KR102121980B1 - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

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

Description

Compounds for organic electrical devices, organic electrical devices using the same, and electronic devices thereof {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}

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

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

Materials used as the organic material layer in the organic electric device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their function.

The most important issues in organic electroluminescent devices are life and efficiency, and as the display becomes larger, these efficiency and life problems must be solved.

Efficiency, life, and driving voltage are related to each other. As the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic substances due to Joule heating generated during driving decreases, resulting in less It shows a tendency to increase life. However, simply improving the organic layer does not maximize efficiency. This is because long life and high efficiency can be achieved at the same time when the optimum combination of energy level and T1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) is achieved.

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

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 for the hole transport layer, since it has to have a low HOMO value, most have a low T1 value, which causes exciton generated in the light emitting layer to pass to the hole transport layer, resulting in charge unbalance in the light emitting layer. As a result, light emission occurs in the hole transport layer or at the interface of the hole transport layer, resulting in a decrease in color purity, reduction in efficiency and lifetime of the organic electric device.

In addition, it is possible to lower the driving voltage by using a material having a fast hole mobility, but the hole mobility is faster than electron mobility, resulting in charge unbalance in the light emitting layer. The color purity and efficiency of the electric device is lowered and the problem of shortening the life occurs. Therefore, a light emitting auxiliary layer having a high T1 value and having 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 diffusion of the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electric device, into the organic layer, stable properties against Joule heating generated during device driving, that is, high glass transition There is a need to develop a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has a property of lowering the uniformity of the thin film surface when driving the device, which has been reported to have a great influence on the device life. In addition, the OLED device is mainly formed by a vapor deposition method, and it is necessary to develop a material that can withstand a long time during vapor deposition, that is, a material having strong heat resistance.

That is, in order to sufficiently exhibit the excellent characteristics of the organic electric device, materials constituting an 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 are stable and efficient It must be preceded by the material, but the development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently achieved. Therefore, the development of new materials continues to be required, and in particular, the development of materials for the light-emitting auxiliary layer and the hole transport layer is urgently required.

The technology underlying the present invention is disclosed in the publications described in the following patent documents.

United States Patent Publication US6242115 (2001.6.5.) Japanese Unexamined Patent Publication No. 2000-302756 (2000.10.31.)

An object of the present invention is to provide a compound capable of improving the device's high luminous efficiency, low driving voltage, high heat resistance, color purity and lifetime, and an organic electric device using the same and its electronic device.

In one aspect, the present invention provides a compound represented by the following formula.

In another aspect, the present invention provides an organic electric device using the compound represented by the formula and an electronic device thereof.

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

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

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

It should be noted that in adding reference numerals to the components of each drawing, the same components have the same reference numerals as possible even though they are displayed on different drawings. In addition, in describing the present invention, when it is determined that detailed descriptions of related well-known structures or functions may obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.

In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only for distinguishing the component from other components, and the nature, order, or order of the component is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, the component may be directly connected to or connected to the other component, but another component between each component It will be understood that elements may be "connected", "coupled" or "connected".

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

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

The term "alkyl" or "alkyl group" used in the present invention has a single bond of 1 to 60 carbon atoms, unless otherwise specified, a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo By 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" used in the present invention means that at least one of the carbon atoms constituting the alkyl group is replaced with a heteroatom.

The term "alkenyl group" or "alkynyl group" as used herein, unless otherwise specified, has a double or triple bond of 2 to 60 carbon atoms, and includes a straight or branched chain group, and is not limited thereto. It is not.

As used herein, the term "cycloalkyl" means an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, and is not limited thereto.

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

As used herein, the terms "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and 2 to 60 unless otherwise specified. It has a carbon number, and is not limited thereto.

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

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, and are not limited thereto unless otherwise specified. In the present invention, an aryl group or an arylene group means a single ring or multi-ring aromatic, and includes an aromatic ring formed by neighboring substituents participating in a bond or reaction. For example, the aryl group may be a phenyl group, biphenyl group, fluorene group, or spirofluorene group.

The prefix "aryl" or "ar" refers to 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 a radical substituted with an aryl group has a carbon number described herein.

Also, when the prefix is named in succession, it means that the substituents are listed in the order described first. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxycarbonyl group, it means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonyl alkenyl group, it 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 alkyl containing one or more heteroatoms, unless otherwise noted. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or an arylene group having 2 to 60 carbon atoms, each of which contains one or more heteroatoms, unless otherwise specified. No, it includes at least one of a single ring and multiple rings, and may be formed by combining adjacent functional devices.

The term "heterocyclic group" used in the present invention includes at least one heteroatom, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, heteroaliphatic ring and hetero, unless otherwise specified. Aromatic rings. Adjacent functional groups may also be formed by bonding.

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

In addition, "heterocyclic group" may include a ring containing SO ₂ instead of carbon forming a ring. For example, "heterocyclic group" includes the following compounds.

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

Unless otherwise specified, the term "ring" used in the present invention refers to an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms or a combination thereof, and Saturated or unsaturated rings.

Other hetero compounds or hetero radicals other than the above-described hetero compounds include one or more hetero atoms, but are not limited thereto.

Unless otherwise specified, the term "carbonyl" used in the present invention is represented by -COR', where R'is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, 3 to 30 carbon atoms. Is a 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" used in the present invention is represented by -RO-R', wherein R or R'are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or 6 to 30 carbon atoms. It is an aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ 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 Means a group, a germanium group, and one or more substituents selected from the group consisting of C ₂ to C ₂₀ heterocyclic groups, and is not limited to these substituents.

In addition, unless otherwise specified, the formula used in the present invention is applied in the same manner as the definition of a substituent based on the index definition of the following formula.

Here, 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 bound to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3 Each of the following bonds, wherein R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, binds to the carbon of the benzene ring in a similar manner, while indicating the hydrogen bonded to the carbon forming the benzene ring. Is omitted.

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

Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180 and a first electrode 110 and a second electrode 180 formed on the substrate 110. ) Between the organic material layer comprising the compound according to the present invention. At this time, 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 material layer may sequentially 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. At this time, layers other than the emission layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light-emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and the electron transport layer 160 may also serve as a hole blocking layer.

In addition, although not shown, the organic electric device according to the present invention may further include a protective layer or a light efficiency improving layer (Capping layer) formed on a surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode.

The compound according to the present invention applied to the organic material layer is a host of a hole injection layer 130, a hole transport layer 140, a light emitting auxiliary layer 151, an electron transport layer 160, an electron injection layer 170, and a light emitting layer 150 Or it may be used as a material for a dopant or a light efficiency improving layer. Preferably, the compound of the present invention may be used as the hole transport layer 140 and/or the light-emitting auxiliary layer 151.

On the other hand, even in the same core, the band gap, electrical properties, and interfacial properties may vary depending on which substituents are attached at which positions, so the selection of the core and the combination of sub-substituents coupled thereto are also very good. It is important, especially when the energy level and T1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined, long life and high efficiency can be achieved simultaneously.

As already described, in order to solve the light emission problem in the hole transport layer in the recent organic electroluminescent device, it is preferable that a light-emitting auxiliary layer is formed between the hole transport layer and the light emitting layer, depending on the respective light emitting layers (R, G, B) It is time to develop different light-emitting auxiliary layers. On the other hand, in the case of the light-emitting auxiliary layer, since it is necessary to grasp the relationship between the hole transport layer and the light-emitting layer (host), even if similar cores are used, it will be very difficult to infer the characteristics of the organic layer used.

Therefore, in the present invention, by forming a hole transport layer or a light-emitting auxiliary layer using the compound represented by Chemical Formula 1, the energy level (level) and T1 value between each organic material layer, the material's intrinsic properties (mobility, interfacial properties, etc.) are optimized. It is possible to simultaneously improve the life and efficiency of the organic electric device.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, an anode 120 is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, and a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, and an electron transport layer are formed thereon. 160) and after forming an organic material layer including the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.

In addition, the organic material layer is a solution process or a solvent process (e.g., spin coating process), nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blade using various polymer materials It can be produced with fewer layers by a method such as a ding process, a screen printing process, or a thermal transfer method. Since the organic material layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the formation method.

The organic electric device according to the present invention may be a front emission type, a back emission type, or a double-sided emission type, depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage of being easy to realize high resolution and excellent processability, and can be manufactured using the color filter technology of the existing LCD. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Typically, R (Red), G (Green), B (Blue) light-emitting parts are arranged in a mutually planar side-by-side manner, and a stacking method in which R, G, and B light-emitting layers are stacked vertically. There is a color conversion material (CCM) method using electroluminescence by the blue (B) organic light-emitting layer and photo-luminescence of the inorganic phosphor using light therefrom. Can be applied to these WOLEDs.

In addition, the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a monochromatic or white lighting device.

Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electric element of the present invention, and a control unit for controlling the display device. At this time, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game machines, various TVs, and various computers.

Hereinafter, a compound according to an aspect of the present invention will be described.

The compound according to an aspect of the present invention is represented by Formula 1 below.

<Formula 1>

In Chemical Formula 1,

m and o are integers from 0 to 4, and n and p are integers from 0 to 3.

R ¹ to R ⁴ are independently of each other, hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; A fused ring group of an aromatic ring of C ₆ to C ₆₀ and an aliphatic ring of C ₃ to C ₆₀ ; C ₂ ~ C ₂₀ alkenyl group; -L ^a -N(Ar ^a )(Ar ^b ); C ₁ ~C ₃₀ Alkoxy group; And C ₆ ~ C ₃₀ Aryloxy group; It may be selected from the group consisting of. For example, R ¹ to R ⁴ may be each independently hydrogen, phenyl or pyridine.

In addition, the R ¹ to R ⁴ may be formed by combining adjacent groups with each other to form at least one ring. At this time, R ¹ to R ⁴ which do not form a ring are the same as defined above, respectively.

On the other hand, the rings formed by bonding adjacent groups are C ₃ ~ C ₆₀ aliphatic ring or C ₆ ~ C ₆₀ aromatic ring, C ₂ ~ C ₆₀ heterocycle, C ₃ ~ C ₆₀ alicyclic ring, or these It may be a fused ring or the like consisting of a combination of, may be a single ring or multiple rings, as well as a saturated or unsaturated ring.

Ar ¹ to Ar ⁴ are independently of each other, a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; A fused ring group of an aromatic ring of C ₆ to C ₆₀ and an aliphatic ring of C ₃ to C ₆₀ ; C ₂ ~ C ₂₀ alkenyl group; -L ^a -N(Ar ^a )(Ar ^b ); C ₁ ~C ₃₀ Alkoxy group; And C ₆ ~ C ₃₀ Aryloxy group; It may be selected from the group consisting of. For example, Ar ¹ to Ar ⁴ are independently of each other, ethyl, phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, pyrene, toluene, fluorophenyl, deuterium-substituted phenyl, propenylphenyl, 9,9- Dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, pyridine, quinoline, isoquinoline, indole, thiophene, benzothiophene, carbazole, dibenzothiophene, dibenzofuran, benzonaphthoty Or offen or 7,7-dibenzo-7H-benzofluorene.

L ^a is a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; A C ₂ to C _{60 divalent} heterocyclic group including at least one hetero atom among O, N, S, Si and P; A divalent fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And divalent aliphatic hydrocarbon group; may be selected from the group consisting of.

The Ar ^a and Ar ^b are independently of each other, C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; A fused ring group of an aromatic ring of C ₆ to C ₆₀ and an aliphatic ring of C ₃ to C ₆₀ ; And C ₂ ~ C ₂₀ alkenyl group; It may be selected from the group consisting of.

The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxyl group, aryloxy group of R ¹ to R ⁴ and Ar ¹ to Ar ⁴ are each deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C ₁ ~ C ₂₀ alkylthio; C ₁ ~ C ₂₀ alkoxyl group; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₆ ~ C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ heterocyclic group; C ₃ ~ C ₂₀ cycloalkyl group; C ₇ ~ C ₂₀ Arylalkyl group; And C ₈ ~ C ₂₀ aryl alkenyl group; It may be substituted with one or more substituents selected from the group consisting of.

L ¹ is independently of each other, a C ₆ ~ C ₆₀ arylene group; Fluorylene group; A C ₂ to C _{60 divalent} heterocyclic group including at least one hetero atom among O, N, S, Si and P; A divalent fused ring group of a C ₃ to C ₆₀ aliphatic ring and a C ₆ to C ₆₀ aromatic ring; And divalent aliphatic hydrocarbon group; may be selected from the group consisting of. For example, L ¹ may be phenyl, biphenyl, naphthyl, phenanthrene, 9,9-dimethyl-9H-fluorene, pyridine, quinoline, benzothiophene, dibenzofuran or dibenzothiophene.

The arylene group, fluorenylene group, divalent heterocyclic group, divalent fused ring group, and divalent aliphatic hydrocarbon group of L ¹ are each deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C ₁ ~ C ₂₀ alkylthio; C ₁ ~ C ₂₀ alkoxyl group; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₆ ~ C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ heterocyclic group; C ₃ ~ C ₂₀ cycloalkyl group; C ₇ ~ C ₂₀ Arylalkyl group; -N(Ar ^c )(Ar ^d ); And C ₈ ~ C ₂₀ Aryl alkenyl group; It may be substituted with one or more substituents selected from the group consisting of,

Ar ^c and Ar ^d are independently of each other, a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; And C ₂ ~ C ₆₀ Heterocyclic group containing at least one hetero atom of O, N, S, Si and P; may be selected from the group consisting of.

In addition, L ¹ of Formula 1 may be one of the following structures.

In the above structure,

Q ¹ is C(R ⁵ ) or N; Q ² may be C(R ⁶ )(R ⁷ ), N(R ⁸ ), S or O.

R ⁵ is hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₁ ~C ₃₀ Alkoxy group; And -N (Ar ^e ) (Ar ^f ); It may be selected from the group consisting of. For example, R ⁵ may be hydrogen, phenyl, -N(Ar ^e )(Ar ^f ), or the like.

Here, Ar ^e and Ar ^f are independently of each other, C ₆ ~ C ₆₀ aryl group; Fluorenyl group; And C ₂ ~ C ₆₀ Heterocyclic group containing at least one hetero atom of O, N, S, Si and P; may be selected from the group consisting of.

R ⁶ to R ⁸ are independently of each other, C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; And C ₁ ~ C ₃₀ alkoxyl group; may be selected from the group consisting of. For example, R ⁶ to R ⁸ may be each independently methyl.

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

In the case of the heterocyclic group, the number of carbon atoms may be 2 to 60, preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and

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

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

Specifically, the compound represented by Formula 1 may be represented by one of the following formulas.

<Formula 2> <Formula 3> <Formula 4>

<Formula 5> <Formula 6> <Formula 7>

<Formula 8> <Formula 9> <Formula 10>

<Formula 11> <Formula 12> <Formula 13>

<Formula 14> <Formula 15> <Formula 16>

<Formula 17> <Formula 18> <Formula 19>

<Formula 20> <Formula 21> <Formula 22>

In Chemical Formulas 2 to 22, Ar ¹ to Ar ⁴ , L ¹ , R ¹ to R ⁴ , m, n, o, and p may be defined in the same manner as defined in Chemical Formula 1.

More specifically, the compound represented by Formula 1 to Formula 22 may be any one of the following compounds.

As another embodiment, the present invention provides a compound for an organic electric device represented by the formula (1).

In another embodiment, the present invention provides an organic electric device containing the compound represented by Formula 1 above.

At this time, the organic electric device includes a first electrode; A second electrode; And an organic material layer positioned between the first electrode and the second electrode. The organic material layer may include a compound represented by Chemical Formula 1, and Chemical Formula 1 is a hole injection layer, a hole transport layer, and a light emitting auxiliary layer of the organic material layer. Or it may be contained in at least one of the light emitting layer. That is, the compound represented by Chemical Formula 1 may be used as a material for a hole injection layer, a hole transport layer, a light emitting auxiliary layer, or a light emitting layer. Specifically, an organic electroluminescent device comprising one of the compounds represented by Chemical Formulas 2 to 22 is provided in the organic material layer, and more specifically, the present invention provides an organic electroluminescent device comprising the compound represented by the individual chemical formula in the organic material layer. Provides

In another embodiment of the present invention, the present invention is a light efficiency improving layer formed on at least one side of the one side of the first electrode opposite to the organic layer or one side of the second electrode opposite to the organic layer. It provides an organic electrical device further comprising a.

Hereinafter, examples of the synthesis of the compound represented by the chemical formula according to the present invention and the manufacturing example of the organic electric device will be specifically described with reference to examples, but the present invention is not limited to the following examples.

Synthetic example

Illustratively, the compound (Final products) according to the present invention is synthesized by reacting Sub 2 and Sub 3 as shown in Reaction Scheme 1 below, but is not limited thereto.

<Scheme 1>

(However, Ar ¹ to Ar ⁴ , L ¹ , R ¹ to R ⁴ , m, n, o and p are the same as defined in Formula 1, Hal ⁸ is Br or Cl.)

I. Sub Synthesis of 1

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

<Reaction Scheme 2>

(However, Hal ¹ and Hal ³ are Br or I, Hal ² is Br or Cl.)

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

One. Sub 1-1 Synthesis Example

<Scheme 3>

(One) Sub 1-I-1 synthesis

After dissolving the starting material phenylboronic acid (113.01g, 926.8mmol) in THF in a round bottom flask, 4-bromo-1-iodo-2-nitrobenzene (455.87g, 1390.3mmol), Pd(PPh ₃ ) ₄ (53.55g , 46.3mmol), K ₂ CO ₃ (384.3g, 2780.5mmol), water was added and stirred at 80°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 183.01 g of product (yield: 71%).

(2) Sub One- II -1 synthesis

Sub 1-I-1 (183.01 g, 658.1 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene in a round bottom flask, triphenylphosphine (431.51 g, 1645.2 mmol) was added and stirred at 200°C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 113.37 g of product (yield: 70%).

(3) Sub One- III -1 synthesis

After dissolving Sub 1-II-1 (113.37g, 460.7mmol) obtained in the synthesis with nitrobenzene in a round bottom flask, iodobenzene (140.97g, 691mmol), Na ₂ SO ₄ (65.43g, 460.7mmol), K ₂ CO ₃ (63.67 g, 460.7 mmol), Cu (8.78 g, 138.2 mmol) was added and stirred at 200°C. When the reaction was completed, nitrobenzene was removed through distillation, and 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 108.35 g of product (yield 73%).

(4) Sub 1-1 synthesis

After dissolving Sub 1-III-1 (108.35g, 336.3mmol) obtained in the synthesis with DMF in a round bottom flask, Bis(pinacolato)diboron (93.93g, 369.9mmol), Pd(dppf)Cl ₂ (8.24g, 10.1mmol), KOAc (99.01 g, 1008.8 mmol) was added and stirred at 90°C. When the reaction was completed, DMF was removed through distillation, and 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 96.86 g of product (yield: 78%).

2. Sub 1-9 Synthesis Example

<Reaction Scheme 4>

(One) Sub 1-I-9 synthesis

Starting material phenylboronic acid (13.22g, 108.4mmol), 1-bromo-4-chloro-2-nitrobenzene (38.45g, 162.6mmol), Pd(PPh ₃ ) ₄ (6.26g, 5.4mmol), K ₂ CO ₃ (44.96 g, 325.3 mmol), THF, and water were obtained using the above Synthesis Example of Sub 1-I-1 to obtain 16.97 g (yield: 67%) of the product.

(2) Sub One- II -9 synthesis

Triphenylphosphine (47.63g, 181.6mmol) and o- dichlorobenzene were added to Sub 1-I-9 (16.97g, 72.6mmol) obtained in the synthesis using the synthesis example of Sub 1-II-1, yielding 10.55g of product (yield: 72 %).

(3) Sub One- III -9 synthesis

Sub-1 II-9 obtained in the above Synthesis 3-bromo-9,9-dimethyl- 9 H -fluorene (21.44g, 78.5mmol) in _{(10.55g, 52.3mmol), Na 2} SO 4 (7.43 g, 52.3 mmol), K ₂ CO ₃ (7.23g, 52.3mmol), Cu (1g, 15.7mmol), and nitrobenzene were obtained using the synthesis example of Sub 1-III-1 to obtain 12.57g of product (yield: 61%).

(4) Sub 1-9 synthesis

Bis(pinacolato)diboron (8.91g, 35.1mmol), Pd(dppf)Cl ₂ (0.78g, 1mmol), KOAc in Sub 1-III-9 (12.57g, 31.9mmol) obtained in the above synthesis (9.4g, 95.7mmol), DMF was obtained using the Synthesis Example of Sub 1-1 above to obtain the product 13.01g (Yield: 84%).

3. Sub 1-19 Synthesis Example

<Reaction Scheme 5>

(One) Sub 1-I-19 synthesis

Starting material phenylboronic acid (194.59g, 1595.9mmol) 4-bromo-2-iodo-1-nitrobenzene (784.95g, 2393.9mmol), Pd(PPh ₃ ) ₄ (92.21g, 79.8mmol), K ₂ CO ₃ (661.71 g, 4787.7 mmol), THF, and water were used to obtain 310.68 g (yield: 70%) of the product using the synthesis example of Sub 1-I-1.

(2) Sub One- II -19 synthesis

Sub 1-I-19 (310.68g, 1117.2mmol) obtained from the synthesis of triphenylphosphine (732.54g, 2792.9mmol), o -dichlorobenzene using the synthesis example of Sub 1-II-1, product 203.45g (Yield: 74 %).

(3) Sub One- III -19 synthesis

Iodobenzene (233g, 1142.1mmol), Na ₂ SO _{4 in} Sub 1-II-19 (187.38g, 761.4mmol) obtained in the above synthesis (108.15g, 761.4mmol), K ₂ CO ₃ (105.23g, 761.4mmol), Cu (14.52g, 228.4mmol), and nitrobenzene were obtained using the synthesis example of Sub 1-III-1 to obtain 179.09g of product (yield 73%).

(4) Sub 1-19 synthesis

Bis(pinacolato)diboron (155.26g, 611.4mmol), Pd(dppf)Cl ₂ (13.62g, 16.7mmol), KOAc in Sub 1-III-19 (179.09g, 555.8mmol) obtained in the above synthesis (163.65g, 1667.5mmol), DMF was obtained 172.41g (yield: 84%) of the product using the synthesis example of Sub 1-1.

4. Sub 1-42 Synthesis Example

<Scheme 6>

(One) Sub One- III -42 synthesis

2-iododibenzo[ b , d ]furan (23.34g, 79.4mmol), Na ₂ SO _{4 in} Sub 1-II-19 (13.02g, 52.9mmol) obtained in the above synthesis. (7.51 g, 52.9 mmol), K ₂ CO ₃ (7.31 g, 52.9 mmol), Cu (1.01 g, 15.9 mmol), and nitrobenzene were obtained using the synthesis example of Sub 1-III-1 to obtain 15.05 g of product (yield 69%).

(2) Sub 1-42 synthesis

Bis(pinacolato)diboron (10.2g, 40.2mmol), Pd(dppf)Cl ₂ (0.89g, 1.1mmol), KOAc in Sub 1-III-42 (15.05g, 36.5mmol) obtained in the above synthesis (10.75g, 109.5mmol), DMF was obtained using the Synthesis Example of Sub 1-1 above, 13.58g of product (yield: 81%).

5. Sub 1-67 Synthesis Example

<Scheme 7>

(One) Sub 1-I-67 synthesis

Starting material phenanthren-9-ylboronic acid (25.93g, 116.8mmol) 4-bromo-1-iodo-2-nitrobenzene (57.44g, 175.2mmol), Pd(PPh ₃ ) ₄ (6.75g, 5.8mmol), K ₂ CO ₃ (48.42 g, 350.3 mmol), THF, and water were obtained 30.48 g (yield: 69%) of the product using the synthesis example of Sub 1-I-1.

(2) Sub One- II -67 synthesis

Sub 1-I-67 (30.48g, 80.6mmol) obtained from the synthesis of triphenylphosphine (52.84g, 201.5mmol), o -dichlorobenzene using the synthesis example of Sub 1-II-1, product 17.58g (Yield: 63 %).

(3) Sub One- III -67 synthesis

Iodobenzene (15.54g, 76.2mmol), Na ₂ SO _{4 in} Sub 1-II-67 (17.58g, 50.8mmol) obtained in the above synthesis (7.21 g, 50.8 mmol), K ₂ CO ₃ (7.02g, 50.8mmol), Cu (0.97g, 15.2mmol), and nitrobenzene were obtained using the synthesis example of Sub 1-III-1 to obtain 15.23g of product (yield: 71%).

(4) Sub 1-67 Synthesis

Bis(pinacolato)diboron (10.07g, 39.7mmol), Pd(dppf)Cl ₂ (0.88g, 1.1mmol), KOAc in Sub 1-III-67 (15.23g, 36.1mmol) obtained in the above synthesis (10.62g, 108.2mmol), DMF was obtained using the above Synthesis Example of Sub 1-1, 13.88g of product (yield: 82%).

6. Sub Synthesis Example 1-70

<Scheme 8>

(One) Sub 1-I-70 synthesis

Starting material phenylboronic acid (43.28g, 355mmol) 4-bromo-1-iodo-2-nitronaphthalene (201.24g, 532.4mmol), Pd(PPh ₃ ) ₄ (20.51g, 17.7mmol), K ₂ CO ₃ ( 147.18 g, 1064.9 mmol), THF, and water were obtained 76.88 g (yield: 66%) of the product using the synthesis example of Sub 1-I-1.

(2) Sub One- II -70 synthesis

Sub 1-I-70 (76.88g, 234.3mmol) obtained in the synthesis of triphenylphosphine (153.62g, 585.7mmol), o -dichlorobenzene using the synthesis example of Sub 1-II-1, product 47.87g (Yield: 69 %).

(3) Sub One- III -70 synthesis

Iodobenzene (49.46g, 242.5mmol), Na ₂ SO _{4 in} Sub 1-II-70 (47.87g, 161.6mmol) obtained in the above synthesis (22.96g, 161.6mmol), K ₂ CO ₃ (22.34g, 161.6mmol), Cu (3.08g, 48.5mmol), and nitrobenzene were obtained using the synthesis example of Sub 1-III-1 to obtain 44.53g of product (yield: 74%).

(4) Sub 1-70 synthesis

Bis(pinacolato)diboron (33.41g, 131.6mmol), Pd(dppf)Cl ₂ (2.93g, 3.6mmol), KOAc in Sub 1-III-70 (44.53g, 119.6mmol) obtained in the above synthesis (35.22g, 358.9mmol), DMF was obtained 40.13g (yield: 80%) of the product using the synthesis example of Sub 1-1.

Meanwhile, examples of Sub 1 (Sub 1A and Sub 1B) according to the synthesis example are as follows, but are not limited thereto, and their FD-MS are shown in Table 1 below.

[Table 1]

II . Sub Synthesis of 2

Sub 2 of Reaction Scheme 1 may be synthesized by the reaction route of Reaction Scheme 9, but is not limited thereto.

<Scheme 9>

(However, Hal ⁴ and Hal ⁵ are Br; Hal ⁶ and Hal ⁸ are Br or Cl; Hal ⁷ is Br or I.)

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

One. Sub 2-1 Synthesis Example

<Reaction Scheme 10>

(One) Sub 2-I-1 synthesis

After dissolving Sub 1-1 (29.36g, 79.5mmol) obtained in the above synthesis in THF in a round bottom flask, 1,3-dibromo-5-chlorobenzene (42.99g, 159mmol), Pd(PPh ₃ ) ₄ (2.76g , 2.4mmol), NaOH (9.54g, 238.5mmol), water was added and stirred at 80°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 24.43 g of product (yield: 71%).

(2) Sub 2- II -1 synthesis

After dissolving Sub 2-I-1 (14.34g, 33.1mmol) obtained in the above synthesis in THF in a round bottom flask, Sub 1-1 (14.68g, 39.8mmol), Pd(PPh ₃ ) ₄ (1.15g, 1mmol) ), NaOH (3.98g, 99.4mmol), water was added and stirred at 80°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried and concentrated with MgSO ₄ , and then the resulting compound was silicagel column and recrystallized to obtain 15.78 g of product (yield: 80%).

(3) Sub 2- III -1 synthesis

After dissolving Sub 2-II-1 (15.78g, 26.5mmol) obtained in the synthesis with DMF in a round bottom flask, Bis(pinacolato)diboron (7.41g, 29.2mmol), Pd(dppf)Cl ₂ (0.65g, 0.8mmol), KOAc (7.81 g, 79.5 mmol) was added and stirred at 90°C. When the reaction was completed, DMF was removed through distillation, and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 14.93 g of product (yield: 82%).

(4) Sub 2-1 Synthesis

After dissolving Sub 2-III-1 (14.93g, 21.7mmol) obtained in the above synthesis in THF in a round bottom flask, 1-bromo-4-iodobenzene (9.23g, 32.6mmol), Pd(PPh ₃ ) ₄ (1.26 g, 1.1mmol), K ₂ CO ₃ (9.02g, 65.2mmol), water was added and stirred at 80°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 13.07 g of product (yield: 84%).

2. Sub 2-6 Synthesis Example

<Scheme 11>

(One) Sub 2- II -6 synthesis

Sub 2-I-1 (8.73g, 20.2mmol) obtained in the above synthesis, Sub 1-9 (11.75g, 24.2mmol), Pd(PPh ₃ ) ₄ (0.7g, 0.6mmol), NaOH (2.42g, 60.5 mmol), THF, and water were used to obtain 10.76 g (yield: 75%) of the product using the synthesis example of Sub 2-II-1.

(2) Sub 2- III -6 synthesis

Bis(pinacolato)diboron (4.23g, 16.6mmol), Pd(dppf)Cl ₂ (0.37g, 0.5mmol), KOAc in Sub 2-II-6 (10.76g, 15.1mmol) obtained in the above synthesis (4.45g, 45.4mmol), DMF was obtained 9.59g (yield: 79%) of the product using the synthesis example of Sub 2-III-1.

(3) Sub 2-6 Synthesis

1-bromo-4-iodobenzene (5.07g, 17.9mmol), Pd(PPh ₃ ) ₄ (0.69g, 0.6mmol), K ₂ CO in Sub 2-III-6 (9.59g, 11.9mmol) obtained in the above synthesis ₃ (4.95g, 35.8mmol), THF, and water were used to obtain 8.15g (yield: 82%) of the product using the synthesis example of Sub 2-1.

3. Sub 2-48 Synthesis Example

<Reaction Scheme 12>

(One) Sub 2-I-48 synthesis

1,3-dibromo-5-chlorobenzene (26.73g, 98.9mmol), Pd(PPh ₃ ) ₄ (1.71g, 1.5mmol), NaOH (5.93) to Sub 1-70 (20.73g, 49.4mmol) obtained in the above synthesis. g, 148.3mmol), THF, and water were used to obtain the product 16.71g (yield: 70%) using the above Synthesis Example of Sub 2-I-1.

(2) Sub 2- II -48 synthesis

Sub 2-I-48 (16.71 g, 34.6 mmol) obtained in the above synthesis, Sub 1-70 (17.42 g, 41.5 mmol), Pd(PPh ₃ ) ₄ (1.2 g, 1 mmol), NaOH (4.15 g, 103.8 mmol) ), THF and water were obtained using the above Synthesis Example of Sub 2-II-1 to obtain 16.12 g of product (yield: 67%).

(3) Sub 2- III -48 synthesis

Bis(pinacolato)diboron (6.48g, 25.5mmol), Pd(dppf)Cl ₂ (0.57g, 0.7mmol), KOAc in Sub 2-II-48 (16.12g, 23.2mmol) obtained in the above synthesis (6.83 g, 69.6 mmol), DMF was obtained using the above Synthesis Example of Sub 2-III-1, 13.68 g of product (yield: 75%).

(4) Sub 2-48 synthesis

Sub 2-III-48 (13.68 g, 17.4 mmol) obtained in the above synthesis, 1-bromo-4-iodonaphthalene (8.68 g, 26.1 mmol), Pd(PPh ₃ ) ₄ (1 g, 0.9 mmol), K ₂ CO ₃ (7.21 g, 52.2 mmol), THF, and water were used to obtain 10.84 g (yield: 72%) of the product using the synthesis example of Sub 2-1.

4. Sub 2-52 Synthesis Example

<Scheme 13>

(One) Sub 2-I-52 synthesis

1,3-dibromo-5-chlorobenzene (191.02g, 706.5mmol), Pd(PPh ₃ ) ₄ (12.25g, 10.6mmol), NaOH (42.39) to Sub 1-19 (130.45g, 353.3mmol) obtained in the above synthesis. g, 1059.8mmol), THF, and water were used to obtain the product 105.48g (yield: 69%) using the synthesis example of Sub 2-I-1.

(2) Sub 2- II -52 synthesis

Sub 2-I-52 (35.09g, 81.1mmol) obtained in the above synthesis, Sub 1-19 (35.93g, 97.3mmol), Pd(PPh ₃ ) ₄ (2.81g, 2.4mmol), NaOH (9.73g, 243.3 mmol), THF, and water were obtained 39.09 g (yield: 81%) of the product using the synthesis example of Sub 2-II-1.

(3) Sub 2- III -52 synthesis

Bis(pinacolato)diboron (18.35g, 72.3mmol), Pd(dppf)Cl ₂ (1.61g, 2mmol), KOAc in Sub 2-II-52 (39.09g, 65.7mmol) obtained in the above synthesis (19.34g, 197mmol), DMF was obtained 35.63g (yield: 79%) of the product using the above Synthesis Example of Sub 2-III-1.

(4) Sub 2-52 synthesis

1-bromo-4-iodobenzene (9.18g, 32.5mmol), Pd(PPh ₃ ) ₄ (1.25g, 1.1mmol), K ₂ CO in Sub 2-III-52 (14.86g, 21.6mmol) obtained in the above synthesis ₃ (8.97 g, 64.9 mmol), THF, and water were obtained by using the above Synthesis Example of Sub 2-1, 13.32 g (yield: 86%) of the product.

5. Sub 2-62 Synthesis Example

<Reaction Scheme 14>

(One) Sub 2- II -62 synthesis

Sub 2-I-52 (9.64 g, 22.3 mmol) obtained in the above synthesis, Sub 1-42 (12.28 g, 26.7 mmol), Pd(PPh ₃ ) ₄ (0.77 g, 0.7 mmol), NaOH (2.67 g, 66.8) mmol), THF, and water were used to obtain 10.84 g (yield: 71%) of the product using the synthesis example of Sub 2-II-1.

(2) Sub 2- III -62 synthesis

Bis(pinacolato)diboron (4.42g, 17.4mmol), Pd(dppf)Cl ₂ (0.39g, 0.5mmol), KOAc in Sub 2-II-62 (10.84g, 15.8mmol) obtained in the above synthesis (4.66g, 47.5mmol), DMF was used to obtain the product 9.46g (yield: 77%) using the synthesis example of Sub 2-III-1.

(3) Sub 2-62 synthesis

1-bromo-4-iodobenzene (5.17g, 18.3mmol), Pd(PPh ₃ ) ₄ (0.7g, 0.6mmol), K ₂ CO in Sub 2-III-62 (9.46g, 12.2mmol) obtained in the above synthesis ₃ (5.05g, 36.5mmol), THF, and water were used to obtain the product 8.05g (yield: 82%) using the synthesis example of Sub 2-1.

6. Sub 2-70 Synthesis Example

<Reaction Scheme 15>

Sub 2-III-52 (8.89 g, 12.9 mmol) obtained in the above synthesis, 2,7-dibromo-9,9-dimethyl-9 H- fluorene (6.84 g, 19.4 mmol), Pd(PPh ₃ ) ₄ (0.75 g, 0.6mmol), K ₂ CO ₃ (5.37g, 38.8mmol), THF, and water were obtained 8.19g (yield: 76%) of the product using the synthesis example of Sub 2-1.

7. Sub 2-73 Synthesis Example

<Reaction Scheme 16>

1-bromo-3-iodobenzene (5.91g, 20.9mmol), Pd(PPh ₃ ) ₄ (0.81g, 0.7mmol), K ₂ CO in Sub 2-III-52 (9.57g, 13.9mmol) obtained in the above synthesis ₃ (5.78 g, 41.8 mmol), THF, and water were used to obtain 8.28 g (yield: 83%) of the product using the synthesis example of Sub 2-1.

8. Sub 2-100 Synthesis Example

<Reaction Scheme 17>

(One) Sub 2- II -100 synthesis

Sub 2-I-52 (43.03 g, 99.4 mmol) obtained in the above synthesis, Sub 1-1 (44.06 g, 119.3 mmol), Pd(PPh ₃ ) ₄ (3.45 g, ₃ mmol), NaOH (11.93 g, 298.3 mmol) ), THF, water was obtained using the above Sub 2-II-1 Synthesis Example 45.57g (yield: 77%) of the product.

(2) Sub 2- III -100 synthesis

Bis(pinacolato)diboron (21.39g, 84.2mmol), Pd(dppf)Cl ₂ (1.88g, 2.3mmol), KOAc in Sub 2-II-100 (45.57g, 76.6mmol) obtained in the above synthesis (22.54g, 229.7mmol), DMF was obtained 42.06g (yield: 80%) of the product using the above Synthesis Example of Sub 2-III-1.

(3) Sub 2-100 synthesis

1-bromo-4-iodobenzene (16.82g, 59.4mmol), Pd(PPh ₃ ) ₄ (2.29g, 2mmol), K ₂ CO _{3 to} Sub 2-III-100 (27.21g, 39.6mmol) obtained in the above synthesis (16.43g, 118.9mmol), THF, and water were used to obtain the product 24.11g (yield: 85%) using the synthesis example of Sub 2-1.

9. Sub 2-132 Synthesis Example

<Reaction Scheme 18>

1-bromo-2-iodobenzene (8.01g, 28.3mmol), Pd(PPh ₃ ) ₄ (1.09g, 0.9mmol), K ₂ CO in Sub 2-III-100 (12.96g, 18.9mmol) obtained in the above synthesis ₃ (7.83g, 56.6mmol), THF, and water were obtained using the above Synthesis Example of Sub 2-1, 8.78g of the product (yield: 65%).

10. Sub Synthesis Example 2-145

<Scheme 19>

(One) Sub 2- II -145 synthesis

Sub 2-I-52 (9.74 g, 22.5 mmol) obtained in the above synthesis, Sub 1-67 (12.68 g, 27 mmol), Pd(PPh ₃ ) ₄ (0.78 g, 0.7 mmol), NaOH (2.7 g, 67.5 mmol) ), THF, and water were obtained 11.42 g (yield: 73%) of the product using the synthesis example of Sub 2-II-1.

(2) Sub 2- III -145 synthesis

Bis(pinacolato)diboron (4.59g, 18.1mmol), Pd(dppf)Cl ₂ (0.4g, 0.5mmol), KOAc in Sub 2-II-145 (11.42g, 16.4mmol) obtained in the above synthesis (4.84g, 49.3mmol), DMF was used to obtain the product 10.08g (yield: 78%) using the Synthesis Example of Sub 2-III-1.

(3) Sub 2-145 synthesis

1-bromo-4-iodobenzene (5.44g, 19.2mmol), Pd(PPh ₃ ) ₄ (0.74g, 0.6mmol), K ₂ CO in Sub 2-III-145 (10.08g, 12.8mmol) obtained in the above synthesis ₃ (5.31 g, 38.4 mmol), THF, and water were obtained using the above Synthesis Example of Sub 2-1, 8.36 g of the product (yield: 80%).

Meanwhile, examples of Sub 2 according to the synthesis example are as follows, but are not limited thereto, and their FD-MS are shown in Table 2 below.

[Table 2]

III . Sub Synthesis of 3

Sub 3 of Reaction Scheme 1 may be synthesized by the reaction route of Reaction Scheme 20 below, but is not limited thereto.

<Reaction Scheme 20>

(However, Hal ⁹ is Br or Cl.)

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

One. Sub 3-1 Synthesis Example

<Reaction Scheme 21>

After the starting material bromobenzene (14.78g, 94.1mmol) was dissolved in toluene in a round bottom flask, aniline (17.53g, 188.3mmol), Pd ₂ (dba) ₃ (2.59g, 2.8mmol), 50% P( t- Bu) ₃ (3.7ml, 7.5mmol), NaO t -Bu (27.14g, 282.4mmol) was added and stirred at 40°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 12.74 g of product (yield: 80%).

2. Sub 3-2 Synthesis Example

<Reaction Scheme 22>

Starting materials 1-bromonaphthalene (8.56g, 41.3mmol) aniline (7.7g, 82.7mmol), Pd ₂ (dba) ₃ (1.14g, 1.2mmol), 50% P( t -Bu) ₃ (1.6ml, 3.3mmol), NaO t -Bu (11.92g, 124mmol), toluene was obtained 6.98g (yield: 77%) of the product using the synthesis example of Sub 3-1.

3. Sub 3-3 Synthesis Example

<Scheme 23>

Starting materials 2-bromonaphthalene (8.91 g, 43 mmol) aniline (8.01 g, 86.1 mmol), Pd ₂ (dba) ₃ (1.18 g, 1.3 mmol), 50% P( t -Bu) ₃ (1.7 ml, 3.4 mmol), NaO t -Bu (12.41 g, 129.1 mmol), toluene was obtained 7.74 g (yield: 82%) of the product using the synthesis example of Sub 3-1.

4. Sub 3-8 Synthesis Example

<Reaction Scheme 24>

Starting materials 4-bromo-1,1'-biphenyl (12.74g, 54.7mmol), aniline (10.18g, 109.3mmol), Pd ₂ (dba) ₃ (1.5g, 1.6mmol), 50% P( t- Bu) ₃ (2.1ml, 4.4mmol), NaO t -Bu (15.76g, 164mmol), toluene was obtained using the Sub 3-1 synthesis example to obtain 11.13g of product (yield: 83%).

5. Sub 3-9 Synthesis Example

<Reaction Scheme 25>

Starting materials 3-bromo-1,1'-biphenyl (8.71g, 37.4mmol), aniline (6.96g, 74.7mmol), Pd ₂ (dba) ₃ (1.03g, 1.1mmol), 50% P( t- Bu) ₃ (1.5ml, 3mmol), NaO t -Bu (10.77g, 112.1mmol), toluene was obtained 7.24g (yield: 79%) of the product using the synthesis example of Sub 3-1.

6. Sub 3-23 Synthesis Example

<Reaction Scheme 26>

Starting materials 2-bromo-9,9-dimethyl-9 H -fluorene (8.89 g, 32.5 mmol) aniline (6.06 g, 65.1 mmol), Pd ₂ (dba) ₃ (0.89 g, 1 mmol), 50% P ( t -Bu) ₃ (1.3ml, 2.6mmol), NaO t -Bu (9.38g, 97.6mmol), toluene was obtained 6.97g (yield: 75%) of the product using the synthesis example of Sub 3-1.

7. Sub 3-24 Synthesis Example

<Reaction Scheme 27>

Starting materials 3-bromo-9,9-dimethyl-9 H -fluorene (11.18 g, 40.9 mmol) aniline (7.62 g, 81.9 mmol), Pd ₂ (dba) ₃ (1.12 g, 1.2 mmol), 50% P( t -Bu) ₃ (1.6ml, 3.3mmol), NaO t -Bu (11.8g, 122.8mmol), toluene was obtained 9.58g (yield: 82%) of the product using the synthesis example of Sub 3-1. .

8. Sub 3-34 Synthesis Example

<Reaction Scheme 28>

Starting materials 2-bromo-9,9-dimethyl-9 H -fluorene (12.28g, 45mmol), pyridin-3-amine (8.46g, 89.9mmol), Pd ₂ (dba) ₃ (1.23g, 1.3mmol) , 50% P( t -Bu) ₃ (1.8ml, 3.6mmol), NaO t -Bu (12.96g, 134.9mmol), toluene 8.63g of product using the synthesis example of Sub 3-1 (Yield: 67% ).

9. Sub 3-42 Synthesis Example

<Reaction Scheme 29>

Starting materials 2-bromodibenzo[ b , d ]furan (8.85g, 35.8mmol), aniline (6.67g, 71.6mmol), Pd ₂ (dba) ₃ (0.98g, 1.1mmol), 50% P( t -Bu ) ₃ (1.4ml, 2.9mmol), NaO t -Bu (10.33g, 107.5mmol), toluene was obtained 7.24g (yield: 78%) of the product using the synthesis example of Sub 3-1.

Meanwhile, examples of Sub 3 according to the synthesis example are as follows, but are not limited thereto, and their FD-MS are shown in Table 3 below.

[Table 3]

IV . Product synthesis

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

1. Synthesis example of P-2

<Scheme 30>

After dissolving Sub 2-1 (6.23 g, 8.7 mmol) obtained in the above synthesis in toluene in a round bottom flask, Sub 3-3 (1.91 g, 8.7 mmol), Pd ₂ (dba) ₃ (0.24 g, 0.3 mmol) , 50% P( t -Bu) ₃ (0.3ml, 0.7mmol), NaO t -Bu (2.51g, 26.1mmol) was added and stirred at 100°C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 6.32 g of product (yield: 85%).

2. Synthesis Example of P-10

<Scheme 31>

Sub 2-6 (7.04 g, 8.5 mmol) obtained in the above synthesis, Sub 3-9 (2.08 g, 8.5 mmol), Pd ₂ (dba) ₃ (0.23 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.3ml, 0.7mmol), NaO t -Bu (2.44g, 25.4mmol), toluene was obtained 6.49g (yield: 77%) of the product using the above P-2 synthesis example.

3. Synthesis of P-15

<Reaction Scheme 32>

Sub 2-1 (6.01 g, 8.4 mmol) obtained in the above synthesis, Sub 3-24 (2.4 g, 8.4 mmol), Pd ₂ (dba) ₃ (0.23 g, 0.3 mmol), 50% P( t -Bu) ₃ (0.3ml, 0.7mmol), NaO t -Bu (2.42g, 25.2mmol), toluene was obtained 6.18g (yield: 80%) of the product using the above P-2 synthesis example.

4. Synthesis Example of P-35

<Reaction Scheme 33>

Sub 2-48 (9.67 g, 11.2 mmol) obtained in the above synthesis, Sub 3-1 (1.89 g, 11.2 mmol), Pd ₂ (dba) ₃ (0.31 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4ml, 0.9mmol), NaO t -Bu (3.22g, 33.5mmol), toluene was obtained 6.93g (yield: 65%) using the P-2 synthesis example.

5. P-69 Synthesis Example

<Scheme 34>

Sub 2-52 (6.23g, 8.7mmol) obtained in the above synthesis, Sub 3-8 (2.14g, 8.7mmol), Pd ₂ (dba) ₃ (0.24g, 0.3mmol), 50% P( t -Bu) ₃ (0.3ml, 0.7mmol), NaO t -Bu (2.51g, 26.1mmol), toluene was obtained 6.21g (yield: 81%) using the P-2 synthesis example.

6. Synthesis Example of P-82

<Scheme 35>

Sub 2-62 (7.71 g, 9.6 mmol) obtained in the above synthesis, Sub 3-3 (2.1 g, 9.6 mmol), Pd ₂ (dba) ₃ (0.26 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4ml, 0.8mmol), NaO t -Bu (2.76g, 28.7mmol), toluene was obtained 6.87g (yield: 76%) of the product using the P-2 synthesis example.

7. Synthesis of P-85

<Scheme 36>

Sub 2-52 (5.96 g, 8.3 mmol) obtained in the above synthesis, Sub 3-23 (2.38 g, 8.3 mmol), Pd ₂ (dba) ₃ (0.23 g, 0.2 mmol), 50% P ( t -Bu) ₃ (0.3ml, 0.7mmol), NaO t -Bu (2.4g, 25mmol), toluene was obtained 6.36g (yield: 83%) of the product using the P-2 synthesis example.

8. P-98 Synthesis Example

<Reaction Scheme 37>

Sub 2-70 (7.47g, 9mmol) obtained in the above synthesis, Sub 3-1 (1.52g, 9mmol), Pd ₂ (dba) ₃ (0.25g, 0.3mmol), 50% P( t -Bu) ₃ ( 0.4ml, 0.7mmol), NaO t -Bu (2.59g, 26.9mmol), and toluene were used to obtain 6.03g of product (yield: 73%) using the P-2 synthesis example.

9. Synthesis Example of P-101

<Scheme 38>

Sub 2-73 (7.35 g, 10.3 mmol) obtained in the above synthesis, Sub 3-1 (1.74 g, 10.3 mmol), Pd ₂ (dba) ₃ (0.28 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4ml, 0.8mmol), NaO t -Bu (2.96g, 30.8mmol), and toluene were obtained using the P-2 synthesis example to give the product 6.52g (yield: 79%).

10. Synthesis Example of P-138

<Scheme 39>

Sub 2-100 (6.42 g, 9 mmol) obtained in the above synthesis, Sub 3-2 (1.97 g, 9 mmol), Pd ₂ (dba) ₃ (0.25 g, 0.3 mmol), 50% P( t -Bu) ₃ ( 0.3ml, 0.7mmol), NaO t -Bu (2.59g, 26.9mmol), and toluene were obtained 6.36g (yield: 83%) using the P-2 synthesis example.

11.P-152 Synthesis Example

<Reaction Scheme 40>

Sub 2-100 (7.54 g, 10.5 mmol) obtained in the above synthesis, Sub 3-34 (3.02 g, 10.5 mmol), Pd ₂ (dba) ₃ (0.29 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4ml, 0.8mmol), NaO t -Bu (3.04g, 31.6mmol), toluene was obtained 6.11g (yield: 63%) of the product using the P-2 synthesis example.

12. Synthesis Example of P-153

<Reaction Scheme 41>

Sub 2-100 (6.61 g, 9.2 mmol) obtained in the above synthesis, Sub 3-42 (2.39 g, 9.2 mmol), Pd ₂ (dba) ₃ (0.25 g, 0.3 mmol), 50% P( t -Bu) ₃ (0.4ml, 0.7mmol), NaO t -Bu (2.66g, 27.7mmol), toluene was obtained using the above P-2 synthesis example to give the product 6.52g (yield: 79%).

13. Synthesis Example of P-195

<Reaction Scheme 42>

Sub 3-132 (3.02g, 10.6mmol), Pd ₂ (dba) ₃ (0.29g, 0.3mmol), 50% P( t -Bu) to Sub 2-132 (7.57g, 10.6mmol) obtained in the above synthesis. ₃ (0.4ml, 0.8mmol), NaO t -Bu (3.05g, 31.7mmol), toluene was obtained 5.94g (yield: 61%) of the product using the above P-2 synthesis example.

14. P-198 Synthesis Example

<Scheme 43>

Sub 2-145 (7.61 g, 9.3 mmol) obtained in the above synthesis, Sub 3-1 (1.58 g, 9.3 mmol), Pd ₂ (dba) ₃ (0.26 g, 0.3 mmol), 50% P ( t -Bu) ₃ (0.4ml, 0.7mmol), NaO t -Bu (2.69g, 28mmol), toluene was obtained 6.33g (yield: 75%) of the product using the P-2 synthesis example.

On the other hand, FD-MS values of the compounds P-1 to P-200 of the present invention prepared according to the above synthesis example are shown in Table 4 below.

[Table 4]

On the other hand, although the exemplary synthetic examples of the compounds according to the present invention have been described above, they are all Suzuki cross-coupling reactions, PPh ₃ -mediated reductive cyclization reactions ( J. Org . Chem . 2005, 70, 5014.), Ullmann reactions , Other substituents defined in Chemical Formula 1 (Ar ¹ to Ar ⁴ , L ¹ , R ¹ to R ⁴ , m, n, o and other substituents specified in the specific synthetic examples based on Miyaura boration reaction and Buchwald-Hartwig cross coupling reaction, etc.) Those skilled in the art will readily understand that the reaction proceeds even when a substituent such as p) is bound. For example, in Reaction Scheme 2, starting materials -> Sub 1-I, Reaction Scheme 9, Sub 1A -> Sub 2-I, Sub 2-I -> Sub 2-II, Sub 2-III -> Sub 2 Based on the Suzuki cross-coupling reaction, the sub 1-I -> Sub 1-II reaction in Scheme 2 is based on the PPh ₃ -mediated reductive cyclization reaction, and the sub 1-II -> Sub 1-III reaction in Scheme 2 is It is based on the Ullmann reaction. Subsequently, in Scheme 2, Sub 1-III -> Sub 1, in Scheme 9, Sub 2-II -> Sub 2-III reaction is based on the Miyaura boration reaction, starting material in Scheme 20 -> Sub 3 and Scheme 30 to Scheme 43 Is based on the Buchwald-Hartwig cross coupling reaction, and these reactions will proceed even if substituents not specifically specified are combined.

Manufacturing evaluation of organic electric devices

[ Example I-1] Green Organic Electroluminescent Device ( Hole transport layer )

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a hole transport layer material. First, 4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as "2-TNATA") on an ITO layer (anode) formed on an organic substrate is vacuum-deposited to a thickness of 60 nm. After forming the hole injection layer, a hole transport layer was formed by vacuum-depositing the compound P-1 of the present invention on the hole injection layer to a thickness of 60 nm.Then, 4,4'-N,N' on the hole transport layer 90 using -dicarbazole-biphenyl (hereinafter abbreviated as "CBP") as a host material and tris(2-phenylpyridine)-iridium (hereinafter abbreviated as "Ir(ppy) ₃ ") as a dopant material: Doped at a weight ratio of 10 to form a light emitting layer by vacuum deposition to a thickness of 30 nm Then, (1,1'-bisphenyl)-4-oleito)bis(2-methyl-8-quinolinoleito)aluminum ( Hereinafter, a "BAlq" abbreviation) is vacuum-deposited to a thickness of 10 nm to form a hole blocking layer, and a tris(8-quinolinol) aluminum (hereinafter abbreviated as "Alq ₃ ") on the hole blocking layer is 40 nm thick. An electron transport layer was formed by vacuum deposition with an organic electroluminescent device by depositing LiF, a halogenated alkali metal, to a thickness of 0.2 nm to form an electron injection layer, and then depositing Al to a thickness of 150 nm to form a cathode. Was prepared.

[ Example I-2] to [ Example I-200] Green Organic Electroluminescent Device ( Hole transport layer )

Organic electroluminescence in the same manner as in Example I-1, except that one of the compounds P-2 to P-200 of the present invention shown in Table 5 below was used instead of the compound P-1 of the present invention as the hole transport layer material. The device was prepared.

[ Comparative example I-1]

An organic electroluminescent device was manufactured in the same manner as in Example I-1, except that the following comparative compound 1 was used instead of the compound P-1 of the present invention as the hole transport layer material.

<Comparative Compound 1>

[ Comparative example I-2]

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

<Comparative Compound 2>

[ Comparative example I-3]

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

<Comparative Compound 3>

PR of photoresearch by applying a net bias DC voltage to the organic electroluminescent elements produced by Examples I-1 to I-200 and Comparative Examples I-1 to Comparative Example I-3 of the present invention The electroluminescence (EL) characteristic was measured at 650, and the T95 life was measured through a life measurement equipment manufactured by Max Science at a luminance of 5000 cd/m ² . The measurement results are shown in Table 5 below.

[Table 5]

As can be seen from the results of Table 5, the organic electroluminescent device using the compound of the present invention as a material for the hole transport layer has a relatively low driving voltage compared to the organic electroluminescent device using Comparative Compounds 1 to 3 as the hole transport layer material, Not only the luminous efficiency was improved, but also the lifespan was improved.

In particular, these results show that the results appear differently depending on whether the linking group L ¹ is introduced through the comparison of the compound of the present invention with comparative compound 2.

In the case of Comparative Compound 2, in which an amine group (-NAr ³ Ar ⁴ ) is directly bonded to a trivalent phenyl group in which two carbazole cores are bonded, a high lifespan is shown, but when comparing the efficiency with a compound of the present invention, it shows a relatively low efficiency. have. In the case of Comparative Compound 2, due to the high T ₁ value, the ability to block electrons is high, indicating a relatively high lifespan, but the difference from the host's HOMO level is increased, and thus it is judged that the compound of the present invention has lower efficiency.

It is judged that the difference between the HOMO level of the comparative compound 2 and the HOMO level of the host material is larger than the difference between the HOMO level of the compound of the present invention and the HOMO level of the host material, and it is difficult to easily move holes, thus reducing the charge balance in the light emitting layer and reducing efficiency. do.

On the other hand, in the case of the compound of the present invention in which the linking group L ¹ having a trivalent phenyl group to which two carbazole cores are bonded, the linkage length L ¹ is present between the trivalent phenyl group and the amine group (-NAr ³ Ar ⁴ ). The conjugation length) is increased and the band gap is narrower than that of Comparative Compound 2, which is considered to have a relatively low T ₁ value and a deep HOMO level.

However, there was almost no decrease in life due to the lowered T ₁ value of the compound of the present invention, but rather it was confirmed that the efficiency increased significantly due to the deep HOMO. Therefore, it is judged that the compound of the present invention has an appropriate T ₁ value capable of blocking electrons and a HOMO level capable of efficiently transporting holes.

Combining the above-described characteristics (deep HOMO energy level, high T ₁ value) shows that the band gap, electrical characteristics, and interface characteristics can be changed significantly depending on whether the connector L ¹ is introduced or not. It can be confirmed that it acts as a factor.

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

[ Example II -One] Blue organic electroluminescent device ( Light emitting 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 vacuum injection layer of 2-TNATA to a thickness of 60 nm is formed on an ITO layer (anode) formed on a glass substrate to form a hole injection layer, and then N,N'-Bis(1-naphthalenyl)-N on the hole injection layer, A hole transport layer was formed by vacuum deposition of N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (hereinafter abbreviated as "NPB") to a thickness of 60 nm. Subsequently, after forming a light-emitting auxiliary layer by vacuum-depositing the compound P-1 of the present invention to a thickness of 20 nm on the hole transport layer, 9,10-Di(2-naphthyl)anthracene (hereinafter referred to as "the light-emitting auxiliary layer") ADN" abbreviated as) as a host material, and BD-052X (manufactured by Idemitsu kosan) as a dopant material was 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 on the hole blocking layer to a thickness of 40 nm. Subsequently, an organic electroluminescent device was manufactured by depositing LiF, a halogenated alkali metal, to a thickness of 0.2 nm to form an electron injection layer, and then depositing Al to a thickness of 150 nm to form a cathode.

[ Example II -2] to [ Example II -80] Blue organic electroluminescent device ( Light emitting auxiliary layer )

Organic electroluminescence in the same manner as in Example II-1, except that one of the compounds P-2 to P-200 of the present invention shown in Table 6 was used instead of the compound P-1 of the present invention as the light-emitting auxiliary layer material. A light emitting device was manufactured.

[ Comparative example II -One]

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

[ Comparative example II -2]

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

[ Comparative example II -3]

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

<Comparative compound 4>

[ Comparative example II -4]

An organic electroluminescent device was manufactured in the same manner as in Example II-1, except that instead of Compound P-1 of the present invention, the following Comparative Compound 5 was used as the light-emitting auxiliary layer material.

<Comparative compound 5>

[ Comparative example II -5]

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

<Comparative compound 6>

[ Comparative example II -6]

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

<Comparative Compound 7>

[ Comparative example II -7]

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

PR of photoresearch by applying a direct bias DC voltage to the organic electroluminescent elements prepared by Examples II-1 to II-77 and Comparative Examples II-1 to II-7 of the present invention The electroluminescence (EL) characteristic was measured at 650, and the T95 life was measured through a life measurement equipment manufactured by Max Science at a luminance of 500 cd/m ² . The measurement results are shown in Table 6 below.

[Table 6]

[ Example III -1] Green organic electroluminescent device ( Light emitting 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 2-TNATA was vacuum-deposited to a thickness of 60 nm on an ITO layer (anode) formed on a glass substrate to form a hole injection layer, and then NPB was vacuum-deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Subsequently, after forming a light-emitting auxiliary layer by vacuum-depositing the compound P-1 of the present invention to a thickness of 20 nm on the hole transport layer, CBP as a host material and Ir(ppy) ₃ dopant on the light-emitting auxiliary layer As a material, doped at a weight ratio of 90:10 to form a light emitting layer by vacuum deposition to a thickness of 30nm. 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 on the hole blocking layer to a thickness of 40 nm. Subsequently, an organic electroluminescent device was manufactured by depositing LiF, a halogenated alkali metal, to a thickness of 0.2 nm to form an electron injection layer, and then depositing Al to a thickness of 150 nm to form a cathode.

[ Example III -2] to [ Example III -135] Green organic electroluminescent device ( Light emitting auxiliary layer )

Organic electrolysis in the same manner as in Example III-1, except that one of the compounds P-2 to P-200 of the present invention described in Table 7 below was used instead of the compound P-1 of the present invention as the light-emitting auxiliary layer material. A light emitting device was manufactured.

[ Comparative example III -One]

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

[ Comparative example III -2]

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

[ Comparative example III -3]

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

[ Comparative example III -4]

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

[ Comparative example III -5]

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

[ Comparative example III -6]

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

[ Comparative example III -7]

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

PR of photoresearch by applying a forward bias DC voltage to the organic electroluminescent elements produced by Examples III-1 to III-129 and Comparative Examples III-1 to Comparative Example III-7 of the present invention Electroluminescence (EL) characteristics were measured at 650, and T95 life was measured through a life measurement equipment manufactured by Max Science at a luminance of 5000 cd/m ² . The measurement results are shown in Table 7 below.

[Table 7]

[ Example IV -One] Red organic electroluminescent device ( Light emitting 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 2-TNATA was vacuum-deposited to a thickness of 60 nm on an ITO layer (anode) formed on a glass substrate to form a hole injection layer, and then NPB was vacuum-deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Subsequently, after forming a light-emitting auxiliary layer by vacuum-depositing the compound P-1 of the present invention to a thickness of 20 nm on the hole transport layer, CBP is used as a host material on the light-emitting auxiliary layer, bis-(1-phenylisoquinolyl)iridium (III) Acetylacetonate (hereinafter abbreviated as "(piq) ₂ Ir(acac)") was used as a dopant material and doped at a weight ratio of 95:5 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 on the hole blocking layer to a thickness of 40 nm. Subsequently, an organic electroluminescent device was manufactured by depositing LiF, a halogenated alkali metal, to a thickness of 0.2 nm to form an electron injection layer, and then depositing Al to a thickness of 150 nm to form a cathode.

[ Example IV -2] to [ Example IV -109] Red organic electroluminescent device ( Light emitting auxiliary layer )

Organic electroluminescence in the same manner as in Example IV-1, except that one of the compounds P-2 to P-200 of the present invention shown in Table 8 was used instead of the compound P-1 of the present invention as the light-emitting auxiliary layer material. A light emitting device was manufactured.

[ Comparative example IV -One]

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

[ Comparative example IV -2]

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

[ Comparative example IV -3]

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

[ Comparative example IV -4]

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

[ Comparative example IV -5]

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

[ Comparative example IV -6]

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

[ Comparative example IV -7]

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

PR of photoresearch by applying a forward bias DC voltage to the organic electroluminescent elements produced by Examples IV-1 to IV-104 and Comparative Examples IV-1 to IV-7 of the present invention The electroluminescence (EL) characteristic was measured at 650, and the T95 life was measured through a life measurement equipment manufactured by Max Science at a reference luminance of 2500 cd/m ² . The measurement results are shown in Table 8 below.

[Table 8]

As can be seen from the results of Tables 6 to 8, the organic electroluminescent device using the compound of the present invention as a material for the light-emitting auxiliary layer compared to the organic electroluminescent devices of Comparative Examples II-1 to IV-4 This improved and the lifespan was significantly improved.

As a result, it can be seen that, in particular, the devices using Comparative Compound 2 to Comparative Compound 7 and the compound of the present invention as a light-emitting auxiliary layer have improved luminous efficiency and lifespan, compared to devices that do not form a light-emitting guard layer. It can be seen that the compound of the compound exhibits significantly higher results in terms of luminous efficiency and life. This is because the introduction of the linking group L ¹ of a trivalent phenyl group in which two carbazole cores are combined acts as a major factor in improving the performance of the device not only in the hole transport layer but also in the light-emitting auxiliary layer (blue fluorescence, green phosphorescence, red phosphorescence), and deep HOMO It is believed that this is because it makes it easy to achieve charge balance in the light emitting layer due to energy level and high T ₁ value. In addition, in the case of Comparative Compounds 4 to 7, as in the compound of the present invention, a structure in which two carbazoles are bonded to a trivalent phenyl group, or a heterocyclic group other than an amine group is bonded. As a result of comparing the device evaluation results of 8, it was confirmed that it exhibits a very slow driving voltage and a very low lifetime than the compound of the present invention containing an amine group. This is because the HOMO level of the comparative compound 4 to the comparative compound 7 is not suitable between the HOMO level of the hole transport layer and the HOMO level of the light emitting host material, so the hole transport ability is very poor, and therefore, the device must maintain a high voltage state when driving the device. In addition, it is judged that the life is reduced due to the thermal damage, and the balance of charge in the light emitting layer is reduced due to the low hole transport ability, so that the life is reduced.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains will be capable of various modifications without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed herein are not intended to limit the present invention, but to explain the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be interpreted by the following claims, and all technologies within the equivalent range should be interpreted as being included in the scope of the present invention.

100: organic electrical element 110: substrate
120: first electrode 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light-emitting layer 151: light-emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (11)

Compound represented by the formula (1):
<Formula 1>

In Chemical Formula 1,
m and o are integers from 0 to 4, n and p are integers from 0 to 3,
R ¹ to R ⁴ are independently of each other, iii) deuterium; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; A fused ring group of an aromatic ring of C ₆ to C ₆₀ and an aliphatic ring of C ₃ to C ₆₀ ; C ₂ ~ C ₂₀ alkenyl group; -L ^a -N(Ar ^a )(Ar ^b ); C ₁ ~C ₃₀ Alkoxy group; And C ₆ ~ C ₃₀ aryloxy group; or ii) adjacent groups are bonded to each other to form at least one ring (however, groups that do not form a ring are defined in i). Same as)),
L ¹ is independently of each other, a C ₆ ~ C ₆₀ arylene group; Fluorylene group; A C ₂ to C _{60 divalent} heterocyclic group including at least one hetero atom among O, N, S, Si and P; And C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C ₆₀ of the ring 2 is a member selected from the group consisting of a fused ring, each of which is deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C ₁ ~ C ₂₀ alkylthio; C ₁ ~ C ₂₀ alkoxyl group; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₆ ~ C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ heterocyclic group; C ₃ ~ C ₂₀ cycloalkyl group; C ₇ ~ C ₂₀ Arylalkyl group; -N(Ar ^c )(Ar ^d ); And C ₈ ~ C ₂₀ Aryl alkenyl group; It may be substituted with one or more substituents selected from the group consisting of, wherein, Ar ^c and Ar ^d are independently of each other, C ₆ ~ C ₆₀ aryl group; fluorenyl group ; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; may be substituted with one or more substituents selected from the group consisting of),
Ar ¹ to Ar ⁴ are independently of each other, a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; A fused ring group of an aromatic ring of C ₆ to C ₆₀ and an aliphatic ring of C ₃ to C ₆₀ ; C ₂ ~ C ₂₀ alkenyl group; -L ^a -N(Ar ^a )(Ar ^b ); C ₁ ~C ₃₀ Alkoxy group; And C ₆ ~ C ₃₀ Aryloxy group; It is selected from the group consisting of,
L ^a is a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; A C ₂ to C _{60 divalent} heterocyclic group including at least one hetero atom among O, N, S, Si and P; And two of the aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C ₆₀ is selected from the group consisting of a fused ring,
The Ar ^a and Ar ^b are independently of each other, C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; A fused ring group of an aromatic ring of C ₆ to C ₆₀ and an aliphatic ring of C ₃ to C ₆₀ ; And C ₂ ~ C ₂₀ alkenyl group; is selected from the group consisting of,
Here, the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxyl group, aryloxy group of R ¹ to R ⁴ and Ar ¹ to Ar ⁴ , respectively, deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C ₁ ~ C ₂₀ alkylthio; C ₁ ~ C ₂₀ alkoxyl group; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₆ ~ C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ heterocyclic group; C ₃ ~ C ₂₀ cycloalkyl group; C ₇ ~ C ₂₀ Arylalkyl group; And C ₈ ~ C ₂₀ Aryl alkenyl group; It may be substituted with one or more substituents selected from the group consisting of,
However, the following compounds are excluded from the compound represented by Formula 1:

,

,

,

. According to claim 1,
L ¹ of Formula 1 is a compound characterized in that one of the following structures:

In the above structure,
Q ¹ is C(R ⁵ ) or N;
Q ² is C(R ⁶ )(R ⁷ ), N(R ⁸ ), S or O,
R ⁵ is hydrogen; heavy hydrogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₁ ~C ₃₀ Alkoxy group; And -N(Ar ^e )(Ar ^f ); wherein Ar ^e and Ar ^f are independently of each other, a C ₆ ~C ₆₀ aryl group; Fluorenyl group; And O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom; is selected from the group consisting of,
R ⁶ to R ⁸ are independently of each other, C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; And C ₁ ~ C ₃₀ alkoxyl group; is selected from the group consisting of. According to claim 1,
Chemical Formula 1 is a compound characterized in that represented by one of the following Chemical Formulas 2 to 22:
<Formula 2><Formula3><Formula4>

<Formula 5><Formula6><Formula7>

<Formula 8><Formula9><Formula10>

<Formula 11><Formula12><Formula13>

<Formula 14><Formula15><Formula16>

<Formula 17><Formula18><Formula19>

<Formula 20><Formula21><Formula22>

In Formulas 2 to 22, Ar ¹ to Ar ⁴ , L ¹ , R ¹ to R ⁴ , m, n, o and p are the same as defined in claim 1. According to claim 1,
The compound represented by Formula 1 is one of the following compounds:

. An organic electric device comprising the compound of any one of claims 1 to 4. The method of claim 5,
A first electrode; A second electrode; And an organic material layer positioned between the first electrode and the second electrode, wherein the compound is contained in the organic material layer. The method of claim 6,
The compound is an organic electroluminescent device characterized in that it is contained in at least one of the hole injection layer, the hole transport layer, the light-emitting auxiliary layer or the light-emitting layer of the organic layer. The method of claim 6,
An organic electric device further comprising a light efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer. The method of claim 6,
The organic layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device comprising the organic electroluminescent element of claim 5; And
And a control unit driving the display device. The method of claim 10,
The organic electric device is an electronic device, characterized in that at least one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a monochromatic or white lighting device.

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