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P; Fused ring group of an aromatic ring of C ₃ -C ₆₀ aliphatic ring with C ₆ -C _60; is selected from the group consisting of any one,

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

7) L 'is a C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And C ₂ ~ C ₆₀ Heterocyclic group; It is selected from the group consisting of, R _a and R _b are independently of each other C ₆ ~ C ₆₀ An aryl group; Fluorenyl group; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P.

Wherein the aryl group, heteroarylene group, fluorenyl group, arylene group, heterocyclic group, fused ring group, and fluorenylene group are each deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; a nitro _{group; -L'-N (R a)} (R b); C 1 ~ C ₂₀ of the import alkylthio; alkyl group of _{C 1 ~ C 20;; C} 1 ~ C 20 alkoxy group of C ₂ ~ C ₂₀ of alkenyl; C ₂ ~ C ₂₀ alkynyl of; an aryl group of a C ₆ ~ C ₂₀ substituted with heavy hydrogen;; C ₆ ~ C ₂₀ aryl group, a fluorenyl group; a heterocyclic group of C ₂ ~ C _20; C ₃ A cycloalkyl group of -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group and C ₈ -C ₂₀ arylalkenyl group may be further substituted with one or more substituents, and these substituents may be bonded to each other to form a ring In this case, the 'ring' may be an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, or a hetero ring having 2 to 60 carbon atoms, or Fused ring consisting of a combination of these, including saturated or unsaturated rings.)}

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

(In Chemical Formulas 2-1 to 2-3, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^８ , a, b, c, d, e, f, L ¹ , L ² , Ar ¹ is the same as defined in Formula 1, D means deuterium.)

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

(In Chemical Formulas 3-1 to 3-4, 4-1 to 4-4, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^８ , a, b, c, d, e, f, L ¹ , L ² , Ar ¹ is the same as defined in Formula 1)

In the present invention, the compound of formula (1) comprises the following compound and provides such a compound.

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

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

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

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

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

Accordingly, the present invention includes a first electrode; Second electrode; And an organic material layer positioned between the first electrode and the second electrode, wherein the organic material layer contains a compound included in Chemical Formula (1).

The present invention may further include an optical efficiency improvement layer formed on at least one of one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer. It provides an organic electric device.

In the present invention, 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, the organic layer is an electron transport material containing the compound It provides an organic electric element, characterized in that.

As another specific example, the present invention provides an organic electric device, characterized in that the same or different compounds of the compound represented by the formula (1) are mixed and used in the organic material layer.

In another aspect, the present invention provides a hole transport layer or light emitting auxiliary layer composition comprising a compound represented by the formula (1), and provides an organic electric device comprising the hole transport layer or light emitting auxiliary layer.

In another aspect, the present invention is a display device comprising the above-mentioned organic electric element; And a controller for driving the display device.

In another aspect, the organic electronic device provides an electronic device according to the present invention, wherein the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a monochromatic or white illumination device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the synthesis examples of the compound represented by the general formula (1) of the present invention and the production examples of the organic electric device of the present invention will be described in detail with reference to Examples, but are not limited to the following Examples of the present invention. .

[ Synthesis Example ]

Compounds (final products) according to the present invention is prepared by the reaction of Sub 1 and Sub 2, as shown in Scheme 1.

<Scheme 1>

X ¹ = Br, Cl, I

Synthesis Example of Sub 1

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

If L is not a single bond

X ² = Cl, Br, I

Synthesis Example of Sub 1-I

Sub 1-I of Scheme 1 may be synthesized by, but are not limited to, reaction Schemes of Schemes 3 and 4.

Scheme 3 X ² = Cl, Br, I

<Scheme 4>

Sub 1-I-1 Synthesis 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 (363ml), the temperature of the reaction was lowered to -78 ℃, n-BuLi (2.44g, 64.06mmol) was slowly added dropwise and the reaction was stirred at room temperature for 4 hours. After completion of the reaction, the reaction mixture was poured into H ₂ O, quenched, water was removed, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 11.93 g of the product. (Yield 86%)

2) Synthesis of Sub 1-I-1

Add HCl and Acetic acid (61ml) to Sub 1-I-I-1 (11.7g, 30.63mmol) and stir at 80 ° C for 1 hour. When the reaction was terminated, after filtration under reduced pressure, the organic solvent was concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 10.23g of product. (Yield 92%)

Sub 1-I-2 Synthesis Example

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

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

2) Synthesis of Sub 1-I-2

Sub 1-I-I-2 (12 g, 31.42 mmol), HCl and Acetic acid (63 ml) were obtained by using the synthesis method of Sub 1-I-1 to obtain 10.03 g of the product. (Yield 88%)

Sub 1-11 Synthesis Example

1) Sub 1-II-1 Synthesis

Sub 1-I-1 (9.50g, 26.18mmol) was dissolved in DMF (165ml) in a round bottom flask, then Bis (pinacolato) diboron (7.31g, 28.79mmol), Pd (dppf) Cl ₂ (0.57g, 0.79mmol), KOAc (7.71 g, 28.79 mmol) was added and stirred at 90 ° C. After the reaction was completed, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was silicagel column and recrystallized to obtain 9.16 g of the product. (Yield 77%)

2) Sub 1-11 Synthesis

Sub 1-II-1 (11.39g, 25.07mmol) and 3-bromo-3'-iodo-1,1'-biphenyl (9g, 25.07mmol) and tetrakis (triphenylphophine) palladium (0) (0.87g, 0.75mmol ) And K ₂ CO ₃ (10.39g, 75.21mmol), add THF (162ml) and water (81ml) and stir at 70 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ , washed with water, a small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was recrystallized with CH ₂ Cl ₂ and hexane solvent. 10.10 g of product was obtained. (Yield 72%)

Sub 1-13 Synthesis Example

1) Sub 1-13 Synthesis

Sub 1-II-1 (10.02g, 22.05mmol), 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (8.80g, 22.05mmol), tetrakis (triphenylphophine) palladium (0) (0.76g , 0.66 mmol), K ₂ CO ₃ (9.14 g, 66.15 mmol), THF (97 ml) and water (49 ml) were obtained using the synthesis method of Sub 1-11 to obtain 10.05 g of the product. (Yield 76%)

Sub 1-21 Synthesis 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 (0.69g, 0.94mmol), KOAc (9.23 g, 94.06 mmol) was obtained in 12.07 g of the product using the Sub 1-II-1 synthesis method. (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 synthesis method of Sub 1-11, to obtain 10 g of the product. (Yield 80%)

Sub 1-26 Synthesis Example

Sub 1-II-2 (g, mmol), 3-bromo-7-iododibenzo [b, d] thiophene (9.30g, 23.90mmol), tetrakis (triphenylphophine) palladium (0) (0.83g, 0.72mmol), K ₂ CO ₃ (9.91 g, 71.71 mmol), THF (105 ml), and water (53 ml) were obtained using the synthesis method of Sub 1-11 to obtain 10.08 g of the product. (Yield 73%)

Sub 1-28 Synthesis Example

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

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

2) Synthesis of Sub 1-28

Sub 1-I-I-3 (17.8 g, 41.69 mmol), HCl, Acetic acid (83 ml) was obtained by using the synthesis method of Sub 1-I-1, to obtain 10.06 g of the product. (Yield 59%)

Sub 1-32 Synthesis 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 (14.9g, 39.55mmol), M 1-1 (7.45g, 39.55 mmol), THF (396 ml) and 13.81 g of the product were obtained using the synthesis method of Sub 1-II-1. (Yield 72%)

2) Synthesis of Sub 1-32

Sub 1-I-I-4 (13.6 g, 28.04 mmol), HCl, Acetic acid (56 ml) were obtained by using the synthesis method of Sub 1-I-1, to obtain 10.08 g of the product. (Yield 77%)

[Note: Synthesis of M 1]

M 1 according to the present invention may be synthesized by, but are not limited to, reaction schemes of Schemes 5 and 6.

Scheme 5

<Scheme 6>

An example of Sub 1 is as follows, but is not limited thereto.

compound FD-MS compound FD-MS Sub1-1 m / z = 358.14 (C ₂₅ H ₇ D ₈ Cl = 358.89) Sub1-3 _{m / z = 362.16 (C 25} H 3 D 12 Cl = 362.92) Sub1-4 _{m / z = 362.16 (C 25} H 3 D 12 Cl = 362.92) Sub1-6 m / z = 482.14 (C ₃₁ H ₇ D ₁₂ Br = 483.47) Sub1-11 m / z = 558.17 (C ₃₇ H ₁₁ D ₁₂ Br = 559.57) Sub1-13 m / z = 598.20 (C ₄₀ H ₁₅ D ₁₂ Br = 599.63) Sub1-14 m / z = 598.20 (C ₄₀ H ₁₅ D ₁₂ Br = 599.63) Sub1-16 m / z = 350.09 (C ₂₅ H ₁₅ Cl = 350.85) Sub1-18 m / z = 350.09 (C ₂₅ H ₁₅ Cl = 350.85) Sub1-20 m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40) Sub1-21 m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40) Sub1-26 m / z = 576.05 (C ₃₇ H ₂₁ BrS = 577.54) Sub1-28 m / z = 408.15 (C ₂₉ H ₉ D ₈ Cl = 408.95) Sub1-31 m / z = 458.17 (C ₃₃ H ₁₁ D ₈ Cl = 459.01) Sub1-32 m / z = 466.22 (C ₃₃ H ₃ D ₁₆ Cl = 467.06)

Synthesis Example of Sub 2

Sub 2 of Scheme 1 may be synthesized by the routes of Scheme 7 and Scheme 8, but is not limited thereto.

Scheme 7

Scheme 8 Hal = Br, I, Cl

Synthesis Example of Sub 2-I

Refer to the synthesis method of M 1 in Scheme 5 and Scheme 6 (R ⁷ ) _e- > (R ⁵ ) _c , (R ⁸ ) _f- > (R ⁶ ) _f

(If R ¹ , R ² are curled, see Schemes 3-4.)

Hal ² = Br, Cl

Synthesis of Sub 2-9

[1,1'-biphenyl] -4-amine (6.20g, 36.61mmol), Sub 2-I-1 (10.00g, 36.61mmol), Pd ₂ (dba) ₃ (1.01g, 1.10mmol) ), P (t-Bu) ₃ (0.59g, 2.93mmol), NaOt-Bu (10.55g, 109.82mmol) and toluene (384ml) were added and the reaction proceeds at 100 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to give the product 10.85 g (yield: 82%).

Synthesis of Sub 2-16

1) Sub 2-II-1 Synthesis

ammonia (0.43g, 25.17mmol), Sub 2-I-2 (10.00g, 25.17mmol), Pd ₂ (dba) ₃ (0.69g, 0.76mmol), P (t-Bu) ₃ (0.41g, 2.01mmol ), NaOt-Bu (7.26 g, 75.51 mmol) and toluene (264 ml) were obtained using the synthesis method of Sub 2-9 to obtain 6.80 g (yield: 81%) of the product.

2) Sub 2-16 Synthesis

Sub 2-II-1 (6.73 g, 20.17 mmol), 3-bromo-9-phenyl-9H-carbazole (6.50 g, 20.17 mmol), Pd ₂ (dba) ₃ (0.55 g, 0.61 mmol), P (t -Bu) ₃ (0.33 g, 1.61 mmol), NaOt-Bu (5.82 g, 60.52 mmol) and toluene (212 ml) were obtained using the synthesis method of Sub 2-9, to obtain 10.09 g (yield: 87%) of the product. .

Synthesis of Sub 2-17

ammonia (0.30g, 17.39mmol), Sub 2-I-1 (9.50g, 34.78mmol), Pd ₂ (dba) ₃ (1.91g, 2.09mmol), P (t-Bu) ₃ (1.13g, 5.56mmol ), NaOt-Bu (13.37 g, 139.11 mmol) and toluene (365 ml) were obtained using the synthesis method of Sub 2-9, to obtain 10.19 g (yield: 73%) of the product.

Synthesis of Sub 2-24

1) Sub 2-II-2 Synthesis

ammonia (0.78g, 45.76mmol), Sub 2-I-1 (12.50g, 45.76mmol), Pd ₂ (dba) ₃ (1.26g, 1.37mmol), P (t-Bu) ₃ (0.74g, 3.66mmol ), NaOt-Bu (13.19 g, 137.28 mmol) and toluene (480 ml) were obtained using 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 ) ₃ (0.54 g, 2.64 mmol), NaOt-Bu (9.53 g, 99.18 mmol) and toluene (347 ml) were obtained using the synthesis method of Sub 2-9, to obtain 10.10 g (yield: 78%) of the product.

Synthesis of Sub 2-32

naphthalen-2-amine (4.22g, 29.49mmol), Sub 2-I-3 (10.30g, 29.49mmol), Pd ₂ (dba) ₃ (0.81g, 0.88mmol), P (t-Bu) ₃ (0.48 g, 2.36 mmol), NaOt-Bu (8.50 g, 88.47 mmol) and toluene (310 ml) were obtained using 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) After dissolving in THF (336ml), the temperature of the reaction was lowered to -78 ℃, n-BuLi (2.26g, 35.32mmol) was slowly added dropwise and the reaction was stirred at room temperature for 4 hours. After completion of the reaction, the reaction mixture was poured into H ₂ O, quenched, water was removed, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 10.40 g of the product. (Yield 82%)

2) Synthesis of Sub 2-I-4

Add HCl and Acetic acid (53ml) to Sub 1-I-I-5 (10g, 26.53mmol) and stir at 80 ° C for 1 hour. When the reaction was terminated, after filtration under reduced pressure, the organic solvent was concentrated and the resulting organic substance was purified by silicagel column and recrystallized to obtain 8.09 g of the product. (Yield 85%)

3) Sub 2-46 Synthesis

4- (9,9-diphenyl-9H-fluoren-3-yl) aniline (7.87g, 19.23mmol), Sub 2-I-4 (6.90g, 19.23mmol), Pd ₂ (dba) ₃ (0.53g, 0.58 mmol), P (t-Bu) ₃ (0.31 g, 1.54 mmol), NaOt-Bu (5.54 g, 57.68 mmol) and toluene (202 ml) were prepared using 10.13 g (10 g) of the product using the synthesis method of Sub 2-9 above. Yield: 72%).

Synthesis of Sub 2-49

1) M 2-I-5 Synthesis

M 1-2 (11.00 g, 50.30 mmol) obtained in the above synthesis was dissolved in ethylene glycol (201 mL), followed by Hydrazine monohydrate (75.55 g, 1509.12 mmol), KOH. (7.06 g, 125.76 mmol) was added, followed by stirring at 185 ° C. When the reaction was completed, the reaction mixture was lowered to 0 ° C., water was added thereto, and the precipitated solid was filtered and washed with a small amount of water. It was dissolved in CH ₂ Cl ₂ again, dried over MgSO ₄ , concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 9.78 g of the product. (Yield 95%)

2) M 2-1 Synthesis

In a round bottom flask, M 2-I-5 (9.50 g, 46.41 mmol), KOt-Bu (15.62 g, 139.23 mmol) and DMSO (302 ml) obtained in the above synthesis were dissolved, stirred at 0 ° C. for 5 minutes, and cooled to room temperature. Raised and added iodomethane (19.76 g, 139.23 mmol). After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to obtain 9.72g of the product. (Yield 90%)

3) Sub 2-II-3 Synthesis

ammonia (0.70 g, 41.25 mmol), M 2-1 (9.60 g, 41.25 mmol), Pd ₂ (dba) ₃ (1.13 g, 1.24 mmol), P (t-Bu) ₃ (0.67 g, 3.30 mmol), 6.25 g (yield: 71%) of NaOt-Bu (11.89 g, 123.74 mmol) and toluene (433 ml) were obtained using the synthesis method of Sub 2-9.

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 ( 0.80g, 0.87mmol), P (t-Bu) ₃ (0.47g, 2.33mmol), NaOt-Bu (8.39g, 87.31mmol), toluene (306ml) using the synthesis method of Sub 2-9 10.00 g (yield: 66%) were obtained.

Synthesis of Sub 2-53

1) M 2-I-6 Synthesis

M 1-3 (11.00 g, 50.30 mmol) obtained in the above synthesis was dissolved in ethylene glycol (201 mL), followed by Hydrazine monohydrate (75.55 g, 1509.12 mmol), KOH. (7.06 g, 125.76 mmol) was added, followed by stirring at 185 ° C. After the reaction was completed, the reaction mixture was lowered to 0 ° C., water was added thereto, and the precipitated solid was filtered and washed with a small amount of water. Dissolved in CH ₂ Cl ₂ again, dried over MgSO ₄ , concentrated, and the resulting compound was silicagel column and recrystallized to give the product 9.58g. (Yield 93%)

2) M 2-2 Synthesis

M 2-I-6 (5.90 g, 28.82 mmol), KOt-Bu (9.70 g, 86.47 mmol), DMSO (187 ml) and iodobenzene (17.64 g, 86.47 mmol) were synthesized using the synthesis method of M 2-1. 9.05 g of 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 (0.41 g, 2.02 mmol), NaOt-Bu (7.27 g, 75.65 mmol) and toluene (265 ml) were obtained using the synthesis method of Sub 2-9, to obtain 10.07 g (yield: 69%) of the product.

Synthesis of Sub 2-57

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

Synthesis of Sub 2-61

4- (naphthalen-2-yl) aniline (6.12g, 27.93mmol), M 2-1 (6.50g, 27.93mmol), Pd ₂ (dba) ₃ (0.77g, 0.84mmol), P (t-Bu) ₃ (0.45 g, 2.23 mmol), NaOt-Bu (8.05 g, 83.78 mmol), and toluene (293 ml) were obtained using the synthesis method of Sub 2-9, to obtain 10.02 g (yield: 73%) of the product.

Synthesis of Sub 2-65

1) M 2-I-7 Synthesis

M 1-4 (13.30g, 60.82mmol), Ethylene glycol (243mL), Hydrazine monohydrate (91.34g, 1824.67mmol), KOH obtained in the above synthesis (8.53 g, 152.06 mmol) was obtained using the synthesis method of M 2-I-6 to obtain 11.20 g of the product. (Yield 90%)

2) M 2-3 synthetic

M 2-I-7 (11g, 53.74mmol), KOt-Bu (18.09g, 161.22mmol), DMSO (349ml), iodomethane (22.88g, 161.22mmol) using the M 1-1 synthesis method to product 11.13 g was obtained. (Yield 89%)

3) M 3-1 Synthesis

M 2-3 (10.80g, 46.40mmol) was dissolved in DMF (292ml) in a round bottom flask, then Bis (pinacolato) diboron (12.96g, 51.04mmol), Pd (dppf) Cl ₂ (1.02g, 1.39mmol), KOAc (13.66 g, 139.21 mmol) was added and stirred at 90 ° C. After the reaction was completed, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was silicagel column and recrystallized to give 12.04g of the product. (Yield 80%)

4) Sub 2-II-5 Synthesis

M 3-1 (11.92g, 36.76mmol) and 3-bromo-7-iododibenzo [b, d] thiophene (36.76g, 36.76mmol) and tetrakis (triphenylphophine) palladium (0) (0.64g, 0.55mmol) and K ₂ CO ₃ (7.62g, 55.13mmol) was added thereto, THF (162ml) and water (81ml) were added thereto, and the mixture was stirred at 70 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ , washed with water, a small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was recrystallized with CH ₂ Cl ₂ and hexane solvent. 12.16 g of 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 using the synthesis method of Sub 2-9 to obtain 9.98 g (yield: 81%) of the product.

An example of Sub 2 is as follows, but is not limited thereto.

<FD-MS of Sub 2>

compound FD-MS compound FD-MS Sub2-5 m / z = 361.18 (C ₂₇ H ₂₃ N = 361.49) Sub2-8 m / z = 286.15 (C ₂₀ H ₁₈ N ₂ = 286.38) Sub2-9 m / z = 361.18 (C ₂₇ H ₂₃ N = 361.49) Sub2-16 m / z = 574.24 (C ₄₃ H ₃₀ N ₂ = 574.73) Sub2-17 m / z = 401.21 (C ₃₀ H ₂₇ N = 401.55) Sub2-24 m / z = 391.14 (C ₂₇ H ₂₁ NS = 391.53) Sub2-31 m / z = 455.22 (C ₃₃ H ₂₁ D ₄ NO = 455.59) Sub2-32 m / z = 411.20 (C ₃₁ H ₂₅ N = 411.55) Sub2-33 m / z = 415.22 (C ₃₁ H ₂₁ D ₄ N = 415.57) Sub2-40 m / z = 415.22 (C ₃₁ H ₂₁ D ₄ N = 415.57) Sub2-41 m / z = 405.24 (C ₃₀ H ₂₃ D ₄ N = 405.58) Sub2-46 m / z = 731.34 (C ₅₆ H ₂₉ D ₈ N = 731.97) Sub2-49 m / z = 520.26 (C ₃₆ H ₂₄ D ₄ N ₄ = 520.67) Sub2-53 m / z = 578.27 (C ₄₃ H ₂₆ D ₄ N ₂ = 578.75) Sub2-57 m / z = 379.19 (C ₂₇ H ₁₇ D ₄ NO = 379.50) Sub2-60 m / z = 493.27 (C ₃₇ H ₂₃ D ₆ N = 493.68) Sub2-61 m / z = 491.26 (C ₃₇ H ₂₅ D ₄ N = 491.67) Sub2-65 m / z = 471.20 (C ₃₃ H ₂₁ D ₄ NS = 471.65) Sub2-74 m / z = 339.19 (C ₂₅ H ₁₇ D ₄ N = 339.47) Sub2-78 m / z = 367.22 (C ₂₇ H ₁₇ D ₆ N = 367.52)

Synthesis of Final Products

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

Synthesis Example of 1-4

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 then Sub 2-17 (4.43 g, 11.02 mmol), Pd ₂ (dba) ₃ (0.30 g, 0.33 mmol), P ( t- Bu) ₃ (0.18 g, 0.88 mmol), NaO t -Bu (3.18 g, 33.07 mmol) were added and stirred at 100 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 6.66g (yield: 83%).

Synthesis Example of 1-13

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

Synthesis Example of 1-18

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 ) obtained in the above synthesis 6.68 g (yield: 81%) of -Bu) ₃ (0.15 g, 0.76 mmol) and NaO t -Bu (2.73 g, 28.41 mmol) were obtained using the synthesis method in Sub 1-4.

Synthesis Example of 1-24

Sub 1-3 obtained in the synthesis (3.50 g, 9.64 mmol), toluene (101 ml), Sub 2-16 (5.54 g, 9.64 mmol), Pd ₂ (dba) ₃ (0.26 g, 0.29 mmol), P ( t 6.69 g (yield: 77%) of -Bu) ₃ (0.16 g, 0.77 mmol) and NaO t -Bu (2.78 g, 28.93 mmol) were obtained using the synthesis method in Sub 1-4.

Synthesis Example of 1-45

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) 6.71 g (yield: 85%) of -Bu) ₃ (0.17 g, 0.86 mmol) and NaO t -Bu (3.10 g, 32.28 mmol) were obtained using the synthesis method of Sub 1-4.

Synthesis Example of 1-48

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

Synthesis Example of 2-15

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

Synthesis Example of 2-20

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 ) obtained in the above synthesis -Bu) ₃ (0.15 g, 0.72 mmol) and NaO t -Bu (2.60 g, 27.01 mmol) were obtained using the synthesis method of Sub 1-4 to give 6.51 g (yield: 73%) of product.

Synthesis 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 obtained by using the synthesis method of Sub 1-4, to yield 6.72 g (yield: 80%) of the product.

Synthesis 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 (0.15 g, 0.75 mmol) and NaO t -Bu (2.71 g, 28.22 mmol) were obtained using the synthesis method of Sub 1-4 to obtain 6.69 g (yield: 68%) of the product.

Synthesis Example of 2-31

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

Synthesis Example of 3-4

Sub 1-3 obtained in the above synthesis (3.90 g, 10.75 mmol), toluene (113 ml), Sub 2-41 (4.36 g, 10.75 mmol), Pd ₂ (dba) ₃ (0.30 g, 0.32 mmol), P ( t 6.53 g (yield: 83%) of -Bu) ₃ (0.17 g, 0.86 mmol) and NaO t -Bu (3.10 g, 32.24 mmol) were obtained using the synthesis method of Sub 1-4.

Synthesis Example of 3-15

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 ) obtained in the above synthesis _{-Bu) 3 (0.17g, 0.86mmol)} , NaO t -Bu (3.10g, 32.24mmol) the use the synthesis method of the Sub 1-4 6.56g (yield product: yield 78%).

Synthesis Example of 3-24

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

Synthesis Example of 4-3

Sub 1-16 (4 g, 11.40 mmol), toluene (120 ml), Sub 2-78 (4.19 g, 11.40 mmol), Pd ₂ (dba) ₃ (0.31 g, 0.34 mmol), P ( t− ) obtained in the above synthesis. Bu) ₃ (0.18 g, 0.91 mmol) and NaO t -Bu (3.29 g, 34.20 mmol) were obtained using 6.69 g (yield: 86%) of the product using the synthesis method of Sub 1-4.

<FD-MS by Final Products>

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)

Manufacturing Evaluation of Organic Electrical Device

[ Example  One] Green Organic Light Emitting Diode  ( Hole transport layer )

An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention as a hole transport material. First, a 2-TNATA film is vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm, and then Compound 1-1 of the present invention is 60 nm thick on the hole injection layer. Vacuum 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 dopant was doped with Ir (ppy) ₃ in a 90:10 weight ratio. A light emitting layer was deposited to a thickness of 30 nm. Subsequently, BAlq was vacuum deposited to a thickness of 10 nm using a hole blocking layer, and Alq ₃ was formed to a thickness of 40 nm using an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to use an organic light emitting diode.

[ Example  2] to [ Example  46] Green Organic Light Emitting Diode

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

[ Comparative example  1] to [ Comparative example  3]

An organic electroluminescent device in the same manner as in Example 1, except that one of Comparative Compounds 1 to 3 shown in Table 4 was used instead of Compound 1-1 according to Example 1 of the present invention as a hole transport layer material. Was prepared.

compound Driving voltage 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 electroluminescent device using the organic electroluminescent device material of the present invention as a hole transport layer exhibits a relatively high efficiency and a high lifetime.

In other words, Comparative Compound 2, which has a structure similar to that of the present invention, compared to NPB Comparative Compound 1, showed better device results in terms of driving voltage, efficiency, and lifetime, and has a general aryl group structure substituted with deuterium than Comparative Compound 2. Comparative Compound 3 shows a device result with a slight increase in efficiency and lifetime.

In particular, when deuterium is substituted with fluorene and spirofluorene (Examples 1 to 46), it was confirmed that efficiency and lifetime are maximized than when deuterium is substituted for general aryl (Comparative Example 3).

Molecules are subject to heat damage due to the movement of electrons during device driving. In particular, structures containing fluorene and spirofluorene are likely to cause defects in the most unstable site, Sp3 carbon. Therefore, the substitution of hydrogen of fluorene and spirofluorene with deuterium increases the packing density, thereby shortening the intermolecular distance during device fabrication. In addition, since the degree of electrical polarization is reduced, the defects concentrated on Sp3 carbon are reduced, and high hole mobility and heat damage are also reduced.

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

Even though they have a similar structure, it is suggested that as the deuterium is substituted, the properties / characteristics of the compound and the results of the device may vary significantly depending on the type of the substituent substituted with deuterium.

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

When deuterium is substituted at the positions of R ¹ to R ² (Examples 45 and 46), sites having Sp 3 carbons can be stabilized. In particular, when deuterium is substituted, zero point energy (ie, zero point energy) is lowered, and as the bond length of deuterium-carbon is shorter than the bond length of hydrogen-carbon, the molecular core volume is increased. Can be reduced, thereby reducing the electrical polarizability. This property can reduce the crystallinity of the thin film, i.e., create an amorphous state, which reduces the grain boundary through isotropic and homogeneous properties, thereby reducing the charge. It was confirmed that the flow of ie, the hole mobility can be increased quickly. Therefore, deuterium substitution seems to play a very effective role in realizing the amorphous state which is essential to increase OLED lifetime and driving characteristics.

This suggests that the physical properties of the compound and the results of the device are significantly changed as it is substituted with deuterium.

[ Example  47] Blue organic electroluminescent device  ( Luminous auxiliary layer )

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, a hole injection layer is formed by vacuum depositing 2-TNATA with a thickness of 60 nm on an ITO layer (anode) formed on a glass substrate, and then a hole transport layer is formed by vacuum depositing NPB with a thickness of 60 nm on the hole injection layer. It was. Subsequently, compound 1-3 of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emitting auxiliary layer, and then 9,10-Di (2-naphthyl) anthracene (hereinafter referred to as a light emitting auxiliary layer). Abbreviation “ADN”) is used as a host material, and BD-052X (manufactured by Idemitsu kosan) is used as a dopant material, and is doped at a weight ratio of 93: 7 to form a light emitting layer by vacuum deposition to a thickness of 30 nm. Subsequently, a hole blocking layer was formed by vacuum depositing BAlq to a thickness of 10 nm on the light emitting layer, and an electron transport layer was formed by vacuum depositing Alq ₃ to a thickness of 40 nm on the hole blocking layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[ Example  48] to [ Example  75] Blue organic electroluminescent device  ( Luminous auxiliary layer )

An organic electroluminescent device was manufactured in the same manner as in Example 47, except for using the compound of the present invention shown in Table 5 below instead of the compound 1-3 of the present invention as a light-emitting auxiliary layer material.

[ Comparative example  4]

An organic electroluminescent device was manufactured in the same manner as in Example 47, except that the light emitting auxiliary layer material was not used.

[ Comparative Example 5 ] To [ Comparative example  6]

An organic electroluminescent device was manufactured in the same manner as in Example 47, except that one of Comparative Compounds 2 to 3 was used instead of Compound 1-3 of the present invention as a light-emitting auxiliary layer material.

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared according to Examples 47 to 78 and Comparative Examples 4 to 6 of the present invention The T95 life was measured using a life measurement device manufactured by McScience Inc. at a luminance of 500 cd / m ² , and the measurement results are shown in Table 5 below.

compound Driving voltage 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 when the material for the organic electroluminescent device of the present invention is used as the light emitting auxiliary layer, the light emitting efficiency and lifespan are significantly improved.

In other words, when the light emitting auxiliary layer was used as the light emitting auxiliary layer rather than when the light emitting auxiliary layer was not used (Comparative Example 4), the efficiency and the lifespan were increased, and Comparative Example 5 and the general aryl group which were not substituted with deuterium were substituted with deuterium. In comparison with Comparative Example 6, the device (Examples 47 to 78) in which the deuterium is substituted with fluorene and spirofluorene as the light emitting auxiliary layer (Examples 47 to 78) was able to lower the driving voltage of the device. Significantly improved. 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 improves the low voltage, high luminous efficiency and device life of the organic electroluminescent device due to the deep HOMO energy level.

This is shown by the deuterium substitution of fluorene and spirofluorene as described in the results of Table 4, which suggests that the properties of the compound may vary significantly depending on where the deuterium is substituted, even though they have similar structures. Doing.

In addition, the evaluation results of the above-described device fabrication described device characteristics in which the compound of the present invention is applied to only one of the hole transport layer and the light emitting auxiliary layer, but the compound of the present invention may be used by applying both the hole transport layer and the light emitting auxiliary layer.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments.

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

Claims (11)

Compound represented by the following formula (1)             Formula (1)

{In the above formula (1), 1) Ar ¹ is C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; An alkenyl group of C ₂ to C ₃₀ ; Alkynyl groups of C ₂ to C ₃₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₆₀ aryloxy group; And -L'-N (R _a ) (R _b ); 2) R ¹ and R ² are a) independently of each other hydrogen; heavy hydrogen; C ₁ -C ₅₀ alkyl group; C ₂ -C ₃₀ alkenyl group; C ₂ -C ₃₀ alkynyl group; An alkoxyl group of C ₁ -C ₃₀ ; And an aryloxy group of C ₆ -C ₆₀ ; C ₁ -C ₃₀ silyl group; C ₆ -C ₆₀ aryl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; And fluorenyl group; or b) R ¹ and R ² may be bonded to each other to form a spiro compound together with carbon or Si to which they are bonded. 3) R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are a) independently of each other, hydrogen; heavy hydrogen; C ₁ -C ₅₀ alkyl group; C ₂ -C ₃₀ alkenyl group; C ₂ -C ₃₀ alkynyl group; An alkoxyl group of C ₁ -C ₃₀ ; And an aryloxy group of C ₆ -C ₆₀ ; C ₁ -C ₃₀ silyl group; C ₆ -C ₆₀ aryl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl group; And -L'-N (R _a ) (R _b ), or b) adjacent R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ combine with each other and at least one Can form a ring, 4) ^{where, R 1, R 2, R} 3, R 4, R 5, R 6, R 7 and R ⁸ must be of more than one is to be replaced by deuterium, 5) L ¹ and L ² are each independently a single bond; C ₆ -C ₆₀ arylene group; Fluorenylene groups; And a C ₂ -C ₆₀ heteroarylene group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P; Fused ring group of an aromatic ring of C ₃ -C ₆₀ aliphatic ring with C ₆ -C _60; is selected from the group consisting of any one, 6) a and d are each independently an integer of 0 to 3, b, c, e, f each independently represent an integer of 0 to 4, 7) L 'is a C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And C ₂ ~ C ₆₀ Heterocyclic group; It is selected from the group consisting of, R _a and R _b are independently of each other C ₆ ~ C ₆₀ An aryl group; Fluorenyl group; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And a C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P. Wherein the aryl group, heteroarylene group, fluorenyl group, arylene group, heterocyclic group, fused ring group, and fluorenylene group are each deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; a nitro _{group; -L'-N (R a)} (R b); C 1 ~ C ₂₀ of the import alkylthio; alkyl group of _{C 1 ~ C 20;; C} 1 ~ C 20 alkoxy group of C ₂ ~ C ₂₀ of alkenyl; C ₂ ~ C ₂₀ alkynyl of; an aryl group of a C ₆ ~ C ₂₀ substituted with heavy hydrogen;; C ₆ ~ C ₂₀ aryl group, a fluorenyl group; a heterocyclic group of C ₂ ~ C _20; C ₃ A cycloalkyl group of -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group and C ₈ -C ₂₀ arylalkenyl group may be further substituted with one or more substituents, and these substituents may be bonded to each other to form a ring In this case, the 'ring' may be an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, or a hetero ring having 2 to 60 carbon atoms, or Fused ring consisting of a combination of these, including saturated or unsaturated rings.)} The compound according to claim 1, wherein the formula (1) is represented by any one of the following Formulas 2-1 to 2-3.

(In Chemical Formulas 2-1 to 2-3, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^８ , a, b, c, d, e, f, L ¹ , L ² , Ar ¹ is the same as defined in claim 1, D means 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.

(In Chemical Formulas 3-1 to 3-4, 4-1 to 4-4, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^８ , a, b, c, d, e, f, L ¹ , L ² , Ar ¹ is the same as defined in Formula 1 of claim 1). According to claim 1, wherein the compound represented by the formula (1) of the following formula 1-1 to 1-48, 2-1 to 2-32, 3-1 to 3-28 and 4-1 to 4-4 Compound characterized in that it is represented by either

A first electrode; Second electrode; And an organic material layer positioned between the first electrode and the second electrode. The organic material layer is an organic electric element comprising the compound according to claim 1 The method of claim 5, The organic material device, characterized in that the organic material layer is a light emitting layer, a hole transport layer or a light emitting auxiliary layer. The method of claim 5, An organic electric device further comprising a light efficiency improvement layer formed on at least one of one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer. The method of claim 5, 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 The method of claim 5, In the organic material layer, the compound is an organic electric device, characterized in that a mixture of the same kind or different kinds of compounds A display device comprising the organic electroluminescent device of claim 5; And a controller for driving the display device. The method of claim 10, The organic electronic device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a monochrome or white lighting device.

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