WO2017122978A1 - Compound for organic electronic element, organic electronic element using same, and electronic device manufactured therewith - Google Patents

Abstract

The present invention provides a compound for use in a hole transport layer or auxiliary light-emitting layer, wherein the compound is capable of improving emission efficiency, stability, and lifespan of an element, an organic electronic element using a compound for a light-emitting layer, and an electronic device manufactured therewith.

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.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

The material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.

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

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

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

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

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

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

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

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

That is, in order to fully exhibit the excellent characteristics of the organic electric device, the materials constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a light emitting auxiliary layer material, etc., are stable and efficient. Supported by the material should be preceded, but development of a stable and efficient organic material layer for an organic electric device has not been made yet. Therefore, the development of new materials continues to be demanded. Furthermore, the combination of the hole transport layer or the light emitting layer and the light emitting layer, more specifically, the light emitting auxiliary layer and the phosphorescent host, and the light emitting auxiliary layer, the phosphorescent host and the dopant, The development of the same device combination is also urgently required.

(Patent Document 1) KR1020060032099 A

Embodiments of the present invention to solve the problems of the above-described background, revealed the optimal combination of the compound for the hole transport layer or the light emitting auxiliary layer and the compound for the light emitting layer, the luminous efficiency of the device when applying these compounds to the organic electronic device It has been found that the stability and lifespan can be greatly improved.

Accordingly, an object of the present invention is to provide an organic electric device and an electronic device using a combination of a compound for a hole transport layer or a light emitting auxiliary layer and a compound for a light emitting layer.

The present invention provides an organic electroluminescent device comprising a hole transport layer or a light emitting auxiliary layer comprising a compound represented by the following formula (1) and a compound represented by the following formulas (2) to (4) as a light emitting layer .

Formula (1)

       Chemical Formula (2) Chemical Formula (3) Chemical Formula (4)

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)

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 the present invention, in an organic electroluminescent device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, the organic material layer is between the first electrode and the light emitting layer. And a hole transport layer and a light emitting layer formed between the light emitting auxiliary layer and the first electrode and the light emitting auxiliary layer, wherein the light emitting layer includes a host and a dopant material, respectively, and the hole transport layer or the light emitting auxiliary layer is represented by the following formula (1): It includes a compound represented by), the light emitting layer provides an organic electric device comprising at least one of the compounds represented by the formula (2) ~ (4).

Formula (1)

Chemical Formula (2) Chemical Formula (3) Chemical Formula (4)

{In the above formulas (1) to (4),

1) Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl 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; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b );

2) a, b, d, e, h, i, k are each independently an integer of 0 to 4, c, f, g are each independently an integer of 0 to 3, j is an integer of 0 to 2, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl 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; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); or R ¹ adjacent to each other, R ² adjacent to each other, R ³ adjacent to each other, R ⁴ adjacent to each other, R adjacent to each other. between each ^{other. 5,} the adjacent R ^6, the adjacent R ⁷ to each other, the adjacent R ⁸ each other, the adjacent R ⁹ together with each other, a small neighborhood to each other by R ^10, neighboring to each other by R ^11, adjacent R ^12, adjacent R ¹³ , Neighboring R ¹⁴ , Neighboring R ¹⁵ , Neighboring R ¹⁶ , Neighboring R ¹⁷ , Neighboring R ¹⁸ , Neighboring R ¹⁹ , Neighboring R ²⁰ , Neighboring R ²¹ , Neighboring One R ²² and the other adjacent R ²³ can combine to form a ring,

3) L ¹ , L ² , L ³ , L ⁴ and L ⁵ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; C ₂ ~ C ₆₀ divalent heterocyclic group; Divalent fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And it is selected from the group consisting of divalent aliphatic hydrocarbon group,

4) X and Y are directly bonded to each other independently; S, O, NR ', CR'R "or SiR'R" and W is S, O, NR', CR'R "or SiR'R";

R ′ and R ″ are each independently selected from hydrogen; C ₆ ~ C ₆₀ aryl group; C ₃ ~ C ₆₀ heterocyclic group; C ₁ ~ C ₅₀ Alkyl group; It is bonded to each other spiro Can form compounds,

5) l and m are each independently an integer of 0 ~ 1, l + m is 1 or more, when l and m is 0, it means a direct bond,

6) Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ , Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are Each independently CR or N, R is hydrogen, an aryl group of C ₆ -C ₆₀ ; Containing at least one heteroatom of O, N, S, Si, P C ₃ ~ C ₆₀ Heterocyclic group; C ₁ ~ C ₅₀ Alkyl group; C ₆ ~ C ₆₀ arylamine group; A fluorene group; selected from the group consisting of: a ring formed by combining with a neighboring group,

7) L 'is a single bond; 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 to C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P.}

In a specific embodiment, the present invention provides an organic electric device, characterized in that the compound represented by the formula (1) is a compound represented by the following formula (5) or (6).

              Formula (5) Formula (6)

(In the formulas (5) and (6), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , a, b, c, d, e, f, g, h, Ar ¹ , Ar ² , L ¹ , L ² , L ³ are as defined in formula (1) above.)

In another aspect, the present invention provides an organic electric device, characterized in that the compound represented by the formula (2) is a compound represented by any one of the following formulas (7) to (12).

     Chemical Formula (7) Chemical Formula (8) Chemical Formula (9)

    Chemical Formula (10) Chemical Formula (11) Chemical Formula (12)

(In the above formulas (7) to (12), R ⁹ , R ¹⁰ , R ¹¹ , i, j, k, Ar ³ , L ⁴ , X, Y are as defined in formula (1) above.)

In another aspect, the present invention provides an organic electric device, characterized in that the compound represented by the formula (3) is a compound represented by any one of the following formulas (13) to (16).

Chemical Formula (13) Chemical Formula (14)

Formula (15) Formula (16)

(In the above formulas (13) to (16), Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ , Z ¹⁴ , Z ¹⁵ , Z ¹⁶ , Ar ⁴ , L ⁵ , R ', R "are as defined in formula (1) above.)

In another aspect, the present invention provides an organic electric device characterized in that the compound represented by the formula (4) is represented by the following formula (17).

               Formula (17)

{In the above formula (17),

1) R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²² , R ²³ , L ', R _a and R _b are as defined in formula (1) above,

2) R ²⁴ is hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl 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; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); n is an integer of 0 to 4, and adjacent R ²⁴ may combine with each other to form a ring,

3) L ⁶ are independently a single bond to each other; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; C ₂ ~ C ₆₀ divalent heterocyclic group; Divalent fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And it is selected from the group consisting of divalent aliphatic hydrocarbon group,

4) T is S, O, NR ', CR'R "or SiR'R", and R' and R "are as defined in Formula 1 above.}

In another aspect, the present invention provides an organic electroluminescent device characterized in that the compound represented by the formula (1), formula (5) or (6) is selected from any one of the compounds represented as follows.

In another aspect, the present invention provides an organic electric device characterized in that the compound represented by the formula (2) or formula (7) to (12) is represented by any one of the compounds represented as follows.

In another aspect, the present invention provides an organic electronic device, characterized in that the compound represented by the formula (3) or formula (13) to (16) is any one of the compounds represented as follows.

In another aspect, the present invention provides an organic electroluminescent device characterized in that the compound represented by the formula (4) or formula (17) is a compound represented by any one of the following.

In another aspect, the present invention provides an organic electric device comprising a compound represented by the following formula (18) dopant in the light emitting layer.

       Formula (18)

(In the formula (18),

1) R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ and R ³² are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ Aryl group; Containing at least one heteroatom of O, N, S, Si, P C ₃ ~ C ₆₀ Heterocyclic group; C ₁ ~ C ₅₀ Alkyl group; A C ₁ to C ₅₀ alkoxy group; C ₂ -C ₂₀ alkenyl group; -L'-N (R _a ) (R _b ); R ²⁵ and R ²⁶ , R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³² Can combine with each other to form a ring,

2) L is an integer from 1 to 3

3) A is an independent ligand represented by the following formula (18-1) or formula (18-2) and has a covalent bond with C, a coordination bond with N, a covalent bond with O, and a coordination bond with another O To form a complex with Ir,

Chemical Formula (18-1) Chemical Formula (18-2)

4) R ³³ , R ³⁴ are independently of each other hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ Aryl group; Containing at least one heteroatom of O, N, S, Si, P C ₃ ~ C ₆₀ Heterocyclic group; C ₁ ~ C ₅₀ Alkyl group; A C ₁ to C ₅₀ alkoxy group; C ₂ -C ₂₀ alkenyl group; -L'-N (R _a ) (R _b ); is selected from the group consisting of).

In another aspect, the present invention provides an organic electric device, characterized in that the compound represented by the formula (18) is any one of the compounds represented as follows.

_

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.

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 compounds represented by the formulas (1) to (4) and (18) of the present invention and the production examples of the organic electric element of the present invention will be described in detail with reference to Examples. It is not limited to the following examples.

Synthesis Example 1

The compound represented by the formula (1) according to the present invention (final product) is prepared by reacting Sub 1 with Sub 2, as shown in Scheme 1 below.

<Scheme 1>

Example of Sub 1 Synthesis (When L ¹ is not a single bond)

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

<Scheme 2>

Sub 1 (6) synthesis  example

Synthesis of Sub 1-2-1

Sub 1-1-1 (55.3 g, 140 mmol) in 980 mL of DMF, followed by bispinacolborate (39.1 g, 154 mmol), PdCl ₂ (dppf) catalyst (3.43 g, 4.2 mmol), KOAc (41.3 g, 420 mmol After 24 hours of stirring), the obtained compound was separated through a silicagel column and recrystallization to obtain 45.8 g (74%) of borate compound Sub 1-2-1.

Synthesis of Sub 1 (6)

Sub 1-2-1 (35.4 g, 80 mmol), THF 360 mL, Sub 1-3-1 (23.8 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol) and 180 mL of water were added, followed by stirring under reflux. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to give 28.7g (76%).

Sub 1 (8) Synthesis  example

Synthesis of Sub 1-2-2

Sub 1-1-2 (55.3 g, 140 mmol) in 980 mL of DMF, followed by bispinacolborate (39.1 g, 154 mmol), PdCl ₂ (dppf) catalyst (3.43 g, 4.2 mmol), KOAc (41.3 g, 420 mmol After 24 hours of stirring), the obtained compound was separated through a silicagel column and recrystallization to obtain 46.4 g (75%) of borate compound Sub 1-2-2.

Synthesis of Sub 1 (8)

Sub 1-2-1 (35.4 g, 80 mmol), THF 360 mL, Sub 1-3-2 (32.7 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol) and 180 mL of water were added, followed by stirring under reflux. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to give the product 33.3g (72%).

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

compound FD-MS compound FD-MS Sub1 (1) m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40) Sub1 (2) m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40) Sub1 (3) m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40) Sub1 (4) m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40) Sub1 (5) m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40) Sub1 (6) m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40) Sub1 (7) m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40) Sub1 (8) m / z = 576.05 (C ₃₇ H ₂₁ BrS = 577.54) Sub1 (9) m / z = 471.06 (C ₃₀ H ₁₈ BrN = 472.39) Sub1 (10) m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40) Sub1 (11) _{m / z = 546.10 (C 37} H 23 Br = 547.50) Sub1 (12) m / z = 470.07 (C ₃₁ H ₁₉ Br = 471.40)

Sub 2 Synthesis Example

Sub 3 of Scheme 1 may be synthesized by the reaction route of Scheme 3, but is not limited thereto.

<Scheme 3>

Synthesis Example of Sub 2 (1)

Sub 2-2-1 (7.7 g, 24 mmol) was dissolved in toluene, then Sub 2-1-1 (5.2 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P (t-Bu ) ₃ (0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol) and toluene (300 mL) were added, and the mixture was stirred and refluxed at 100 ° C. for 24 hours. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 6.8 g (yield: 68%) of the final compound.

Synthesis Example of Sub 2 (18)

Sub 2-2-2 (11.5 g, 24 mmol) was dissolved in toluene, and then Sub 2-1-2 (6.7 g, 20 mmol) was added to 11.1 g of the final compound using the synthesis method of Sub 2 (1) (yield: 76 %) Was obtained.

Synthesis Example of Sub 2 (1)

Sub 2-1-1 (6.2 g, 24 mmol) was dissolved in toluene, and Sub 2-2-1 (6.4 g, 20 mmol) was dissolved in Sub 2 (1) to give 9.1 g of the final compound (yield: 76). %) Was obtained.

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

compound FD-MS compound FD-MS Sub 2 (1) m / z = 499.20 (C ₃₆ H ₂₅ N ₃ = 499.62) Sub 2 (2) _{m / z = 549.22 (C 40} H 27 N 3 = 549.68) Sub 2 (3) _{m / z = 549.22 (C 40} H 27 N 3 = 549.68) Sub 2 (4) m / z = 575.24 (C ₄₂ H ₂₉ N ₃ = 575.72) Sub 2 (5) m / z = 651.27 (C ₄₈ H ₃₃ N ₃ = 651.81) Sub 2 (6) m / z = 599.24 (C ₄₄ H ₂₉ N ₃ = 599.74) Sub 2 (7) m / z = 649.25 (C ₄₈ H ₃₁ N ₃ = 649.80) Sub 2 (8) m / z = 654.25 (C ₄₅ H ₃₀ N ₆ = 654.78) Sub 2 (9) m / z = 627.24 (C ₄₄ H ₂₉ N ₅ = 627.75) Sub 2 (10) _{m / z = 615.27 (C 45} H 33 N 3 = 615.78) Sub 2 (11) m / z = 605.19 (C ₄₂ H ₂₇ N ₃ S = 605.76) Sub 2 (12) m / z = 664.26 (C ₄₈ H ₃₂ N ₄ = 664.814) Sub 2 (13) m / z = 574.24 (C ₄₂ H ₂₉ N ₃ = 575.72) Sub 2 (14) _{m / z = 625.25 (C 46} H 31 N 3 = 625.78) Sub 2 (15) m / z = 731.24 (C ₅₂ H ₃₃ N ₃ S = 731.92) Sub 2 (16) m / z = 727.30 (C ₅₄ H ₃₇ N ₃ = 727.91) Sub 2 (17) m / z = 725.28 (C ₅₄ H ₃₅ N ₃ = 725.90) Sub 2 (18) m / z = 730.28 (C ₅₁ H ₃₄ N ₆ = 730.88) Sub 2 (19) m / z = 677.26 (C ₄₈ H ₃₁ N ₅ = 677.81) Sub 2 (20) m / z = 665.28 (C ₄₉ H ₃₅ N ₃ = 665.84) Sub 2 (21) m / z = 499.20 (C ₃₆ H ₂₅ N ₃ = 499.62) Sub 2 (22) _{m / z = 549.22 (C 40} H 27 N 3 = 549.68) Sub 2 (23) _{m / z = 549.22 (C 40} H 27 N 3 = 549.68) Sub 2 (24) m / z = 575.24 (C ₄₂ H ₂₉ N ₃ = 575.72)

Final Products Synthesis Example

Synthesis Example of 1-4

Sub 1 (13) (9.5g, 24mmol) was dissolved in toluene, Sub 2 (24) was added (11.5g, 20mmol) and Pd ₂ (dba) ₃ (0.5g, 0.6mmol), P (t-Bu ) ₃ (0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol) and toluene (300 mL) were added, and the mixture was stirred and refluxed at 100 ° C. for 24 hours. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 16.2 g (yield: 76%) of the final compound.

Synthesis Example of 2-8

Sub 1 (14) (9.5g, 24mmol) was dissolved in toluene, Sub 2 (25) (13.1g, 20mmol) was added thereto, and the final compound 16.7g (yield: 72%) was obtained using the synthesis method of 1-4. Got it.

Synthesis Example of 3-14

Sub 1 (15) (9.5g, 24mmol) was dissolved in toluene, Sub 2 (26) (12.5g, 20mmol) was added thereto, and the final compound 16.7g (yield: 74%) was obtained using the synthesis method of 1-4. Got it.

Synthesis Example of 4-1

Sub 1 (16) (9.5g, 24mmol) was dissolved in toluene, Sub 2 (21) (10.0g, 20mmol) was added thereto, and the final compound 15.2 (yield: 78%) was obtained by using the synthesis method of 1-4. .

Synthesis Example of 5-4

Sub 1 (16) (9.5g, 24mmol) was dissolved in toluene, Sub 2 (27) (11.5g, 20mmol) was added thereto, and the final compound 15.8g (yield: 74%) was obtained using the synthesis method of 1-4. Got it.

Synthesis Example of 6-8

Sub 1 (16) (9.5g, 24mmol) was dissolved in toluene, Sub 2 (28) (13.1g, 20mmol) was added thereto, and the resulting compound 17.7g (yield: 76%) was obtained using the synthesis method of 1-4. Got it.

Synthesis Example of 7-14

Sub 1 (16) (9.5g, 24mmol) was dissolved in toluene, Sub 2 (29) (12.5g, 20mmol) was added thereto, and 16.9g (yield: 75%) of the final compound was obtained using the synthesis method of 1-4. Got it.

Synthesis Example of 8-1

After Sub 1 (16) (9.5g, 24mmol) was dissolved in toluene, Sub 2 (30) (10.0g, 20mmol) was added thereto to obtain 15.0 (yield: 77%) of the final compound. Got it.

compound FD-MS compound FD-MS 1-1 m / z = 813.31 (C ₆₁ H ₃₉ N ₃ = 814.00) 1-2 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 1-3 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 1-4 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 1-5 m / z = 965.38 (C ₇₃ H ₄₇ N ₃ = 966.20) 1-6 m / z = 913.35 (C ₆₉ H ₄₃ N ₃ = 914.12) 1-7 _{m / z = 963.36 (C 73} H 45 N 3 = 964.18) 1-8 m / z = 968.36 (C ₇₀ H ₄₄ N ₆ = 969.16) 1-9 m / z = 941.35 (C ₆₉ H ₄₃ N ₅ = 942.14) 1-10 m / z = 929.38 (C ₆₉ H ₄₃ N ₅ = 942.14) 1-11 m / z = 919.30 (C ₆₇ H ₄₁ N ₃ S = 920.15) 1-12 m / z = 978.37 (C ₇₃ H ₄₆ N ₄ = 979.20) 1-13 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 1-14 m / z = 939.36 (C ₇₁ H ₄₅ N ₃ = 940.16) 1-15 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 1-16 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 1-17 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 1-18 m / z = 989.38 (C ₇₅ H ₄₇ N ₃ = 990.22) 1-19 m / z = 1115.42 (C ₈₅ H ₅₃ N ₃ = 1116.38) 1-20 _{m / z = 1196.46 (C 88} H 56 N 6 = 1197.46) 1-21 m / z = 991.37 (C ₇₃ H ₄₅ N ₅ = 992.20) 1-22 m / z = 979.39 (C ₇₄ H ₄₉ N ₃ = 980.23) 1-23 m / z = 1095.36 (C ₈₁ H ₄₉ N ₃ S = 1096.36) 1-24 m / z = 1028.39 (C ₇₇ H ₄₈ N ₄ = 1029.26) 1-25 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 1-26 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 1-27 m / z = 939.36 (C ₇₁ H ₄₅ N ₂ = 940.16) 1-28 _{m / z = 1042.40 (C 78} H 50 N 4 = 1043.29) 2-1 m / z = 813.31 (C ₆₁ H ₃₉ N ₃ = 814.00) 2-2 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 2-3 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 2-4 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 2-5 m / z = 965.38 (C ₇₃ H ₄₇ N ₃ = 966.20) 2-6 m / z = 913.35 (C ₆₉ H ₄₃ N ₃ = 914.12) 2-7 _{m / z = 963.36 (C 73} H 45 N 3 = 964.18) 2-8 m / z = 968.36 (C ₇₀ H ₄₄ N ₆ = 969.16) 2-9 m / z = 941.35 (C ₆₉ H ₄₃ N ₅ = 942.14) 2-10 m / z = 929.38 (C ₆₉ H ₄₃ N ₅ = 942.14) 2-11 m / z = 919.30 (C ₆₇ H ₄₁ N ₃ S = 920.15) 2-12 m / z = 978.37 (C ₇₃ H ₄₆ N ₄ = 979.20) 2-13 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 2-14 m / z = 939.36 (C ₇₁ H ₄₅ N ₃ = 940.16) 2-15 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 2-16 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 2-17 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 2-18 m / z = 989.38 (C ₇₅ H ₄₇ N ₃ = 990.22) 2-19 m / z = 1115.42 (C ₈₅ H ₅₃ N ₃ = 1116.38) 2-20 _{m / z = 1196.46 (C 88} H 56 N 6 = 1197.46) 2-21 m / z = 991.37 (C ₇₃ H ₄₅ N ₅ = 992.20) 2-22 m / z = 979.39 (C ₇₄ H ₄₉ N ₃ = 980.23) 2-23 m / z = 1095.36 (C ₈₁ H ₄₉ N ₃ S = 1096.36) 2-24 m / z = 1028.39 (C ₇₇ H ₄₈ N ₄ = 1029.26) 2-25 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 2-26 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 2-27 m / z = 939.36 (C ₇₁ H ₄₅ N ₂ = 940.16) 2-28 _{m / z = 1042.40 (C 78} H 50 N 4 = 1043.29) 3-1 m / z = 813.31 (C ₆₁ H ₃₉ N ₃ = 814.00) 3-2 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 3-3 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 3-4 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 3-5 m / z = 965.38 (C ₇₃ H ₄₇ N ₃ = 966.20) 3-6 m / z = 913.35 (C ₆₉ H ₄₃ N ₃ = 914.12) 3-7 _{m / z = 963.36 (C 73} H 45 N 3 = 964.18) 3-8 m / z = 968.36 (C ₇₀ H ₄₄ N ₆ = 969.16) 3-9 m / z = 941.35 (C ₆₉ H ₄₃ N ₅ = 942.14) 3-10 m / z = 929.38 (C ₆₉ H ₄₃ N ₅ = 942.14) 3-11 m / z = 919.30 (C ₆₇ H ₄₁ N ₃ S = 920.15) 3-12 m / z = 978.37 (C ₇₃ H ₄₆ N ₄ = 979.20) 3-13 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 3-14 m / z = 939.36 (C ₇₁ H ₄₅ N ₃ = 940.16) 3-15 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 3-16 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 3-17 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 3-18 m / z = 989.38 (C ₇₅ H ₄₇ N ₃ = 990.22) 3-19 m / z = 1115.42 (C ₈₅ H ₅₃ N ₃ = 1116.38) 3-20 _{m / z = 1196.46 (C 88} H 56 N 6 = 1197.46) 3-21 m / z = 991.37 (C ₇₃ H ₄₅ N ₅ = 992.20) 3-22 m / z = 979.39 (C ₇₄ H ₄₉ N ₃ = 980.23) 3-23 m / z = 1095.36 (C ₈₁ H ₄₉ N ₃ S = 1096.36) 3-24 m / z = 1028.39 (C ₇₇ H ₄₈ N ₄ = 1029.26) 3-25 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 3-26 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 3-27 m / z = 939.36 (C ₇₁ H ₄₅ N ₂ = 940.16) 3-28 _{m / z = 1042.40 (C 78} H 50 N 4 = 1043.29) 4-1 m / z = 813.31 (C ₆₁ H ₃₉ N ₃ = 814.00) 4-2 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 4-3 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 4-4 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 4-5 m / z = 965.38 (C ₇₃ H ₄₇ N ₃ = 966.20) 4-6 m / z = 913.35 (C ₆₉ H ₄₃ N ₃ = 914.12) 4-7 _{m / z = 963.36 (C 73} H 45 N 3 = 964.18) 4-8 m / z = 968.36 (C ₇₀ H ₄₄ N ₆ = 969.16) 4-9 m / z = 941.35 (C ₆₉ H ₄₃ N ₅ = 942.14) 4-10 m / z = 929.38 (C ₆₉ H ₄₃ N ₅ = 942.14) 4-11 m / z = 919.30 (C ₆₇ H ₄₁ N ₃ S = 920.15) 4-12 m / z = 978.37 (C ₇₃ H ₄₆ N ₄ = 979.20) 4-13 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 4-14 m / z = 939.36 (C ₇₁ H ₄₅ N ₃ = 940.16) 4-15 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 4-16 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 4-17 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 4-18 m / z = 989.38 (C ₇₅ H ₄₇ N ₃ = 990.22) 4-19 m / z = 1115.42 (C ₈₅ H ₅₃ N ₃ = 1116.38) 4-20 _{m / z = 1196.46 (C 88} H 56 N 6 = 1197.46) 4-21 m / z = 991.37 (C ₇₃ H ₄₅ N ₅ = 992.20) 4-22 m / z = 979.39 (C ₇₄ H ₄₉ N ₃ = 980.23) 4-23 m / z = 1095.36 (C ₈₁ H ₄₉ N ₃ S = 1096.36) 4-24 m / z = 1028.39 (C ₇₇ H ₄₈ N ₄ = 1029.26) 4-25 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 4-26 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 4-27 m / z = 939.36 (C ₇₁ H ₄₅ N ₂ = 940.16) 4-28 _{m / z = 1042.40 (C 78} H 50 N 4 = 1043.29) 5-1 m / z = 813.31 (C ₆₁ H ₃₉ N ₃ = 814.00) 5-2 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 5-3 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 5-4 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 5-5 m / z = 965.38 (C ₇₃ H ₄₇ N ₃ = 966.20) 5-6 m / z = 913.35 (C ₆₉ H ₄₃ N ₃ = 914.12) 5-7 _{m / z = 963.36 (C 73} H 45 N 3 = 964.18) 5-8 m / z = 968.36 (C ₇₀ H ₄₄ N ₆ = 969.16) 5-9 m / z = 941.35 (C ₆₉ H ₄₃ N ₅ = 942.14) 5-10 m / z = 929.38 (C ₆₉ H ₄₃ N ₅ = 942.14) 5-11 m / z = 919.30 (C ₆₇ H ₄₁ N ₃ S = 920.15) 5-12 m / z = 978.37 (C ₇₃ H ₄₆ N ₄ = 979.20) 5-13 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 5-14 m / z = 939.36 (C ₇₁ H ₄₅ N ₃ = 940.16) 5-15 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 5-16 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 5-17 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 5-18 m / z = 989.38 (C ₇₅ H ₄₇ N ₃ = 990.22) 5-19 m / z = 1115.42 (C ₈₅ H ₅₃ N ₃ = 1116.38) 5-20 _{m / z = 1196.46 (C 88} H 56 N 6 = 1197.46) 5-21 m / z = 991.37 (C ₇₃ H ₄₅ N ₅ = 992.20) 5-22 m / z = 979.39 (C ₇₄ H ₄₉ N ₃ = 980.23) 5-23 m / z = 1095.36 (C ₈₁ H ₄₉ N ₃ S = 1096.36) 5-24 m / z = 1028.39 (C ₇₇ H ₄₈ N ₄ = 1029.26) 5-25 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 5-26 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 5-27 m / z = 939.36 (C ₇₁ H ₄₅ N ₂ = 940.16) 5-28 _{m / z = 1042.40 (C 78} H 50 N 4 = 1043.29) 6-1 m / z = 813.31 (C ₆₁ H ₃₉ N ₃ = 814.00) 6-2 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 6-3 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 6-4 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 6-5 m / z = 965.38 (C ₇₃ H ₄₇ N ₃ = 966.20) 6-6 m / z = 913.35 (C ₆₉ H ₄₃ N ₃ = 914.12) 6-7 _{m / z = 963.36 (C 73} H 45 N 3 = 964.18) 6-8 m / z = 968.36 (C ₇₀ H ₄₄ N ₆ = 969.16) 6-9 m / z = 941.35 (C ₆₉ H ₄₃ N ₅ = 942.14) 6-10 m / z = 929.38 (C ₆₉ H ₄₃ N ₅ = 942.14) 6-11 m / z = 919.30 (C ₆₇ H ₄₁ N ₃ S = 920.15) 6-12 m / z = 978.37 (C ₇₃ H ₄₆ N ₄ = 979.20) 6-13 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 6-14 m / z = 939.36 (C ₇₁ H ₄₅ N ₃ = 940.16) 6-15 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 6-16 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 6-17 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 6-18 m / z = 989.38 (C ₇₅ H ₄₇ N ₃ = 990.22) 6-19 m / z = 1115.42 (C ₈₅ H ₅₃ N ₃ = 1116.38) 6-20 _{m / z = 1196.46 (C 88} H 56 N 6 = 1197.46) 6-21 m / z = 991.37 (C ₇₃ H ₄₅ N ₅ = 992.20) 6-22 m / z = 979.39 (C ₇₄ H ₄₉ N ₃ = 980.23) 6-23 m / z = 1095.36 (C ₈₁ H ₄₉ N ₃ S = 1096.36) 6-24 m / z = 1028.39 (C ₇₇ H ₄₈ N ₄ = 1029.26) 6-25 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 6-26 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 6-27 m / z = 939.36 (C ₇₁ H ₄₅ N ₂ = 940.16) 6-28 _{m / z = 1042.40 (C 78} H 50 N 4 = 1043.29) 7-1 m / z = 813.31 (C ₆₁ H ₃₉ N ₃ = 814.00) 7-2 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 7-3 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 7-4 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 7-5 m / z = 965.38 (C ₇₃ H ₄₇ N ₃ = 966.20) 7-6 m / z = 913.35 (C ₆₉ H ₄₃ N ₃ = 914.12) 7-7 _{m / z = 963.36 (C 73} H 45 N 3 = 964.18) 7-8 m / z = 968.36 (C ₇₀ H ₄₄ N ₆ = 969.16) 7-9 m / z = 941.35 (C ₆₉ H ₄₃ N ₅ = 942.14) 7-10 m / z = 929.38 (C ₆₉ H ₄₃ N ₅ = 942.14) 7-11 m / z = 919.30 (C ₆₇ H ₄₁ N ₃ S = 920.15) 7-12 m / z = 978.37 (C ₇₃ H ₄₆ N ₄ = 979.20) 7-13 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 7-14 m / z = 939.36 (C ₇₁ H ₄₅ N ₃ = 940.16) 7-15 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 7-16 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 7-17 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 7-18 m / z = 989.38 (C ₇₅ H ₄₇ N ₃ = 990.22) 7-19 m / z = 1115.42 (C ₈₅ H ₅₃ N ₃ = 1116.38) 7-20 _{m / z = 1196.46 (C 88} H 56 N 6 = 1197.46) 7-21 m / z = 991.37 (C ₇₃ H ₄₅ N ₅ = 992.20) 7-22 m / z = 979.39 (C ₇₄ H ₄₉ N ₃ = 980.23) 7-23 m / z = 1095.36 (C ₈₁ H ₄₉ N ₃ S = 1096.36) 7-24 m / z = 1028.39 (C ₇₇ H ₄₈ N ₄ = 1029.26) 7-25 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 7-26 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 7-27 m / z = 939.36 (C ₇₁ H ₄₅ N ₂ = 940.16) 7-28 _{m / z = 1042.40 (C 78} H 50 N 4 = 1043.29) 8-1 m / z = 813.31 (C ₆₁ H ₃₉ N ₃ = 814.00) 8-2 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 8-3 _{m / z = 864.33 (C 65} H 41 N 3 = 864.06) 8-4 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 8-5 m / z = 965.38 (C ₇₃ H ₄₇ N ₃ = 966.20) 8-6 m / z = 913.35 (C ₆₉ H ₄₃ N ₃ = 914.12) 8-7 _{m / z = 963.36 (C 73} H 45 N 3 = 964.18) 8-8 m / z = 968.36 (C ₇₀ H ₄₄ N ₆ = 969.16) 8-9 m / z = 941.35 (C ₆₉ H ₄₃ N ₅ = 942.14) 8-10 m / z = 929.38 (C ₆₉ H ₄₃ N ₅ = 942.14) 8-11 m / z = 919.30 (C ₆₇ H ₄₁ N ₃ S = 920.15) 8-12 m / z = 978.37 (C ₇₃ H ₄₆ N ₄ = 979.20) 8-13 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 8-14 m / z = 939.36 (C ₇₁ H ₄₅ N ₃ = 940.16) 8-15 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 8-16 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 8-17 m / z = 1041.41 (C ₇₉ H ₅₁ N ₃ = 1042.30) 8-18 m / z = 989.38 (C ₇₅ H ₄₇ N ₃ = 990.22) 8-19 m / z = 1115.42 (C ₈₅ H ₅₃ N ₃ = 1116.38) 8-20 _{m / z = 1196.46 (C 88} H 56 N 6 = 1197.46) 8-21 m / z = 991.37 (C ₇₃ H ₄₅ N ₅ = 992.20) 8-22 m / z = 979.39 (C ₇₄ H ₄₉ N ₃ = 980.23) 8-23 m / z = 1095.36 (C ₈₁ H ₄₉ N ₃ S = 1096.36) 8-24 m / z = 1028.39 (C ₇₇ H ₄₈ N ₄ = 1029.26) 8-25 _{m / z = 889.35 (C 67} H 43 N 3 = 890.10) 8-26 _{m / z = 1045.35 (C 77} H 47 N 3 S = 1046.30) 8-27 m / z = 939.36 (C ₇₁ H ₄₅ N ₂ = 940.16) 8-28 _{m / z = 1042.40 (C 78} H 50 N 4 = 1043.29)

Synthesis Example 2

Synthesis examples of Product 9-9 among the compounds represented by Formula 2 according to the present invention are the same as in Scheme 4, but are not limited thereto.

<Scheme 4>

Sub 9-2 Synthesis

Sub 9-1 was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reaction was stirred at 0 ° C for 1 hour. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtered under reduced pressure, the resulting product by concentration of the organic solvent was separated by column chromatography to give the desired Sub 9-2.

Sub 9-3 Synthesis

Sub 9-2, 1-iodo-2-nitrobenzene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ obtained were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired Sub 9-3.

Sub 9-4 Synthesis

Sub 9-3 and triphenylphosphine obtained were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and then the concentrated product was separated by column chromatography to obtain the desired Sub 9-4.

Product 9-9 Synthesis

Sub 9-4 (1 equiv) and Sub 9-6 (1.1 equiv) were added to toluene and Pd ₂ (dba) ₃ (0.05 equiv), PPh ₃ (0.1 equiv) and NaO t -Bu (3 equiv) were added respectively, followed by stirring under reflux for 24 hours at 100 ° C. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain Product 9-9.

compound FD-MS compound FD-MS 9-1 m / z = 349.09 (C ₂₄ H ₁₅ NS = 349.45) 9-2 m / z = 504.14 (C ₃₃ H ₂₀ N ₄ S = 504.60) 9-3 m / z = 503.15 (C ₃₄ H ₂₁ N ₃ S = 503.62) 9-4 m / z = 477.13 (C ₃₂ H ₁₉ N ₃ S = 477.58) 9-5 m / z = 527.15 (C ₃₆ H ₂₁ N ₃ S = 527.64) 9-6 _{m / z = 653.19 (C 46} H 27 N 3 S = 653.79) 9-7 m / z = 720.17 (C ₅₀ H ₂₈ N ₂ S ₂ = 720.90) 9-8 m / z = 579.18 (C ₄₀ H ₂₅ N ₃ S = 579.71) 9-9 m / z = 503.15 (C ₃₄ H ₂₁ N ₃ S = 503.62) 9-10 m / z = 504.14 (C ₃₃ H ₂₀ N ₄ S = 504.60) 9-11 m / z = 477.13 (C ₃₂ H ₁₉ N ₃ S = 477.58) 9-12 m / z = 541.16 (C ₃₇ H ₂₃ N ₃ S = 541.66) 9-13 m / z = 527.15 (C ₃₆ H ₂₁ N ₃ S = 527.64) 9-14 m / z = 527.15 (C ₃₆ H ₂₁ N ₃ S = 527.64) 9-15 _{m / z = 527.15 (C 36} H 21 N 3 S = 527.64) 9-16 m / z = 553.16 (C ₃₈ H ₂₃ N ₃ S = 553.67) 9-17 m / z = 774.23 (C ₅₂ H ₃₂ N ₄ S = 744.90) 9-18 m / z = 554.16 (C ₃₇ H ₂₂ N ₄ S = 554.66) 9-19 m / z = 577.16 (C ₄₀ H ₂₃ N ₃ S = 577.70) 9-20 m / z = 641.19 (C ₄₅ H ₂₇ N ₃ S = 641.78) 9-21 m / z = 563.21 (C ₃₉ H ₂₅ N ₅ = 563.65) 9-22 m / z = 562.22 (C ₄₀ H ₂₆ N ₄ = 562.66) 9-23 _{m / z = 504.14 (C 33} H 20 N 4 S = 504.60) 9-24 m / z = 563.21 (C ₃₉ H ₂₅ N ₅ = 563.65) 9-25 m / z = 514.22 (C ₃₆ H ₂₆ N ₄ = 514.62) 9-26 m / z = 488.16 (C ₃₃ H ₂₀ N ₄ O = 488.54) 9-27 m / z = 427.11 (C ₂₈ H ₁₇ N ₃ S = 427.52) 9-28 m / z = 514.22 (C ₃₆ H ₂₆ N ₄ = 514.62) 9-29 _{m / z = 680.26 (C 48} H 32 N 4 O = 680.79) 9-30 m / z = 590.25 (C ₄₂ H ₃₀ N ₄ = 590.71) 9-31 m / z = 694.22 (C ₄₈ H ₃₀ N ₄ S = 694.84) 9-32 m / z = 513.22 (C ₃₇ H ₂₇ N ₃ = 513.63) 9-33 m / z = 577.16 (C ₄₀ H ₂₃ N ₃ S = 577.71) 9-34 m / z = 577.16 (C ₄₀ H ₂₃ N ₃ S = 577.71) 9-35 m / z = 567.14 (C ₃₈ H ₂₁ N ₃ OS = 567.67) 9-36 m / z = 583.12 (C ₃₈ H ₂₁ N ₃ S ₂ = 583.73)

Synthesis Example 3

Synthesis examples of Product 10-1 among the compounds represented by Formula 3 according to the present invention are prepared by reacting with the following Scheme 5, but are not limited thereto.

Scheme 5

3-bromo-9-phenyl-9H-carbazole (6.4 g, 20 mmol) was dissolved in THF, followed by (9- (4,6-diphenyl-1,3,5-triazin-2-yl) -9H-carbazol- 3-yl) boronic acid (8.8g, 20mmol), Pd (PPh ₃ ) ₄ (0.03 equiv), K ₂ CO ₃ (3 equiv), and water are added followed by stirring under reflux. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 9.2 g (yield: 72%) of the product.

compound FD-MS compound FD-MS 10-1 m / z = 639.24 (C ₄₅ H ₂₉ N ₅ = 639.75) 10-2 _{m / z = 715.27 (C 51} H 33 N 5 = 715.84) 10-3 m / z = 780.33 (C ₅₇ H ₄₀ N ₄ = 780.95) 10-4 m / z = 639.24 (C ₄₅ H ₂₉ N ₅ = 639.75) 10-5 m / z = 715.27 (C ₅₁ H ₃₃ N ₅ = 715.84) 10-6 m / z = 780.33 (C ₅₇ H ₄₀ N ₄ = 780.95) 10-7 m / z = 612.23 (C ₄₄ H ₂₈ N ₄ = 612.72) 10-8 m / z = 612.23 (C ₄₄ H ₂₈ N ₄ = 612.72) 10-9 m / z = 662.25 (C ₄₈ H ₃₀ N ₄ = 662.78) 10-10 m / z = 484.19 (C ₃₆ H ₂₄ N ₂ = 484.59) 10-11 m / z = 639.24 (C ₄₅ H ₂₉ N ₅ = 639.75) 10-12 m / z = 715.27 (C ₅₁ H ₃₃ N ₅ = 715.84) 10-13 m / z = 715.27 (C ₅₁ H ₃₃ N ₅ = 715.84) 10-14 m / z = 638.25 (C ₄₆ H ₃₀ N ₄ = 638.76) 10-15 m / z = 579.18 (C ₄₀ H ₂₅ N ₃ S = 579.71) 10-16 m / z = 410.14 (C ₂₉ H ₁₈ N ₂ S = 410.47) 10-17 m / z = 486.17 (C ₃₅ H ₂₂ N ₂ O = 486.56) 10-18 m / z = 486.17 (C ₃₅ H ₂₂ N ₂ O = 486.56) 10-19 m / z = 486.17 (C ₃₅ H ₂₂ N ₂ O = 486.56) 10-20 m / z = 563.20 (C ₄₀ H ₂₅ N ₃ O = 563.65) 10-21 m / z = 460.16 (C ₃₃ H ₂₀ N ₂ O = 460.52) 10-22 m / z = 536.19 (C ₃₉ H ₂₄ N ₂ O = 536.62) 10-23 _{m / z = 689.26 (C 49} H 31 N 5 = 689.80) 10-24 m / z = 585.22 (C ₄₃ H ₂₇ N ₃ = 585.69) 10-25 m / z = 484.19 (C ₃₆ H ₂₄ N ₂ = 484.60) 10-26 _{m / z = 534.21 (C 40} H 26 N 2 = 534.66) 10-27 m / z = 560.23 (C ₄₂ H ₂₈ N ₂ = 560.70) 10-28 m / z = 560.23 (C ₄₂ H ₂₈ N ₂ = 560.70)

Synthesis Example 4

Examples of the synthesis of Product 11-6 among the compounds represented by Formula 4 according to the present invention are prepared by reacting with the following Scheme 6, but are not limited thereto.

<Scheme 6>

triphenylen-2-ylboronic acid (5.4g, 20mmol) was dissolved in THF and then 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (7.8g, 20mmol), Pd (PPh ₃ ) ₄ (0.03 equiv), K ₂ CO ₃ (3 equiv), and water are added followed by stirring under reflux. After the reaction was completed, the mixture was extracted with ether 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 obtain 7.5g (yield: 70%) of the product.

compound FD-MS compound FD-MS 11-1 _{m / z = 401.11 (C 30} H 18 S = 410.53) 11-2 m / z = 401.11 (C ₃₀ H ₁₈ S = 410.53) 11-3 m / z = 486.14 (C ₃₆ H ₂₂ S = 486.62) 11-4 m / z = 486.14 (C ₃₆ H ₂₂ S = 486.62) 11-5 m / z = 534.21 (C ₄₀ H ₂₆ N ₂ = 534.65) 11-6 m / z = 535.20 (C ₃₉ H ₂₅ N ₃ = 535.64) 11-7 m / z = 536.16 (C ₄₀ H ₂₄ S = 536.68) 11-8 m / z = 536.16 (C ₄₀ H ₂₄ S = 536.68) 11-9 m / z = 575.17 (C ₄₂ H ₂₅ NS = 575.72) 11-10 m / z = 559.19 (C ₄₂ H ₂₅ NO = 559.65) 11-11 m / z = 585.25 (C ₄₅ H ₃₁ N = 585.73) 11-12 m / z = 575.17 (C ₄₂ H ₂₅ NS = 575.72)

Synthesis Example 5

Compounds represented by the formula (18) according to the present invention is prepared by reacting with the following scheme 7 or scheme 8, but is not limited thereto.

If L is 3

<Scheme 8> When L is 1 ~ 2

Synthesis Example of Sub 18

Sub 18 of Scheme 7 is prepared by reacting with the following Scheme 9, but is not limited thereto.

Scheme 9

After 2-chloropyridine (1 equiv) was dissolved in THF, phenylboronic acid (1 equiv), Pd (PPh ₃ ) ₄ (0.05 equiv), K ₂ CO ₃ (3 equiv) and water were added, followed by stirring at 80 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a product.

An example of Sub 18 is as follows, but is not limited thereto.

compound FD-MS compound FD-MS Sub 18-1 m / z = 205.09 (C ₁₅ H ₁₁ N = 205.25) Sub 18-2 m / z = 219.10 (C ₁₆ H ₁₃ N = 219.28) Sub 18-3 m / z = 255.10 (C ₁₉ H ₁₃ N = 255.31) Sub 18-4 m / z = 233.12 (C ₁₇ H ₁₅ N = 233.31) Sub 18-5 m / z = 261.15 (C ₁₉ H ₁₉ N = 261.36) Sub 18-6 m / z = 255.10 (C ₁₉ H ₁₃ N = 255.31) Sub 18-7 m / z = 205.09 (C ₁₅ H ₁₁ N = 205.25) Sub 18-8 m / z = 219.10 (C ₁₆ H ₁₃ N = 219.28) Sub 18-9 m / z = 247.14 (C ₁₈ H ₁₇ N = 247.33) Sub 18-10 m / z = 281.12 (C ₂₁ H ₁₅ N = 281.35) Sub 18-11 m / z = 219.10 (C ₁₆ H ₁₃ N = 219.28) Sub 18-12 m / z = 269.12 (C ₂₀ H ₁₅ N = 269.34) Sub 18-13 _{m / z = 223.08 (C 15} H 10 FN = 223.25) Sub 18-14 m / z = 223.08 (C ₁₅ H ₁₀ FN = 223.25) Sub 18-15 m / z = 229.09 (C ₁₇ H ₁₁ N = 229.28) Sub 18-16 m / z = 183.10 (C ₁₃ H ₁₃ N = 183.25) Sub 18-17 m / z = 245.12 (C ₁₈ H ₁₅ N = 245.32) Sub 18-18 m / z = 245.12 (C ₁₈ H ₁₅ N = 245.32) Sub 18-19 m / z = 259.14 (C ₁₉ H ₁₇ N = 259.34) Sub 18-20 m / z = 259.14 (C ₁₉ H ₁₇ N = 259.34) Sub 18-21 m / z = 259.14 (C ₁₉ H ₁₇ N = 259.34) Sub 18-22 m / z = 245.12 (C ₁₈ H ₁₅ N = 245.32) Sub 18-23 m / z = 321.15 (C ₂₄ H ₁₉ N = 321.41) Sub 18-24 m / z = 183.10 (C ₁₃ H ₁₃ N = 183.25) Sub 18-25 m / z = 245.12 (C ₁₈ H ₁₅ N = 245.32) Sub 18-26 m / z = 245.12 (C ₁₈ H ₁₅ N = 245.32) Sub 18-27 m / z = 187.08 (C ₁₂ H ₁₀ FN = 187.21) Sub 18-28 m / z = 191.05 (C ₁₁ H ₇ F ₂ N = 191.18) Sub 18-29 m / z = 215.09 (C ₁₃ H ₁₃ NO ₂ = 215.25) Sub 18-30 m / z = 281.12 (C ₂₁ H ₁₅ N = 281.35) Sub 18-31 m / z = 261.06 (C ₁₇ H ₁₁ NS = 261.34) Sub 18-32 m / z = 211.05 (C ₁₃ H ₉ NS = 211.28) Sub 18-33 m / z = 225.06 (C ₁₄ H ₁₁ NS = 225.31) Sub 18-34 m / z = 267.11 (C ₁₇ H ₁₇ NS = 267.39) Sub 18-35 m / z = 261.06 (C ₁₇ H ₁₁ NS = 261.34) Sub 18-36 m / z = 377.12 (C ₂₆ H ₁₉ NS = 377.50) Sub 18-37 m / z = 219.10 (C ₁₆ H ₁₃ N = 219.28) Sub 18-38 m / z = 219.10 (C ₁₆ H ₁₃ N = 219.28)

Synthesis Example of Product 18

Ir (acac) ₃ (1 equivalent) was added to Sub 18 (4 equivalents) and refluxed with Glycerol under nitrogen for 24 hours. After the reaction was completed, the obtained solid material was filtered through column chromatography and dried for 3 hours under a vacuum pump to obtain a final compound.

18-4 synthetic

Ir (acac) ₃ (489.54g, 20mmol) was added to 2- (m-tolyl) pyridine (13.5g, 80mmol) and refluxed with Glycerol under nitrogen for 24 hours. After completion of the reaction, the obtained solid material was filtered and purified by column chromatography, dried under vacuum pump for 3 hours to obtain 42.5g (yield: 76%) of the final compound.

18-6 synthetic

Ir (acac) ₃ (489.54g, 20mmol) was added to 2,4-diphenylpyridine (18.5g, 80mmol) and refluxed under nitrogen with Glycerol for 24 hours. After the completion of the reaction, the obtained solid material was filtered and purified by column chromatography, dried under vacuum pump for 3 hours to give 52.5g (yield: 74%) of the final compound.

Synthesis Example of Product 19-1

Product 19-1 of Scheme 8 is prepared by reacting with the following Scheme 10, but is not limited thereto.

Scheme 10

Sub 18 (3) synthesis  example

IrCl ₃ (1 equivalent) was added to 2-phenylpyridine (2.5 equivalents), and 2-ethoxy ethanol: H ₂ O was added to a solution having a ratio of 3: 1, and reacted at 140 ° C. for 24 hours under nitrogen. After the reaction was completed, the obtained solid material was filtered through column chromatography and dried for 3 hours under a vacuum pump to obtain a final compound.

Product 19- 1 Synthesis  example

Pentane-2,4-dione (10 equivalents), Na ₂ CO ₃ (10 equivalents), and 2-ethoxy ethanol were added to Sub 18 (3) (1 equivalent) and reacted at 130 ° C. for 24 hours under nitrogen. After the reaction was completed, the obtained solid material was filtered through column chromatography and dried for 3 hours under a vacuum pump to obtain a final compound.

19-2 Synthesis

2,2,6,6-tetramethylheptane-3,5-dione (10 equiv), Na ₂ CO ₃ (10 equiv) and 2-ethoxy ethanol were added to an Ir compound (1 equiv) for 24 hours at 130 ° C. under nitrogen. I was. After the reaction was completed, the obtained solid material was filtered through column chromatography and dried for 3 hours under a vacuum pump to give the final compound 19-2.

19-6 Synthesis

Pentane-2,4-dione (10 equiv), Na ₂ CO ₃ (10 equiv) and 2-ethoxy ethanol were added to an Ir compound (1 equiv) and reacted at 130 ° C. for 24 hours under nitrogen. After the reaction was completed, the obtained solid material was filtered through column chromatography and dried for 3 hours under a vacuum pump to give the final compound 19-6.

Synthesis Example of Product 19-2

Product 19-1 (1 equiv) and Sub 19 (2 equiv) were added and microwaved with Glycerol for 20 minutes. After the reaction was completed, the obtained solid material was filtered through column chromatography and dried for 3 hours under a vacuum pump to obtain a final compound.

Sub 19 is the same as the example of Sub 18.

19-7 synthesis

Ancillary ligand 2-([1,1'-biphenyl] -3-yl) pyridine (9.3g, 40mmol) was added to Ir compound (12.2g, 20mmol) as a ligand, and microwave was applied for 20 minutes at 240 ℃ with Glycerol. . After completion of the reaction, the obtained solid material was filtered and purified through column chromatography, dried under vacuum pump for 3 hours to obtain 8.8 g (60% yield) of the final compound.

Product 19-39 Synthesis

Ancillary ligand 2-([1,1'-biphenyl] -3-yl) pyridine (6.2g, 40mmol) was added to Ir compound (18.1g, 20mmol) as a ligand, and microwave was applied for 20 minutes with Glycerol for 240 minutes. . After completion of the reaction, the obtained solid material was filtered and purified through column chromatography, dried under vacuum pump for 3 hours to obtain 11.3 g (58% yield) of the final compound.

Manufacturing Evaluation of Organic Electrical Device

Comparative Experiment Example 1) Fabrication and test of green organic light emitting device

First, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N ¹ on the ITO layer (anode) formed on the glass substrate. -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a hole injection layer having a thickness of 60 nm, and then 4,4-bis [N- (1) as a hole transport compound on the hole injection layer. -Naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Subsequently, the inventive compound represented by Chemical Formula 1 as a light emitting auxiliary layer material was vacuum deposited to a thickness of 20 nm to form a light emitting auxiliary layer. After the light emission auxiliary layer is formed, the above-described compound represented by the formulas (2) to (4) is represented as a host on the light-emitting auxiliary layer, and 18-1 of the compound represented by the formula (18) as a dopant is 95 A light emitting layer having a thickness of 30 nm was deposited on the light emitting auxiliary layer by doping at a weight of 5: 5. As a hole blocking layer, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm, and the electron transport layer Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed into a 40 nm thick film. Thereafter, LiF, 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 device.

The electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measurement result was measured at a luminance of 5000 cd / m2. The T95 life was measured using a life measurement instrument manufactured by McScience. The following table shows the results of device fabrication and evaluation.

Comparative Examples 1-3

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the light emitting auxiliary layer was not used.

Comparative Examples 4-6)

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 was used as the light emitting auxiliary layer.

Comparative Examples 7-12)

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 2 was used as a host.

         Comparative Compound 1 Comparative Compound 2

Light emitting auxiliary compound Host compound Voltage Current density Brightness (cd / m2) Efficiency LifetimeT (95) Comparative Example (1) none Compound (9-9) 5.3 17.4 5000.0 28.7 71.8 Comparative Example (2) Compound (10-28) 5.5 18.7 5000.0 26.8 86.2 Comparative Example (3) Compound (11-4) 5.8 19.9 5000.0 25.1 91.2 Comparative Example (4) Comparative Compound 1 Compound (9-9) 5.5 12.6 5000.0 39.6 101.2 Comparative Example (5) Compound (10-28) 5.8 13.1 5000.0 38.1 107.5 Comparative Example (6) Compound (11-4) 6.2 14.0 5000.0 35.8 112.7 Comparative Example (7) Compound (1-1) Comparative Compound 2 5.8 13.5 5000.0 37.1 110.0 Comparative Example (8) Compound (2-8) 5.7 12.8 5000.0 39.1 109.5 Comparative Example (9) Compound (3-4) 5.7 13.2 5000.0 38.0 102.2 Comparative Example (10) Compound (4-1) 5.2 12.5 5000.0 39.9 115.5 Comparative Example (11) Compound (6-1) 5.4 13.7 5000.0 36.5 101.5 Comparative Example (12) Compound (7-1) 5.3 13.6 5000.0 36.7 109.0 Example (1) Compound (1-1) Compound (9-9) 4.3 10.2 5000.0 49.0 123.5 Example (2) Compound (2-8) 4.5 10.2 5000.0 49.0 128.3 Example (3) Compound (3-4) 4.4 10.4 5000.0 48.0 121.9 Example (4) Compound (4-1) 4.3 10.0 5000.0 50.2 121.3 Example (5) Compound (6-1) 4.5 10.1 5000.0 49.4 120.9 Example (6) Compound (7-1) 4.3 10.1 5000.0 49.7 122.8 Example (7) Compound (1-1) Compound (10-28) 4.7 10.7 5000.0 46.8 124.1 Example (8) Compound (2-8) 4.8 10.8 5000.0 46.4 124.8 Example (9) Compound (3-4) 4.5 10.6 5000.0 47.4 125.6 Example (10) Compound (4-1) 4.5 10.4 5000.0 48.3 124.0 Example (11) Compound (6-1) 4.6 10.9 5000.0 46.0 126.8 Example (12) Compound (7-1) 4.7 10.4 5000.0 48.0 122.5 Example (13) Compound (1-1) Compound (11-4) 4.8 11.4 5000.0 43.7 130.5 Example (14) Compound (2-8) 4.8 11.4 5000.0 43.9 131.2 Example (15) Compound (3-4) 4.9 11.4 5000.0 43.8 132.4 Example (16) Compound (4-1) 4.8 10.9 5000.0 45.8 132.3 Example (17) Compound (6-1) 4.9 11.6 5000.0 43.2 133.3 Example (18) Compound (7-1) 4.8 11.5 5000.0 43.5 132.4

As can be seen from the results of Table 8, the compound represented by the formula (1) is used as the light emitting auxiliary layer, and the compound represented by the formulas (2) to (4) is represented by the host of the light emitting layer, represented by the formula (18). Examples in which the compound is used as a dopant of the light emitting layer do not use the light emitting auxiliary layer (Comparative Examples 1 to 3), Comparative Compound 1 is used as the light emitting auxiliary layer (Comparative Examples 4 to 6), or Comparative Compound 2 is applied to the light emitting layer. It can be seen that the driving voltage, efficiency, and lifespan of the organic electroluminescent light emitter are remarkably improved from those of Comparative Examples 7 to 12 used for the present invention.

In other words, Comparative Examples 4 to 12 and Examples 1 to 18 using Comparative Compound 1 or Inventive Compound as light emitting auxiliary layers, compared to Comparative Examples 1 to 3 without using the light emitting auxiliary layer, improved driving voltage, lifetime, and particularly efficiency. Able to know. That is, it shows that the use of the light emitting auxiliary layer can increase the efficiency than the unused device.

In addition, Examples 1 to 12 using Comparative Compound 1 and Comparative Compound 2 as the light emitting auxiliary layer or the host compound Example 1 using the compound represented by the formula (1) as a light emitting auxiliary layer as a host compound 1 to 18 showed remarkable results in driving voltage, efficiency, and lifetime. The compound represented by Formula 1 has characteristics such as deep HOMO, high T1 and high passion stability compared to Comparative Compound 1, By using the compounds represented by 2) to (4) as a phosphorescent host, the combination of these devices is considered to be synergistically electrochemically improving the performance of the whole device.

That is, the combination of the compound represented by the formula (1) and the compound represented by the formula (2-4) showed a significantly superior performance than the other combinations it can be seen that the most ideal combination.

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 thereto.

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 (16)

An organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode. The organic material layer includes a light emitting auxiliary layer formed between the first electrode and the light emitting layer, and a hole transport layer and a light emitting layer formed between the first electrode and the light emitting auxiliary layer, wherein the light emitting layer includes a host and a dopant material, respectively. The hole transport layer or the light emitting auxiliary layer comprises a compound represented by the following formula (1), wherein the light emitting layer comprises at least one of compounds represented by the following formula (2), (3) or (4) Organic electric element. Formula (1)

Chemical Formula (2) Chemical Formula (3) Chemical Formula (4)

{In the above formulas (1) to (4), 1) Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl 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; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); 2) a, b, d, e, h, i, k are each independently an integer of 0 to 4, c, f, g are each independently an integer of 0 to 3, j is an integer of 0 to 2, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl 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; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); or R ¹ adjacent to each other, R ² adjacent to each other, R ³ adjacent to each other, R ⁴ adjacent to each other, R adjacent to each other. between each ^{other. 5,} the adjacent R ^6, the adjacent R ⁷ to each other, the adjacent R ⁸ each other, the adjacent R ⁹ together with each other, a small neighborhood to each other by R ^10, neighboring to each other by R ^11, adjacent R ^12, adjacent R ¹³ , Neighboring R ¹⁴ , Neighboring R ¹⁵ , Neighboring R ¹⁶ , Neighboring R ¹⁷ , Neighboring R ¹⁸ , Neighboring R ¹⁹ , Neighboring R ²⁰ , Neighboring R ²¹ , Neighboring One R ²² and the other adjacent R ²³ can combine to form a ring, 3) L ¹ , L ² , L ³ , L ⁴ and L ⁵ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; C ₂ ~ C ₆₀ divalent heterocyclic group; Divalent fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And it is selected from the group consisting of divalent aliphatic hydrocarbon group, 4) X and Y are directly bonded to each other independently; S, O, NR ', CR'R "or SiR'R" and W is S, O, NR', CR'R "or SiR'R"; R ′ and R ″ are each independently selected from hydrogen; C ₆ ~ C ₆₀ aryl group; C ₃ ~ C ₆₀ heterocyclic group; C ₁ ~ C ₅₀ Alkyl group; It is bonded to each other spiro Can form compounds, 5) l and m are each independently an integer of 0 ~ 1, l + m is 1 or more, when l and m is 0, it means a direct bond, 6) Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ , Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are Each independently CR or N, R is hydrogen, an aryl group of C ₆ -C ₆₀ ; Containing at least one heteroatom of O, N, S, Si, P C ₃ ~ C ₆₀ Heterocyclic group; C ₁ ~ C ₅₀ Alkyl group; C ₆ ~ C ₆₀ arylamine group; A fluorene group; selected from the group consisting of: a ring formed by combining with a neighboring group, 7) L 'is a single bond; 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 to C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P.} The method of claim 1, An organic electric device, wherein the compound represented by the formula (1) is a compound represented by the following formula (5) or (6).               Formula (5) Formula (6)

(In the formulas (5) and (6), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , a, b, c, d, e, f, g, h, Ar ¹ , Ar ² , L ¹ , L ² , L ³ are as defined in claim 1 above.) An organic electric element according to claim 1, wherein the compound represented by the formula (2) is a compound represented by any one of the following formulas (7) to (12).      Chemical Formula (7) Chemical Formula (8) Chemical Formula (9)

    Chemical Formula (10) Chemical Formula (11) Chemical Formula (12)

(In the above formulas (7) to (12), R ⁹ , R ¹⁰ , R ¹¹ , i, j, k, Ar ³ , L ⁴ , X, Y are as defined in claim 1 above.) An organic electric element according to claim 1, wherein the compound represented by the formula (3) is a compound represented by any one of the following formulas (13) to (16). Chemical Formula (13) Chemical Formula (14)

Formula (15) Formula (16)

(In the above formulas (13) to (16), Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ , Z ¹⁴ , Z ¹⁵ , Z ¹⁶ , Ar ⁴ , L ⁵ , R ', R "are as defined in claim 1 above.) An organic electric device according to claim 1, wherein the compound represented by the formula (4) is represented by the following formula (17).                Formula (17)

{In the above formula (17), 1) R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²² , R ²³ , L ', R _a and R _b are as defined in claim 1 above, 2) R ²⁴ is hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl 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; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); n is an integer of 0 to 4, and adjacent R ²⁴ may combine with each other to form a ring, 3) L ⁶ are independently a single bond to each other; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; C ₂ ~ C ₆₀ divalent heterocyclic group; Divalent fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And it is selected from the group consisting of divalent aliphatic hydrocarbon group, 4) T is S, O, NR ', CR'R "or SiR'R" and R' and R "are as defined in claim 1 above. The organic electroluminescence device according to claim 2, wherein the compound represented by the formula (1), the formula (5) or (6) is selected from one of the compounds represented by

The organic electroluminescence device according to claim 3, wherein the compound represented by the formula (2) or the formulas (7) to (12) is represented by any one of the compounds represented as follows.

The organic electroluminescence device according to claim 4, wherein the compound represented by the general formula (3) or the general formulas (13) to (16) is any one of the compounds represented as follows.

An organic electric element according to claim 5, wherein the compound represented by the formula (4) or the formula (17) is a compound represented by any one of the following compounds.

The organic electronic device of claim 1, wherein the dopant in the emission layer comprises a compound represented by the following Formula (18).        Formula (18)

{In the above formula (18), 1) R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ and R ³² are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ Aryl group; Containing at least one heteroatom of O, N, S, Si, P C ₃ ~ C ₆₀ Heterocyclic group; C ₁ ~ C ₅₀ Alkyl group; A C ₁ to C ₅₀ alkoxy group; C ₂ -C ₂₀ alkenyl group; -L'-N (R _a ) (R _b ); R ²⁵ and R ²⁶ , R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³² Can combine with each other to form a ring, 2) L is an integer from 1 to 3 3) A is an independent ligand represented by the following formula (18-1) or formula (18-2) and has a covalent bond with C, a coordination bond with N, a covalent bond with O, and a coordination bond with another O To form a complex with Ir, Chemical Formula (18-1) Chemical Formula (18-2)

4) R ³³ , R ³⁴ are independently of each other hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ Aryl group; Containing at least one heteroatom of O, N, S, Si, P C ₃ ~ C ₆₀ Heterocyclic group; C ₁ ~ C ₅₀ Alkyl group; A C ₁ to C ₅₀ alkoxy group; C ₂ -C ₂₀ alkenyl group; -L'-N (R _a ) (R _b );}. 11. An organic electroluminescence device according to claim 10, wherein the compound represented by the formula (18) is any one of the compounds represented as follows.

The method of claim 1, And 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. The method of claim 1, 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 1, In the organic layer The hole transport layer or the light emitting auxiliary layer is a compound represented by the following formula (1), The light emitting layer is a compound represented by the following formula (2), (3) or (4), An organic electric device, characterized in that used by mixing the same or different types of compounds. A display device comprising the organic electroluminescent element of claim 1; And a controller for driving the display device. The method of claim 15, 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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